The structures of eleven (4-phen­yl)piperazinium salts containing organic anions

Eleven (4-phen­yl)piperazinium salts containing organic anions have been prepared and structurally characterized, namely, 4-phenyl­piperazin-1-ium 4-fluoro­benzoate monohydrate, C₁₀H₁₅N₂⁺·C₇H₄FO₂⁻·H₂O, 1; 4-phenyl­piperazin-1-ium 4-bromo­benzoate monohydrate, C₁₀H₁₅N₂⁺·C₇H₄BrO₂⁻·H₂O, 3; 4-phenyl­piperazin-1-ium 4-iodo­benzoate, C₁₀H₁₅N₂⁺·C₇H₄IO₂⁻, 4; 4-phenyl­piperazin-1-ium 4-nitro­benzoate, C₁₀H₁₅N₂⁺·C₇H₄NO₄⁻, 5; 4-phenyl­piperazin-1-ium 3,5-di­nitro­salicylate, C₁₀H₁₅N₂⁺·C₇H₃N₂O₇⁻, 6; 4-phenyl­piperazin-1-ium 3,5-di­nitro­benzoate, C₁₀H₁₅N₂⁺·C₇H₃N₂O₆⁻, 7; 4-phenyl­piperazin-1-ium picrate, C₁₀H₁₅N₂⁺·C₆H₂N₃O₇⁻, 8; 4-phenyl­piperazin-1-ium benzoate monohydrate, C₁₀H₁₅N₂⁺·C₇H₅O₂⁻·H₂O, 9; 4-phenyl­piperazin-1-ium p-toluene­sulfonate, C₁₀H₁₅N₂⁺·C₇H₇O₃S⁻, 10; 4-phenyl­piperazin-1-ium tartarate monohydrate, C₁₀H₁₅N₂⁺·C₄H₅O₆⁻·H₂O, 11; and 4-phenyl­piperazin-1-ium fumarate, C₁₀H₁₅N₂⁺·C₄H₃O₄⁻, 12. Compounds 1 and 3–12 are all 1:1 salts with the acid proton transferred to the phenyl­piperaizine basic N atom (the secondary amine) with the exception of 3 where there is disorder in the proton position with it being 68% attached to the base and 32% attached to the acid. Of the structures with similar stoichiometries only 3 and 9 are isomorphous. The 4-phenyl substituent in all cases occupies an equatorial position except for 12 where it is in an axial position. The crystal chosen for structure 7 was refined as a non-merohedral twin. There is disorder in 5, 6, 10 and 11. For both 5 and 6, a nitro group is disordered and was modeled with two equivalent orientations with occupancies of 0.62 (3)/0.38 (3) and 0.690 (11)/0.310 (11), respectively. For 6, 10 and 11, this disorder is associated with the phenyl ring of the phenyl­piperazinium cation with occupancies of 0.687 (10)/0.313 (10), 0.51 (7)/0.49 (7) and 0.611 (13)/389 (13), respectively. For all salts, the packing is dominated by the N—H⋯O hydrogen bonds formed by the cation and anion. In addition, several structures contain C—H⋯π (1, 3, 4, 8, 9, 10, and 12) and aromatic π–π stacking inter­actions (6 and 8) and one structure (5) contains a –NO₂⋯π inter­action. For all structures, the Hirshfeld surface fingerprint plots show the expected prominent spikes as a result of the N—H⋯O and O—H⋯O hydrogen bonds.

1. Chemical context

The pharmacological properties of phenyl­piperazines and their derivatives have been described by various researchers (Cohen et al. 1982; Conrado et al. 2010; Neves et al. 2003; Hanano et al. 2000). The design and synthesis of phenyl­piperazine derivatives as potent anti­cancer agents for prostate cancer have been reported (Demirci et al., 2019). Many pharmaceutical compounds are derived from 1-phenyl­piperazine, including oxypertine (Archer et al., 1962), trazodone (Alhaider, 1992) and nefazodone. Derivatives of 1-phenyl­piperazine have shown other inter­esting properties, such as (C₁₀H₁₅N₂)⁺₄(Pb₃Cl₁₀)^4– where dielectric relaxation spectroscopy has shown different mol­ecular motions and measurements of AC conductivity as a function of frequency at different temperatures indicated a hopping conduction mechanism (Mathlouthi et al., 2017) and new organic–inorganic hybrid materials of formula (C₁₀H₁₅N₂)₇(Sb₂Cl₁₀)(Sb₂Cl₉)(SbCl₅)₂(SbCl₄)₂Cl·7H₂O (Lah­bib et al., 2017).

As part of our ongoing studies of hydrogen-bonding patterns in mol­ecular salts (Sagar et al., 2017; Kiran Kumar et al., 2019a,b, 2020, Harish Chinthal et al., 2020), the present paper reports the syntheses and crystal structures of eleven mol­ecular salts of 1-phenyl­piperazine, C₁₀H₁₄N₂, viz.: 4-phen­yl­piperazin-1-ium 4-fluoro­benzoate monohydrate, C₁₀H₁₅N₂⁺·C₇H₄FO₂⁻·H₂O, 1; phenyl­piperazin-1-ium 4-bro­mo­benzoate monohydrate, C₁₀H₁₅N₂⁺·C₇H₄BrO₂⁻·H₂O, 3; phenyl­piperazin-1-ium 4-iodo­benzoate, C₁₀H₁₅N₂⁺·C₇H₄IO₂⁻, 4; phenyl­piperazin-1-ium 4-nitro­benzoate, C₁₀H₁₅N₂⁺·C₇H₄NO₄⁻, 5; phenyl­piperazin-1-ium 3,5-di­nitro­salicylate, C₁₀H₁₅N₂⁺·C₇H₃N₂O₇⁻, 6; phenyl­piperazin-1-ium 3,5-di­nitro­benzoate, C₁₀H₁₅N₂⁺·C₇H₃N₂O₆⁻, 7; phenyl­piperazin-1-ium picrate, C₁₀H₁₅N₂⁺·C₆H₂N₃O₇⁻, 8; phenyl­piperazin-1-ium benzoate monohydrate, C₁₀H₁₅N₂⁺·C₇H₅O₂⁻·H₂O, 9; phenyl­piperazin-1-ium p-toluene­sulfonate, C₁₀H₁₅N₂⁺·C₇H₇O₃S⁻, 10; phenyl­piperazin-1-ium tartarate monohydrate, C₁₀H₁₅N₂⁺·C₄H₅O₆⁻·H₂O, 11; and phenyl­piperazin-1-ium fumarate, C₁₀H₁₅N₂⁺·C₄H₃O₄⁻, 12.

2. Structural commentary

Compounds 1 and 3–12 (Figs. 1–11) are all 1:1 mol­ecular salts with the acid proton transferred to the secondary N atom of the phenyl­piperaizine base with the exception of 3 where there is disorder in the proton position with it being 68% attached to the base and 32% attached to the acid. Compounds 1, 3 and 9 crystallize as mono-hydrates but the remaining crystals are solvent free. In compounds 1, 3, 4, 5 and 9, the anions are all benzoate ions or p-substituted benzoates but only 3 and 9 are isomorphous. Compounds 6, 7 and 8 contain picrate or nitrated benzoate anions while 10 contains a tosyl­ate anion and 11 and 12 contain hydrogen tartarate and hydrogen fumarate mono-anions. Apart from the disorder in the acidic proton position mentioned above, there is disorder in 5, 6, 10 and 11. For 5 this disorder is confined to the nitro substituent on the benzoate anion, which is disordered over two orientations with occupancies of 0.62 (3)/0.38 (2). For 6, 10 and 11 the disorder is associated with the phenyl ring of the phenyl­piperazinium cation, with occupancies of 0.687 (10)/0.313 (10), 0.51 (7)/0.49 (7) and 0.611 (13)/389 (13), respectively. This is a common feature of this moiety as shown in a recent study (Kiran Kumar et al., 2019a) of 12 salts of the 4-meth­oxy­phenyl­piperazinium cation, of which four were found to contain similar disorder of the phenyl ring.

Figure 1 The mol­ecular structure of 1 with hydrogen bonds shown as dashed lines. Atomic displacement parameters are at the 30% probability level.

Figure 2 The mol­ecular structure of 3 with hydrogen bonds shown as dashed lines. Atomic displacement parameters are at the 30% probability level.

Figure 3 The mol­ecular structure of 4 with hydrogen bonds shown as dashed lines. Atomic displacement parameters are at the 30% probability level.

Figure 4 The mol­ecular structure of 5 with hydrogen bonds shown as dashed lines and disorder of the nitro group indicated. Atomic displacement parameters are at the 30% probability level.

Figure 5 The mol­ecular structure of 6 with hydrogen bonds shown as dashed lines and disorder of the phenyl ring and one nitro group indicated. Atomic displacement parameters are at the 30% probability level.

Figure 6 The mol­ecular structure of 7 with hydrogen bonds shown as dashed lines. Atomic displacement parameters are at the 30% probability level.

Figure 7 The mol­ecular structure of 8 with hydrogen bonds shown as dashed lines. Atomic displacement parameters are at the 30% probability level.

Figure 8 The mol­ecular structure of 9 with hydrogen bonds shown as dashed lines. Atomic displacement parameters are at the 30% probability level.

Figure 9 The mol­ecular structure of 10 with hydrogen bonds shown as dashed lines and disorder of the phenyl rings indicated. Atomic displacement parameters are at the 30% probability level.

Figure 10 The mol­ecular structure of 11 with hydrogen bonds shown as dashed lines and disorder of the phenyl ring indicated. Atomic displacement parameters are at the 30% probability level.

Figure 11 The mol­ecular structure of 12 with hydrogen bonds shown as dashed lines. Atomic displacement parameters are at the 30% probability level. Note the axial conformation of the phenyl ring.

For the structures containing benzoate or p-substituted benzoate anions, the C—O distances fall into two groups. In one group (3, 5), these distances are the same within experimental error at 2.246 (4) Å, while in the second group (1, 4, and 9) these are substanti­ally different and average 2.235 (4) and 2.255 (4) Å.

For the structures containing the 3,5-di­nitro­salicylic (6), 3,5-di­nitro­benzoate (7) and 2,3,5-tri­nitro­phenolate ions (8), some inter­esting patterns emerge. In the anion of compound 6, the carboxyl group is unionized, with C—O distances of 1.211 (4) and 1.309 (4) Å and it is the phenolic H atom that has been lost (Fig. 5). The C12—O3 distance, 1.283 (4) Å, is closer to that normally found in ketones than to that typical of phenols or phenolates (Allen et al., 1987). In addition, the C11—C12 and C12—C13 distances, 1.428 (4) and 1.449 (5) Å, respectively, are significantly larger than the other C—C distances in this ring, which lie in the rather narrow range 1.370 (4)–1.398 (4) Å, but the C—N and N—O distances of the nitro substituents are all typical of their types. These observations indicate that the negative charge in this anion is delocalized over the five atoms C11, C13, C14, C15 and C16, but without any significant delocalization onto the nitro groups, as has been observed in tri­nitro­phenolate (picrate) anions (Kavitha et al., 2006; Sagar et al., 2017; Shaibah et al., 2017a,b). The carboxyl­ate anion in 7 contains similar C—O distances [C17—O1 = 1.251 (14); C17—O2 = 1.256 (14) Å]. Structure 8 contains a picrate anion. Here the situation is similar to that of 6 in that the C—O distance is even shorter at 1.244 (3) Å and in the phenyl ring the C—C bonds are not equal with C11—C12 and C11—C16 being 1.443 (3) and 1.445 (3) Å, respectively, while the remaining C—C bonds range from 1.360 (3) to 1.386 (3) Å. For the nitro groups the C—N distances range from 1.441 (3) to 1.456 (3) Å, indicating that the negative charge in this anion is also delocalized over the five atoms C11, C13, C14, C15 and C16, but without any significant delocalization onto the nitro groups.

Structure 10 contains the tosyl­ate anion. There are two formula units in the asymmetric unit and in both anions the S—O distances are almost equal within experimental error ranging from 1.448 (12) to 1.462 (11) Å and 1.430 (13) to 1.473 (11) Å. Structures 11 and 12 contain the mono-anions of the di-carb­oxy­lic acids tartaric acid and fumaric acid. For both structures the metrical parameters of both cation and anion are in the normal range for such species. It notable that in 1 and 3–11, the phenyl substituent occupies an equatorial position in the piperazinium cation, but for 12 this substituent occupies an axial position.

3. Supra­molecular features

In discussing the supra­molecular features of these eleven mol­ecular salts it is convenient to break these up into four groups based on the nature of the anion and the stoichiometry of the resulting salt. In the first group are structures 1, 3, 4, 5, and 9, which contain benzoate and substituted benzoate anions. In the second group are 6, 7, and 8 in which the anions contain nitrated phenyl rings. In the third group, 10 contains a tosyl­ate anion, and in the fourth group, 11 and 12 contain the mono-deprotonated di­carboxyl­ate anions hydrogen tartarate and hydrogen fumarate. The hydrogen bonds for 1 and 3–12 are listed in Tables 1–11.

Table 1
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1	0.90 (2)	2.65 (4)	3.215 (6)	122 (3)
N2—H21⋯O2	0.90 (2)	1.89 (2)	2.791 (5)	175 (4)
N2—H22⋯O3^i	0.88 (2)	1.96 (2)	2.812 (5)	163 (4)
C8—H8A⋯O2^ii	0.97	2.53	3.481 (6)	168
C8—H8B⋯O3	0.97	2.60	3.341 (5)	133
C9—H9A⋯O3^iii	0.97	2.59	3.416 (6)	143
O3—H31⋯O1^iv	0.83 (2)	1.79 (2)	2.619 (5)	176 (6)
O3—H32⋯O2	0.83 (2)	1.96 (2)	2.773 (5)	167 (6)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) x+1, y, z.

Table 2
Hydrogen-bond geometry (Å, °) for 3

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N1⋯O2	0.89	1.90	2.780 (11)	170
N2—H2N2⋯O3	0.89	1.94	2.803 (12)	164
C8—H8A⋯O3^i	0.97	2.64	3.377 (14)	133
C8—H8B⋯O2^ii	0.97	2.53	3.475 (14)	166
C9—H9B⋯O3^iii	0.97	2.59	3.403 (14)	142
O2—H2O⋯N2	0.82	2.00	2.780 (11)	159
O3—H31⋯O2^i	0.81 (2)	1.98 (2)	2.782 (12)	170 (7)
Symmetry codes: (i) ; (ii) ; (iii) .

Table 3
Hydrogen-bond geometry (Å, °) for 4

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O3	0.97	2.63	3.218 (4)	119
N2—H21N⋯O1^i	0.88 (2)	1.94 (2)	2.780 (4)	160 (3)
N2—H22N⋯O4	0.90 (2)	1.74 (2)	2.627 (4)	173 (3)
N4—H41N⋯O1	0.87 (2)	2.63 (3)	3.285 (4)	133 (3)
N4—H41N⋯O2	0.87 (2)	1.78 (2)	2.643 (4)	169 (3)
N4—H42N⋯O3^ii	0.85 (2)	1.97 (2)	2.809 (4)	169 (4)
Symmetry codes: (i) ; (ii) .

Table 4
Hydrogen-bond geometry (Å, °) for 5

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2^i	0.90 (1)	1.96 (2)	2.846 (2)	173 (2)
N2—H22⋯O1	0.93 (1)	1.78 (2)	2.7135 (19)	179 (2)
N2—H22⋯O2	0.93 (1)	2.49 (2)	3.057 (2)	120 (1)
C8—H8B⋯O1^ii	0.97	2.50	3.468 (2)	176
C10—H10B⋯O4A^iii	0.97	2.61	3.276 (15)	126
Symmetry codes: (i) ; (ii) ; (iii) .

Table 5
Hydrogen-bond geometry (Å, °) for 6

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O3	0.84 (2)	1.69 (2)	2.487 (3)	156 (4)
N2—H21⋯O3	0.88 (2)	2.03 (2)	2.873 (4)	159 (3)
N2—H21⋯O4	0.88 (2)	2.37 (3)	2.950 (6)	123 (3)
N2—H21⋯O4A	0.88 (2)	2.40 (4)	2.966 (10)	122 (3)
N2—H22⋯O1^i	0.87 (2)	2.10 (2)	2.947 (4)	164 (4)
N2—H22⋯O2^i	0.87 (2)	2.62 (3)	3.270 (4)	132 (3)
C8—H8A⋯O7^ii	0.97	2.36	3.134 (5)	137
C8—H8B⋯O4	0.97	2.44	3.000 (6)	116
C9—H9A⋯O4A	0.97	2.60	3.166 (8)	118
C9—H9B⋯O5^iii	0.97	2.58	3.311 (8)	132
C9—H9B⋯O5A^iii	0.97	2.29	3.040 (13)	133
Symmetry codes: (i) ; (ii) ; (iii) x+1, y, z.

Table 6
Hydrogen-bond geometry (Å, °) for 7

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O3^i	0.97	2.43	3.250 (14)	142
C10—H10B⋯O5^ii	0.97	2.58	3.366 (16)	138
N2—H21⋯O2	0.87 (3)	1.81 (4)	2.672 (13)	172 (13)
N2—H22⋯O1^iii	0.87 (3)	1.94 (4)	2.792 (13)	166 (12)
Symmetry codes: (i) ; (ii) ; (iii) x+1, y, z.

Table 7
Hydrogen-bond geometry (Å, °) for 8

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O4^i	0.97	2.42	3.265 (4)	145
C9—H9A⋯O4^ii	0.97	2.60	3.353 (4)	134
C9—H9A⋯O6^iii	0.97	2.61	3.455 (4)	146
N2—H21⋯O2	0.83 (3)	2.06 (3)	2.871 (3)	166 (3)
N2—H21⋯O7^iv	0.83 (3)	2.60 (3)	2.985 (3)	110 (2)
N2—H22⋯O1^iv	0.98 (3)	1.74 (3)	2.705 (3)	168 (3)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) x+1, y, z.

Table 8
Hydrogen-bond geometry (Å, °) for 9

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1	0.90 (2)	1.92 (2)	2.813 (3)	173 (2)
N2—H21⋯O2	0.90 (2)	2.56 (2)	3.112 (4)	121 (2)
N2—H22⋯O3^i	0.89 (2)	1.92 (2)	2.812 (3)	173 (2)
C9—H9A⋯O1^ii	0.97	2.48	3.420 (4)	164
C9—H9B⋯O3^iii	0.97	2.60	3.340 (4)	133
O3—H31⋯O1^iv	0.83 (2)	1.96 (2)	2.772 (3)	166 (4)
O3—H32⋯O2	0.83 (2)	1.77 (2)	2.599 (3)	179 (4)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) x+1, y, z.

Table 9
Hydrogen-bond geometry (Å, °) for 10

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21N⋯O6	0.89	2.07	2.884 (18)	151
N2—H22N⋯O4^i	0.89	1.92	2.774 (17)	161
C9—H9B⋯O1^ii	0.97	2.64	3.534 (19)	154
N4—H41N⋯O3^ii	0.89	1.92	2.788 (16)	163
N4—H42N⋯O1	0.89	2.09	2.890 (18)	149
N4—H42N⋯O5	0.89	2.43	2.865 (18)	111
C25—H25A⋯O6^iii	0.97	2.63	3.520 (18)	153
Symmetry codes: (i) ; (ii) ; (iii) .

Table 10
Hydrogen-bond geometry (Å, °) for 11

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O7^i	0.88 (2)	1.95 (2)	2.808 (5)	164 (4)
N2—H22⋯O1^ii	0.86 (2)	2.52 (3)	3.069 (4)	122 (3)
N2—H22⋯O5	0.86 (2)	2.22 (3)	2.820 (3)	127 (3)
N2—H22⋯O6^iii	0.86 (2)	2.41 (3)	2.992 (3)	125 (3)
C9—H9B⋯O2^iv	0.97	2.61	3.276 (4)	126
O3—H3O⋯O2	0.83 (2)	2.17 (3)	2.614 (3)	114 (3)
O3—H3O⋯O4^ii	0.83 (2)	2.04 (2)	2.789 (3)	150 (3)
O4—H4O⋯O1^ii	0.79 (2)	2.06 (3)	2.773 (3)	151 (3)
O6—H6O⋯O2^v	0.83 (2)	1.67 (2)	2.501 (3)	174 (3)
O7—H71O⋯O3	0.84 (2)	1.95 (2)	2.780 (3)	171 (4)
O7—H72O⋯O1^vi	0.85 (2)	1.97 (2)	2.821 (3)	178 (4)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Table 11
Hydrogen-bond geometry (Å, °) for 12

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O4	0.87 (2)	1.88 (2)	2.741 (2)	168 (2)
N2—H22⋯O1^i	0.89 (2)	1.89 (2)	2.775 (2)	172 (2)
C7—H7A⋯O2^ii	0.97	2.51	3.317 (3)	141
C8—H8B⋯O3^iii	0.97	2.55	3.203 (3)	124
C9—H9A⋯O2^iv	0.97	2.66	3.318 (3)	126
O2—H2O⋯O3^v	0.92 (2)	1.54 (2)	2.4610 (18)	174 (2)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) x, y+1, z.

Even though 1, 3, 4, 5, and 9 contain similar anions, only 3 and 9 are isomorphous. For 1 (Fig. 12), which contains a water mol­ecule of crystallization, there are R₆³(12) rings (Etter et al., 1990) made up of N—H⋯O and O—H⋯O hydrogen bonds, which involve the water mol­ecule, and R₄²(10) rings made up of N—H⋯O hydrogen bonds, which do not involve the water mol­ecule. This combination of R₆³(12) and R₄²(10) rings form ribbons propagating in the a-axis direction. In addition, there is a C—H⋯π inter­action involving C2—H2 and the C11–C16 phenyl ring (Cg1) [C2⋯Cg1 = 3.610 (6) Å; C2—H2⋯Cg1 = 133°; symmetry operation −x, 1 − y, 1 − z]. In the packing arrangement for 3 shown in Fig. 13, both R₄⁴(12) rings exhibit N—H⋯O and O—H⋯O hydrogen bonds involving the cation, anion and water mol­ecule as well as R₄²(10) rings showing O—H⋯O hydrogen bonds just associated with the cation and anion. These link the cations, anions and water mol­ecules into ribbons propagating in the [101] direction. In addition there is a C—H⋯π inter­action involving C2—H2 and the C11–C16 phenyl ring (Cg1) [C2⋯Cg1 = 3.6040 (14) Å; C2—H2⋯Cg1 = 133°; symmetry operation 1 − x, 1 − y, 1 − z].

Figure 12 Packing diagram for 1 viewed along the a axis showing the R6^3(12) rings made up of N—H⋯O and O—H⋯O hydrogen bonds, which involve the water mol­ecule, and R4^2(10) rings made up of N—H⋯O hydrogen bonds, which do not involve the water mol­ecule. This combination of R6^3(12) and R4^2(10) rings form ribbons propagating in the a-axis direction.

Figure 13 Packing diagram for 3 viewed along the [101] direction showing both R4^4(12) rings demonstrating N—H⋯O and O—H⋯O hydrogen bonds involving the cations, anions and water mol­ecule as well as R4^2(10) rings showing O—H⋯O hydrogen bonds just associated with the cations and anions. These link the cations, anions and water mol­ecules into ribbons propagating in the [101] direction.

In 4, there is no water mol­ecule of crystallization. In this case there is an R₈⁸(24) ring with a topology analogous to the seam of a tennis ball (Fig. 14) involving N—H⋯O hydrogen bonds. These collections of cations and anions linked by R₈⁸(24) rings pack in the a-axis direction (Fig. 15). In addition there is a C—H⋯π inter­action involving C19—H19 and the C21–C26 phenyl ring (Cg1) [C19⋯Cg1 = 3.750 (4) Å; C19—H19B⋯Cg1 = 154°; symmetry operation 1 − x, 1 − y, 1 − z]. In 5, R₄⁴(12) rings link the cations and anions via N—H⋯O hydrogen bonds and this collection forms ribbons in the b-axis direction (Fig. 16). In addition, the –NO₂ group accepts an N—H⋯(O,O) bifurcated hydrogen bond. There is a further inter­action with a phenyl ring (C11–C16, Cg1) involving the nitro substituent [N3⋯Cg1 = 3.530 (14) Å; N3—O3⋯Cg1 = 140.6 (13)°, symmetry operation x,  − y,  + z].

Figure 14 Partial packing diagram for 4 showing the R8^8(24) ring with a topology analogous to the seam of a tennis ball involving N—H⋯O hydrogen bonds.

Figure 15 Packing diagram for 4 viewed along the c axis showing how the R8^8(24) rings pack in the a-axis direction.

Figure 16 Packing diagram for 5 showing how the R4^4(12) rings link the cation and anion via N—H⋯O hydrogen bonds and this collection forms ribbons propagating in the b-axis direction.

In 6, there are R₄⁴(16) loops linking the phenyl­piperazinium cations and the 3,5-dintrosalicylate anions via N—H⋯O hydrogen bonds (Fig. 17). In addition, there are π–π inter­actions involving the phenyl ring (C11–C16, Cg1) of the 3,5-dintrosalicylate anions, which form offset stacks (slippages of 1.580 and 1.900 Å) in the [110] direction [Cg1⋯Cg1 = 3.3600 (15) Å; symmetry operation −x, 1 − y, 1 − z; Cg1⋯Cg1 = 3.3690 (15) Å; symmetry operation −x, 2 − y, 1 − z].

Figure 17 Packing diagram for 6 showing R4^4(16) loops linking the phenyl­piperazinium cations and the 3,5-dintrosalicylate anions via N—H⋯O and O—H⋯O hydrogen bonds.

The packing of 7 is composed of R₄⁴(22) rings in the (101) plane made up of N—H⋯O hydrogen bonds involving the phenyl­piperazinium cation and carboxyl­ate group of the 3,5-di­nitro­benzoate anion (Fig. 18). These planes are linked in the [111] direction by C₂²(6) chains also involving N—H⋯O hydrogen-bonding inter­actions involving the phenyl­piperazinium cation and carboxyl­ate group of the 3,5-di­nitro­benzoate anion and weak C—H⋯O inter­actions (Fig. 19). In this structure there are no C—H⋯π or π–π inter­actions.

Figure 18 Partial packing diagram for 7 showing R4^4(22) rings in the (101) plane made up of N—H⋯O hydrogen-bonding inter­actions involving the phenyl­piperazinium cation and carboxyl­ate group of the 3,5-di­nitro­benzoate anion.

Figure 19 Packing diagram for 7 showing how the R4^4(22) rings shown in the previous figure are linked in the [111] direction by C2^2(6) chains also involving N—H⋯O hydrogen bonds involving the phenyl­piperazinium cation and carboxyl­ate group of the 3,5-di­nitro­benzoate anion and weak C—H⋯O inter­actions.

In 8 there are C₂²(8) chains made up of N—H⋯O hydrogen bonds involving the phenyl­piperazinium cation and a nitro group of the picrate anion (Fig. 20). In addition, the picrate anions form strong π–π inter­actions (C1–C6, Cg1) in the a-axis direction [Cg1⋯Cg1 = 3.4395 (5) Å; symmetry operation 2 − x, 1 − y, −z; Cg1⋯Cg1 = 3.4223 (5) Å; symmetry operation 2 − x, −y, −z] (Fig. 21). Furthermore, there are C—H⋯π inter­actions involving the phenyl ring (C1–C6, Cg1) of the phenyl­piperazinium cation [C3⋯Cg1 = 3.683 (3) Å, C3—H3⋯Cg1 = 134°, symmetry operation 2 − x,  + y,  − z; C8⋯Cg1 = 3.512 (3) Å, C8—H8A⋯Cg1 = 160°, symmetry operation 1 − x, − + y,  − z] (one example shown in Fig. 22).

Figure 20 Partial packing diagram for 8 showing the C2^2(8) chains made up of N—H⋯O hydrogen bonds involving the phenyl­piperazinium cation and a nitro group of the picrate anion. Hydrogen-bonding inter­actions are shown by dashed lines.

Figure 21 Packing diagram for 8 viewed along the b axis showing how the picrate anions form π–π inter­actions in the a-axis direction.

Figure 22 Partial packing diagram for 8 showing one of the C—H⋯π inter­actions involving the phenyl ring of the phenyl­piperazinium cation.

In the case of 9 there are two anti-parallel C₂²(6) chains linked by N—H⋯O hydrogen bonds as well as C—H⋯O inter­actions involving the water oxygen atom, which combine to form ribbons propagating in the a-axis direction (Fig. 23). In addition, there are C—H⋯π inter­actions (C11–C16, Cg1) involving the benzoate phenyl ring [C2⋯Cg1 = 3.710 (4) Å, C2—H2⋯Cg1 = 141°, symmetry operation −x, 1 − y, 1 − z; C6⋯Cg1 = 3.656 (4) Å, C6—H6⋯Cg1 = 142°, symmetry operation 1 − x, 1 − y, 2 − z]. The overall packing is shown in Fig. 24.

Figure 23 Partial packing diagram for 9 showing one of the two anti-parallel C2^2(6) chains linked by N—H⋯O hydrogen bonds and C—H⋯O inter­actions propagating in the a-axis direction.

Figure 24 Packing diagram for 9 viewed along the c-axis direction showing the two anti-parallel C2^2(6) chains linked by N—H⋯O and C—H⋯O inter­actions involving the water oxygen atom, which combine to form ribbons in the a-axis direction.

The structure of 10 contains the tosyl­ate anion, which contains the non-planar –SO₃⁻ group. This results in a packing arrangement in which N—H⋯O hydrogen bonds involving the phenyl­piperazinium cations and tosyl­ate anions are arranged such that there are hydro­philic and hydro­phobic (110) planes (Fig. 25). This structure also contains C—H⋯π inter­actions involving one of the phenyl­piperazinium cations (C18–C23, Cg1) and tosyl­ate anions [C30⋯Cg1 = 3.74 (3) Å, C30—H30⋯Cg1 = 144°, symmetry operation 1 − x, − + y, −z].

Figure 25 Packing diagram for 10 viewed down the b axis showing the three-dimensional network of N—H⋯O hydrogen bonds involving phenyl­piperazinium cations and tosyl­ate anions, which arrange the ions such that there are hydro­philic and hydro­phobic (110) planes in the a-axis direction.

Structure 11 has a complicated packing arrangement as in addition to the phenyl­piperazinium NH₂ group, the flexible tartarate anion contains four OH groups and there is a water mol­ecule of crystallization. Multiple N—H⋯O and O—H⋯O hydrogen-bonding inter­actions combine to form a three-dimensional array (Fig. 26).

Figure 26 Packing diagram for 11 viewed along the a axis where multiple N—H⋯O and O—H⋯O hydrogen bonds involving the phenyl­piperazinium NH2 group, the tartarate anion and water mol­ecule of crystallization combine to form a three-dimensional network.

Structure 12 contains a phenyl­piperazinium cation and the monoanion of fumaric acid. In the packing of this structure, there are two C₁¹(7) chains in the b-axis direction involving the fumarate anions and composed of O—H⋯O hydrogen bonds. These chains are in turn cross-linked by both N—H⋯O hydrogen bonds and C—H⋯O inter­actions (Fig. 27). There are also C—H⋯π inter­actions involving the phenyl ring (C1–C6, Cg1) of the phenyl­piperazinium cation [C5⋯Cg1 = 3.723 (3) Å, C5—H5⋯Cg1 =144°, symmetry operation −x, 1 − y,  + z; C10⋯Cg1 = 3.608 (3) Å, C10—H10A⋯Cg1 = 145°, symmetry operation −x, −y, − + z].

Figure 27 Packing diagram for 12 viewed along the c-axis direction showing the two C1^1(7) chains propagating in the b-axis direction involving the fumarate anions and composed of O—H⋯O hydrogen bonds which are in turn cross-linked by both N—H⋯O hydrogen bonds and C—H⋯O inter­actions.

The Hirshfeld surface fingerprint plots for 1 and 3–12 generated using CrystalExplorer are available in the supporting information. All of them show the distinctive `pincer spikes' associated with the N—H⋯O and/or O—H⋯O hydrogen bonds (Spackman et al., 2021).

4. Database survey

The structural versatility of the 1-phenyl­piperazine moiety itself is shown by its involvement in many structural forms, including as neutral co-crystals [Cambridge Structural Database (Groom et al., 2016) refcodes HINQUR and HINRAY, Müller-Buschbaum & Zurawski, 2007], as neutral ligands (HIWJAY, Stocker et al., 1999; HIWJAY01, VIYPIE, VIYPOK, VIYPUQ; Pike et al., 2014), as simultaneously both neutral ligands and co-crystals (FITTEI and FITTIM, Quitmann & Müller-Buschbaum, 2005; HOCBEH, HOCBIL, PIYXEB, Zurawski & Müller-Buschbaum, 2008). In addition, there have been many structural investigations of 1-phenyl­piperazine as a cation, combined with simple anions (DMPIPZ, Cho­thia & Pauling, 1978; JEHXIE, Batsanov et al., 2006; KUZWUY, Marouani et al., 2010; LOHQIL, Oueslati et al., 2019; QORVEB, Marouani et al., 2012; SUYXEQ, Essid et al., 2010), with simple anionic metal salts (BEBKAX, Lahbib et al., 2017; CEBHIB, Garbia et al., 2005; PENWAJ, Mathlouthi et al., 2017; PHPIPZ, Battaglia et al., 1979; QIZPIA, Dhieb et al., 2014; SUKKAM, Dhieb et al., 2015; ZAMHUQ, Zouari et al., 1995), combined with anionic carboxyl­ates (IGOGUI, Pang et al., 2015; VAKCIW, Zong et al., 2016; Mahesha et al., 2022), combined with anionic pyrimidines (DUPMUY, DUPNAF, Al-Alshaikh et al., 2015), combined with anionic ligands (WOVKAW, Lo et al., 2019), combined with a clathrate (GUBHOB, Wu et al., 2009), and combined with anionic metal complexes (DUJPIK, Shin et al., 2020; SICGUJ, Nasr et al., 2018; SICGUJ01, Khedhiri et al. 2018).

5. Synthesis and crystallization

For the synthesis of salts 1–12, a solution of commercially available 1-phenyl­piperazine (100 mg, 0.62 mol) (from Sigma-Aldrich) in methanol (10 ml) was mixed with an equimolar solution of (1) 4-fluoro­benzoic acid (87 mg, 0.62 mol), (2) 4-chloro­benzoic acid (97 mg, 0.62 mol), (3) 4-bromo­benzoic acid (125 mg, 0.62 mol), (4) 4-iodo­benzoic acid (154 mg, 0.62 mol), (5) 4-nitro­benzoic acid (104 mg, 0.62 mol), (6) 3,5-di­nitro­salicylic acid (104 mg, 0.62 mol), (7) 3,5-di­nitro­benzoic acid (132 mg, 0.62 mol), (8) picric acid (142 mg, 0.62 mol), (9) benzoic acid (76 mg, 0.62 mol), (10) p-toluene­sulfonic acid (107 mg, 0.62 mol), (11) tartaric acid (93 mg, 0.62 mol) and (12) fumaric acid (72 mg, 0.62 mol). The resulting mixture was stirred for 30 min at 323 K and allowed to stand at room temperature. X-ray quality crystals of 1 and 3–12 were formed on slow evaporation after one week (m.p.: 381–384 K (1), 382–387 K (3), 413–418 K (4), 423–428 K (5), 431–436 K (6), 427–429 K (7), 430–433 K (8), 455–457 K (9), 377–380 K (10), 416–420 K (11) and 438–440 K (12). No crystals of (2) (m.p. 488–490 K) suitable for X-ray diffraction were obtained.

6. Refinement

Crystal data, data collection and structure refinement details for structures 1 and 3–12 are summarized in Table 12. All hydrogen atoms were positioned geometrically with their U_iso values 1.2 times that of their attached atoms. For some structures (6, 10, and 11), the phenyl ring of the piperazinium cation was disordered over two orientations in ratios of 0.687 (10)/0.313 (10); 0.51 (7)/0.49 (7), and 0.611 (13)/0.389 (13) for 6, 10, and 11, respectively. For both 5 and 6, a nitro group was disordered and modeled with two orientations with occupancies of 0.62 (3)/0.38 (3) and 0.690 (11)/0.310 (11), respectively.

Table 12
Experimental details

	1	3	4	5
Crystal data
Chemical formula	C10H15N2^+·C7H4FO2^−·H2O	C10H15N2^+·C7H4BrO2^−·H2O	C10H15N2^+·C7H4IO2^−	C10H15N2^+·C7H4NO4^−
Mr	320.36	381.27	410.24	329.35
Crystal system, space group	Triclinic, P	Monoclinic, P21/c	Monoclinic, P21/c	Monoclinic, P21/c
Temperature (K)	293	293	293	293
a, b, c (Å)	6.239 (1), 7.496 (1), 17.817 (3)	6.183 (2), 37.748 (7), 7.506 (2)	10.8507 (4), 23.4045 (7), 13.3019 (4)	13.0683 (9), 15.7868 (9), 7.9255 (5)
α, β, γ (°)	93.55 (2), 92.94 (2), 94.87 (2)	90, 93.69 (4), 90	90, 102.491 (4), 90	90, 95.137 (6), 90
V (Å^3)	827.3 (2)	1748.2 (8)	3298.13 (19)	1628.52 (18)
Z	2	4	8	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm^−1)	0.10	2.37	1.95	0.10
Crystal size (mm)	0.44 × 0.32 × 0.16	0.46 × 0.20 × 0.12	0.48 × 0.48 × 0.40	0.48 × 0.44 × 0.16
Data collection
Diffractometer	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur with Sapphire CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
Tmin, Tmax	0.613, 1.000	0.613, 1.000	0.575, 1.000	0.790, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4669, 3013, 1611	6103, 3170, 1374	14154, 7079, 4641	11699, 3587, 2088
Rint	0.033	0.061	0.024	0.035
(sin θ/λ)max (Å^−1)	0.602	0.602	0.657	0.660
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.090, 0.226, 1.10	0.138, 0.375, 1.03	0.037, 0.084, 1.02	0.054, 0.117, 1.10
No. of reflections	3013	3170	7079	3587
No. of parameters	220	215	409	251
No. of restraints	4	7	4	83
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å^−3)	0.27, −0.20	0.49, −0.61	0.77, −1.25	0.15, −0.13
Absolute structure	–	–	–	–
Absolute structure parameter	–	–	–	–

	6	7	8	9
Crystal data
Chemical formula	C10H15N2^+·C7H3N2O7^−	C10H15N2^+·C7H3N2O6^−	C10H15N2^+·C6H2N3O7^−	C10H15N2^+·C7H5O2^−·H2O
Mr	390.35	374.35	391.34	302.36
Crystal system, space group	Monoclinic, P21/c	Triclinic, P	Monoclinic, P21/c	Monoclinic, P21/c
Temperature (K)	293	293	293	293
a, b, c (Å)	7.779 (3), 7.411 (3), 31.357 (9)	5.707 (2), 12.505 (3), 13.116 (3)	8.517 (1), 6.825 (1), 30.265 (4)	6.202 (2), 34.573 (9), 7.596 (2)
α, β, γ (°)	90, 96.82 (3), 90	97.41 (2), 93.28 (2), 102.82 (2)	90, 95.33 (1), 90	90, 93.83 (2), 90
V (Å^3)	1794.9 (11)	901.5 (4)	1751.7 (4)	1625.1 (8)
Z	4	2	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm^−1)	0.11	0.11	0.12	0.09
Crystal size (mm)	0.20 × 0.18 × 0.12	0.48 × 0.08 × 0.04	0.50 × 0.36 × 0.20	0.32 × 0.20 × 0.16
Data collection
Diffractometer	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur with Sapphire CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
Tmin, Tmax	0.959, 1.000	0.647, 1.000	0.835, 1.000	0.985, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7737, 3882, 1590	7800, 7800, 2647	12427, 3893, 2389	6075, 3492, 1387
Rint	0.055	0.087	0.076	0.039
(sin θ/λ)max (Å^−1)	0.661	0.663	0.660	0.656
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.085, 0.155, 1.03	0.147, 0.297, 1.13	0.064, 0.149, 1.05	0.065, 0.144, 0.95
No. of reflections	3882	7800	3893	3492
No. of parameters	321	251	260	211
No. of restraints	288	2	0	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å^−3)	0.18, −0.20	0.28, −0.30	0.26, −0.20	0.24, −0.16
Absolute structure	–	–	–	–
Absolute structure parameter	–	–	–	–

	10	11	12
Crystal data
Chemical formula	C10H15N2^+·C7H7O3S^−	C10H15N2^+·C4H5O6^−·H2O	C10H15N2^+·C4H3O4^−
Mr	334.42	330.33	278.30
Crystal system, space group	Monoclinic, P21	Orthorhombic, P212121	Orthorhombic, Pca21
Temperature (K)	293	293	293
a, b, c (Å)	8.325 (1), 10.949 (2), 18.418 (4)	7.1185 (7), 7.5255 (8), 29.955 (3)	26.702 (1), 7.9626 (3), 6.7571 (3)
α, β, γ (°)	90, 92.67 (2), 90	90, 90, 90	90, 90, 90
V (Å^3)	1677.0 (5)	1604.7 (3)	1436.68 (10)
Z	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm^−1)	0.21	0.11	0.10
Crystal size (mm)	0.50 × 0.36 × 0.14	0.42 × 0.32 × 0.24	0.48 × 0.44 × 0.40
Data collection
Diffractometer	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur with Sapphire CCD	Oxford Diffraction Xcalibur with Sapphire CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
Tmin, Tmax	0.696, 1.000	0.883, 1.000	0.894, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6123, 4918, 2767	6773, 3354, 2808	9534, 3127, 2770
Rint	0.044	0.019	0.018
(sin θ/λ)max (Å^−1)	0.654	0.657	0.657
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.126, 0.298, 1.12	0.045, 0.100, 1.09	0.034, 0.077, 1.06
No. of reflections	4918	3354	3127
No. of parameters	480	260	191
No. of restraints	853	211	4
H-atom treatment	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å^−3)	1.08, −0.41	0.20, −0.16	0.17, −0.13
Absolute structure	Flack x determined using 597 quotients [(I^+)−(I^−)]/[(I^+)+(I^−)] (Parsons et al., 2013)	Flack x determined using 912 quotients [(I^+)−(I^−)]/[(I^+)+(I^−)] (Parsons et al., 2013)	Flack x determined using 1130 quotients [(I^+)−(I^−)]/[(I^+)+(I^−)] (Parsons et al., 2013)
Absolute structure parameter	0.00 (11)	−0.2 (5)	0.3 (3)
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2007), SHELXT (Sheldrick, 2015a), SHELXL (Sheldrick, 2015b) and SHELXTL (Sheldrick, 2008).

Supporting information

Computing details

For all structures, data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007). Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for (1), (3), (4), (5), (6), (7), (8), (9), (10), (11); SHELXT2014 (Sheldrick, 2015a) for (12). Program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b) for (1), (3), (4), (5), (6), (7), (8), (9), (10); SHELXL2014/6 (Sheldrick, 2015b) for (11), (12). For all structures, molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

4-Phenylpiperazin-1-ium 4-fluorobenzoate monohydrate (1)

Crystal data

C10H15N2^+·C7H4FO2^−·H2O	Z = 2
Mr = 320.36	F(000) = 340
Triclinic, P1	Dx = 1.286 Mg m^−3
a = 6.239 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.496 (1) Å	Cell parameters from 1437 reflections
c = 17.817 (3) Å	θ = 2.8–27.7°
α = 93.55 (2)°	µ = 0.10 mm^−1
β = 92.94 (2)°	T = 293 K
γ = 94.87 (2)°	Rod, colourless
V = 827.3 (2) Å^3	0.44 × 0.32 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	1611 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.033
ω and φ scans	θmax = 25.3°, θmin = 2.9°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −7→7
Tmin = 0.613, Tmax = 1.000	k = −9→8
4669 measured reflections	l = −21→20
3013 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.090	Hydrogen site location: mixed
wR(F^2) = 0.226	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0717P)^2 + 0.6694P] where P = (Fo^2 + 2Fc^2)/3
3013 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 0.27 e Å^−3
4 restraints	Δρmin = −0.20 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.1673 (5)	0.6916 (4)	0.28754 (18)	0.0488 (8)
N2	0.2637 (6)	0.7578 (5)	0.4474 (2)	0.0582 (10)
H21	0.321 (6)	0.736 (6)	0.4932 (14)	0.070*
H22	0.222 (6)	0.867 (3)	0.453 (2)	0.070*
C1	0.1054 (6)	0.7113 (5)	0.2116 (2)	0.0517 (10)
C2	−0.0937 (8)	0.6442 (7)	0.1796 (3)	0.0795 (15)
H2	−0.193159	0.589826	0.210092	0.095*
C3	−0.1510 (9)	0.6546 (8)	0.1045 (3)	0.1007 (19)
H3	−0.285388	0.604546	0.084997	0.121*
C4	−0.0122 (11)	0.7376 (9)	0.0585 (3)	0.1030 (19)
H4	−0.049909	0.745192	0.007649	0.124*
C5	0.1822 (10)	0.8090 (10)	0.0887 (3)	0.122 (3)
H5	0.278723	0.865814	0.057892	0.147*
C6	0.2409 (9)	0.7997 (8)	0.1637 (3)	0.0979 (19)
H6	0.373978	0.853592	0.182809	0.117*
C7	0.3620 (6)	0.8019 (6)	0.3177 (2)	0.0608 (11)
H7A	0.332558	0.927034	0.320838	0.073*
H7B	0.476070	0.788623	0.283301	0.073*
C8	0.4378 (7)	0.7509 (6)	0.3946 (2)	0.0616 (12)
H8A	0.484338	0.630572	0.390672	0.074*
H8B	0.560050	0.832523	0.413731	0.074*
C9	0.0695 (7)	0.6398 (6)	0.4170 (2)	0.0599 (11)
H9A	−0.045974	0.649597	0.451027	0.072*
H9B	0.103679	0.515781	0.413417	0.072*
C10	−0.0033 (6)	0.6933 (6)	0.3403 (2)	0.0558 (11)
H10A	−0.124568	0.611513	0.320378	0.067*
H10B	−0.051786	0.812879	0.345074	0.067*
F1	0.5316 (7)	0.7684 (6)	0.94599 (18)	0.1434 (15)
O1	0.1448 (6)	0.8383 (6)	0.6190 (2)	0.1136 (14)
O2	0.4185 (6)	0.6849 (4)	0.59104 (18)	0.0761 (10)
C11	0.3677 (6)	0.7628 (5)	0.7197 (2)	0.0519 (10)
C12	0.5515 (7)	0.6900 (6)	0.7457 (2)	0.0605 (11)
H12	0.639144	0.638731	0.711219	0.073*
C13	0.6074 (8)	0.6918 (7)	0.8214 (3)	0.0777 (14)
H13	0.731513	0.642435	0.838182	0.093*
C14	0.4782 (10)	0.7668 (8)	0.8711 (3)	0.0885 (16)
C15	0.2959 (10)	0.8423 (8)	0.8486 (3)	0.0890 (16)
H15	0.210580	0.894321	0.883627	0.107*
C16	0.2416 (7)	0.8393 (6)	0.7725 (3)	0.0723 (13)
H16	0.117563	0.889726	0.756336	0.087*
C17	0.3049 (7)	0.7617 (6)	0.6375 (3)	0.0609 (12)
O3	0.7825 (5)	0.8718 (5)	0.5423 (2)	0.0747 (10)
H31	0.898 (5)	0.857 (8)	0.565 (3)	0.112*
H32	0.674 (6)	0.829 (8)	0.562 (3)	0.112*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0464 (19)	0.0462 (19)	0.053 (2)	−0.0029 (14)	0.0061 (15)	0.0075 (14)
N2	0.072 (2)	0.048 (2)	0.055 (2)	0.0064 (18)	−0.0066 (19)	0.0061 (17)
C1	0.058 (3)	0.048 (2)	0.048 (3)	0.0003 (19)	0.005 (2)	0.0056 (18)
C2	0.079 (3)	0.094 (4)	0.060 (3)	−0.022 (3)	−0.005 (3)	0.017 (3)
C3	0.104 (4)	0.118 (5)	0.070 (4)	−0.036 (4)	−0.021 (3)	0.017 (3)
C4	0.129 (5)	0.120 (5)	0.056 (3)	−0.015 (4)	−0.006 (3)	0.014 (3)
C5	0.116 (5)	0.185 (7)	0.059 (4)	−0.045 (5)	0.008 (3)	0.029 (4)
C6	0.088 (4)	0.141 (5)	0.058 (3)	−0.039 (4)	0.003 (3)	0.020 (3)
C7	0.049 (2)	0.072 (3)	0.059 (3)	−0.009 (2)	0.004 (2)	0.009 (2)
C8	0.053 (3)	0.065 (3)	0.065 (3)	0.000 (2)	−0.002 (2)	0.003 (2)
C9	0.064 (3)	0.056 (3)	0.058 (3)	−0.008 (2)	0.005 (2)	0.007 (2)
C10	0.049 (2)	0.058 (3)	0.060 (3)	−0.0019 (19)	0.006 (2)	0.006 (2)
F1	0.180 (4)	0.187 (4)	0.060 (2)	0.003 (3)	−0.002 (2)	0.004 (2)
O1	0.090 (3)	0.140 (4)	0.114 (3)	0.037 (3)	−0.027 (2)	0.029 (3)
O2	0.097 (2)	0.069 (2)	0.061 (2)	0.0018 (18)	−0.0046 (18)	0.0101 (16)
C11	0.049 (2)	0.041 (2)	0.066 (3)	−0.0054 (18)	0.007 (2)	0.0126 (19)
C12	0.062 (3)	0.056 (3)	0.062 (3)	0.004 (2)	−0.001 (2)	0.006 (2)
C13	0.082 (3)	0.083 (4)	0.067 (3)	0.009 (3)	−0.009 (3)	0.010 (3)
C14	0.105 (4)	0.098 (4)	0.059 (3)	−0.005 (3)	−0.002 (3)	0.004 (3)
C15	0.097 (4)	0.093 (4)	0.079 (4)	0.004 (3)	0.031 (3)	0.001 (3)
C16	0.057 (3)	0.066 (3)	0.096 (4)	0.002 (2)	0.012 (3)	0.018 (3)
C17	0.056 (3)	0.049 (3)	0.076 (3)	−0.012 (2)	−0.009 (2)	0.020 (2)
O3	0.071 (2)	0.065 (2)	0.088 (3)	0.0124 (18)	−0.0088 (18)	0.0039 (17)

Geometric parameters (Å, º)

N1—C1	1.408 (5)	C8—H8B	0.9700
N1—C10	1.456 (5)	C9—C10	1.507 (5)
N1—C7	1.468 (5)	C9—H9A	0.9700
N2—C8	1.475 (5)	C9—H9B	0.9700
N2—C9	1.495 (5)	C10—H10A	0.9700
N2—H21	0.904 (19)	C10—H10B	0.9700
N2—H22	0.881 (19)	F1—C14	1.358 (6)
C1—C2	1.381 (6)	O1—C17	1.235 (5)
C1—C6	1.389 (6)	O2—C17	1.261 (5)
C2—C3	1.377 (6)	C11—C12	1.382 (5)
C2—H2	0.9300	C11—C16	1.386 (6)
C3—C4	1.361 (8)	C11—C17	1.496 (6)
C3—H3	0.9300	C12—C13	1.375 (6)
C4—C5	1.355 (8)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.356 (7)
C5—C6	1.375 (7)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.366 (7)
C6—H6	0.9300	C15—C16	1.377 (7)
C7—C8	1.509 (5)	C15—H15	0.9300
C7—H7A	0.9700	C16—H16	0.9300
C7—H7B	0.9700	O3—H31	0.83 (2)
C8—H8A	0.9700	O3—H32	0.83 (2)
C1—N1—C10	116.2 (3)	C7—C8—H8B	109.5
C1—N1—C7	115.9 (3)	H8A—C8—H8B	108.1
C10—N1—C7	111.5 (3)	N2—C9—C10	110.4 (3)
C8—N2—C9	110.3 (3)	N2—C9—H9A	109.6
C8—N2—H21	107 (3)	C10—C9—H9A	109.6
C9—N2—H21	117 (3)	N2—C9—H9B	109.6
C8—N2—H22	111 (3)	C10—C9—H9B	109.6
C9—N2—H22	106 (3)	H9A—C9—H9B	108.1
H21—N2—H22	105 (4)	N1—C10—C9	112.3 (3)
C2—C1—C6	115.5 (4)	N1—C10—H10A	109.1
C2—C1—N1	122.4 (4)	C9—C10—H10A	109.1
C6—C1—N1	122.2 (4)	N1—C10—H10B	109.1
C3—C2—C1	122.7 (5)	C9—C10—H10B	109.1
C3—C2—H2	118.7	H10A—C10—H10B	107.9
C1—C2—H2	118.7	C12—C11—C16	117.8 (4)
C4—C3—C2	120.5 (5)	C12—C11—C17	121.9 (4)
C4—C3—H3	119.8	C16—C11—C17	120.2 (4)
C2—C3—H3	119.8	C13—C12—C11	121.4 (4)
C5—C4—C3	118.2 (5)	C13—C12—H12	119.3
C5—C4—H4	120.9	C11—C12—H12	119.3
C3—C4—H4	120.9	C14—C13—C12	118.8 (5)
C4—C5—C6	121.8 (5)	C14—C13—H13	120.6
C4—C5—H5	119.1	C12—C13—H13	120.6
C6—C5—H5	119.1	C13—C14—F1	119.2 (6)
C5—C6—C1	121.3 (5)	C13—C14—C15	122.3 (5)
C5—C6—H6	119.4	F1—C14—C15	118.5 (6)
C1—C6—H6	119.4	C14—C15—C16	118.3 (5)
N1—C7—C8	112.4 (3)	C14—C15—H15	120.9
N1—C7—H7A	109.1	C16—C15—H15	120.9
C8—C7—H7A	109.1	C15—C16—C11	121.4 (5)
N1—C7—H7B	109.1	C15—C16—H16	119.3
C8—C7—H7B	109.1	C11—C16—H16	119.3
H7A—C7—H7B	107.9	O1—C17—O2	123.6 (5)
N2—C8—C7	110.8 (3)	O1—C17—C11	117.7 (5)
N2—C8—H8A	109.5	O2—C17—C11	118.7 (4)
C7—C8—H8A	109.5	H31—O3—H32	115 (6)
N2—C8—H8B	109.5
C10—N1—C1—C2	−33.4 (6)	C1—N1—C10—C9	170.1 (3)
C7—N1—C1—C2	−167.2 (4)	C7—N1—C10—C9	−54.1 (4)
C10—N1—C1—C6	146.6 (5)	N2—C9—C10—N1	55.9 (4)
C7—N1—C1—C6	12.8 (6)	C16—C11—C12—C13	0.5 (6)
C6—C1—C2—C3	3.5 (8)	C17—C11—C12—C13	−180.0 (4)
N1—C1—C2—C3	−176.4 (5)	C11—C12—C13—C14	0.0 (7)
C1—C2—C3—C4	−1.9 (9)	C12—C13—C14—F1	179.7 (4)
C2—C3—C4—C5	0.0 (10)	C12—C13—C14—C15	−0.7 (8)
C3—C4—C5—C6	−0.2 (11)	C13—C14—C15—C16	0.8 (9)
C4—C5—C6—C1	2.1 (11)	F1—C14—C15—C16	−179.6 (4)
C2—C1—C6—C5	−3.6 (8)	C14—C15—C16—C11	−0.3 (8)
N1—C1—C6—C5	176.4 (6)	C12—C11—C16—C15	−0.4 (6)
C1—N1—C7—C8	−170.5 (3)	C17—C11—C16—C15	−179.9 (4)
C10—N1—C7—C8	53.5 (5)	C12—C11—C17—O1	−176.1 (4)
C9—N2—C8—C7	56.3 (4)	C16—C11—C17—O1	3.4 (6)
N1—C7—C8—N2	−55.1 (5)	C12—C11—C17—O2	3.2 (6)
C8—N2—C9—C10	−56.6 (4)	C16—C11—C17—O2	−177.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1	0.90 (2)	2.65 (4)	3.215 (6)	122 (3)
N2—H21···O2	0.90 (2)	1.89 (2)	2.791 (5)	175 (4)
N2—H22···O3^i	0.88 (2)	1.96 (2)	2.812 (5)	163 (4)
C8—H8A···O2^ii	0.97	2.53	3.481 (6)	168
C8—H8B···O3	0.97	2.60	3.341 (5)	133
C9—H9A···O3^iii	0.97	2.59	3.416 (6)	143
O3—H31···O1^iv	0.83 (2)	1.79 (2)	2.619 (5)	176 (6)
O3—H32···O2	0.83 (2)	1.96 (2)	2.773 (5)	167 (6)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) x+1, y, z.

4-Phenylpiperazin-1-ium 4-bromobenzoate monohydrate (3)

Crystal data

C10H15N2^+·C7H4BrO2^−·H2O	F(000) = 784
Mr = 381.27	Dx = 1.449 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.183 (2) Å	Cell parameters from 1437 reflections
b = 37.748 (7) Å	θ = 2.8–27.7°
c = 7.506 (2) Å	µ = 2.37 mm^−1
β = 93.69 (4)°	T = 293 K
V = 1748.2 (8) Å^3	Rod, colourless
Z = 4	0.46 × 0.20 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	1374 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.061
ω and φ scans	θmax = 25.4°, θmin = 2.8°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −4→7
Tmin = 0.613, Tmax = 1.000	k = −45→24
6103 measured reflections	l = −8→9
3170 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.138	Hydrogen site location: mixed
wR(F^2) = 0.375	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1282P)^2 + 10.0601P] where P = (Fo^2 + 2Fc^2)/3
3170 reflections	(Δ/σ)max = 0.003
215 parameters	Δρmax = 0.49 e Å^−3
7 restraints	Δρmin = −0.61 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.7034 (12)	0.4002 (2)	0.2295 (10)	0.047 (2)
N2	0.7744 (14)	0.4754 (2)	0.2661 (11)	0.057 (2)
H2N1	0.816948	0.495983	0.221941	0.068*	0.68 (16)
H2N2	0.734325	0.479226	0.376244	0.068*
C1	0.6526 (17)	0.3649 (3)	0.2644 (14)	0.052 (3)
C2	0.4510 (19)	0.3499 (3)	0.2008 (17)	0.077 (4)
H2	0.347995	0.364177	0.140653	0.092*
C3	0.406 (2)	0.3151 (4)	0.226 (2)	0.095 (4)
H3	0.275365	0.305737	0.179024	0.114*
C4	0.552 (3)	0.2938 (4)	0.320 (2)	0.101 (5)
H4	0.518855	0.270118	0.340272	0.122*
C5	0.745 (3)	0.3071 (4)	0.385 (2)	0.109 (5)
H5	0.846262	0.292510	0.444957	0.131*
C6	0.790 (2)	0.3418 (3)	0.361 (2)	0.091 (4)
H6	0.919874	0.350644	0.411615	0.109*
C7	0.8936 (15)	0.4148 (3)	0.3321 (15)	0.056 (3)
H7A	0.863266	0.416060	0.457161	0.067*
H7B	1.015626	0.398972	0.321899	0.067*
C8	0.9530 (18)	0.4502 (3)	0.2711 (16)	0.066 (3)
H8A	1.070611	0.459306	0.349995	0.080*
H8B	1.005544	0.448322	0.152505	0.080*
C9	0.5886 (17)	0.4613 (3)	0.1532 (15)	0.063 (3)
H9A	0.628083	0.459435	0.030616	0.075*
H9B	0.466823	0.477483	0.156218	0.075*
C10	0.5255 (17)	0.4260 (3)	0.2189 (14)	0.057 (3)
H10A	0.471137	0.428689	0.336512	0.069*
H10B	0.408395	0.416774	0.140070	0.069*
Br1	0.9708 (5)	0.72340 (4)	0.1736 (4)	0.1674 (14)
O1	0.6289 (16)	0.5558 (3)	0.3222 (15)	0.114 (4)
O2	0.9081 (15)	0.5426 (2)	0.1687 (11)	0.077 (2)
H2O	0.853628	0.522821	0.170738	0.093*	0.32 (16)
C11	0.8325 (17)	0.6031 (3)	0.2219 (13)	0.053 (3)
C12	1.0163 (19)	0.6155 (3)	0.1465 (14)	0.063 (3)
H12	1.115409	0.599557	0.104078	0.076*
C13	1.053 (2)	0.6508 (3)	0.1343 (16)	0.072 (3)
H13	1.177707	0.658367	0.083258	0.086*
C14	0.919 (3)	0.6747 (4)	0.1911 (19)	0.088 (4)
C15	0.741 (3)	0.6638 (4)	0.277 (2)	0.097 (5)
H15	0.650657	0.680550	0.324796	0.116*
C16	0.694 (2)	0.6281 (4)	0.2929 (17)	0.080 (4)
H16	0.572770	0.620785	0.349992	0.096*
C17	0.787 (2)	0.5643 (4)	0.2376 (14)	0.062 (3)
O3	0.7207 (13)	0.4796 (2)	0.6335 (11)	0.073 (2)
H31	0.830 (14)	0.4755 (18)	0.696 (17)	0.109*
H32	0.697 (5)	0.5004 (5)	0.635 (5)	0.109*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.044 (5)	0.050 (5)	0.046 (5)	0.003 (4)	0.002 (4)	−0.005 (4)
N2	0.063 (6)	0.056 (5)	0.052 (5)	−0.003 (5)	0.011 (4)	0.000 (4)
C1	0.054 (6)	0.053 (6)	0.048 (6)	0.007 (5)	−0.001 (5)	−0.010 (5)
C2	0.066 (8)	0.085 (9)	0.076 (8)	−0.005 (7)	−0.021 (7)	0.021 (7)
C3	0.092 (10)	0.077 (9)	0.113 (12)	−0.021 (8)	−0.018 (9)	0.004 (9)
C4	0.119 (13)	0.067 (9)	0.116 (12)	−0.010 (9)	−0.015 (10)	0.016 (9)
C5	0.127 (13)	0.062 (9)	0.134 (14)	0.012 (9)	−0.021 (11)	0.010 (9)
C6	0.085 (9)	0.068 (8)	0.117 (12)	−0.004 (7)	−0.015 (8)	0.000 (8)
C7	0.039 (6)	0.060 (7)	0.068 (7)	0.003 (5)	0.000 (5)	−0.003 (6)
C8	0.056 (7)	0.084 (9)	0.061 (7)	−0.004 (6)	0.010 (6)	0.004 (6)
C9	0.054 (7)	0.068 (7)	0.066 (7)	0.003 (6)	0.005 (6)	0.006 (6)
C10	0.065 (7)	0.060 (7)	0.045 (6)	0.004 (6)	−0.012 (5)	−0.003 (5)
Br1	0.266 (3)	0.0626 (11)	0.169 (2)	−0.0154 (13)	−0.020 (2)	−0.0006 (12)
O1	0.091 (7)	0.131 (9)	0.123 (8)	−0.028 (6)	0.036 (7)	0.037 (7)
O2	0.098 (6)	0.063 (5)	0.072 (6)	−0.005 (5)	0.015 (5)	0.005 (4)
C11	0.052 (6)	0.074 (7)	0.033 (5)	0.004 (6)	0.006 (5)	−0.005 (5)
C12	0.069 (7)	0.074 (8)	0.047 (6)	0.004 (6)	0.008 (6)	−0.003 (6)
C13	0.085 (9)	0.069 (8)	0.060 (8)	−0.015 (7)	−0.003 (6)	0.000 (7)
C14	0.128 (13)	0.067 (8)	0.071 (9)	0.011 (9)	0.012 (9)	0.006 (7)
C15	0.110 (12)	0.090 (11)	0.089 (10)	0.036 (9)	0.006 (10)	−0.016 (9)
C16	0.079 (9)	0.102 (11)	0.060 (7)	0.006 (8)	0.010 (6)	0.009 (8)
C17	0.058 (7)	0.089 (9)	0.037 (6)	−0.009 (7)	−0.013 (5)	0.008 (6)
O3	0.081 (6)	0.073 (5)	0.064 (5)	−0.015 (4)	0.010 (4)	−0.006 (4)

Geometric parameters (Å, º)

N1—C1	1.398 (12)	C9—C10	1.483 (14)
N1—C10	1.467 (12)	C9—H9A	0.9700
N1—C7	1.471 (12)	C9—H9B	0.9700
N2—C8	1.456 (13)	C10—H10A	0.9700
N2—C9	1.481 (13)	C10—H10B	0.9700
N2—H2N1	0.8900	Br1—C14	1.872 (14)
N2—H2N2	0.8900	O1—C17	1.242 (13)
C1—C6	1.387 (16)	O2—C17	1.244 (14)
C1—C2	1.424 (15)	O2—H2O	0.8200
C2—C3	1.356 (17)	C11—C12	1.384 (14)
C2—H2	0.9300	C11—C16	1.402 (16)
C3—C4	1.38 (2)	C11—C17	1.495 (16)
C3—H3	0.9300	C12—C13	1.354 (16)
C4—C5	1.35 (2)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.312 (18)
C5—C6	1.352 (17)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.38 (2)
C6—H6	0.9300	C15—C16	1.385 (19)
C7—C8	1.467 (14)	C15—H15	0.9300
C7—H7A	0.9700	C16—H16	0.9300
C7—H7B	0.9700	O3—H31	0.81 (2)
C8—H8A	0.9700	O3—H32	0.796 (19)
C8—H8B	0.9700
C1—N1—C10	117.8 (8)	C7—C8—H8B	108.9
C1—N1—C7	116.2 (8)	H8A—C8—H8B	107.7
C10—N1—C7	110.5 (7)	N2—C9—C10	110.1 (9)
C8—N2—C9	109.8 (8)	N2—C9—H9A	109.6
C8—N2—H2N1	109.7	C10—C9—H9A	109.6
C9—N2—H2N1	109.7	N2—C9—H9B	109.6
C8—N2—H2N2	109.7	C10—C9—H9B	109.6
C9—N2—H2N2	109.7	H9A—C9—H9B	108.2
H2N1—N2—H2N2	108.2	N1—C10—C9	113.8 (9)
C6—C1—N1	124.0 (10)	N1—C10—H10A	108.8
C6—C1—C2	114.6 (10)	C9—C10—H10A	108.8
N1—C1—C2	121.3 (9)	N1—C10—H10B	108.8
C3—C2—C1	121.5 (11)	C9—C10—H10B	108.8
C3—C2—H2	119.3	H10A—C10—H10B	107.7
C1—C2—H2	119.3	C17—O2—H2O	109.5
C2—C3—C4	120.3 (13)	C12—C11—C16	117.6 (11)
C2—C3—H3	119.8	C12—C11—C17	121.9 (10)
C4—C3—H3	119.8	C16—C11—C17	120.4 (11)
C5—C4—C3	120.0 (14)	C13—C12—C11	120.4 (11)
C5—C4—H4	120.0	C13—C12—H12	119.8
C3—C4—H4	120.0	C11—C12—H12	119.8
C6—C5—C4	119.8 (15)	C14—C13—C12	123.0 (13)
C6—C5—H5	120.1	C14—C13—H13	118.5
C4—C5—H5	120.1	C12—C13—H13	118.5
C5—C6—C1	123.7 (13)	C13—C14—C15	119.1 (13)
C5—C6—H6	118.2	C13—C14—Br1	122.7 (13)
C1—C6—H6	118.2	C15—C14—Br1	118.1 (12)
C8—C7—N1	112.7 (9)	C14—C15—C16	120.5 (13)
C8—C7—H7A	109.0	C14—C15—H15	119.7
N1—C7—H7A	109.0	C16—C15—H15	119.7
C8—C7—H7B	109.0	C15—C16—C11	119.2 (12)
N1—C7—H7B	109.0	C15—C16—H16	120.4
H7A—C7—H7B	107.8	C11—C16—H16	120.4
N2—C8—C7	113.5 (9)	O1—C17—O2	123.8 (12)
N2—C8—H8A	108.9	O1—C17—C11	116.9 (12)
C7—C8—H8A	108.9	O2—C17—C11	119.3 (10)
N2—C8—H8B	108.9	H31—O3—H32	109 (4)
C10—N1—C1—C6	−147.2 (11)	C1—N1—C10—C9	−170.7 (9)
C7—N1—C1—C6	−12.7 (15)	C7—N1—C10—C9	52.4 (11)
C10—N1—C1—C2	33.1 (14)	N2—C9—C10—N1	−55.9 (12)
C7—N1—C1—C2	167.6 (10)	C16—C11—C12—C13	−3.5 (15)
C6—C1—C2—C3	−3.4 (18)	C17—C11—C12—C13	−180.0 (10)
N1—C1—C2—C3	176.3 (12)	C11—C12—C13—C14	−0.2 (19)
C1—C2—C3—C4	3 (2)	C12—C13—C14—C15	4 (2)
C2—C3—C4—C5	−2 (3)	C12—C13—C14—Br1	−180.0 (9)
C3—C4—C5—C6	2 (3)	C13—C14—C15—C16	−4 (2)
C4—C5—C6—C1	−3 (3)	Br1—C14—C15—C16	179.6 (11)
N1—C1—C6—C5	−175.8 (14)	C14—C15—C16—C11	1 (2)
C2—C1—C6—C5	4 (2)	C12—C11—C16—C15	3.2 (17)
C1—N1—C7—C8	172.4 (9)	C17—C11—C16—C15	179.7 (11)
C10—N1—C7—C8	−50.0 (11)	C12—C11—C17—O1	173.4 (10)
C9—N2—C8—C7	−55.9 (12)	C16—C11—C17—O1	−3.0 (15)
N1—C7—C8—N2	53.6 (12)	C12—C11—C17—O2	−5.8 (15)
C8—N2—C9—C10	55.7 (11)	C16—C11—C17—O2	177.8 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N1···O2	0.89	1.90	2.780 (11)	170
N2—H2N2···O3	0.89	1.94	2.803 (12)	164
C8—H8A···O3^i	0.97	2.64	3.377 (14)	133
C8—H8B···O2^ii	0.97	2.53	3.475 (14)	166
C9—H9B···O3^iii	0.97	2.59	3.403 (14)	142
O2—H2O···N2	0.82	2.00	2.780 (11)	159
O3—H31···O2^i	0.81 (2)	1.98 (2)	2.782 (12)	170 (7)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+1, −y+1, −z+1.

4-Phenylpiperazin-1-ium 4-iodobenzoate (4)

Crystal data

C10H15N2^+·C7H4IO2^−	F(000) = 1632
Mr = 410.24	Dx = 1.652 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.8507 (4) Å	Cell parameters from 6801 reflections
b = 23.4045 (7) Å	θ = 2.6–27.8°
c = 13.3019 (4) Å	µ = 1.95 mm^−1
β = 102.491 (4)°	T = 293 K
V = 3298.13 (19) Å^3	Prism, colourless
Z = 8	0.48 × 0.48 × 0.40 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	4641 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.024
Rotation method data acquisition using ω scans.	θmax = 27.8°, θmin = 2.8°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −7→13
Tmin = 0.575, Tmax = 1.000	k = −30→15
14154 measured reflections	l = −17→17
7079 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: mixed
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0402P)^2] where P = (Fo^2 + 2Fc^2)/3
7079 reflections	(Δ/σ)max = 0.002
409 parameters	Δρmax = 0.77 e Å^−3
4 restraints	Δρmin = −1.25 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6237 (3)	0.57603 (14)	0.0843 (2)	0.0363 (8)
C2	0.4969 (3)	0.58795 (15)	0.0505 (3)	0.0431 (9)
H2	0.437868	0.568638	0.079160	0.052*
C3	0.4565 (4)	0.62827 (17)	−0.0255 (3)	0.0535 (10)
H3	0.370693	0.635548	−0.047848	0.064*
C4	0.5422 (4)	0.65774 (17)	−0.0684 (3)	0.0587 (11)
H4	0.514944	0.685086	−0.119018	0.070*
C5	0.6689 (4)	0.64613 (17)	−0.0351 (3)	0.0578 (11)
H5	0.727710	0.665869	−0.063350	0.069*
C6	0.7087 (3)	0.60578 (16)	0.0390 (3)	0.0488 (9)
H6	0.794547	0.598015	0.059728	0.059*
C7	0.5780 (3)	0.49980 (14)	0.1955 (2)	0.0399 (8)
H7A	0.522273	0.482727	0.136209	0.048*
H7B	0.527435	0.523672	0.230538	0.048*
C8	0.6407 (3)	0.45316 (15)	0.2676 (3)	0.0461 (9)
H8A	0.576921	0.431322	0.291939	0.055*
H8B	0.685619	0.427387	0.231077	0.055*
C9	0.8241 (3)	0.51415 (16)	0.3220 (3)	0.0506 (10)
H9A	0.875290	0.490380	0.287377	0.061*
H9B	0.879334	0.531571	0.381165	0.061*
C10	0.7615 (3)	0.56009 (15)	0.2497 (3)	0.0437 (9)
H10A	0.716702	0.586020	0.286126	0.052*
H10B	0.825224	0.581826	0.225187	0.052*
C11	0.1383 (3)	0.57882 (14)	0.0931 (3)	0.0378 (8)
C12	0.0736 (3)	0.62745 (16)	0.1107 (3)	0.0500 (10)
H12	0.060684	0.634674	0.176404	0.060*
C13	0.0276 (4)	0.66576 (16)	0.0312 (3)	0.0604 (11)
H13	−0.014418	0.698638	0.044310	0.072*
C14	0.0443 (4)	0.65500 (19)	−0.0669 (3)	0.0609 (12)
H14	0.012708	0.680304	−0.120126	0.073*
C15	0.1071 (3)	0.60727 (17)	−0.0854 (3)	0.0519 (10)
H15	0.117968	0.600061	−0.151708	0.062*
C16	0.1549 (3)	0.56928 (15)	−0.0072 (3)	0.0435 (9)
H16	0.198547	0.537080	−0.021249	0.052*
C17	0.1510 (4)	0.48047 (15)	0.1505 (3)	0.0540 (10)
H17A	0.154730	0.470809	0.080323	0.065*
H17B	0.064339	0.476153	0.157480	0.065*
C18	0.2346 (4)	0.44063 (16)	0.2238 (3)	0.0516 (10)
H18A	0.203871	0.401837	0.210497	0.062*
H18B	0.319385	0.442244	0.211451	0.062*
C19	0.1817 (3)	0.55429 (15)	0.2758 (3)	0.0441 (9)
H19A	0.094917	0.550003	0.282589	0.053*
H19B	0.206022	0.593865	0.289794	0.053*
C20	0.2659 (3)	0.51623 (15)	0.3526 (3)	0.0480 (9)
H20A	0.353238	0.523724	0.350540	0.058*
H20B	0.254904	0.525406	0.421236	0.058*
C21	0.5418 (3)	0.35843 (13)	0.5875 (2)	0.0330 (7)
C22	0.6116 (3)	0.31980 (14)	0.5442 (3)	0.0403 (8)
H22	0.609882	0.321699	0.474075	0.048*
C23	0.6838 (3)	0.27831 (14)	0.6037 (3)	0.0421 (9)
H23	0.730730	0.252638	0.573877	0.050*
C24	0.6857 (3)	0.27537 (14)	0.7075 (3)	0.0378 (8)
C25	0.6173 (3)	0.31365 (15)	0.7525 (3)	0.0422 (9)
H25	0.618742	0.311707	0.822587	0.051*
C26	0.5467 (3)	0.35490 (15)	0.6916 (3)	0.0439 (9)
H26	0.501084	0.381014	0.721785	0.053*
C27	0.4575 (3)	0.40162 (15)	0.5219 (3)	0.0393 (8)
C28	1.0539 (3)	0.35016 (13)	0.5371 (2)	0.0332 (7)
C29	1.0084 (3)	0.32960 (15)	0.6197 (3)	0.0435 (9)
H29	0.927288	0.339430	0.625776	0.052*
C30	1.0812 (3)	0.29473 (14)	0.6934 (3)	0.0436 (9)
H30	1.050319	0.282046	0.749431	0.052*
C31	1.2002 (3)	0.27904 (13)	0.6825 (3)	0.0365 (8)
C32	1.2455 (3)	0.29675 (14)	0.5995 (3)	0.0411 (8)
H32	1.324481	0.284729	0.591371	0.049*
C33	1.1730 (3)	0.33275 (14)	0.5275 (3)	0.0413 (8)
H33	1.204660	0.345427	0.471774	0.050*
C34	0.9773 (3)	0.39127 (14)	0.4615 (3)	0.0419 (9)
I1	0.78561 (3)	0.21027 (2)	0.79917 (2)	0.05702 (10)
I2	1.31203 (3)	0.22704 (2)	0.79616 (2)	0.05455 (10)
N1	0.6722 (2)	0.53483 (12)	0.1613 (2)	0.0367 (7)
N2	0.7303 (3)	0.47858 (13)	0.3568 (2)	0.0450 (8)
H21N	0.684 (3)	0.4978 (14)	0.392 (2)	0.054*
H22N	0.771 (3)	0.4508 (12)	0.397 (2)	0.054*
N3	0.1911 (2)	0.53973 (11)	0.1718 (2)	0.0367 (7)
N4	0.2388 (3)	0.45488 (14)	0.3322 (2)	0.0460 (8)
H41N	0.300 (3)	0.4353 (14)	0.370 (2)	0.055*
H42N	0.170 (2)	0.4466 (15)	0.350 (3)	0.055*
O1	0.4122 (2)	0.44040 (11)	0.56598 (19)	0.0571 (7)
O2	0.4359 (2)	0.39436 (11)	0.42592 (19)	0.0561 (7)
O3	1.0238 (2)	0.41261 (12)	0.3931 (2)	0.0644 (8)
O4	0.8680 (2)	0.40136 (11)	0.4733 (2)	0.0645 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.043 (2)	0.033 (2)	0.0308 (18)	−0.0001 (16)	0.0052 (16)	−0.0052 (15)
C2	0.039 (2)	0.046 (2)	0.041 (2)	−0.0046 (17)	0.0016 (17)	−0.0035 (17)
C3	0.051 (2)	0.056 (3)	0.047 (2)	0.003 (2)	−0.0029 (19)	0.004 (2)
C4	0.071 (3)	0.055 (3)	0.046 (2)	0.009 (2)	0.004 (2)	0.0126 (19)
C5	0.059 (3)	0.062 (3)	0.055 (3)	−0.001 (2)	0.018 (2)	0.016 (2)
C6	0.045 (2)	0.053 (2)	0.047 (2)	0.0058 (19)	0.0084 (19)	0.0039 (19)
C7	0.039 (2)	0.040 (2)	0.038 (2)	−0.0020 (16)	0.0033 (16)	−0.0034 (16)
C8	0.049 (2)	0.043 (2)	0.047 (2)	−0.0008 (18)	0.0116 (19)	0.0044 (18)
C9	0.051 (2)	0.045 (2)	0.047 (2)	−0.0004 (19)	−0.0076 (19)	−0.0001 (18)
C10	0.045 (2)	0.040 (2)	0.041 (2)	−0.0041 (17)	−0.0035 (17)	−0.0029 (17)
C11	0.0287 (18)	0.034 (2)	0.045 (2)	−0.0064 (15)	−0.0052 (16)	0.0021 (16)
C12	0.052 (2)	0.041 (2)	0.052 (2)	0.0060 (18)	−0.0013 (19)	0.0017 (18)
C13	0.055 (3)	0.038 (2)	0.079 (3)	0.0053 (19)	−0.007 (2)	0.008 (2)
C14	0.055 (3)	0.056 (3)	0.063 (3)	−0.005 (2)	−0.006 (2)	0.025 (2)
C15	0.047 (2)	0.055 (3)	0.050 (2)	−0.011 (2)	0.0033 (19)	0.015 (2)
C16	0.038 (2)	0.042 (2)	0.048 (2)	−0.0036 (16)	0.0020 (18)	0.0056 (17)
C17	0.068 (3)	0.036 (2)	0.047 (2)	−0.0018 (19)	−0.011 (2)	0.0027 (17)
C18	0.069 (3)	0.035 (2)	0.045 (2)	0.0006 (18)	−0.001 (2)	0.0045 (17)
C19	0.047 (2)	0.042 (2)	0.040 (2)	0.0026 (17)	0.0040 (18)	0.0009 (17)
C20	0.054 (2)	0.048 (2)	0.037 (2)	0.0068 (19)	−0.0002 (18)	0.0008 (17)
C21	0.0347 (18)	0.0315 (19)	0.0323 (18)	−0.0013 (15)	0.0060 (15)	−0.0008 (15)
C22	0.042 (2)	0.045 (2)	0.0341 (19)	0.0010 (17)	0.0088 (16)	−0.0007 (16)
C23	0.050 (2)	0.035 (2)	0.043 (2)	0.0115 (16)	0.0121 (18)	−0.0007 (16)
C24	0.0397 (19)	0.0293 (19)	0.0396 (19)	−0.0034 (15)	−0.0018 (16)	0.0035 (15)
C25	0.051 (2)	0.045 (2)	0.0300 (18)	0.0019 (18)	0.0073 (17)	−0.0025 (16)
C26	0.049 (2)	0.043 (2)	0.040 (2)	0.0125 (17)	0.0076 (17)	−0.0043 (17)
C27	0.037 (2)	0.038 (2)	0.041 (2)	0.0022 (16)	0.0039 (17)	0.0011 (16)
C28	0.0345 (18)	0.0255 (18)	0.0378 (19)	−0.0007 (15)	0.0040 (16)	−0.0040 (14)
C29	0.040 (2)	0.038 (2)	0.057 (2)	0.0005 (17)	0.0202 (18)	−0.0016 (18)
C30	0.056 (2)	0.034 (2)	0.046 (2)	0.0014 (18)	0.0232 (19)	0.0025 (17)
C31	0.049 (2)	0.0234 (18)	0.0368 (19)	−0.0023 (15)	0.0091 (17)	−0.0032 (14)
C32	0.0384 (19)	0.041 (2)	0.045 (2)	0.0062 (16)	0.0121 (17)	0.0039 (17)
C33	0.047 (2)	0.040 (2)	0.039 (2)	0.0017 (17)	0.0147 (17)	0.0038 (16)
C34	0.043 (2)	0.032 (2)	0.048 (2)	−0.0049 (16)	0.0022 (19)	−0.0041 (17)
I1	0.0741 (2)	0.03693 (15)	0.05275 (17)	0.00927 (12)	−0.00227 (14)	0.00844 (12)
I2	0.07106 (19)	0.04819 (17)	0.04096 (15)	0.00624 (13)	0.00451 (13)	0.00842 (11)
N1	0.0384 (16)	0.0353 (17)	0.0340 (15)	−0.0029 (13)	0.0024 (13)	−0.0008 (13)
N2	0.055 (2)	0.039 (2)	0.0394 (18)	0.0156 (15)	0.0074 (16)	0.0050 (14)
N3	0.0403 (16)	0.0308 (16)	0.0344 (15)	−0.0016 (13)	−0.0020 (13)	−0.0011 (12)
N4	0.0415 (19)	0.050 (2)	0.0430 (19)	0.0044 (16)	0.0021 (16)	0.0144 (15)
O1	0.0706 (18)	0.0487 (17)	0.0495 (16)	0.0268 (14)	0.0076 (14)	−0.0019 (13)
O2	0.0652 (18)	0.0619 (18)	0.0362 (15)	0.0221 (14)	0.0001 (13)	0.0015 (13)
O3	0.0583 (18)	0.074 (2)	0.0632 (18)	0.0164 (15)	0.0181 (15)	0.0297 (16)
O4	0.0441 (16)	0.0659 (19)	0.085 (2)	0.0157 (14)	0.0169 (15)	0.0297 (16)

Geometric parameters (Å, º)

C1—C2	1.380 (4)	C18—N4	1.472 (4)
C1—C6	1.393 (5)	C18—H18A	0.9700
C1—N1	1.422 (4)	C18—H18B	0.9700
C2—C3	1.383 (5)	C19—N3	1.450 (4)
C2—H2	0.9300	C19—C20	1.506 (5)
C3—C4	1.376 (5)	C19—H19A	0.9700
C3—H3	0.9300	C19—H19B	0.9700
C4—C5	1.377 (5)	C20—N4	1.479 (5)
C4—H4	0.9300	C20—H20A	0.9700
C5—C6	1.367 (5)	C20—H20B	0.9700
C5—H5	0.9300	C21—C26	1.377 (4)
C6—H6	0.9300	C21—C22	1.382 (4)
C7—N1	1.458 (4)	C21—C27	1.509 (4)
C7—C8	1.514 (4)	C22—C23	1.384 (4)
C7—H7A	0.9700	C22—H22	0.9300
C7—H7B	0.9700	C23—C24	1.378 (4)
C8—N2	1.485 (4)	C23—H23	0.9300
C8—H8A	0.9700	C24—C25	1.380 (5)
C8—H8B	0.9700	C24—I1	2.101 (3)
C9—N2	1.465 (5)	C25—C26	1.381 (4)
C9—C10	1.503 (5)	C25—H25	0.9300
C9—H9A	0.9700	C26—H26	0.9300
C9—H9B	0.9700	C27—O1	1.238 (4)
C10—N1	1.477 (4)	C27—O2	1.258 (4)
C10—H10A	0.9700	C28—C29	1.385 (4)
C10—H10B	0.9700	C28—C33	1.387 (4)
C11—C12	1.384 (5)	C28—C34	1.506 (5)
C11—C16	1.403 (5)	C29—C30	1.384 (5)
C11—N3	1.415 (4)	C29—H29	0.9300
C12—C13	1.394 (5)	C30—C31	1.380 (5)
C12—H12	0.9300	C30—H30	0.9300
C13—C14	1.378 (6)	C31—C32	1.366 (4)
C13—H13	0.9300	C31—I2	2.109 (3)
C14—C15	1.358 (5)	C32—C33	1.386 (4)
C14—H14	0.9300	C32—H32	0.9300
C15—C16	1.381 (5)	C33—H33	0.9300
C15—H15	0.9300	C34—O3	1.237 (4)
C16—H16	0.9300	C34—O4	1.253 (4)
C17—N3	1.463 (4)	N2—H21N	0.877 (18)
C17—C18	1.503 (5)	N2—H22N	0.897 (18)
C17—H17A	0.9700	N4—H41N	0.869 (18)
C17—H17B	0.9700	N4—H42N	0.851 (18)
C2—C1—C6	117.7 (3)	N3—C19—C20	110.5 (3)
C2—C1—N1	124.0 (3)	N3—C19—H19A	109.5
C6—C1—N1	118.3 (3)	C20—C19—H19A	109.5
C1—C2—C3	120.8 (3)	N3—C19—H19B	109.5
C1—C2—H2	119.6	C20—C19—H19B	109.5
C3—C2—H2	119.6	H19A—C19—H19B	108.1
C4—C3—C2	120.6 (4)	N4—C20—C19	112.5 (3)
C4—C3—H3	119.7	N4—C20—H20A	109.1
C2—C3—H3	119.7	C19—C20—H20A	109.1
C3—C4—C5	119.0 (4)	N4—C20—H20B	109.1
C3—C4—H4	120.5	C19—C20—H20B	109.1
C5—C4—H4	120.5	H20A—C20—H20B	107.8
C6—C5—C4	120.4 (4)	C26—C21—C22	118.3 (3)
C6—C5—H5	119.8	C26—C21—C27	120.6 (3)
C4—C5—H5	119.8	C22—C21—C27	121.0 (3)
C5—C6—C1	121.5 (3)	C21—C22—C23	120.9 (3)
C5—C6—H6	119.3	C21—C22—H22	119.5
C1—C6—H6	119.3	C23—C22—H22	119.5
N1—C7—C8	110.7 (3)	C24—C23—C22	119.5 (3)
N1—C7—H7A	109.5	C24—C23—H23	120.3
C8—C7—H7A	109.5	C22—C23—H23	120.3
N1—C7—H7B	109.5	C23—C24—C25	120.6 (3)
C8—C7—H7B	109.5	C23—C24—I1	120.8 (2)
H7A—C7—H7B	108.1	C25—C24—I1	118.5 (3)
N2—C8—C7	110.1 (3)	C24—C25—C26	118.8 (3)
N2—C8—H8A	109.6	C24—C25—H25	120.6
C7—C8—H8A	109.6	C26—C25—H25	120.6
N2—C8—H8B	109.6	C21—C26—C25	121.8 (3)
C7—C8—H8B	109.6	C21—C26—H26	119.1
H8A—C8—H8B	108.2	C25—C26—H26	119.1
N2—C9—C10	111.1 (3)	O1—C27—O2	125.0 (3)
N2—C9—H9A	109.4	O1—C27—C21	118.0 (3)
C10—C9—H9A	109.4	O2—C27—C21	116.9 (3)
N2—C9—H9B	109.4	C29—C28—C33	118.1 (3)
C10—C9—H9B	109.4	C29—C28—C34	120.8 (3)
H9A—C9—H9B	108.0	C33—C28—C34	121.1 (3)
N1—C10—C9	110.6 (3)	C30—C29—C28	121.3 (3)
N1—C10—H10A	109.5	C30—C29—H29	119.3
C9—C10—H10A	109.5	C28—C29—H29	119.3
N1—C10—H10B	109.5	C31—C30—C29	119.1 (3)
C9—C10—H10B	109.5	C31—C30—H30	120.5
H10A—C10—H10B	108.1	C29—C30—H30	120.5
C12—C11—C16	117.8 (3)	C32—C31—C30	120.8 (3)
C12—C11—N3	123.1 (3)	C32—C31—I2	120.2 (2)
C16—C11—N3	119.1 (3)	C30—C31—I2	119.0 (3)
C11—C12—C13	120.8 (4)	C31—C32—C33	119.5 (3)
C11—C12—H12	119.6	C31—C32—H32	120.2
C13—C12—H12	119.6	C33—C32—H32	120.2
C14—C13—C12	120.1 (4)	C32—C33—C28	121.1 (3)
C14—C13—H13	119.9	C32—C33—H33	119.5
C12—C13—H13	119.9	C28—C33—H33	119.5
C15—C14—C13	119.7 (4)	O3—C34—O4	124.4 (3)
C15—C14—H14	120.1	O3—C34—C28	119.7 (3)
C13—C14—H14	120.1	O4—C34—C28	115.9 (3)
C14—C15—C16	120.9 (4)	C1—N1—C7	115.5 (3)
C14—C15—H15	119.5	C1—N1—C10	112.3 (3)
C16—C15—H15	119.5	C7—N1—C10	111.1 (3)
C15—C16—C11	120.6 (4)	C9—N2—C8	110.8 (3)
C15—C16—H16	119.7	C9—N2—H21N	113 (2)
C11—C16—H16	119.7	C8—N2—H21N	106 (2)
N3—C17—C18	110.5 (3)	C9—N2—H22N	108 (2)
N3—C17—H17A	109.5	C8—N2—H22N	110 (2)
C18—C17—H17A	109.5	H21N—N2—H22N	109 (3)
N3—C17—H17B	109.5	C11—N3—C19	116.9 (3)
C18—C17—H17B	109.5	C11—N3—C17	114.5 (3)
H17A—C17—H17B	108.1	C19—N3—C17	109.1 (3)
N4—C18—C17	112.4 (3)	C18—N4—C20	111.3 (3)
N4—C18—H18A	109.1	C18—N4—H41N	108 (2)
C17—C18—H18A	109.1	C20—N4—H41N	108 (2)
N4—C18—H18B	109.1	C18—N4—H42N	112 (3)
C17—C18—H18B	109.1	C20—N4—H42N	109 (3)
H18A—C18—H18B	107.9	H41N—N4—H42N	109 (3)
C6—C1—C2—C3	−0.2 (5)	C33—C28—C29—C30	2.8 (5)
N1—C1—C2—C3	−179.4 (3)	C34—C28—C29—C30	−175.8 (3)
C1—C2—C3—C4	−0.6 (6)	C28—C29—C30—C31	−1.7 (5)
C2—C3—C4—C5	0.6 (6)	C29—C30—C31—C32	−1.0 (5)
C3—C4—C5—C6	0.2 (6)	C29—C30—C31—I2	179.0 (3)
C4—C5—C6—C1	−1.1 (6)	C30—C31—C32—C33	2.6 (5)
C2—C1—C6—C5	1.1 (5)	I2—C31—C32—C33	−177.5 (3)
N1—C1—C6—C5	−179.7 (3)	C31—C32—C33—C28	−1.4 (5)
N1—C7—C8—N2	56.9 (4)	C29—C28—C33—C32	−1.3 (5)
N2—C9—C10—N1	−56.4 (4)	C34—C28—C33—C32	177.3 (3)
C16—C11—C12—C13	−0.5 (5)	C29—C28—C34—O3	174.3 (3)
N3—C11—C12—C13	177.5 (3)	C33—C28—C34—O3	−4.3 (5)
C11—C12—C13—C14	1.1 (6)	C29—C28—C34—O4	−5.8 (5)
C12—C13—C14—C15	−0.8 (6)	C33—C28—C34—O4	175.6 (3)
C13—C14—C15—C16	−0.2 (6)	C2—C1—N1—C7	7.2 (4)
C14—C15—C16—C11	0.8 (5)	C6—C1—N1—C7	−172.0 (3)
C12—C11—C16—C15	−0.5 (5)	C2—C1—N1—C10	−121.7 (3)
N3—C11—C16—C15	−178.5 (3)	C6—C1—N1—C10	59.2 (4)
N3—C17—C18—N4	56.1 (4)	C8—C7—N1—C1	173.3 (3)
N3—C19—C20—N4	−55.9 (4)	C8—C7—N1—C10	−57.3 (3)
C26—C21—C22—C23	0.4 (5)	C9—C10—N1—C1	−172.1 (3)
C27—C21—C22—C23	−176.6 (3)	C9—C10—N1—C7	56.8 (4)
C21—C22—C23—C24	0.3 (5)	C10—C9—N2—C8	56.7 (4)
C22—C23—C24—C25	−0.6 (5)	C7—C8—N2—C9	−56.5 (4)
C22—C23—C24—I1	176.5 (2)	C12—C11—N3—C19	−3.6 (5)
C23—C24—C25—C26	0.2 (5)	C16—C11—N3—C19	174.3 (3)
I1—C24—C25—C26	−177.0 (3)	C12—C11—N3—C17	125.8 (4)
C22—C21—C26—C25	−0.9 (5)	C16—C11—N3—C17	−56.2 (4)
C27—C21—C26—C25	176.2 (3)	C20—C19—N3—C11	−167.4 (3)
C24—C25—C26—C21	0.6 (5)	C20—C19—N3—C17	60.7 (4)
C26—C21—C27—O1	13.6 (5)	C18—C17—N3—C11	165.9 (3)
C22—C21—C27—O1	−169.4 (3)	C18—C17—N3—C19	−60.9 (4)
C26—C21—C27—O2	−164.6 (3)	C17—C18—N4—C20	−50.0 (4)
C22—C21—C27—O2	12.4 (5)	C19—C20—N4—C18	49.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O3	0.97	2.63	3.218 (4)	119
N2—H21N···O1^i	0.88 (2)	1.94 (2)	2.780 (4)	160 (3)
N2—H22N···O4	0.90 (2)	1.74 (2)	2.627 (4)	173 (3)
N4—H41N···O1	0.87 (2)	2.63 (3)	3.285 (4)	133 (3)
N4—H41N···O2	0.87 (2)	1.78 (2)	2.643 (4)	169 (3)
N4—H42N···O3^ii	0.85 (2)	1.97 (2)	2.809 (4)	169 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z.

4-Phenylpiperazin-1-ium 4-nitrobenzoate (5)

Crystal data

C10H15N2^+·C7H4NO4^−	F(000) = 696
Mr = 329.35	Dx = 1.343 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.0683 (9) Å	Cell parameters from 4084 reflections
b = 15.7868 (9) Å	θ = 2.6–27.9°
c = 7.9255 (5) Å	µ = 0.10 mm^−1
β = 95.137 (6)°	T = 293 K
V = 1628.52 (18) Å^3	Prism, yellow
Z = 4	0.48 × 0.44 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	2088 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.035
Rotation method data acquisition using ω scans.	θmax = 28.0°, θmin = 2.9°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −12→17
Tmin = 0.790, Tmax = 1.000	k = −19→20
11699 measured reflections	l = −10→10
3587 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: mixed
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0406P)^2 + 0.2296P] where P = (Fo^2 + 2Fc^2)/3
3587 reflections	(Δ/σ)max < 0.001
251 parameters	Δρmax = 0.15 e Å^−3
83 restraints	Δρmin = −0.13 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.31713 (11)	0.63737 (9)	0.06853 (18)	0.0443 (4)
N2	0.42384 (12)	0.61812 (10)	0.3978 (2)	0.0497 (4)
H21	0.4059 (14)	0.5640 (10)	0.412 (2)	0.060*
H22	0.4650 (13)	0.6358 (11)	0.493 (2)	0.060*
C1	0.25304 (14)	0.61655 (11)	−0.0794 (2)	0.0451 (5)
C2	0.16112 (15)	0.66029 (13)	−0.1177 (3)	0.0592 (5)
H2	0.141977	0.702437	−0.044776	0.071*
C3	0.09843 (17)	0.64191 (16)	−0.2618 (3)	0.0711 (7)
H3	0.037601	0.671965	−0.285079	0.085*
C4	0.12406 (19)	0.58034 (18)	−0.3709 (3)	0.0786 (7)
H4	0.080984	0.567936	−0.467562	0.094*
C5	0.21412 (19)	0.53709 (16)	−0.3360 (3)	0.0769 (7)
H5	0.232309	0.495042	−0.409926	0.092*
C6	0.27853 (16)	0.55500 (13)	−0.1925 (2)	0.0603 (6)
H6	0.339789	0.525251	−0.171661	0.072*
C7	0.41360 (13)	0.59047 (11)	0.0927 (2)	0.0482 (5)
H7A	0.450391	0.596351	−0.007625	0.058*
H7B	0.398842	0.530823	0.107119	0.058*
C8	0.48078 (14)	0.62161 (12)	0.2451 (2)	0.0546 (5)
H8A	0.541877	0.586642	0.261820	0.066*
H8B	0.502144	0.679404	0.226049	0.066*
C9	0.33189 (14)	0.67211 (12)	0.3727 (2)	0.0551 (5)
H9A	0.352164	0.730174	0.353462	0.066*
H9B	0.294913	0.670810	0.473427	0.066*
C10	0.26333 (14)	0.64092 (12)	0.2229 (2)	0.0525 (5)
H10A	0.238174	0.584849	0.247440	0.063*
H10B	0.204495	0.678299	0.204255	0.063*
O1	0.54550 (10)	0.66915 (8)	0.67450 (17)	0.0659 (4)
O2	0.62576 (10)	0.55694 (8)	0.58251 (17)	0.0596 (4)
N3	0.9330 (8)	0.6415 (18)	1.2296 (16)	0.0790 (18)	0.62 (3)
O3	0.9183 (12)	0.6862 (8)	1.3520 (19)	0.108 (3)	0.62 (3)
O4	1.0096 (8)	0.5973 (11)	1.2186 (12)	0.095 (2)	0.62 (3)
N3A	0.9219 (15)	0.647 (3)	1.244 (3)	0.082 (3)	0.38 (3)
O3A	0.8898 (15)	0.6659 (14)	1.380 (2)	0.095 (3)	0.38 (3)
O4A	1.0127 (12)	0.6352 (18)	1.223 (2)	0.101 (3)	0.38 (3)
C11	0.70169 (13)	0.62778 (10)	0.8251 (2)	0.0422 (4)
C12	0.68311 (14)	0.67242 (11)	0.9690 (2)	0.0505 (5)
H12	0.620157	0.699232	0.974825	0.061*
C13	0.75707 (16)	0.67767 (12)	1.1045 (3)	0.0591 (5)
H13	0.744175	0.706602	1.202574	0.071*
C14	0.84977 (16)	0.63922 (13)	1.0907 (3)	0.0567 (5)
C15	0.87192 (15)	0.59666 (13)	0.9479 (3)	0.0603 (6)
H15	0.936114	0.572184	0.940687	0.072*
C16	0.79686 (14)	0.59106 (12)	0.8155 (2)	0.0523 (5)
H16	0.810377	0.562065	0.717750	0.063*
C17	0.61816 (14)	0.61734 (11)	0.6823 (2)	0.0465 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0417 (9)	0.0431 (8)	0.0468 (9)	0.0018 (7)	−0.0038 (7)	0.0015 (7)
N2	0.0525 (10)	0.0434 (9)	0.0505 (10)	0.0009 (7)	−0.0110 (8)	−0.0029 (8)
C1	0.0461 (11)	0.0442 (10)	0.0437 (11)	−0.0081 (8)	−0.0027 (8)	0.0094 (9)
C2	0.0514 (12)	0.0637 (13)	0.0606 (13)	−0.0023 (10)	−0.0057 (10)	0.0071 (11)
C3	0.0526 (14)	0.0923 (17)	0.0657 (16)	−0.0093 (12)	−0.0104 (11)	0.0187 (14)
C4	0.0733 (17)	0.112 (2)	0.0476 (14)	−0.0251 (15)	−0.0141 (12)	0.0100 (14)
C5	0.092 (2)	0.0928 (18)	0.0446 (13)	−0.0129 (14)	−0.0014 (12)	−0.0059 (12)
C6	0.0661 (14)	0.0663 (13)	0.0472 (12)	0.0008 (10)	−0.0018 (10)	0.0001 (11)
C7	0.0458 (11)	0.0493 (10)	0.0489 (12)	0.0022 (9)	0.0014 (8)	0.0022 (9)
C8	0.0457 (12)	0.0565 (12)	0.0603 (13)	0.0002 (9)	−0.0025 (10)	0.0042 (10)
C9	0.0561 (12)	0.0510 (11)	0.0562 (12)	0.0111 (9)	−0.0070 (9)	−0.0086 (10)
C10	0.0478 (12)	0.0564 (12)	0.0522 (12)	0.0093 (9)	−0.0026 (9)	−0.0065 (9)
O1	0.0597 (9)	0.0622 (8)	0.0710 (10)	0.0133 (7)	−0.0213 (7)	−0.0130 (7)
O2	0.0715 (10)	0.0475 (7)	0.0567 (9)	0.0020 (7)	−0.0117 (7)	−0.0087 (7)
N3	0.068 (4)	0.100 (5)	0.065 (3)	−0.018 (4)	−0.019 (3)	0.005 (3)
O3	0.106 (5)	0.126 (5)	0.084 (5)	−0.009 (4)	−0.036 (4)	−0.028 (4)
O4	0.056 (3)	0.140 (6)	0.084 (3)	0.000 (4)	−0.0213 (18)	0.014 (4)
N3A	0.064 (5)	0.105 (6)	0.071 (5)	−0.007 (5)	−0.024 (5)	0.007 (5)
O3A	0.091 (7)	0.124 (7)	0.066 (5)	−0.011 (5)	−0.025 (4)	−0.011 (5)
O4A	0.050 (4)	0.146 (8)	0.102 (5)	−0.018 (6)	−0.023 (3)	0.020 (6)
C11	0.0450 (11)	0.0361 (9)	0.0444 (11)	−0.0045 (8)	−0.0029 (8)	0.0032 (8)
C12	0.0491 (12)	0.0475 (11)	0.0538 (12)	0.0021 (9)	−0.0014 (9)	−0.0022 (9)
C13	0.0690 (15)	0.0557 (12)	0.0510 (12)	−0.0014 (11)	−0.0046 (10)	−0.0104 (10)
C14	0.0520 (13)	0.0599 (13)	0.0550 (13)	−0.0116 (10)	−0.0127 (10)	0.0058 (10)
C15	0.0414 (12)	0.0722 (14)	0.0664 (15)	0.0017 (10)	−0.0008 (10)	0.0060 (12)
C16	0.0500 (12)	0.0564 (12)	0.0500 (12)	0.0033 (10)	0.0016 (9)	−0.0033 (9)
C17	0.0498 (12)	0.0389 (10)	0.0492 (12)	−0.0040 (9)	−0.0044 (9)	0.0045 (9)

Geometric parameters (Å, º)

N1—C1	1.417 (2)	C9—H9A	0.9700
N1—C7	1.460 (2)	C9—H9B	0.9700
N1—C10	1.466 (2)	C10—H10A	0.9700
N2—C9	1.472 (2)	C10—H10B	0.9700
N2—C8	1.477 (3)	O1—C17	1.250 (2)
N2—H21	0.896 (14)	O2—C17	1.248 (2)
N2—H22	0.931 (14)	N3—O4	1.229 (10)
C1—C6	1.383 (3)	N3—O3	1.229 (9)
C1—C2	1.395 (3)	N3—C14	1.477 (8)
C2—C3	1.376 (3)	N3A—O4A	1.229 (10)
C2—H2	0.9300	N3A—O3A	1.229 (9)
C3—C4	1.363 (3)	N3A—C14	1.474 (14)
C3—H3	0.9300	C11—C16	1.380 (2)
C4—C5	1.367 (3)	C11—C12	1.381 (2)
C4—H4	0.9300	C11—C17	1.510 (2)
C5—C6	1.383 (3)	C12—C13	1.381 (3)
C5—H5	0.9300	C12—H12	0.9300
C6—H6	0.9300	C13—C14	1.368 (3)
C7—C8	1.510 (2)	C13—H13	0.9300
C7—H7A	0.9700	C14—C15	1.370 (3)
C7—H7B	0.9700	C15—C16	1.374 (3)
C8—H8A	0.9700	C15—H15	0.9300
C8—H8B	0.9700	C16—H16	0.9300
C9—C10	1.504 (2)
C1—N1—C7	115.50 (14)	N2—C9—H9A	109.7
C1—N1—C10	114.03 (14)	C10—C9—H9A	109.7
C7—N1—C10	112.51 (13)	N2—C9—H9B	109.7
C9—N2—C8	109.43 (15)	C10—C9—H9B	109.7
C9—N2—H21	110.4 (12)	H9A—C9—H9B	108.2
C8—N2—H21	107.1 (13)	N1—C10—C9	112.01 (16)
C9—N2—H22	110.0 (11)	N1—C10—H10A	109.2
C8—N2—H22	110.9 (12)	C9—C10—H10A	109.2
H21—N2—H22	108.9 (16)	N1—C10—H10B	109.2
C6—C1—C2	117.37 (17)	C9—C10—H10B	109.2
C6—C1—N1	122.71 (16)	H10A—C10—H10B	107.9
C2—C1—N1	119.91 (17)	O4—N3—O3	124.7 (4)
C3—C2—C1	120.9 (2)	O4—N3—C14	118.9 (9)
C3—C2—H2	119.6	O3—N3—C14	116.4 (9)
C1—C2—H2	119.6	O4A—N3A—O3A	124.6 (5)
C4—C3—C2	121.0 (2)	O4A—N3A—C14	115.4 (12)
C4—C3—H3	119.5	O3A—N3A—C14	120.0 (12)
C2—C3—H3	119.5	C16—C11—C12	119.07 (16)
C3—C4—C5	118.9 (2)	C16—C11—C17	120.49 (17)
C3—C4—H4	120.5	C12—C11—C17	120.42 (17)
C5—C4—H4	120.5	C11—C12—C13	120.68 (18)
C4—C5—C6	120.9 (2)	C11—C12—H12	119.7
C4—C5—H5	119.5	C13—C12—H12	119.7
C6—C5—H5	119.5	C14—C13—C12	118.33 (19)
C5—C6—C1	120.9 (2)	C14—C13—H13	120.8
C5—C6—H6	119.6	C12—C13—H13	120.8
C1—C6—H6	119.6	C13—C14—C15	122.52 (18)
N1—C7—C8	111.92 (15)	C13—C14—N3A	113.8 (8)
N1—C7—H7A	109.2	C15—C14—N3A	123.7 (8)
C8—C7—H7A	109.2	C13—C14—N3	121.9 (5)
N1—C7—H7B	109.2	C15—C14—N3	115.6 (5)
C8—C7—H7B	109.2	C14—C15—C16	118.29 (19)
H7A—C7—H7B	107.9	C14—C15—H15	120.9
N2—C8—C7	110.09 (16)	C16—C15—H15	120.9
N2—C8—H8A	109.6	C15—C16—C11	121.07 (19)
C7—C8—H8A	109.6	C15—C16—H16	119.5
N2—C8—H8B	109.6	C11—C16—H16	119.5
C7—C8—H8B	109.6	O2—C17—O1	124.86 (16)
H8A—C8—H8B	108.2	O2—C17—C11	117.72 (16)
N2—C9—C10	109.78 (15)	O1—C17—C11	117.41 (17)
C7—N1—C1—C6	1.1 (2)	C11—C12—C13—C14	1.5 (3)
C10—N1—C1—C6	−131.49 (19)	C12—C13—C14—C15	0.6 (3)
C7—N1—C1—C2	−177.35 (16)	C12—C13—C14—N3A	−179 (2)
C10—N1—C1—C2	50.0 (2)	C12—C13—C14—N3	−179.8 (14)
C6—C1—C2—C3	0.6 (3)	O4A—N3A—C14—C13	−160 (3)
N1—C1—C2—C3	179.11 (18)	O3A—N3A—C14—C13	18 (5)
C1—C2—C3—C4	0.2 (3)	O4A—N3A—C14—C15	21 (5)
C2—C3—C4—C5	−0.6 (3)	O3A—N3A—C14—C15	−161 (3)
C3—C4—C5—C6	0.1 (4)	O4—N3—C14—C13	171.1 (17)
C4—C5—C6—C1	0.7 (3)	O3—N3—C14—C13	−7 (3)
C2—C1—C6—C5	−1.0 (3)	O4—N3—C14—C15	−9 (3)
N1—C1—C6—C5	−179.50 (18)	O3—N3—C14—C15	173.1 (18)
C1—N1—C7—C8	175.30 (15)	C13—C14—C15—C16	−1.5 (3)
C10—N1—C7—C8	−51.4 (2)	N3A—C14—C15—C16	177 (2)
C9—N2—C8—C7	−60.00 (19)	N3—C14—C15—C16	178.8 (13)
N1—C7—C8—N2	55.4 (2)	C14—C15—C16—C11	0.4 (3)
C8—N2—C9—C10	60.4 (2)	C12—C11—C16—C15	1.5 (3)
C1—N1—C10—C9	−173.98 (14)	C17—C11—C16—C15	−176.86 (17)
C7—N1—C10—C9	52.0 (2)	C16—C11—C17—O2	20.4 (3)
N2—C9—C10—N1	−56.4 (2)	C12—C11—C17—O2	−157.93 (17)
C16—C11—C12—C13	−2.5 (3)	C16—C11—C17—O1	−160.75 (18)
C17—C11—C12—C13	175.88 (17)	C12—C11—C17—O1	20.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2^i	0.90 (1)	1.96 (2)	2.846 (2)	173 (2)
N2—H22···O1	0.93 (1)	1.78 (2)	2.7135 (19)	179 (2)
N2—H22···O2	0.93 (1)	2.49 (2)	3.057 (2)	120 (1)
C8—H8B···O1^ii	0.97	2.50	3.468 (2)	176
C10—H10B···O4A^iii	0.97	2.61	3.276 (15)	126

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z−1/2; (iii) x−1, y, z−1.

4-Phenylpiperazin-1-ium 2-hydroxy-4,6-dinitrophenolate (6)

Crystal data

C10H15N2^+·C7H3N2O7^−	F(000) = 816
Mr = 390.35	Dx = 1.444 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.779 (3) Å	Cell parameters from 1200 reflections
b = 7.411 (3) Å	θ = 2.6–27.9°
c = 31.357 (9) Å	µ = 0.11 mm^−1
β = 96.82 (3)°	T = 293 K
V = 1794.9 (11) Å^3	Prism, yellow
Z = 4	0.20 × 0.18 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	1590 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.055
Rotation method data acquisition using ω scans.	θmax = 28.0°, θmin = 2.6°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −9→9
Tmin = 0.959, Tmax = 1.000	k = −9→9
7737 measured reflections	l = −40→26
3882 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.085	Hydrogen site location: mixed
wR(F^2) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0396P)^2 + 0.7929P] where P = (Fo^2 + 2Fc^2)/3
3882 reflections	(Δ/σ)max < 0.001
321 parameters	Δρmax = 0.18 e Å^−3
288 restraints	Δρmin = −0.20 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.2174 (3)	0.5690 (4)	0.40623 (8)	0.0678 (9)
O2	0.3815 (3)	0.5542 (4)	0.46760 (8)	0.0644 (9)
H2O	0.372 (5)	0.581 (6)	0.4933 (7)	0.077*
O3	0.2737 (3)	0.6604 (4)	0.53481 (7)	0.0538 (8)
N3	0.0028 (7)	0.8237 (11)	0.57913 (17)	0.0504 (16)	0.690 (11)
O4	0.1059 (7)	0.7315 (9)	0.60356 (18)	0.069 (2)	0.690 (11)
O5	−0.0948 (7)	0.9353 (9)	0.5930 (2)	0.0602 (19)	0.690 (11)
N3A	−0.0015 (11)	0.825 (2)	0.5769 (3)	0.053 (3)	0.310 (11)
O4A	0.1438 (10)	0.818 (2)	0.5983 (4)	0.065 (4)	0.310 (11)
O5A	−0.1263 (11)	0.898 (2)	0.5910 (5)	0.053 (4)	0.310 (11)
O6	−0.4591 (3)	0.9346 (4)	0.45916 (8)	0.0725 (9)
O7	−0.3746 (3)	0.8095 (4)	0.40327 (8)	0.0738 (9)
N4	−0.3514 (4)	0.8515 (5)	0.44113 (10)	0.0517 (9)
C11	0.0978 (4)	0.6775 (5)	0.46853 (11)	0.0390 (9)
C12	0.1281 (4)	0.7048 (5)	0.51389 (11)	0.0418 (9)
C13	−0.0142 (4)	0.7862 (5)	0.53288 (10)	0.0400 (9)
C14	−0.1672 (4)	0.8346 (5)	0.50932 (11)	0.0398 (9)
H14	−0.254887	0.888430	0.522579	0.048*
C15	−0.1890 (4)	0.8024 (5)	0.46600 (11)	0.0393 (9)
C16	−0.0579 (4)	0.7232 (5)	0.44552 (11)	0.0413 (10)
H16	−0.075920	0.701222	0.416128	0.050*
C17	0.2359 (5)	0.5974 (5)	0.44453 (12)	0.0477 (10)
N1	0.6156 (4)	0.6931 (4)	0.70321 (9)	0.0467 (8)
N2	0.4692 (4)	0.6095 (6)	0.61759 (11)	0.0666 (11)
H21	0.387 (4)	0.620 (5)	0.5958 (9)	0.080*
H22	0.548 (4)	0.538 (4)	0.6091 (11)	0.080*
C1	0.7285 (5)	0.6958 (7)	0.74341 (14)	0.0502 (14)	0.687 (10)
C2	0.8534 (7)	0.8298 (8)	0.75105 (14)	0.0631 (17)	0.687 (10)
H2A	0.863427	0.918478	0.730495	0.076*	0.687 (10)
C3	0.9631 (6)	0.8314 (9)	0.78940 (16)	0.0671 (17)	0.687 (10)
H3A	1.046662	0.921115	0.794514	0.081*	0.687 (10)
C4	0.9481 (6)	0.6989 (9)	0.82012 (14)	0.0613 (17)	0.687 (10)
H4A	1.021562	0.699993	0.845781	0.074*	0.687 (10)
C5	0.8233 (7)	0.5649 (7)	0.81248 (16)	0.0652 (17)	0.687 (10)
H5A	0.813228	0.476232	0.833028	0.078*	0.687 (10)
C6	0.7135 (7)	0.5633 (7)	0.77412 (17)	0.0585 (16)	0.687 (10)
H6A	0.629992	0.473592	0.769009	0.070*	0.687 (10)
C1A	0.7263 (12)	0.7159 (17)	0.7414 (3)	0.054 (2)	0.313 (10)
C2A	0.8039 (15)	0.8840 (16)	0.7482 (3)	0.062 (2)	0.313 (10)
H2AA	0.782198	0.974477	0.727712	0.075*	0.313 (10)
C3A	0.9139 (16)	0.9170 (17)	0.7856 (4)	0.066 (2)	0.313 (10)
H3AA	0.965778	1.029454	0.790219	0.080*	0.313 (10)
C4A	0.9463 (13)	0.782 (2)	0.8163 (3)	0.064 (2)	0.313 (10)
H4AA	1.019913	0.803779	0.841325	0.076*	0.313 (10)
C5A	0.8688 (16)	0.6136 (17)	0.8094 (4)	0.059 (2)	0.313 (10)
H5AA	0.890467	0.523125	0.829924	0.070*	0.313 (10)
C6A	0.7588 (16)	0.5806 (15)	0.7720 (4)	0.059 (2)	0.313 (10)
H6AA	0.706886	0.468144	0.767417	0.071*	0.313 (10)
C7	0.5365 (5)	0.5189 (6)	0.69241 (12)	0.0624 (12)
H7A	0.488024	0.471054	0.717189	0.075*
H7B	0.624264	0.435314	0.685038	0.075*
C8	0.3961 (5)	0.5342 (6)	0.65535 (12)	0.0674 (13)
H8A	0.346810	0.416157	0.648371	0.081*
H8B	0.304749	0.612321	0.663122	0.081*
C9	0.5459 (5)	0.7883 (6)	0.62835 (12)	0.0652 (13)
H9A	0.456601	0.870777	0.635373	0.078*
H9B	0.595482	0.836462	0.603764	0.078*
C10	0.6842 (5)	0.7725 (6)	0.66592 (12)	0.0645 (13)
H10A	0.777785	0.697905	0.657962	0.077*
H10B	0.730882	0.891256	0.673425	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0641 (18)	0.097 (2)	0.0424 (17)	0.0242 (16)	0.0060 (13)	−0.0135 (18)
O2	0.0490 (17)	0.099 (2)	0.0463 (17)	0.0219 (16)	0.0089 (14)	0.0024 (19)
O3	0.0412 (15)	0.077 (2)	0.0425 (16)	0.0074 (14)	0.0000 (12)	0.0002 (15)
N3	0.047 (3)	0.068 (4)	0.037 (3)	−0.003 (3)	0.006 (3)	−0.006 (3)
O4	0.062 (3)	0.104 (5)	0.040 (3)	0.015 (3)	0.000 (2)	0.005 (3)
O5	0.059 (3)	0.070 (4)	0.053 (3)	−0.002 (3)	0.015 (3)	−0.018 (3)
N3A	0.045 (5)	0.072 (6)	0.042 (6)	−0.001 (5)	0.003 (5)	−0.006 (6)
O4A	0.053 (5)	0.093 (8)	0.045 (6)	0.009 (6)	−0.008 (5)	−0.005 (6)
O5A	0.049 (5)	0.078 (8)	0.032 (6)	−0.002 (5)	0.006 (5)	−0.021 (6)
O6	0.0612 (18)	0.096 (2)	0.0589 (19)	0.0335 (17)	0.0024 (14)	−0.0098 (18)
O7	0.074 (2)	0.103 (3)	0.0416 (17)	0.0259 (17)	−0.0089 (13)	−0.0162 (18)
N4	0.049 (2)	0.059 (2)	0.047 (2)	0.0105 (18)	0.0045 (16)	−0.004 (2)
C11	0.041 (2)	0.039 (2)	0.037 (2)	0.0007 (18)	0.0059 (17)	0.001 (2)
C12	0.040 (2)	0.044 (2)	0.042 (2)	−0.0043 (19)	0.0037 (17)	−0.001 (2)
C13	0.048 (2)	0.043 (3)	0.030 (2)	−0.0043 (19)	0.0082 (17)	−0.007 (2)
C14	0.041 (2)	0.036 (2)	0.044 (2)	0.0019 (18)	0.0103 (17)	−0.002 (2)
C15	0.038 (2)	0.043 (2)	0.037 (2)	0.0041 (18)	0.0025 (16)	−0.002 (2)
C16	0.051 (2)	0.040 (3)	0.032 (2)	0.0016 (19)	0.0056 (17)	−0.0001 (19)
C17	0.042 (2)	0.056 (3)	0.046 (3)	0.006 (2)	0.0065 (19)	0.001 (2)
N1	0.0485 (18)	0.055 (2)	0.0368 (18)	−0.0090 (17)	0.0049 (14)	0.0003 (18)
N2	0.054 (2)	0.103 (3)	0.042 (2)	0.022 (2)	−0.0011 (16)	−0.015 (2)
C1	0.047 (3)	0.067 (3)	0.038 (3)	−0.006 (3)	0.010 (2)	−0.006 (3)
C2	0.061 (3)	0.076 (4)	0.050 (3)	−0.016 (3)	−0.004 (3)	0.007 (3)
C3	0.065 (3)	0.080 (4)	0.055 (3)	−0.019 (3)	−0.001 (3)	0.008 (3)
C4	0.069 (3)	0.076 (4)	0.038 (3)	−0.015 (3)	0.003 (2)	−0.004 (3)
C5	0.064 (3)	0.089 (4)	0.043 (3)	−0.020 (3)	0.011 (3)	0.009 (3)
C6	0.057 (3)	0.081 (3)	0.038 (3)	−0.014 (3)	0.008 (2)	0.007 (3)
C1A	0.051 (4)	0.075 (4)	0.037 (4)	−0.011 (4)	0.011 (4)	0.003 (4)
C2A	0.058 (4)	0.081 (5)	0.049 (4)	−0.014 (4)	0.010 (4)	−0.004 (4)
C3A	0.062 (4)	0.084 (5)	0.053 (4)	−0.013 (4)	0.007 (4)	−0.001 (4)
C4A	0.064 (4)	0.084 (5)	0.043 (4)	−0.025 (4)	0.011 (4)	0.002 (4)
C5A	0.060 (4)	0.080 (4)	0.037 (4)	−0.023 (4)	0.008 (4)	0.009 (4)
C6A	0.057 (4)	0.079 (4)	0.041 (4)	−0.020 (4)	0.005 (4)	0.005 (4)
C7	0.073 (3)	0.067 (3)	0.046 (3)	−0.008 (2)	−0.001 (2)	0.003 (2)
C8	0.069 (3)	0.081 (4)	0.051 (3)	−0.013 (2)	0.002 (2)	−0.009 (3)
C9	0.059 (3)	0.086 (4)	0.050 (3)	−0.001 (3)	0.0037 (19)	0.018 (3)
C10	0.058 (3)	0.089 (4)	0.045 (2)	−0.013 (2)	0.0022 (19)	0.015 (3)

Geometric parameters (Å, º)

O1—C17	1.211 (4)	C1—C6	1.3900
O2—C17	1.309 (4)	C2—C3	1.3900
O2—H2O	0.841 (18)	C2—H2A	0.9300
O3—C12	1.283 (4)	C3—C4	1.3900
N3—O5	1.236 (4)	C3—H3A	0.9300
N3—O4	1.246 (5)	C4—C5	1.3900
N3—C13	1.467 (6)	C4—H4A	0.9300
N3A—O5A	1.237 (4)	C5—C6	1.3900
N3A—O4A	1.246 (5)	C5—H5A	0.9300
N3A—C13	1.401 (10)	C6—H6A	0.9300
O6—N4	1.230 (3)	C1A—C2A	1.3900
O7—N4	1.220 (3)	C1A—C6A	1.3900
N4—C15	1.450 (4)	C2A—C3A	1.3900
C11—C16	1.376 (4)	C2A—H2AA	0.9300
C11—C12	1.428 (4)	C3A—C4A	1.3900
C11—C17	1.505 (5)	C3A—H3AA	0.9300
C12—C13	1.449 (5)	C4A—C5A	1.3900
C13—C14	1.372 (4)	C4A—H4AA	0.9300
C14—C15	1.370 (4)	C5A—C6A	1.3900
C14—H14	0.9300	C5A—H5AA	0.9300
C15—C16	1.398 (4)	C6A—H6AA	0.9300
C16—H16	0.9300	C7—C8	1.501 (5)
N1—C1A	1.399 (9)	C7—H7A	0.9700
N1—C1	1.448 (5)	C7—H7B	0.9700
N1—C7	1.453 (5)	C8—H8A	0.9700
N1—C10	1.465 (4)	C8—H8B	0.9700
N2—C9	1.476 (5)	C9—C10	1.503 (5)
N2—C8	1.482 (5)	C9—H9A	0.9700
N2—H21	0.884 (18)	C9—H9B	0.9700
N2—H22	0.874 (18)	C10—H10A	0.9700
C1—C2	1.3900	C10—H10B	0.9700
C17—O2—H2O	108 (3)	C4—C3—H3A	120.0
O5—N3—O4	121.9 (4)	C5—C4—C3	120.0
O5—N3—C13	119.2 (5)	C5—C4—H4A	120.0
O4—N3—C13	118.7 (5)	C3—C4—H4A	120.0
O5A—N3A—O4A	121.8 (6)	C6—C5—C4	120.0
O5A—N3A—C13	118.4 (8)	C6—C5—H5A	120.0
O4A—N3A—C13	118.4 (8)	C4—C5—H5A	120.0
O7—N4—O6	123.1 (3)	C5—C6—C1	120.0
O7—N4—C15	118.5 (3)	C5—C6—H6A	120.0
O6—N4—C15	118.4 (3)	C1—C6—H6A	120.0
C16—C11—C12	121.2 (3)	C2A—C1A—C6A	120.0
C16—C11—C17	118.1 (3)	C2A—C1A—N1	116.8 (8)
C12—C11—C17	120.7 (3)	C6A—C1A—N1	123.1 (8)
O3—C12—C11	120.3 (3)	C1A—C2A—C3A	120.0
O3—C12—C13	124.6 (3)	C1A—C2A—H2AA	120.0
C11—C12—C13	115.1 (3)	C3A—C2A—H2AA	120.0
C14—C13—N3A	115.6 (4)	C4A—C3A—C2A	120.0
C14—C13—C12	122.9 (3)	C4A—C3A—H3AA	120.0
N3A—C13—C12	121.5 (4)	C2A—C3A—H3AA	120.0
C14—C13—N3	117.0 (3)	C3A—C4A—C5A	120.0
C12—C13—N3	120.1 (3)	C3A—C4A—H4AA	120.0
C15—C14—C13	119.1 (3)	C5A—C4A—H4AA	120.0
C15—C14—H14	120.5	C4A—C5A—C6A	120.0
C13—C14—H14	120.5	C4A—C5A—H5AA	120.0
C14—C15—C16	121.2 (3)	C6A—C5A—H5AA	120.0
C14—C15—N4	119.1 (3)	C5A—C6A—C1A	120.0
C16—C15—N4	119.7 (3)	C5A—C6A—H6AA	120.0
C11—C16—C15	120.5 (3)	C1A—C6A—H6AA	120.0
C11—C16—H16	119.8	N1—C7—C8	111.2 (3)
C15—C16—H16	119.8	N1—C7—H7A	109.4
O1—C17—O2	119.9 (3)	C8—C7—H7A	109.4
O1—C17—C11	123.8 (3)	N1—C7—H7B	109.4
O2—C17—C11	116.2 (3)	C8—C7—H7B	109.4
C1A—N1—C7	120.5 (6)	H7A—C7—H7B	108.0
C1—N1—C7	114.3 (3)	N2—C8—C7	109.5 (3)
C1A—N1—C10	112.9 (5)	N2—C8—H8A	109.8
C1—N1—C10	116.6 (3)	C7—C8—H8A	109.8
C7—N1—C10	110.8 (3)	N2—C8—H8B	109.8
C9—N2—C8	109.8 (3)	C7—C8—H8B	109.8
C9—N2—H21	109 (3)	H8A—C8—H8B	108.2
C8—N2—H21	110 (3)	N2—C9—C10	110.0 (4)
C9—N2—H22	109 (3)	N2—C9—H9A	109.7
C8—N2—H22	111 (3)	C10—C9—H9A	109.7
H21—N2—H22	107 (4)	N2—C9—H9B	109.7
C2—C1—C6	120.0	C10—C9—H9B	109.7
C2—C1—N1	119.9 (3)	H9A—C9—H9B	108.2
C6—C1—N1	120.1 (3)	N1—C10—C9	111.2 (3)
C3—C2—C1	120.0	N1—C10—H10A	109.4
C3—C2—H2A	120.0	C9—C10—H10A	109.4
C1—C2—H2A	120.0	N1—C10—H10B	109.4
C2—C3—C4	120.0	C9—C10—H10B	109.4
C2—C3—H3A	120.0	H10A—C10—H10B	108.0
C16—C11—C12—O3	179.6 (3)	C7—N1—C1—C2	159.1 (3)
C17—C11—C12—O3	−0.4 (5)	C10—N1—C1—C2	27.7 (5)
C16—C11—C12—C13	−1.2 (5)	C7—N1—C1—C6	−20.2 (4)
C17—C11—C12—C13	178.8 (3)	C10—N1—C1—C6	−151.6 (3)
O5A—N3A—C13—C14	0.4 (19)	C6—C1—C2—C3	0.0
O4A—N3A—C13—C14	−166.2 (13)	N1—C1—C2—C3	−179.3 (4)
O5A—N3A—C13—C12	178.7 (12)	C1—C2—C3—C4	0.0
O4A—N3A—C13—C12	12 (2)	C2—C3—C4—C5	0.0
O3—C12—C13—C14	179.0 (4)	C3—C4—C5—C6	0.0
C11—C12—C13—C14	−0.2 (5)	C4—C5—C6—C1	0.0
O3—C12—C13—N3A	0.8 (10)	C2—C1—C6—C5	0.0
C11—C12—C13—N3A	−178.4 (9)	N1—C1—C6—C5	179.3 (4)
O3—C12—C13—N3	0.2 (6)	C7—N1—C1A—C2A	176.7 (5)
C11—C12—C13—N3	−179.0 (5)	C10—N1—C1A—C2A	42.6 (8)
O5—N3—C13—C14	−18.9 (9)	C7—N1—C1A—C6A	−4.1 (9)
O4—N3—C13—C14	155.4 (6)	C10—N1—C1A—C6A	−138.2 (6)
O5—N3—C13—C12	160.0 (6)	C6A—C1A—C2A—C3A	0.0
O4—N3—C13—C12	−25.7 (9)	N1—C1A—C2A—C3A	179.2 (8)
N3A—C13—C14—C15	179.4 (9)	C1A—C2A—C3A—C4A	0.0
C12—C13—C14—C15	1.1 (5)	C2A—C3A—C4A—C5A	0.0
N3—C13—C14—C15	179.9 (5)	C3A—C4A—C5A—C6A	0.0
C13—C14—C15—C16	−0.6 (6)	C4A—C5A—C6A—C1A	0.0
C13—C14—C15—N4	179.3 (3)	C2A—C1A—C6A—C5A	0.0
O7—N4—C15—C14	−174.3 (4)	N1—C1A—C6A—C5A	−179.2 (9)
O6—N4—C15—C14	6.1 (5)	C1A—N1—C7—C8	168.3 (6)
O7—N4—C15—C16	5.6 (5)	C1—N1—C7—C8	168.9 (3)
O6—N4—C15—C16	−174.0 (3)	C10—N1—C7—C8	−56.9 (4)
C12—C11—C16—C15	1.7 (5)	C9—N2—C8—C7	−58.8 (4)
C17—C11—C16—C15	−178.3 (3)	N1—C7—C8—N2	58.3 (5)
C14—C15—C16—C11	−0.8 (6)	C8—N2—C9—C10	58.3 (4)
N4—C15—C16—C11	179.3 (3)	C1A—N1—C10—C9	−165.4 (6)
C16—C11—C17—O1	−0.9 (6)	C1—N1—C10—C9	−170.9 (4)
C12—C11—C17—O1	179.1 (4)	C7—N1—C10—C9	56.1 (5)
C16—C11—C17—O2	−179.4 (3)	N2—C9—C10—N1	−57.0 (5)
C12—C11—C17—O2	0.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3	0.84 (2)	1.69 (2)	2.487 (3)	156 (4)
N2—H21···O3	0.88 (2)	2.03 (2)	2.873 (4)	159 (3)
N2—H21···O4	0.88 (2)	2.37 (3)	2.950 (6)	123 (3)
N2—H21···O4A	0.88 (2)	2.40 (4)	2.966 (10)	122 (3)
N2—H22···O1^i	0.87 (2)	2.10 (2)	2.947 (4)	164 (4)
N2—H22···O2^i	0.87 (2)	2.62 (3)	3.270 (4)	132 (3)
C8—H8A···O7^ii	0.97	2.36	3.134 (5)	137
C8—H8B···O4	0.97	2.44	3.000 (6)	116
C9—H9A···O4A	0.97	2.60	3.166 (8)	118
C9—H9B···O5^iii	0.97	2.58	3.311 (8)	132
C9—H9B···O5A^iii	0.97	2.29	3.040 (13)	133

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x+1, y, z.

4-Phenylpiperazin-1-ium 2-hydroxy-4,6-dinitrophenolate (7)

Crystal data

C10H15N2^+·C7H3N2O6^−	Z = 2
Mr = 374.35	F(000) = 392
Triclinic, P1	Dx = 1.379 Mg m^−3
a = 5.707 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.505 (3) Å	Cell parameters from 838 reflections
c = 13.116 (3) Å	θ = 3.1–28.1°
α = 97.41 (2)°	µ = 0.11 mm^−1
β = 93.28 (2)°	T = 293 K
γ = 102.82 (2)°	Needle, yellow
V = 901.5 (4) Å^3	0.48 × 0.08 × 0.04 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	2647 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.087
Rotation method data acquisition using ω scans.	θmax = 28.1°, θmin = 3.2°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −7→7
Tmin = 0.647, Tmax = 1.000	k = −16→15
7800 measured reflections	l = −16→17
7800 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.147	Hydrogen site location: mixed
wR(F^2) = 0.297	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 3.195P] where P = (Fo^2 + 2Fc^2)/3
7800 reflections	(Δ/σ)max < 0.001
251 parameters	Δρmax = 0.28 e Å^−3
2 restraints	Δρmin = −0.30 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	1.122 (2)	0.6276 (12)	0.8824 (9)	0.051 (4)
C2	1.091 (2)	0.7342 (12)	0.9003 (10)	0.062 (4)
H2	0.954536	0.750440	0.869306	0.074*
C3	1.256 (3)	0.8180 (14)	0.9629 (11)	0.089 (5)
H3	1.229141	0.889054	0.974939	0.107*
C4	1.462 (3)	0.7954 (17)	1.0076 (11)	0.090 (6)
H4	1.577146	0.850571	1.049126	0.108*
C5	1.491 (3)	0.6892 (17)	0.9888 (11)	0.084 (5)
H5	1.626416	0.672664	1.019709	0.101*
C6	1.329 (2)	0.6064 (13)	0.9265 (10)	0.066 (4)
H6	1.358012	0.535803	0.913969	0.079*
C7	0.956 (2)	0.4298 (10)	0.8199 (9)	0.055 (4)
H7A	0.973803	0.416389	0.890828	0.066*
H7B	1.095257	0.415218	0.786306	0.066*
C8	0.729 (2)	0.3532 (10)	0.7652 (9)	0.056 (4)
H8A	0.738219	0.276750	0.765936	0.067*
H8B	0.590703	0.365439	0.800390	0.067*
C9	0.700 (2)	0.4918 (11)	0.6524 (9)	0.063 (4)
H9A	0.557086	0.508210	0.681256	0.076*
H9B	0.694830	0.504487	0.580979	0.076*
C10	0.920 (2)	0.5662 (10)	0.7114 (9)	0.055 (4)
H10A	1.061481	0.555114	0.677531	0.066*
H10B	0.911569	0.642726	0.711107	0.066*
C11	−0.018 (2)	0.1731 (10)	0.4335 (9)	0.041 (3)
C12	0.037 (2)	0.0713 (10)	0.4039 (8)	0.046 (3)
H12	0.169558	0.053646	0.436202	0.055*
C13	−0.106 (2)	−0.0027 (11)	0.3270 (10)	0.046 (3)
C14	−0.307 (2)	0.0161 (10)	0.2780 (9)	0.054 (4)
H14	−0.406231	−0.036584	0.227934	0.065*
C15	−0.353 (2)	0.1182 (12)	0.3079 (10)	0.052 (4)
C16	−0.219 (2)	0.1950 (10)	0.3858 (9)	0.047 (3)
H16	−0.264440	0.261054	0.406096	0.056*
C17	0.144 (3)	0.2554 (12)	0.5164 (10)	0.056 (4)
N1	0.9454 (16)	0.5450 (8)	0.8180 (7)	0.046 (3)
N2	0.7030 (19)	0.3750 (10)	0.6575 (9)	0.060 (3)
H21	0.585 (14)	0.323 (8)	0.625 (8)	0.072*
H22	0.817 (15)	0.354 (9)	0.624 (8)	0.072*
N3	−0.040 (2)	−0.1092 (10)	0.2942 (9)	0.063 (3)
N4	−0.560 (2)	0.1460 (14)	0.2536 (10)	0.075 (4)
O1	0.0892 (15)	0.3455 (7)	0.5441 (7)	0.069 (3)
O2	0.3327 (15)	0.2290 (7)	0.5475 (7)	0.071 (3)
O3	0.1442 (18)	−0.1237 (7)	0.3359 (7)	0.076 (3)
O4	−0.1697 (18)	−0.1757 (8)	0.2251 (7)	0.099 (4)
O5	−0.5922 (18)	0.2403 (11)	0.2752 (8)	0.094 (4)
O6	−0.6948 (17)	0.0739 (10)	0.1901 (8)	0.090 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.045 (9)	0.059 (11)	0.043 (8)	0.005 (8)	−0.004 (7)	−0.001 (7)
C2	0.068 (10)	0.053 (11)	0.064 (10)	0.012 (9)	0.006 (8)	0.005 (8)
C3	0.102 (14)	0.073 (13)	0.072 (11)	−0.006 (12)	0.001 (10)	−0.014 (9)
C4	0.074 (13)	0.108 (17)	0.057 (10)	−0.029 (12)	−0.011 (9)	−0.012 (11)
C5	0.082 (13)	0.111 (16)	0.055 (10)	0.012 (13)	0.004 (9)	0.017 (10)
C6	0.054 (10)	0.080 (13)	0.053 (9)	0.002 (9)	−0.004 (8)	−0.001 (8)
C7	0.058 (9)	0.061 (11)	0.052 (8)	0.023 (8)	0.007 (7)	0.012 (7)
C8	0.064 (10)	0.039 (9)	0.062 (9)	0.008 (7)	0.011 (8)	0.000 (7)
C9	0.069 (10)	0.055 (11)	0.062 (9)	0.011 (8)	−0.010 (8)	0.006 (7)
C10	0.055 (9)	0.047 (9)	0.058 (9)	0.013 (7)	−0.005 (7)	−0.005 (7)
C11	0.035 (7)	0.026 (8)	0.058 (8)	0.002 (6)	0.010 (7)	0.006 (6)
C12	0.048 (8)	0.048 (9)	0.036 (8)	0.000 (7)	−0.004 (7)	0.013 (6)
C13	0.035 (8)	0.055 (10)	0.050 (8)	0.015 (7)	−0.001 (7)	0.010 (7)
C14	0.050 (9)	0.038 (10)	0.061 (9)	−0.012 (8)	0.004 (8)	0.000 (7)
C15	0.039 (9)	0.067 (11)	0.047 (8)	0.001 (8)	−0.006 (7)	0.018 (8)
C16	0.038 (8)	0.042 (9)	0.068 (9)	0.019 (7)	0.016 (7)	0.010 (7)
C17	0.058 (10)	0.050 (11)	0.052 (9)	0.004 (8)	0.016 (8)	−0.008 (8)
N1	0.048 (7)	0.045 (8)	0.045 (7)	0.015 (6)	0.001 (6)	0.004 (5)
N2	0.050 (8)	0.058 (10)	0.061 (9)	0.005 (6)	0.005 (6)	−0.015 (6)
N3	0.078 (10)	0.053 (9)	0.062 (8)	0.026 (8)	0.003 (7)	−0.002 (7)
N4	0.055 (9)	0.111 (14)	0.069 (9)	0.028 (10)	0.012 (8)	0.028 (9)
O1	0.070 (7)	0.048 (7)	0.083 (7)	0.008 (5)	0.019 (5)	−0.009 (5)
O2	0.051 (6)	0.063 (7)	0.087 (7)	0.012 (5)	−0.013 (6)	−0.021 (5)
O3	0.079 (8)	0.056 (7)	0.096 (8)	0.028 (6)	0.000 (6)	0.001 (5)
O4	0.136 (9)	0.061 (8)	0.083 (7)	0.022 (7)	−0.022 (7)	−0.032 (6)
O5	0.077 (8)	0.130 (12)	0.100 (9)	0.060 (8)	0.019 (6)	0.042 (8)
O6	0.056 (7)	0.132 (11)	0.080 (7)	0.017 (7)	−0.009 (6)	0.029 (7)

Geometric parameters (Å, º)

C1—C6	1.377 (15)	C10—N1	1.461 (13)
C1—C2	1.377 (16)	C10—H10A	0.9700
C1—N1	1.418 (14)	C10—H10B	0.9700
C2—C3	1.384 (17)	C11—C16	1.374 (14)
C2—H2	0.9300	C11—C12	1.390 (15)
C3—C4	1.385 (19)	C11—C17	1.507 (15)
C3—H3	0.9300	C12—C13	1.367 (14)
C4—C5	1.37 (2)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.363 (14)
C5—C6	1.365 (18)	C13—N3	1.481 (15)
C5—H5	0.9300	C14—C15	1.373 (16)
C6—H6	0.9300	C14—H14	0.9300
C7—N1	1.459 (13)	C15—C16	1.372 (14)
C7—C8	1.507 (14)	C15—N4	1.473 (15)
C7—H7A	0.9700	C16—H16	0.9300
C7—H7B	0.9700	C17—O1	1.251 (14)
C8—N2	1.479 (15)	C17—O2	1.256 (14)
C8—H8A	0.9700	N2—H21	0.87 (3)
C8—H8B	0.9700	N2—H22	0.87 (3)
C9—N2	1.475 (16)	N3—O3	1.219 (11)
C9—C10	1.492 (14)	N3—O4	1.230 (12)
C9—H9A	0.9700	N4—O5	1.233 (15)
C9—H9B	0.9700	N4—O6	1.234 (14)
C6—C1—C2	118.0 (13)	N1—C10—H10B	109.2
C6—C1—N1	122.7 (14)	C9—C10—H10B	109.2
C2—C1—N1	119.3 (13)	H10A—C10—H10B	107.9
C1—C2—C3	121.9 (15)	C16—C11—C12	118.5 (11)
C1—C2—H2	119.1	C16—C11—C17	122.3 (12)
C3—C2—H2	119.1	C12—C11—C17	119.2 (12)
C2—C3—C4	119.5 (17)	C13—C12—C11	119.5 (11)
C2—C3—H3	120.2	C13—C12—H12	120.2
C4—C3—H3	120.2	C11—C12—H12	120.2
C5—C4—C3	117.8 (16)	C14—C13—C12	123.6 (13)
C5—C4—H4	121.1	C14—C13—N3	117.6 (12)
C3—C4—H4	121.1	C12—C13—N3	118.7 (12)
C6—C5—C4	122.9 (17)	C13—C14—C15	115.2 (12)
C6—C5—H5	118.5	C13—C14—H14	122.4
C4—C5—H5	118.5	C15—C14—H14	122.4
C5—C6—C1	119.8 (15)	C16—C15—C14	123.7 (13)
C5—C6—H6	120.1	C16—C15—N4	118.4 (14)
C1—C6—H6	120.1	C14—C15—N4	117.9 (13)
N1—C7—C8	110.1 (10)	C15—C16—C11	119.2 (12)
N1—C7—H7A	109.6	C15—C16—H16	120.4
C8—C7—H7A	109.6	C11—C16—H16	120.4
N1—C7—H7B	109.6	O1—C17—O2	125.5 (13)
C8—C7—H7B	109.6	O1—C17—C11	118.5 (14)
H7A—C7—H7B	108.2	O2—C17—C11	115.8 (13)
N2—C8—C7	109.2 (10)	C1—N1—C7	117.2 (11)
N2—C8—H8A	109.8	C1—N1—C10	113.8 (10)
C7—C8—H8A	109.8	C7—N1—C10	110.0 (9)
N2—C8—H8B	109.8	C9—N2—C8	111.8 (9)
C7—C8—H8B	109.8	C9—N2—H21	119 (9)
H8A—C8—H8B	108.3	C8—N2—H21	107 (8)
N2—C9—C10	109.9 (10)	C9—N2—H22	112 (8)
N2—C9—H9A	109.7	C8—N2—H22	109 (8)
C10—C9—H9A	109.7	H21—N2—H22	96 (10)
N2—C9—H9B	109.7	O3—N3—O4	124.1 (13)
C10—C9—H9B	109.7	O3—N3—C13	117.2 (12)
H9A—C9—H9B	108.2	O4—N3—C13	118.6 (13)
N1—C10—C9	111.9 (11)	O5—N4—O6	123.1 (15)
N1—C10—H10A	109.2	O5—N4—C15	118.1 (15)
C9—C10—H10A	109.2	O6—N4—C15	118.8 (15)
C6—C1—C2—C3	−2 (2)	C16—C11—C17—O1	1.7 (18)
N1—C1—C2—C3	179.6 (12)	C12—C11—C17—O1	−178.2 (12)
C1—C2—C3—C4	1 (2)	C16—C11—C17—O2	−174.2 (12)
C2—C3—C4—C5	−1 (2)	C12—C11—C17—O2	5.8 (17)
C3—C4—C5—C6	1 (3)	C6—C1—N1—C7	15.3 (16)
C4—C5—C6—C1	−2 (2)	C2—C1—N1—C7	−166.4 (11)
C2—C1—C6—C5	2.3 (19)	C6—C1—N1—C10	−115.1 (13)
N1—C1—C6—C5	−179.3 (12)	C2—C1—N1—C10	63.3 (15)
N1—C7—C8—N2	58.8 (12)	C8—C7—N1—C1	168.3 (10)
N2—C9—C10—N1	−55.4 (13)	C8—C7—N1—C10	−59.6 (12)
C16—C11—C12—C13	1.7 (17)	C9—C10—N1—C1	−167.8 (10)
C17—C11—C12—C13	−178.4 (11)	C9—C10—N1—C7	58.3 (13)
C11—C12—C13—C14	−1.8 (18)	C10—C9—N2—C8	55.0 (13)
C11—C12—C13—N3	178.0 (11)	C7—C8—N2—C9	−56.9 (13)
C12—C13—C14—C15	2.8 (18)	C14—C13—N3—O3	177.5 (12)
N3—C13—C14—C15	−177.0 (12)	C12—C13—N3—O3	−2.3 (17)
C13—C14—C15—C16	−4.0 (19)	C14—C13—N3—O4	−0.4 (18)
C13—C14—C15—N4	176.5 (11)	C12—C13—N3—O4	179.8 (12)
C14—C15—C16—C11	4.2 (19)	C16—C15—N4—O5	5.4 (18)
N4—C15—C16—C11	−176.4 (11)	C14—C15—N4—O5	−175.0 (14)
C12—C11—C16—C15	−2.8 (16)	C16—C15—N4—O6	−173.4 (13)
C17—C11—C16—C15	177.3 (11)	C14—C15—N4—O6	6.1 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O3^i	0.97	2.43	3.250 (14)	142
C10—H10B···O5^ii	0.97	2.58	3.366 (16)	138
N2—H21···O2	0.87 (3)	1.81 (4)	2.672 (13)	172 (13)
N2—H22···O1^iii	0.87 (3)	1.94 (4)	2.792 (13)	166 (12)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1; (iii) x+1, y, z.

4-Phenylpiperazin-1-ium 2,4,6-trinitrophenolate (8)

Crystal data

C10H15N2^+·C6H2N3O7^−	F(000) = 816
Mr = 391.34	Dx = 1.484 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.517 (1) Å	Cell parameters from 2640 reflections
b = 6.825 (1) Å	θ = 2.6–27.9°
c = 30.265 (4) Å	µ = 0.12 mm^−1
β = 95.33 (1)°	T = 293 K
V = 1751.7 (4) Å^3	Prism, yellow
Z = 4	0.50 × 0.36 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	2389 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.076
ω and φ scans	θmax = 28.0°, θmin = 2.6°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −10→10
Tmin = 0.835, Tmax = 1.000	k = −8→4
12427 measured reflections	l = −34→38
3893 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.064	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.149	w = 1/[σ^2(Fo^2) + (0.0504P)^2 + 0.8725P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3893 reflections	Δρmax = 0.26 e Å^−3
260 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: dual	Extinction coefficient: 0.0131 (17)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7177 (3)	0.4179 (4)	0.26101 (7)	0.0433 (6)
C2	0.7900 (3)	0.5991 (4)	0.25921 (9)	0.0570 (7)
H2	0.780507	0.690261	0.281649	0.068*
C3	0.8768 (3)	0.6449 (5)	0.22386 (10)	0.0688 (9)
H3	0.923005	0.768012	0.222678	0.083*
C4	0.8954 (3)	0.5133 (6)	0.19100 (10)	0.0694 (9)
H4	0.953581	0.545868	0.167535	0.083*
C5	0.8277 (3)	0.3334 (5)	0.19292 (9)	0.0669 (8)
H5	0.841487	0.241929	0.170835	0.080*
C6	0.7388 (3)	0.2847 (4)	0.22725 (8)	0.0556 (7)
H6	0.692475	0.161451	0.227796	0.067*
C7	0.6520 (3)	0.1721 (4)	0.31432 (9)	0.0593 (7)
H7A	0.753277	0.171429	0.331875	0.071*
H7B	0.656412	0.077286	0.290590	0.071*
C8	0.5257 (3)	0.1140 (4)	0.34299 (9)	0.0608 (8)
H8A	0.425199	0.106259	0.325154	0.073*
H8B	0.549272	−0.014205	0.355756	0.073*
C9	0.4869 (3)	0.4552 (5)	0.35981 (10)	0.0659 (8)
H9A	0.485333	0.550341	0.383577	0.079*
H9B	0.384923	0.457927	0.342652	0.079*
C10	0.6136 (3)	0.5090 (4)	0.33044 (9)	0.0574 (7)
H10A	0.591245	0.637189	0.317528	0.069*
H10B	0.714497	0.515872	0.348122	0.069*
C11	−0.1176 (3)	0.2795 (3)	0.46054 (8)	0.0401 (5)
C12	0.0517 (3)	0.2586 (3)	0.46416 (7)	0.0378 (5)
C13	0.1453 (3)	0.2289 (3)	0.50261 (8)	0.0403 (5)
H13	0.253635	0.212835	0.502247	0.048*
C14	0.0762 (3)	0.2232 (3)	0.54215 (7)	0.0393 (5)
C15	−0.0855 (3)	0.2447 (3)	0.54264 (8)	0.0406 (6)
H15	−0.131175	0.242523	0.569377	0.049*
C16	−0.1766 (3)	0.2689 (3)	0.50371 (8)	0.0395 (5)
N1	0.6227 (2)	0.3663 (3)	0.29532 (6)	0.0426 (5)
N2	0.5157 (3)	0.2589 (4)	0.37874 (8)	0.0600 (7)
H21	0.446 (4)	0.227 (4)	0.3950 (10)	0.072*
H22	0.614 (4)	0.265 (4)	0.3984 (10)	0.072*
N3	0.1308 (3)	0.2645 (3)	0.42356 (7)	0.0491 (5)
N4	0.1728 (3)	0.1928 (3)	0.58323 (7)	0.0551 (6)
N5	−0.3455 (3)	0.2877 (4)	0.50670 (8)	0.0561 (6)
O1	−0.1980 (2)	0.3022 (3)	0.42443 (6)	0.0645 (6)
O2	0.2413 (2)	0.1487 (3)	0.42128 (6)	0.0648 (6)
O3	0.0884 (3)	0.3800 (3)	0.39444 (6)	0.0705 (6)
O4	0.3160 (3)	0.1892 (4)	0.58218 (7)	0.0770 (7)
O5	0.1098 (3)	0.1737 (3)	0.61764 (6)	0.0763 (7)
O6	−0.3873 (3)	0.3692 (4)	0.53943 (8)	0.0982 (9)
O7	−0.4365 (2)	0.2218 (4)	0.47735 (8)	0.0836 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0335 (12)	0.0615 (16)	0.0346 (12)	0.0028 (11)	0.0017 (10)	0.0009 (11)
C2	0.0524 (16)	0.0688 (19)	0.0505 (16)	−0.0122 (14)	0.0088 (13)	−0.0012 (14)
C3	0.0500 (17)	0.092 (2)	0.0650 (19)	−0.0185 (15)	0.0072 (14)	0.0147 (18)
C4	0.0457 (16)	0.117 (3)	0.0474 (17)	0.0019 (17)	0.0123 (13)	0.0096 (18)
C5	0.0599 (18)	0.098 (3)	0.0439 (16)	0.0138 (17)	0.0087 (13)	−0.0068 (16)
C6	0.0541 (16)	0.0721 (19)	0.0410 (14)	0.0017 (13)	0.0066 (12)	−0.0043 (14)
C7	0.0650 (18)	0.0619 (18)	0.0530 (16)	0.0100 (14)	0.0154 (13)	0.0096 (14)
C8	0.0599 (17)	0.0671 (19)	0.0548 (17)	−0.0037 (14)	0.0028 (13)	0.0169 (15)
C9	0.0609 (18)	0.079 (2)	0.0621 (18)	−0.0024 (15)	0.0273 (15)	−0.0079 (16)
C10	0.0589 (17)	0.0638 (18)	0.0524 (16)	−0.0096 (13)	0.0198 (13)	−0.0097 (14)
C11	0.0419 (13)	0.0392 (13)	0.0393 (13)	−0.0045 (10)	0.0040 (10)	−0.0039 (10)
C12	0.0437 (13)	0.0337 (12)	0.0375 (12)	−0.0070 (10)	0.0114 (10)	−0.0035 (10)
C13	0.0387 (12)	0.0326 (12)	0.0501 (14)	−0.0034 (10)	0.0059 (10)	−0.0017 (11)
C14	0.0481 (14)	0.0324 (12)	0.0369 (13)	−0.0025 (10)	0.0012 (10)	0.0030 (10)
C15	0.0519 (14)	0.0337 (12)	0.0377 (13)	−0.0024 (10)	0.0119 (11)	−0.0022 (10)
C16	0.0401 (12)	0.0337 (12)	0.0458 (14)	−0.0007 (10)	0.0094 (10)	−0.0039 (10)
N1	0.0411 (11)	0.0501 (12)	0.0374 (10)	−0.0014 (9)	0.0082 (8)	−0.0003 (9)
N2	0.0369 (12)	0.102 (2)	0.0419 (13)	−0.0107 (12)	0.0070 (10)	0.0129 (13)
N3	0.0497 (13)	0.0538 (14)	0.0456 (13)	−0.0141 (11)	0.0136 (10)	−0.0062 (11)
N4	0.0633 (15)	0.0533 (14)	0.0476 (13)	−0.0044 (11)	−0.0016 (11)	0.0095 (11)
N5	0.0466 (13)	0.0710 (16)	0.0522 (14)	0.0037 (11)	0.0115 (11)	−0.0040 (12)
O1	0.0492 (11)	0.0992 (16)	0.0439 (11)	−0.0128 (10)	−0.0022 (8)	0.0049 (10)
O2	0.0475 (11)	0.0813 (15)	0.0695 (13)	−0.0011 (10)	0.0256 (9)	−0.0093 (11)
O3	0.0900 (16)	0.0759 (15)	0.0487 (11)	−0.0030 (11)	0.0225 (11)	0.0104 (11)
O4	0.0533 (13)	0.1053 (18)	0.0699 (14)	0.0007 (11)	−0.0073 (10)	0.0184 (12)
O5	0.0829 (15)	0.1026 (18)	0.0430 (11)	−0.0078 (12)	0.0044 (10)	0.0215 (11)
O6	0.0651 (15)	0.161 (3)	0.0722 (15)	0.0199 (15)	0.0266 (12)	−0.0310 (16)
O7	0.0460 (12)	0.131 (2)	0.0738 (15)	−0.0125 (12)	0.0081 (11)	−0.0182 (14)

Geometric parameters (Å, º)

C1—C2	1.385 (4)	C10—N1	1.449 (3)
C1—C6	1.392 (3)	C10—H10A	0.9700
C1—N1	1.419 (3)	C10—H10B	0.9700
C2—C3	1.391 (4)	C11—O1	1.244 (3)
C2—H2	0.9300	C11—C12	1.443 (3)
C3—C4	1.361 (4)	C11—C16	1.445 (3)
C3—H3	0.9300	C12—C13	1.363 (3)
C4—C5	1.359 (4)	C12—N3	1.456 (3)
C4—H4	0.9300	C13—C14	1.382 (3)
C5—C6	1.382 (4)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.386 (3)
C6—H6	0.9300	C14—N4	1.441 (3)
C7—N1	1.457 (3)	C15—C16	1.360 (3)
C7—C8	1.497 (4)	C15—H15	0.9300
C7—H7A	0.9700	C16—N5	1.455 (3)
C7—H7B	0.9700	N2—H21	0.83 (3)
C8—N2	1.474 (4)	N2—H22	0.98 (3)
C8—H8A	0.9700	N3—O3	1.212 (3)
C8—H8B	0.9700	N3—O2	1.236 (3)
C9—N2	1.469 (4)	N4—O5	1.222 (3)
C9—C10	1.506 (3)	N4—O4	1.223 (3)
C9—H9A	0.9700	N5—O7	1.210 (3)
C9—H9B	0.9700	N5—O6	1.218 (3)
C2—C1—C6	117.8 (2)	N1—C10—H10B	109.4
C2—C1—N1	122.4 (2)	C9—C10—H10B	109.4
C6—C1—N1	119.8 (2)	H10A—C10—H10B	108.0
C1—C2—C3	120.1 (3)	O1—C11—C12	122.9 (2)
C1—C2—H2	120.0	O1—C11—C16	126.2 (2)
C3—C2—H2	120.0	C12—C11—C16	110.8 (2)
C4—C3—C2	121.3 (3)	C13—C12—C11	125.5 (2)
C4—C3—H3	119.3	C13—C12—N3	116.4 (2)
C2—C3—H3	119.3	C11—C12—N3	118.1 (2)
C5—C4—C3	119.1 (3)	C12—C13—C14	118.7 (2)
C5—C4—H4	120.4	C12—C13—H13	120.6
C3—C4—H4	120.4	C14—C13—H13	120.6
C4—C5—C6	120.9 (3)	C13—C14—C15	120.6 (2)
C4—C5—H5	119.6	C13—C14—N4	119.7 (2)
C6—C5—H5	119.6	C15—C14—N4	119.6 (2)
C5—C6—C1	120.8 (3)	C16—C15—C14	119.4 (2)
C5—C6—H6	119.6	C16—C15—H15	120.3
C1—C6—H6	119.6	C14—C15—H15	120.3
N1—C7—C8	111.3 (2)	C15—C16—C11	124.8 (2)
N1—C7—H7A	109.4	C15—C16—N5	116.4 (2)
C8—C7—H7A	109.4	C11—C16—N5	118.7 (2)
N1—C7—H7B	109.4	C1—N1—C10	116.3 (2)
C8—C7—H7B	109.4	C1—N1—C7	115.2 (2)
H7A—C7—H7B	108.0	C10—N1—C7	109.9 (2)
N2—C8—C7	110.0 (2)	C9—N2—C8	110.2 (2)
N2—C8—H8A	109.7	C9—N2—H21	112 (2)
C7—C8—H8A	109.7	C8—N2—H21	111 (2)
N2—C8—H8B	109.7	C9—N2—H22	107.5 (17)
C7—C8—H8B	109.7	C8—N2—H22	111.7 (17)
H8A—C8—H8B	108.2	H21—N2—H22	105 (3)
N2—C9—C10	110.5 (2)	O3—N3—O2	123.5 (2)
N2—C9—H9A	109.6	O3—N3—C12	120.1 (2)
C10—C9—H9A	109.6	O2—N3—C12	116.3 (2)
N2—C9—H9B	109.6	O5—N4—O4	122.5 (2)
C10—C9—H9B	109.6	O5—N4—C14	119.4 (2)
H9A—C9—H9B	108.1	O4—N4—C14	118.1 (2)
N1—C10—C9	111.0 (2)	O7—N5—O6	123.4 (2)
N1—C10—H10A	109.4	O7—N5—C16	119.4 (2)
C9—C10—H10A	109.4	O6—N5—C16	117.1 (2)
C6—C1—C2—C3	1.7 (4)	O1—C11—C16—N5	−0.6 (4)
N1—C1—C2—C3	−177.4 (2)	C12—C11—C16—N5	179.8 (2)
C1—C2—C3—C4	−1.3 (4)	C2—C1—N1—C10	−4.1 (3)
C2—C3—C4—C5	−0.1 (5)	C6—C1—N1—C10	176.8 (2)
C3—C4—C5—C6	1.1 (5)	C2—C1—N1—C7	−134.9 (3)
C4—C5—C6—C1	−0.7 (4)	C6—C1—N1—C7	46.0 (3)
C2—C1—C6—C5	−0.7 (4)	C9—C10—N1—C1	169.3 (2)
N1—C1—C6—C5	178.5 (2)	C9—C10—N1—C7	−57.6 (3)
N1—C7—C8—N2	−58.0 (3)	C8—C7—N1—C1	−168.0 (2)
N2—C9—C10—N1	57.4 (3)	C8—C7—N1—C10	58.3 (3)
O1—C11—C12—C13	−178.4 (2)	C10—C9—N2—C8	−56.6 (3)
C16—C11—C12—C13	1.2 (3)	C7—C8—N2—C9	56.8 (3)
O1—C11—C12—N3	0.0 (3)	C13—C12—N3—O3	−141.4 (2)
C16—C11—C12—N3	179.6 (2)	C11—C12—N3—O3	40.1 (3)
C11—C12—C13—C14	−2.0 (3)	C13—C12—N3—O2	37.9 (3)
N3—C12—C13—C14	179.6 (2)	C11—C12—N3—O2	−140.6 (2)
C12—C13—C14—C15	0.8 (3)	C13—C14—N4—O5	−174.7 (2)
C12—C13—C14—N4	−179.8 (2)	C15—C14—N4—O5	4.7 (3)
C13—C14—C15—C16	0.9 (3)	C13—C14—N4—O4	6.0 (3)
N4—C14—C15—C16	−178.5 (2)	C15—C14—N4—O4	−174.6 (2)
C14—C15—C16—C11	−1.7 (4)	C15—C16—N5—O7	−146.1 (3)
C14—C15—C16—N5	179.1 (2)	C11—C16—N5—O7	34.6 (3)
O1—C11—C16—C15	−179.7 (2)	C15—C16—N5—O6	33.4 (3)
C12—C11—C16—C15	0.6 (3)	C11—C16—N5—O6	−145.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O4^i	0.97	2.42	3.265 (4)	145
C9—H9A···O4^ii	0.97	2.60	3.353 (4)	134
C9—H9A···O6^iii	0.97	2.61	3.455 (4)	146
N2—H21···O2	0.83 (3)	2.06 (3)	2.871 (3)	166 (3)
N2—H21···O7^iv	0.83 (3)	2.60 (3)	2.985 (3)	110 (2)
N2—H22···O1^iv	0.98 (3)	1.74 (3)	2.705 (3)	168 (3)
N2—H21···O7^iv	0.83 (3)	2.60 (3)	2.985 (3)	110 (2)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) x+1, y, z.

4-Phenylpiperazin-1-ium benzoate monohydrate (9)

Crystal data

C10H15N2^+·C7H5O2^−·H2O	F(000) = 648
Mr = 302.36	Dx = 1.236 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.202 (2) Å	Cell parameters from 885 reflections
b = 34.573 (9) Å	θ = 2.7–27.8°
c = 7.596 (2) Å	µ = 0.09 mm^−1
β = 93.83 (2)°	T = 293 K
V = 1625.1 (8) Å^3	Rod, colourless
Z = 4	0.32 × 0.20 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	1387 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.039
ω and φ scans	θmax = 27.8°, θmin = 2.9°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −7→8
Tmin = 0.985, Tmax = 1.000	k = −32→44
6075 measured reflections	l = −8→9
3492 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: mixed
wR(F^2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0549P)^2] where P = (Fo^2 + 2Fc^2)/3
3492 reflections	(Δ/σ)max < 0.001
211 parameters	Δρmax = 0.24 e Å^−3
4 restraints	Δρmin = −0.16 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.2813 (3)	0.60989 (6)	0.7704 (3)	0.0434 (6)
N2	0.2143 (4)	0.52769 (7)	0.7340 (3)	0.0540 (7)
H21	0.175 (4)	0.5046 (6)	0.776 (3)	0.065*
H22	0.244 (4)	0.5249 (8)	0.621 (2)	0.065*
C1	0.3322 (4)	0.64902 (8)	0.7364 (3)	0.0458 (7)
C2	0.1985 (5)	0.67263 (9)	0.6301 (4)	0.0732 (9)
H2	0.073519	0.662304	0.574143	0.088*
C3	0.2469 (6)	0.71136 (9)	0.6050 (5)	0.0890 (11)
H3	0.153321	0.726509	0.533416	0.107*
C4	0.4287 (7)	0.72754 (10)	0.6834 (5)	0.0871 (11)
H4	0.460834	0.753486	0.666273	0.105*
C5	0.5623 (6)	0.70463 (10)	0.7878 (5)	0.0849 (11)
H5	0.687062	0.715266	0.842693	0.102*
C6	0.5172 (5)	0.66585 (9)	0.8144 (4)	0.0684 (9)
H6	0.612551	0.650963	0.885571	0.082*
C7	0.4623 (4)	0.58257 (7)	0.7779 (4)	0.0500 (7)
H7A	0.579852	0.592960	0.854289	0.060*
H7B	0.513636	0.579710	0.660752	0.060*
C8	0.4003 (4)	0.54349 (7)	0.8453 (4)	0.0554 (8)
H8A	0.522296	0.525995	0.842923	0.067*
H8B	0.361408	0.545749	0.966498	0.067*
C9	0.0303 (4)	0.55502 (8)	0.7319 (4)	0.0586 (8)
H9A	−0.018777	0.557418	0.849982	0.070*
H9B	−0.088519	0.545041	0.655591	0.070*
C10	0.0951 (4)	0.59416 (8)	0.6670 (4)	0.0544 (7)
H10A	0.129289	0.592100	0.544591	0.065*
H10B	−0.025699	0.611834	0.672570	0.065*
O1	0.0826 (4)	0.45352 (6)	0.8352 (3)	0.0739 (6)
O2	0.3636 (4)	0.44271 (8)	0.6833 (4)	0.1271 (11)
C11	0.1746 (4)	0.38836 (9)	0.7732 (3)	0.0488 (7)
C12	0.3158 (5)	0.36281 (11)	0.6979 (4)	0.0710 (9)
H12	0.434100	0.372529	0.643180	0.085*
C13	0.2834 (6)	0.32351 (12)	0.7030 (4)	0.0850 (11)
H13	0.378578	0.306980	0.650576	0.102*
C14	0.1131 (7)	0.30867 (10)	0.7841 (5)	0.0841 (10)
H14	0.092772	0.282041	0.788617	0.101*
C15	−0.0285 (5)	0.33305 (10)	0.8592 (4)	0.0758 (10)
H15	−0.145442	0.322946	0.914408	0.091*
C16	0.0017 (4)	0.37282 (8)	0.8532 (4)	0.0566 (8)
H16	−0.096028	0.389140	0.903761	0.068*
C17	0.2108 (5)	0.43133 (10)	0.7647 (4)	0.0605 (8)
O3	0.7231 (3)	0.47794 (7)	0.6283 (3)	0.0737 (7)
H31	0.816 (5)	0.4679 (11)	0.697 (4)	0.111*
H32	0.609 (4)	0.4665 (9)	0.645 (5)	0.111*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0406 (13)	0.0418 (14)	0.0472 (14)	−0.0004 (11)	−0.0012 (10)	−0.0001 (11)
N2	0.0689 (17)	0.0449 (15)	0.0493 (16)	−0.0092 (14)	0.0112 (14)	0.0018 (14)
C1	0.0524 (17)	0.0389 (16)	0.0463 (17)	−0.0012 (14)	0.0049 (13)	−0.0033 (14)
C2	0.074 (2)	0.050 (2)	0.092 (2)	−0.0010 (17)	−0.0224 (19)	0.0050 (19)
C3	0.109 (3)	0.048 (2)	0.106 (3)	0.004 (2)	−0.026 (2)	0.010 (2)
C4	0.133 (3)	0.044 (2)	0.082 (3)	−0.014 (2)	−0.012 (2)	0.000 (2)
C5	0.105 (3)	0.060 (2)	0.086 (3)	−0.031 (2)	−0.024 (2)	0.000 (2)
C6	0.074 (2)	0.054 (2)	0.075 (2)	−0.0112 (18)	−0.0153 (17)	0.0072 (17)
C7	0.0442 (16)	0.0485 (18)	0.0566 (18)	−0.0019 (14)	−0.0008 (13)	−0.0016 (15)
C8	0.0595 (18)	0.0498 (18)	0.0556 (18)	0.0000 (15)	−0.0066 (15)	0.0025 (15)
C9	0.0512 (17)	0.0590 (19)	0.0659 (19)	−0.0085 (16)	0.0071 (14)	−0.0031 (17)
C10	0.0434 (16)	0.0507 (18)	0.068 (2)	−0.0008 (14)	−0.0024 (14)	0.0025 (16)
O1	0.0960 (16)	0.0529 (14)	0.0741 (15)	−0.0102 (12)	0.0157 (13)	0.0002 (12)
O2	0.0889 (17)	0.104 (2)	0.195 (3)	−0.0264 (15)	0.0568 (19)	0.035 (2)
C11	0.0447 (16)	0.0594 (19)	0.0417 (16)	0.0016 (15)	−0.0014 (13)	0.0053 (15)
C12	0.062 (2)	0.089 (3)	0.063 (2)	0.017 (2)	0.0069 (16)	0.0160 (19)
C13	0.106 (3)	0.077 (3)	0.072 (2)	0.040 (2)	0.007 (2)	0.002 (2)
C14	0.125 (3)	0.053 (2)	0.073 (2)	0.003 (2)	−0.009 (2)	−0.004 (2)
C15	0.087 (2)	0.062 (2)	0.079 (2)	−0.023 (2)	0.0130 (19)	0.000 (2)
C16	0.0602 (18)	0.055 (2)	0.0557 (18)	−0.0061 (16)	0.0122 (15)	−0.0043 (15)
C17	0.056 (2)	0.066 (2)	0.059 (2)	−0.0128 (18)	−0.0014 (16)	0.0198 (18)
O3	0.0697 (16)	0.0830 (17)	0.0700 (15)	−0.0213 (13)	0.0159 (12)	−0.0070 (13)

Geometric parameters (Å, º)

N1—C1	1.417 (3)	C8—H8B	0.9700
N1—C10	1.458 (3)	C9—C10	1.504 (3)
N1—C7	1.465 (3)	C9—H9A	0.9700
N2—C9	1.481 (3)	C9—H9B	0.9700
N2—C8	1.488 (3)	C10—H10A	0.9700
N2—H21	0.898 (17)	C10—H10B	0.9700
N2—H22	0.893 (16)	O1—C17	1.251 (3)
C1—C6	1.384 (3)	O2—C17	1.230 (3)
C1—C2	1.384 (3)	C11—C16	1.376 (3)
C2—C3	1.388 (4)	C11—C12	1.393 (4)
C2—H2	0.9300	C11—C17	1.504 (4)
C3—C4	1.360 (4)	C12—C13	1.375 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.362 (4)	C13—C14	1.358 (4)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.387 (4)	C14—C15	1.369 (4)
C5—H5	0.9300	C14—H14	0.9300
C6—H6	0.9300	C15—C16	1.389 (4)
C7—C8	1.504 (3)	C15—H15	0.9300
C7—H7A	0.9700	C16—H16	0.9300
C7—H7B	0.9700	O3—H31	0.830 (18)
C8—H8A	0.9700	O3—H32	0.826 (18)
C1—N1—C10	115.8 (2)	C7—C8—H8B	109.7
C1—N1—C7	116.32 (19)	H8A—C8—H8B	108.2
C10—N1—C7	110.9 (2)	N2—C9—C10	110.8 (2)
C9—N2—C8	109.8 (2)	N2—C9—H9A	109.5
C9—N2—H21	110.3 (17)	C10—C9—H9A	109.5
C8—N2—H21	110.0 (17)	N2—C9—H9B	109.5
C9—N2—H22	105.5 (17)	C10—C9—H9B	109.5
C8—N2—H22	112.5 (17)	H9A—C9—H9B	108.1
H21—N2—H22	109 (3)	N1—C10—C9	112.3 (2)
C6—C1—C2	116.7 (3)	N1—C10—H10A	109.2
C6—C1—N1	120.8 (2)	C9—C10—H10A	109.2
C2—C1—N1	122.5 (3)	N1—C10—H10B	109.2
C1—C2—C3	121.5 (3)	C9—C10—H10B	109.2
C1—C2—H2	119.3	H10A—C10—H10B	107.9
C3—C2—H2	119.3	C16—C11—C12	117.6 (3)
C4—C3—C2	121.2 (3)	C16—C11—C17	121.8 (3)
C4—C3—H3	119.4	C12—C11—C17	120.6 (3)
C2—C3—H3	119.4	C13—C12—C11	121.2 (3)
C3—C4—C5	118.0 (3)	C13—C12—H12	119.4
C3—C4—H4	121.0	C11—C12—H12	119.4
C5—C4—H4	121.0	C14—C13—C12	120.4 (3)
C4—C5—C6	121.7 (3)	C14—C13—H13	119.8
C4—C5—H5	119.1	C12—C13—H13	119.8
C6—C5—H5	119.1	C13—C14—C15	119.7 (3)
C1—C6—C5	120.9 (3)	C13—C14—H14	120.1
C1—C6—H6	119.5	C15—C14—H14	120.1
C5—C6—H6	119.5	C14—C15—C16	120.3 (3)
N1—C7—C8	112.3 (2)	C14—C15—H15	119.9
N1—C7—H7A	109.1	C16—C15—H15	119.9
C8—C7—H7A	109.1	C11—C16—C15	120.8 (3)
N1—C7—H7B	109.1	C11—C16—H16	119.6
C8—C7—H7B	109.1	C15—C16—H16	119.6
H7A—C7—H7B	107.9	O2—C17—O1	123.5 (3)
N2—C8—C7	110.0 (2)	O2—C17—C11	117.4 (3)
N2—C8—H8A	109.7	O1—C17—C11	119.1 (3)
C7—C8—H8A	109.7	H31—O3—H32	106 (4)
N2—C8—H8B	109.7
C10—N1—C1—C6	−173.8 (2)	C8—N2—C9—C10	57.0 (3)
C7—N1—C1—C6	−40.8 (3)	C1—N1—C10—C9	−170.5 (2)
C10—N1—C1—C2	8.5 (3)	C7—N1—C10—C9	54.1 (3)
C7—N1—C1—C2	141.5 (3)	N2—C9—C10—N1	−56.0 (3)
C6—C1—C2—C3	−0.8 (4)	C16—C11—C12—C13	0.1 (4)
N1—C1—C2—C3	177.0 (3)	C17—C11—C12—C13	−179.3 (3)
C1—C2—C3—C4	0.4 (5)	C11—C12—C13—C14	−0.8 (5)
C2—C3—C4—C5	−0.1 (5)	C12—C13—C14—C15	0.9 (5)
C3—C4—C5—C6	0.2 (5)	C13—C14—C15—C16	−0.2 (5)
C2—C1—C6—C5	0.8 (4)	C12—C11—C16—C15	0.5 (4)
N1—C1—C6—C5	−177.0 (3)	C17—C11—C16—C15	179.9 (3)
C4—C5—C6—C1	−0.6 (5)	C14—C15—C16—C11	−0.5 (5)
C1—N1—C7—C8	170.0 (2)	C16—C11—C17—O2	−176.6 (3)
C10—N1—C7—C8	−54.7 (3)	C12—C11—C17—O2	2.8 (4)
C9—N2—C8—C7	−57.2 (3)	C16—C11—C17—O1	1.4 (4)
N1—C7—C8—N2	56.6 (3)	C12—C11—C17—O1	−179.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1	0.90 (2)	1.92 (2)	2.813 (3)	173 (2)
N2—H21···O2	0.90 (2)	2.56 (2)	3.112 (4)	121 (2)
N2—H22···O3^i	0.89 (2)	1.92 (2)	2.812 (3)	173 (2)
C9—H9A···O1^ii	0.97	2.48	3.420 (4)	164
C9—H9B···O3^iii	0.97	2.60	3.340 (4)	133
O3—H31···O1^iv	0.83 (2)	1.96 (2)	2.772 (3)	166 (4)
O3—H32···O2	0.83 (2)	1.77 (2)	2.599 (3)	179 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+2; (iii) x−1, y, z; (iv) x+1, y, z.

4-Phenylpiperazin-1-ium 4-methylbenzenesulfonate (10)

Crystal data

C10H15N2^+·C7H7O3S^−	F(000) = 712
Mr = 334.42	Dx = 1.325 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 8.325 (1) Å	Cell parameters from 2252 reflections
b = 10.949 (2) Å	θ = 2.9–27.6°
c = 18.418 (4) Å	µ = 0.21 mm^−1
β = 92.67 (2)°	T = 293 K
V = 1677.0 (5) Å^3	Plate, colourless
Z = 4	0.50 × 0.36 × 0.14 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	2767 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.044
Rotation method data acquisition using ω scans.	θmax = 27.7°, θmin = 2.9°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −10→9
Tmin = 0.696, Tmax = 1.000	k = −14→11
6123 measured reflections	l = −24→20
4918 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.126	H-atom parameters constrained
wR(F^2) = 0.298	w = 1/[σ^2(Fo^2) + (0.0541P)^2 + 11.2654P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
4918 reflections	Δρmax = 1.08 e Å^−3
480 parameters	Δρmin = −0.41 e Å^−3
853 restraints	Absolute structure: Flack x determined using 597 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.00 (11)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.3198 (15)	0.0451 (12)	0.1981 (8)	0.044 (3)
N2	0.3315 (13)	−0.0070 (11)	0.0453 (8)	0.041 (3)
H21N	0.301100	0.008772	−0.000733	0.050*
H22N	0.400866	−0.068854	0.045658	0.050*
C1	0.345 (5)	0.050 (4)	0.2756 (14)	0.056 (4)	0.49 (7)
C2	0.244 (4)	−0.010 (4)	0.322 (2)	0.058 (4)	0.49 (7)
H2	0.163707	−0.061632	0.302457	0.069*	0.49 (7)
C3	0.263 (4)	0.006 (5)	0.3965 (19)	0.060 (4)	0.49 (7)
H3	0.195547	−0.034965	0.427260	0.073*	0.49 (7)
C4	0.383 (5)	0.082 (4)	0.4252 (14)	0.062 (4)	0.49 (7)
H4	0.395978	0.092749	0.475215	0.074*	0.49 (7)
C5	0.484 (6)	0.143 (3)	0.3791 (18)	0.061 (4)	0.49 (7)
H5	0.564573	0.193797	0.398368	0.074*	0.49 (7)
C6	0.465 (5)	0.127 (4)	0.3044 (17)	0.058 (4)	0.49 (7)
H6	0.532736	0.167132	0.273565	0.070*	0.49 (7)
C1A	0.338 (4)	0.047 (3)	0.2748 (13)	0.055 (3)	0.51 (7)
C2A	0.259 (5)	−0.042 (4)	0.3132 (19)	0.057 (4)	0.51 (7)
H2A	0.204660	−0.104759	0.288426	0.069*	0.51 (7)
C3A	0.261 (4)	−0.038 (4)	0.3887 (19)	0.061 (4)	0.51 (7)
H3A	0.207972	−0.097323	0.414372	0.073*	0.51 (7)
C4A	0.342 (5)	0.056 (4)	0.4258 (13)	0.062 (4)	0.51 (7)
H4A	0.342913	0.059306	0.476246	0.075*	0.51 (7)
C5A	0.420 (7)	0.146 (2)	0.3874 (18)	0.060 (4)	0.51 (7)
H5A	0.474543	0.208501	0.412173	0.072*	0.51 (7)
C6A	0.418 (5)	0.141 (3)	0.3119 (18)	0.059 (4)	0.51 (7)
H6A	0.471233	0.201067	0.286226	0.070*	0.51 (7)
C7	0.4521 (18)	0.0840 (15)	0.1564 (9)	0.049 (4)
H7A	0.537245	0.023733	0.161521	0.059*
H7B	0.493647	0.160291	0.176389	0.059*
C8	0.411 (2)	0.1017 (15)	0.0780 (9)	0.052 (4)
H8A	0.339429	0.171509	0.071858	0.063*
H8B	0.507744	0.119164	0.052790	0.063*
C9	0.1907 (17)	−0.0413 (16)	0.0857 (9)	0.046 (4)
H9A	0.144478	−0.115915	0.065528	0.056*
H9B	0.110126	0.022516	0.080775	0.056*
C10	0.2369 (19)	−0.0603 (15)	0.1653 (10)	0.049 (4)
H10A	0.140631	−0.076696	0.191354	0.059*
H10B	0.306204	−0.131345	0.170331	0.059*
S1	0.1579 (4)	0.7481 (4)	−0.1011 (2)	0.0439 (10)
O1	0.1787 (12)	0.6159 (9)	−0.0944 (6)	0.049 (3)
O2	0.2928 (18)	0.8175 (11)	−0.0705 (7)	0.076 (4)
O3	0.0028 (16)	0.7862 (13)	−0.0762 (7)	0.082 (5)
C11	0.1506 (16)	0.7750 (13)	−0.1938 (8)	0.036 (3)
C12	0.2354 (19)	0.8746 (17)	−0.2240 (10)	0.054 (4)
H12	0.298418	0.925481	−0.193938	0.065*
C13	0.224 (2)	0.8952 (19)	−0.2971 (11)	0.067 (5)
H13	0.283222	0.959399	−0.315160	0.081*
C14	0.133 (2)	0.830 (2)	−0.3450 (11)	0.070 (5)
C15	0.042 (2)	0.735 (2)	−0.3146 (10)	0.069 (5)
H15	−0.025524	0.687927	−0.344707	0.083*
C16	0.051 (2)	0.7130 (15)	−0.2414 (9)	0.060 (5)
H16	−0.013532	0.652069	−0.223331	0.072*
C17	0.121 (3)	0.853 (3)	−0.4249 (11)	0.101 (8)
H17A	0.138438	0.778329	−0.450528	0.152*
H17B	0.200838	0.911924	−0.437227	0.152*
H17C	0.015970	0.884299	−0.438319	0.152*
N3	0.2216 (15)	0.5462 (13)	0.1956 (8)	0.046 (3)
N4	0.1795 (13)	0.4911 (11)	0.0439 (8)	0.041 (3)
H41N	0.110853	0.428961	0.045763	0.049*
H42N	0.200180	0.504089	−0.002420	0.049*
C18	0.212 (4)	0.553 (3)	0.2730 (13)	0.052 (3)	0.53 (7)
C19	0.321 (4)	0.490 (4)	0.3187 (18)	0.055 (4)	0.53 (7)
H19	0.395669	0.437535	0.299289	0.066*	0.53 (7)
C20	0.319 (3)	0.506 (4)	0.3935 (17)	0.058 (4)	0.53 (7)
H20	0.392116	0.464559	0.424139	0.070*	0.53 (7)
C21	0.208 (5)	0.585 (3)	0.4226 (13)	0.060 (4)	0.53 (7)
H21	0.206786	0.596177	0.472606	0.071*	0.53 (7)
C22	0.099 (6)	0.648 (3)	0.3768 (17)	0.058 (4)	0.53 (7)
H22	0.025007	0.700772	0.396224	0.070*	0.53 (7)
C23	0.101 (5)	0.632 (3)	0.3020 (16)	0.056 (4)	0.53 (7)
H23	0.028557	0.673749	0.271374	0.067*	0.53 (7)
C18A	0.222 (5)	0.547 (4)	0.2737 (15)	0.053 (3)	0.47 (7)
C19A	0.308 (5)	0.459 (4)	0.313 (2)	0.054 (4)	0.47 (7)
H19A	0.355887	0.394865	0.289012	0.065*	0.47 (7)
C20A	0.322 (4)	0.466 (4)	0.388 (2)	0.057 (4)	0.47 (7)
H20A	0.379451	0.406632	0.414826	0.069*	0.47 (7)
C21A	0.250 (6)	0.562 (4)	0.4245 (15)	0.059 (4)	0.47 (7)
H21A	0.259318	0.566251	0.474911	0.071*	0.47 (7)
C22A	0.164 (7)	0.650 (3)	0.385 (2)	0.058 (4)	0.47 (7)
H22A	0.115621	0.714105	0.409183	0.070*	0.47 (7)
C23A	0.150 (6)	0.643 (3)	0.310 (2)	0.057 (4)	0.47 (7)
H23A	0.092056	0.702341	0.283368	0.068*	0.47 (7)
C24	0.2995 (19)	0.4424 (17)	0.1647 (10)	0.053 (4)
H24A	0.233128	0.370513	0.170301	0.064*
H24B	0.401590	0.428310	0.190816	0.064*
C25	0.3281 (16)	0.4609 (14)	0.0851 (9)	0.042 (3)
H25A	0.405263	0.526314	0.079855	0.051*
H25B	0.373358	0.386948	0.065500	0.051*
C26	0.107 (2)	0.6013 (14)	0.0745 (9)	0.049 (4)
H26A	0.005379	0.618567	0.048646	0.058*
H26B	0.177715	0.670632	0.068350	0.058*
C27	0.0796 (19)	0.5836 (16)	0.1541 (9)	0.050 (4)
H27A	0.040882	0.659632	0.173988	0.059*
H27B	−0.003443	0.522492	0.159258	0.059*
S2	0.3197 (4)	0.2483 (4)	−0.1000 (2)	0.0434 (10)
O4	0.4827 (15)	0.2874 (13)	−0.0758 (7)	0.082 (5)
O5	0.1897 (18)	0.3143 (12)	−0.0704 (7)	0.076 (4)
O6	0.3029 (13)	0.1184 (10)	−0.0925 (6)	0.055 (3)
C28	0.3101 (15)	0.2744 (12)	−0.1926 (7)	0.030 (3)
C29	0.398 (2)	0.2104 (14)	−0.2397 (9)	0.056 (4)
H29	0.464748	0.148626	−0.221269	0.067*
C30	0.393 (2)	0.2318 (19)	−0.3126 (9)	0.069 (5)
H30	0.454820	0.183365	−0.341942	0.083*
C31	0.299 (3)	0.3227 (19)	−0.3444 (11)	0.067 (5)
C32	0.213 (2)	0.3916 (17)	−0.2971 (11)	0.063 (5)
H32	0.149972	0.455303	−0.315993	0.076*
C33	0.2151 (19)	0.3708 (15)	−0.2229 (11)	0.051 (4)
H33	0.154699	0.419715	−0.193132	0.061*
C34	0.291 (3)	0.347 (3)	−0.4236 (12)	0.108 (9)
H34A	0.211715	0.408803	−0.434536	0.163*
H34B	0.261493	0.273269	−0.449234	0.163*
H34C	0.393878	0.374298	−0.438393	0.163*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.035 (6)	0.025 (6)	0.073 (6)	−0.004 (5)	0.003 (5)	0.004 (5)
N2	0.022 (6)	0.028 (7)	0.075 (9)	−0.001 (5)	0.003 (5)	−0.001 (6)
C1	0.057 (8)	0.041 (8)	0.070 (6)	−0.002 (7)	0.006 (6)	0.002 (6)
C2	0.060 (8)	0.043 (8)	0.070 (7)	−0.006 (7)	0.006 (6)	0.000 (7)
C3	0.065 (8)	0.046 (9)	0.071 (7)	−0.008 (8)	0.007 (6)	−0.001 (7)
C4	0.065 (9)	0.049 (9)	0.072 (7)	−0.009 (8)	0.005 (7)	0.000 (7)
C5	0.062 (9)	0.049 (8)	0.073 (7)	−0.007 (8)	0.006 (7)	−0.002 (7)
C6	0.059 (9)	0.045 (8)	0.071 (6)	−0.004 (7)	0.007 (7)	−0.001 (7)
C1A	0.056 (8)	0.041 (7)	0.070 (6)	−0.002 (7)	0.007 (6)	0.002 (6)
C2A	0.058 (8)	0.044 (8)	0.071 (6)	−0.004 (7)	0.007 (6)	0.001 (7)
C3A	0.065 (8)	0.046 (9)	0.071 (7)	−0.009 (8)	0.007 (7)	0.001 (7)
C4A	0.065 (9)	0.050 (8)	0.072 (7)	−0.009 (8)	0.005 (7)	0.001 (7)
C5A	0.061 (9)	0.048 (8)	0.072 (7)	−0.007 (8)	0.006 (7)	−0.001 (7)
C6A	0.059 (9)	0.046 (8)	0.071 (6)	−0.006 (7)	0.007 (7)	0.000 (6)
C7	0.033 (7)	0.041 (10)	0.073 (7)	−0.010 (7)	0.004 (6)	−0.009 (8)
C8	0.051 (9)	0.029 (8)	0.077 (8)	−0.016 (7)	0.004 (7)	0.005 (8)
C9	0.031 (7)	0.036 (9)	0.073 (8)	−0.007 (6)	0.009 (6)	−0.010 (8)
C10	0.038 (9)	0.035 (9)	0.076 (8)	−0.012 (7)	0.012 (7)	0.003 (7)
S1	0.042 (2)	0.029 (2)	0.061 (3)	0.009 (2)	0.0026 (17)	−0.003 (2)
O1	0.046 (7)	0.018 (5)	0.083 (8)	0.002 (5)	0.006 (5)	0.004 (5)
O2	0.114 (10)	0.036 (7)	0.076 (9)	−0.037 (7)	−0.030 (8)	0.007 (7)
O3	0.077 (8)	0.095 (11)	0.078 (8)	0.057 (8)	0.038 (7)	0.019 (8)
C11	0.031 (4)	0.034 (4)	0.043 (4)	0.001 (3)	0.002 (3)	−0.003 (3)
C12	0.037 (9)	0.057 (10)	0.068 (8)	−0.018 (8)	0.000 (7)	0.005 (8)
C13	0.064 (12)	0.068 (13)	0.070 (9)	−0.016 (9)	0.011 (8)	0.013 (9)
C14	0.067 (12)	0.080 (13)	0.062 (9)	0.005 (9)	0.002 (8)	0.000 (9)
C15	0.076 (11)	0.064 (12)	0.067 (8)	−0.009 (10)	−0.017 (8)	−0.012 (9)
C16	0.069 (10)	0.039 (11)	0.069 (8)	−0.017 (8)	−0.013 (8)	−0.002 (7)
C17	0.108 (19)	0.13 (2)	0.068 (10)	0.026 (17)	0.009 (11)	0.013 (12)
N3	0.033 (6)	0.037 (7)	0.067 (5)	−0.005 (5)	−0.002 (5)	0.001 (6)
N4	0.024 (6)	0.023 (6)	0.076 (8)	−0.006 (5)	0.006 (5)	0.005 (6)
C18	0.048 (8)	0.040 (7)	0.067 (6)	−0.001 (7)	−0.002 (5)	0.004 (6)
C19	0.052 (7)	0.044 (8)	0.068 (6)	0.004 (7)	−0.003 (6)	0.002 (7)
C20	0.058 (8)	0.046 (9)	0.069 (6)	0.007 (8)	−0.002 (6)	0.003 (7)
C21	0.058 (9)	0.049 (8)	0.071 (7)	0.008 (8)	−0.002 (6)	0.003 (7)
C22	0.055 (9)	0.048 (8)	0.071 (7)	0.007 (8)	−0.003 (7)	0.000 (7)
C23	0.051 (8)	0.045 (7)	0.071 (6)	0.005 (7)	−0.003 (6)	0.001 (7)
C18A	0.049 (8)	0.041 (7)	0.067 (6)	−0.001 (7)	−0.002 (6)	0.003 (6)
C19A	0.051 (8)	0.043 (8)	0.068 (6)	0.002 (7)	−0.002 (6)	0.003 (7)
C20A	0.057 (8)	0.045 (9)	0.069 (6)	0.008 (8)	−0.003 (6)	0.003 (7)
C21A	0.058 (9)	0.048 (8)	0.071 (7)	0.009 (8)	−0.001 (7)	0.002 (7)
C22A	0.056 (9)	0.047 (8)	0.072 (7)	0.007 (8)	−0.002 (7)	0.000 (7)
C23A	0.053 (9)	0.045 (7)	0.071 (6)	0.003 (8)	−0.003 (7)	0.000 (6)
C24	0.029 (8)	0.052 (10)	0.079 (8)	0.010 (7)	0.000 (7)	0.004 (8)
C25	0.022 (6)	0.022 (8)	0.083 (8)	−0.004 (6)	0.003 (6)	−0.005 (7)
C26	0.052 (9)	0.021 (7)	0.073 (8)	0.012 (7)	0.003 (7)	0.008 (7)
C27	0.047 (4)	0.047 (5)	0.054 (4)	0.005 (3)	0.001 (3)	−0.002 (3)
S2	0.041 (2)	0.030 (2)	0.059 (3)	−0.014 (2)	0.0019 (17)	−0.002 (2)
O4	0.072 (7)	0.087 (11)	0.082 (9)	−0.056 (7)	−0.035 (6)	0.031 (8)
O5	0.107 (10)	0.048 (8)	0.076 (9)	0.008 (7)	0.035 (8)	0.000 (7)
O6	0.058 (7)	0.026 (6)	0.082 (9)	−0.017 (5)	−0.004 (6)	0.009 (6)
C28	0.025 (4)	0.025 (4)	0.039 (4)	−0.008 (3)	0.002 (3)	−0.003 (3)
C29	0.075 (11)	0.033 (10)	0.061 (8)	0.011 (7)	0.011 (8)	−0.004 (7)
C30	0.097 (13)	0.053 (12)	0.059 (8)	0.003 (9)	0.018 (8)	−0.015 (8)
C31	0.069 (12)	0.063 (12)	0.068 (9)	−0.021 (8)	−0.005 (8)	0.005 (8)
C32	0.058 (12)	0.044 (11)	0.087 (9)	0.000 (8)	−0.008 (8)	0.019 (9)
C33	0.035 (8)	0.031 (8)	0.087 (9)	0.005 (6)	0.001 (8)	0.007 (8)
C34	0.11 (2)	0.13 (2)	0.076 (10)	−0.039 (18)	−0.012 (11)	0.022 (13)

Geometric parameters (Å, º)

N1—C1A	1.41 (3)	N3—C18	1.43 (3)
N1—C1	1.44 (3)	N3—C27	1.437 (19)
N1—C7	1.437 (19)	N3—C18A	1.44 (3)
N1—C10	1.461 (19)	N3—C24	1.44 (2)
N2—C9	1.467 (18)	N4—C25	1.459 (19)
N2—C8	1.475 (19)	N4—C26	1.473 (18)
N2—H21N	0.8900	N4—H41N	0.8900
N2—H22N	0.8900	N4—H42N	0.8900
C1—C2	1.3900	C18—C19	1.3900
C1—C6	1.3900	C18—C23	1.3900
C2—C3	1.3900	C19—C20	1.3900
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.3900	C20—C21	1.3900
C3—H3	0.9300	C20—H20	0.9300
C4—C5	1.3900	C21—C22	1.3900
C4—H4	0.9300	C21—H21	0.9300
C5—C6	1.3900	C22—C23	1.3900
C5—H5	0.9300	C22—H22	0.9300
C6—H6	0.9300	C23—H23	0.9300
C1A—C2A	1.3900	C18A—C19A	1.3900
C1A—C6A	1.3900	C18A—C23A	1.3900
C2A—C3A	1.3900	C19A—C20A	1.3900
C2A—H2A	0.9300	C19A—H19A	0.9300
C3A—C4A	1.3900	C20A—C21A	1.3900
C3A—H3A	0.9300	C20A—H20A	0.9300
C4A—C5A	1.3900	C21A—C22A	1.3900
C4A—H4A	0.9300	C21A—H21A	0.9300
C5A—C6A	1.3900	C22A—C23A	1.3900
C5A—H5A	0.9300	C22A—H22A	0.9300
C6A—H6A	0.9300	C23A—H23A	0.9300
C7—C8	1.48 (2)	C24—C25	1.51 (2)
C7—H7A	0.9700	C24—H24A	0.9700
C7—H7B	0.9700	C24—H24B	0.9700
C8—H8A	0.9700	C25—H25A	0.9700
C8—H8B	0.9700	C25—H25B	0.9700
C9—C10	1.51 (2)	C26—C27	1.51 (2)
C9—H9A	0.9700	C26—H26A	0.9700
C9—H9B	0.9700	C26—H26B	0.9700
C10—H10A	0.9700	C27—H27A	0.9700
C10—H10B	0.9700	C27—H27B	0.9700
S1—O2	1.448 (12)	S2—O5	1.430 (13)
S1—O3	1.451 (12)	S2—O6	1.436 (11)
S1—O1	1.462 (11)	S2—O4	1.473 (11)
S1—C11	1.731 (15)	S2—C28	1.728 (14)
C11—C16	1.358 (19)	C28—C29	1.355 (19)
C11—C12	1.43 (2)	C28—C33	1.42 (2)
C12—C13	1.36 (2)	C29—C30	1.36 (2)
C12—H12	0.9300	C29—H29	0.9300
C13—C14	1.34 (3)	C30—C31	1.38 (3)
C13—H13	0.9300	C30—H30	0.9300
C14—C15	1.41 (3)	C31—C32	1.38 (3)
C14—C17	1.49 (3)	C31—C34	1.48 (3)
C15—C16	1.37 (2)	C32—C33	1.39 (3)
C15—H15	0.9300	C32—H32	0.9300
C16—H16	0.9300	C33—H33	0.9300
C17—H17A	0.9600	C34—H34A	0.9600
C17—H17B	0.9600	C34—H34B	0.9600
C17—H17C	0.9600	C34—H34C	0.9600
C1A—N1—C7	118.8 (19)	C18—N3—C27	115.7 (18)
C1—N1—C7	116.1 (19)	C27—N3—C18A	119 (2)
C1A—N1—C10	116.9 (19)	C18—N3—C24	118.7 (19)
C1—N1—C10	119.1 (19)	C27—N3—C24	112.9 (14)
C7—N1—C10	111.9 (13)	C18A—N3—C24	115 (2)
C9—N2—C8	110.6 (13)	C25—N4—C26	109.8 (13)
C9—N2—H21N	109.5	C25—N4—H41N	109.7
C8—N2—H21N	109.5	C26—N4—H41N	109.7
C9—N2—H22N	109.5	C25—N4—H42N	109.7
C8—N2—H22N	109.5	C26—N4—H42N	109.7
H21N—N2—H22N	108.1	H41N—N4—H42N	108.2
C2—C1—C6	120.0	C19—C18—C23	120.0
C2—C1—N1	122 (2)	C19—C18—N3	121 (2)
C6—C1—N1	118 (2)	C23—C18—N3	119 (2)
C3—C2—C1	120.0	C20—C19—C18	120.0
C3—C2—H2	120.0	C20—C19—H19	120.0
C1—C2—H2	120.0	C18—C19—H19	120.0
C2—C3—C4	120.0	C21—C20—C19	120.0
C2—C3—H3	120.0	C21—C20—H20	120.0
C4—C3—H3	120.0	C19—C20—H20	120.0
C3—C4—C5	120.0	C22—C21—C20	120.0
C3—C4—H4	120.0	C22—C21—H21	120.0
C5—C4—H4	120.0	C20—C21—H21	120.0
C6—C5—C4	120.0	C21—C22—C23	120.0
C6—C5—H5	120.0	C21—C22—H22	120.0
C4—C5—H5	120.0	C23—C22—H22	120.0
C5—C6—C1	120.0	C22—C23—C18	120.0
C5—C6—H6	120.0	C22—C23—H23	120.0
C1—C6—H6	120.0	C18—C23—H23	120.0
C2A—C1A—C6A	120.0	C19A—C18A—C23A	120.0
C2A—C1A—N1	118 (2)	C19A—C18A—N3	119 (3)
C6A—C1A—N1	122 (2)	C23A—C18A—N3	120 (3)
C1A—C2A—C3A	120.0	C20A—C19A—C18A	120.0
C1A—C2A—H2A	120.0	C20A—C19A—H19A	120.0
C3A—C2A—H2A	120.0	C18A—C19A—H19A	120.0
C4A—C3A—C2A	120.0	C19A—C20A—C21A	120.0
C4A—C3A—H3A	120.0	C19A—C20A—H20A	120.0
C2A—C3A—H3A	120.0	C21A—C20A—H20A	120.0
C3A—C4A—C5A	120.0	C20A—C21A—C22A	120.0
C3A—C4A—H4A	120.0	C20A—C21A—H21A	120.0
C5A—C4A—H4A	120.0	C22A—C21A—H21A	120.0
C6A—C5A—C4A	120.0	C23A—C22A—C21A	120.0
C6A—C5A—H5A	120.0	C23A—C22A—H22A	120.0
C4A—C5A—H5A	120.0	C21A—C22A—H22A	120.0
C5A—C6A—C1A	120.0	C22A—C23A—C18A	120.0
C5A—C6A—H6A	120.0	C22A—C23A—H23A	120.0
C1A—C6A—H6A	120.0	C18A—C23A—H23A	120.0
N1—C7—C8	114.2 (13)	N3—C24—C25	111.9 (14)
N1—C7—H7A	108.7	N3—C24—H24A	109.2
C8—C7—H7A	108.7	C25—C24—H24A	109.2
N1—C7—H7B	108.7	N3—C24—H24B	109.2
C8—C7—H7B	108.7	C25—C24—H24B	109.2
H7A—C7—H7B	107.6	H24A—C24—H24B	107.9
N2—C8—C7	111.8 (13)	N4—C25—C24	111.5 (12)
N2—C8—H8A	109.3	N4—C25—H25A	109.3
C7—C8—H8A	109.3	C24—C25—H25A	109.3
N2—C8—H8B	109.3	N4—C25—H25B	109.3
C7—C8—H8B	109.3	C24—C25—H25B	109.3
H8A—C8—H8B	107.9	H25A—C25—H25B	108.0
N2—C9—C10	110.8 (12)	N4—C26—C27	110.5 (13)
N2—C9—H9A	109.5	N4—C26—H26A	109.6
C10—C9—H9A	109.5	C27—C26—H26A	109.6
N2—C9—H9B	109.5	N4—C26—H26B	109.6
C10—C9—H9B	109.5	C27—C26—H26B	109.6
H9A—C9—H9B	108.1	H26A—C26—H26B	108.1
N1—C10—C9	112.7 (13)	N3—C27—C26	113.3 (13)
N1—C10—H10A	109.1	N3—C27—H27A	108.9
C9—C10—H10A	109.1	C26—C27—H27A	108.9
N1—C10—H10B	109.1	N3—C27—H27B	108.9
C9—C10—H10B	109.1	C26—C27—H27B	108.9
H10A—C10—H10B	107.8	H27A—C27—H27B	107.7
O2—S1—O3	114.3 (10)	O5—S2—O6	112.7 (8)
O2—S1—O1	113.6 (8)	O5—S2—O4	116.2 (9)
O3—S1—O1	111.2 (8)	O6—S2—O4	110.6 (8)
O2—S1—C11	106.6 (7)	O5—S2—C28	106.9 (8)
O3—S1—C11	105.8 (7)	O6—S2—C28	105.0 (7)
O1—S1—C11	104.5 (7)	O4—S2—C28	104.5 (7)
C16—C11—C12	115.3 (15)	C29—C28—C33	116.1 (14)
C16—C11—S1	123.0 (12)	C29—C28—S2	123.0 (12)
C12—C11—S1	121.3 (12)	C33—C28—S2	120.7 (12)
C13—C12—C11	119.8 (17)	C28—C29—C30	123.4 (16)
C13—C12—H12	120.1	C28—C29—H29	118.3
C11—C12—H12	120.1	C30—C29—H29	118.3
C14—C13—C12	124.9 (19)	C29—C30—C31	122.3 (18)
C14—C13—H13	117.5	C29—C30—H30	118.9
C12—C13—H13	117.5	C31—C30—H30	118.9
C13—C14—C15	115.2 (19)	C30—C31—C32	115.3 (19)
C13—C14—C17	124 (2)	C30—C31—C34	123 (2)
C15—C14—C17	120 (2)	C32—C31—C34	121 (2)
C16—C15—C14	121.0 (18)	C31—C32—C33	123.4 (18)
C16—C15—H15	119.5	C31—C32—H32	118.3
C14—C15—H15	119.5	C33—C32—H32	118.3
C11—C16—C15	123.5 (17)	C32—C33—C28	119.5 (16)
C11—C16—H16	118.3	C32—C33—H33	120.2
C15—C16—H16	118.3	C28—C33—H33	120.2
C14—C17—H17A	109.5	C31—C34—H34A	109.5
C14—C17—H17B	109.5	C31—C34—H34B	109.5
H17A—C17—H17B	109.5	H34A—C34—H34B	109.5
C14—C17—H17C	109.5	C31—C34—H34C	109.5
H17A—C17—H17C	109.5	H34A—C34—H34C	109.5
H17B—C17—H17C	109.5	H34B—C34—H34C	109.5
C7—N1—C1—C2	−165 (2)	C27—N3—C18—C19	163 (2)
C10—N1—C1—C2	−26 (3)	C24—N3—C18—C19	23 (3)
C7—N1—C1—C6	21 (3)	C27—N3—C18—C23	−23 (3)
C10—N1—C1—C6	159 (2)	C24—N3—C18—C23	−162 (2)
C6—C1—C2—C3	0.0	C23—C18—C19—C20	0.0
N1—C1—C2—C3	−174 (3)	N3—C18—C19—C20	174 (3)
C1—C2—C3—C4	0.0	C18—C19—C20—C21	0.0
C2—C3—C4—C5	0.0	C19—C20—C21—C22	0.0
C3—C4—C5—C6	0.0	C20—C21—C22—C23	0.0
C4—C5—C6—C1	0.0	C21—C22—C23—C18	0.0
C2—C1—C6—C5	0.0	C19—C18—C23—C22	0.0
N1—C1—C6—C5	174 (3)	N3—C18—C23—C22	−174 (3)
C7—N1—C1A—C2A	−147 (2)	C27—N3—C18A—C19A	146 (2)
C10—N1—C1A—C2A	−8 (3)	C24—N3—C18A—C19A	6 (3)
C7—N1—C1A—C6A	39 (3)	C27—N3—C18A—C23A	−41 (3)
C10—N1—C1A—C6A	178 (2)	C24—N3—C18A—C23A	−180 (2)
C6A—C1A—C2A—C3A	0.0	C23A—C18A—C19A—C20A	0.0
N1—C1A—C2A—C3A	−174 (3)	N3—C18A—C19A—C20A	174 (3)
C1A—C2A—C3A—C4A	0.0	C18A—C19A—C20A—C21A	0.0
C2A—C3A—C4A—C5A	0.0	C19A—C20A—C21A—C22A	0.0
C3A—C4A—C5A—C6A	0.0	C20A—C21A—C22A—C23A	0.0
C4A—C5A—C6A—C1A	0.0	C21A—C22A—C23A—C18A	0.0
C2A—C1A—C6A—C5A	0.0	C19A—C18A—C23A—C22A	0.0
N1—C1A—C6A—C5A	174 (3)	N3—C18A—C23A—C22A	−174 (3)
C1A—N1—C7—C8	−168 (2)	C18—N3—C24—C25	−168.7 (18)
C1—N1—C7—C8	−168 (2)	C27—N3—C24—C25	51.1 (17)
C10—N1—C7—C8	50.7 (18)	C18A—N3—C24—C25	−167 (2)
C9—N2—C8—C7	54.6 (17)	C26—N4—C25—C24	57.4 (16)
N1—C7—C8—N2	−52.8 (19)	N3—C24—C25—N4	−54.9 (17)
C8—N2—C9—C10	−55.4 (17)	C25—N4—C26—C27	−56.2 (16)
C1A—N1—C10—C9	167 (2)	C18—N3—C27—C26	167.3 (19)
C1—N1—C10—C9	169 (2)	C18A—N3—C27—C26	169 (2)
C7—N1—C10—C9	−51.2 (17)	C24—N3—C27—C26	−51.3 (19)
N2—C9—C10—N1	54.4 (18)	N4—C26—C27—N3	53.6 (19)
O2—S1—C11—C16	171.6 (14)	O5—S2—C28—C29	−168.7 (13)
O3—S1—C11—C16	−66.3 (15)	O6—S2—C28—C29	−48.8 (14)
O1—S1—C11—C16	51.1 (15)	O4—S2—C28—C29	67.7 (14)
O2—S1—C11—C12	−16.1 (15)	O5—S2—C28—C33	15.2 (14)
O3—S1—C11—C12	105.9 (14)	O6—S2—C28—C33	135.1 (12)
O1—S1—C11—C12	−136.7 (13)	O4—S2—C28—C33	−108.5 (13)
C16—C11—C12—C13	−5 (2)	C33—C28—C29—C30	−3 (2)
S1—C11—C12—C13	−178.3 (14)	S2—C28—C29—C30	−178.9 (14)
C11—C12—C13—C14	2 (3)	C28—C29—C30—C31	1 (3)
C12—C13—C14—C15	2 (3)	C29—C30—C31—C32	1 (3)
C12—C13—C14—C17	180 (2)	C29—C30—C31—C34	−179.4 (19)
C13—C14—C15—C16	−2 (3)	C30—C31—C32—C33	−1 (3)
C17—C14—C15—C16	−179.9 (19)	C34—C31—C32—C33	178.8 (19)
C12—C11—C16—C15	6 (3)	C31—C32—C33—C28	0 (3)
S1—C11—C16—C15	178.4 (15)	C29—C28—C33—C32	2 (2)
C14—C15—C16—C11	−2 (3)	S2—C28—C33—C32	178.3 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21N···O6	0.89	2.07	2.884 (18)	151
N2—H22N···O4^i	0.89	1.92	2.774 (17)	161
C9—H9B···O1^ii	0.97	2.64	3.534 (19)	154
N4—H41N···O3^ii	0.89	1.92	2.788 (16)	163
N4—H42N···O1	0.89	2.09	2.890 (18)	149
N4—H42N···O5	0.89	2.43	2.865 (18)	111
C25—H25A···O6^iii	0.97	2.63	3.520 (18)	153

Symmetry codes: (i) −x+1, y−1/2, −z; (ii) −x, y−1/2, −z; (iii) −x+1, y+1/2, −z.

4-Phenylpiperazin-1-ium 4-carboxy-2,3-dihydroxybutanoate monohydrate (11)

Crystal data

C10H15N2^+·C4H5O6^−·H2O	Dx = 1.367 Mg m^−3
Mr = 330.33	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 3790 reflections
a = 7.1185 (7) Å	θ = 2.9–27.8°
b = 7.5255 (8) Å	µ = 0.11 mm^−1
c = 29.955 (3) Å	T = 293 K
V = 1604.7 (3) Å^3	Prism, colourless
Z = 4	0.42 × 0.32 × 0.24 mm
F(000) = 704

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	2808 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.019
Rotation method data acquisition using ω scans.	θmax = 27.8°, θmin = 2.9°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −9→9
Tmin = 0.883, Tmax = 1.000	k = −6→9
6773 measured reflections	l = −36→38
3354 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0359P)^2 + 0.5036P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
3354 reflections	Δρmax = 0.20 e Å^−3
260 parameters	Δρmin = −0.16 e Å^−3
211 restraints	Absolute structure: Flack x determined using 912 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: −0.2 (5)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.2138 (4)	0.3376 (4)	0.69293 (7)	0.0428 (6)
N2	0.0481 (4)	0.3028 (5)	0.60649 (9)	0.0515 (8)
H21	0.057 (6)	0.189 (3)	0.6004 (13)	0.062*
H22	−0.007 (5)	0.338 (5)	0.5825 (9)	0.062*
C1	0.3025 (8)	0.3071 (7)	0.7352 (2)	0.0393 (16)	0.611 (13)
C2	0.4926 (8)	0.2687 (11)	0.73967 (16)	0.0489 (16)	0.611 (13)
H2	0.566167	0.250879	0.714417	0.059*	0.611 (13)
C3	0.5726 (8)	0.2568 (12)	0.78189 (19)	0.0596 (18)	0.611 (13)
H3	0.699769	0.231094	0.784885	0.071*	0.611 (13)
C4	0.4626 (12)	0.2834 (8)	0.81965 (16)	0.0629 (19)	0.611 (13)
H4	0.516140	0.275436	0.847893	0.076*	0.611 (13)
C5	0.2725 (11)	0.3218 (11)	0.8152 (2)	0.0565 (19)	0.611 (13)
H5	0.198908	0.339564	0.840434	0.068*	0.611 (13)
C6	0.1925 (8)	0.3336 (10)	0.7730 (3)	0.0469 (17)	0.611 (13)
H6	0.065303	0.359351	0.769967	0.056*	0.611 (13)
C1A	0.3005 (14)	0.3277 (13)	0.7366 (4)	0.044 (2)	0.389 (13)
C2A	0.4913 (13)	0.3634 (19)	0.7408 (3)	0.054 (2)	0.389 (13)
H2A	0.561166	0.395753	0.715828	0.065*	0.389 (13)
C3A	0.5777 (13)	0.3508 (18)	0.7823 (3)	0.058 (2)	0.389 (13)
H3A	0.705291	0.374729	0.785092	0.069*	0.389 (13)
C4A	0.4732 (18)	0.3026 (13)	0.8196 (3)	0.060 (3)	0.389 (13)
H4A	0.531021	0.294126	0.847328	0.073*	0.389 (13)
C5A	0.2825 (18)	0.2669 (16)	0.8154 (4)	0.052 (2)	0.389 (13)
H5A	0.212626	0.234547	0.840300	0.062*	0.389 (13)
C6A	0.1961 (13)	0.2795 (15)	0.7739 (5)	0.044 (2)	0.389 (13)
H6A	0.068497	0.255570	0.771037	0.053*	0.389 (13)
C7	0.0322 (4)	0.2513 (6)	0.68665 (10)	0.0600 (10)
H7A	−0.044378	0.269546	0.713032	0.072*
H7B	0.051046	0.124480	0.683019	0.072*
C8	−0.0694 (5)	0.3230 (6)	0.64654 (11)	0.0615 (11)
H8A	−0.186632	0.259277	0.642510	0.074*
H8B	−0.098445	0.447573	0.651123	0.074*
C9	0.2345 (5)	0.3864 (6)	0.61270 (11)	0.0626 (11)
H9A	0.219400	0.513976	0.615495	0.075*
H9B	0.311852	0.363336	0.586672	0.075*
C10	0.3310 (4)	0.3153 (6)	0.65361 (9)	0.0516 (9)
H10A	0.358743	0.190224	0.649445	0.062*
H10B	0.448994	0.377545	0.657941	0.062*
O1	0.3807 (3)	0.8465 (3)	0.42742 (7)	0.0391 (5)
O2	0.0905 (3)	0.9424 (3)	0.44164 (9)	0.0536 (6)
O3	−0.0601 (3)	0.6256 (3)	0.44303 (8)	0.0403 (5)
H3O	−0.097 (5)	0.721 (3)	0.4540 (10)	0.048*
O4	0.1952 (3)	0.6293 (3)	0.51830 (6)	0.0405 (5)
H4O	0.091 (3)	0.613 (5)	0.5267 (11)	0.049*
O5	0.0826 (3)	0.2841 (3)	0.51284 (7)	0.0513 (6)
O6	0.1893 (3)	0.2612 (2)	0.44300 (6)	0.0369 (5)
H6O	0.153 (4)	0.156 (3)	0.4444 (11)	0.044*
C11	0.2097 (4)	0.8232 (3)	0.43575 (9)	0.0323 (6)
C12	0.1380 (3)	0.6322 (3)	0.43867 (9)	0.0277 (5)
H12	0.173538	0.569709	0.411225	0.033*
C13	0.2286 (4)	0.5366 (3)	0.47836 (8)	0.0284 (6)
H13	0.364670	0.533612	0.473374	0.034*
C14	0.1588 (4)	0.3466 (4)	0.48051 (8)	0.0311 (6)
O7	−0.3916 (4)	0.5658 (4)	0.39633 (9)	0.0629 (7)
H71O	−0.286 (4)	0.586 (6)	0.4077 (13)	0.075*
H72O	−0.462 (5)	0.649 (4)	0.4054 (14)	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0367 (13)	0.0643 (16)	0.0275 (11)	−0.0036 (13)	−0.0040 (10)	0.0023 (12)
N2	0.0418 (14)	0.083 (2)	0.0299 (13)	−0.0080 (17)	−0.0080 (11)	0.0064 (15)
C1	0.042 (3)	0.047 (3)	0.029 (3)	0.000 (3)	−0.004 (3)	−0.009 (3)
C2	0.044 (3)	0.067 (4)	0.037 (2)	0.012 (3)	−0.003 (2)	0.001 (3)
C3	0.056 (3)	0.075 (5)	0.048 (3)	0.012 (4)	−0.017 (2)	0.003 (4)
C4	0.074 (4)	0.079 (4)	0.036 (3)	0.007 (4)	−0.016 (3)	0.002 (3)
C5	0.067 (3)	0.069 (5)	0.033 (3)	0.005 (4)	−0.002 (3)	−0.002 (3)
C6	0.048 (3)	0.056 (4)	0.037 (3)	0.009 (3)	−0.002 (2)	−0.005 (3)
C1A	0.044 (4)	0.051 (5)	0.036 (4)	0.003 (4)	−0.005 (4)	0.010 (4)
C2A	0.050 (4)	0.072 (5)	0.039 (4)	−0.001 (5)	−0.003 (3)	0.006 (4)
C3A	0.052 (4)	0.078 (6)	0.043 (4)	0.000 (5)	−0.016 (3)	−0.001 (5)
C4A	0.068 (5)	0.078 (5)	0.036 (4)	0.001 (5)	−0.017 (4)	−0.002 (4)
C5A	0.065 (4)	0.058 (5)	0.032 (4)	0.005 (4)	0.001 (4)	0.001 (4)
C6A	0.048 (4)	0.048 (5)	0.036 (4)	0.002 (4)	−0.001 (3)	0.003 (4)
C7	0.0388 (17)	0.108 (3)	0.0335 (16)	−0.015 (2)	0.0016 (13)	0.0005 (19)
C8	0.0405 (18)	0.101 (3)	0.0431 (18)	0.007 (2)	−0.0058 (14)	−0.010 (2)
C9	0.051 (2)	0.097 (3)	0.0398 (17)	−0.023 (2)	−0.0084 (15)	0.0173 (19)
C10	0.0357 (16)	0.085 (3)	0.0343 (15)	−0.0079 (18)	−0.0012 (12)	0.0073 (17)
O1	0.0305 (10)	0.0412 (11)	0.0458 (11)	−0.0059 (9)	0.0039 (9)	−0.0013 (10)
O2	0.0379 (12)	0.0274 (10)	0.0954 (18)	0.0020 (9)	0.0058 (12)	−0.0045 (12)
O3	0.0255 (10)	0.0319 (10)	0.0635 (14)	−0.0007 (9)	−0.0047 (10)	−0.0087 (11)
O4	0.0355 (11)	0.0538 (12)	0.0323 (10)	−0.0080 (11)	0.0028 (9)	−0.0162 (10)
O5	0.0641 (15)	0.0544 (13)	0.0354 (11)	−0.0131 (12)	0.0138 (10)	0.0052 (10)
O6	0.0472 (12)	0.0257 (9)	0.0379 (10)	−0.0018 (9)	0.0084 (9)	−0.0025 (9)
C11	0.0325 (14)	0.0308 (14)	0.0336 (14)	−0.0019 (13)	−0.0026 (12)	−0.0016 (12)
C12	0.0231 (12)	0.0276 (13)	0.0326 (13)	0.0017 (11)	−0.0013 (11)	−0.0044 (12)
C13	0.0249 (13)	0.0353 (14)	0.0248 (12)	−0.0001 (12)	0.0015 (11)	−0.0045 (11)
C14	0.0291 (14)	0.0349 (14)	0.0293 (13)	0.0013 (12)	0.0002 (11)	0.0009 (12)
O7	0.0411 (13)	0.0784 (19)	0.0691 (16)	0.0049 (14)	−0.0092 (12)	−0.0320 (15)

Geometric parameters (Å, º)

N1—C1	1.434 (6)	C5A—H5A	0.9300
N1—C1A	1.448 (9)	C6A—H6A	0.9300
N1—C10	1.453 (4)	C7—C8	1.502 (5)
N1—C7	1.459 (4)	C7—H7A	0.9700
N2—C8	1.470 (4)	C7—H7B	0.9700
N2—C9	1.480 (4)	C8—H8A	0.9700
N2—H21	0.88 (2)	C8—H8B	0.9700
N2—H22	0.86 (2)	C9—C10	1.503 (4)
C1—C2	1.3900	C9—H9A	0.9700
C1—C6	1.3900	C9—H9B	0.9700
C2—C3	1.3900	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700
C3—C4	1.3900	O1—C11	1.255 (3)
C3—H3	0.9300	O2—C11	1.247 (3)
C4—C5	1.3900	O3—C12	1.417 (3)
C4—H4	0.9300	O3—H3O	0.83 (2)
C5—C6	1.3900	O4—C13	1.405 (3)
C5—H5	0.9300	O4—H4O	0.79 (2)
C6—H6	0.9300	O5—C14	1.205 (3)
C1A—C2A	1.3900	O6—C14	1.312 (3)
C1A—C6A	1.3900	O6—H6O	0.83 (2)
C2A—C3A	1.3900	C11—C12	1.528 (4)
C2A—H2A	0.9300	C12—C13	1.532 (4)
C3A—C4A	1.3900	C12—H12	0.9800
C3A—H3A	0.9300	C13—C14	1.516 (4)
C4A—C5A	1.3900	C13—H13	0.9800
C4A—H4A	0.9300	O7—H71O	0.84 (2)
C5A—C6A	1.3900	O7—H72O	0.85 (2)
C1—N1—C10	116.4 (3)	N1—C7—C8	111.7 (3)
C1A—N1—C10	118.8 (5)	N1—C7—H7A	109.3
C1—N1—C7	115.6 (3)	C8—C7—H7A	109.3
C1A—N1—C7	118.1 (5)	N1—C7—H7B	109.3
C10—N1—C7	110.7 (2)	C8—C7—H7B	109.3
C8—N2—C9	111.3 (3)	H7A—C7—H7B	107.9
C8—N2—H21	108 (3)	N2—C8—C7	110.0 (3)
C9—N2—H21	112 (3)	N2—C8—H8A	109.7
C8—N2—H22	113 (3)	C7—C8—H8A	109.7
C9—N2—H22	112 (3)	N2—C8—H8B	109.7
H21—N2—H22	99 (4)	C7—C8—H8B	109.7
C2—C1—C6	120.0	H8A—C8—H8B	108.2
C2—C1—N1	123.2 (5)	N2—C9—C10	111.2 (3)
C6—C1—N1	116.6 (5)	N2—C9—H9A	109.4
C1—C2—C3	120.0	C10—C9—H9A	109.4
C1—C2—H2	120.0	N2—C9—H9B	109.4
C3—C2—H2	120.0	C10—C9—H9B	109.4
C4—C3—C2	120.0	H9A—C9—H9B	108.0
C4—C3—H3	120.0	N1—C10—C9	110.9 (3)
C2—C3—H3	120.0	N1—C10—H10A	109.5
C3—C4—C5	120.0	C9—C10—H10A	109.5
C3—C4—H4	120.0	N1—C10—H10B	109.5
C5—C4—H4	120.0	C9—C10—H10B	109.5
C4—C5—C6	120.0	H10A—C10—H10B	108.0
C4—C5—H5	120.0	C12—O3—H3O	109 (2)
C6—C5—H5	120.0	C13—O4—H4O	111 (3)
C5—C6—C1	120.0	C14—O6—H6O	112 (2)
C5—C6—H6	120.0	O2—C11—O1	126.0 (3)
C1—C6—H6	120.0	O2—C11—C12	116.2 (2)
C2A—C1A—C6A	120.0	O1—C11—C12	117.8 (2)
C2A—C1A—N1	119.3 (7)	O3—C12—C11	111.7 (2)
C6A—C1A—N1	120.7 (7)	O3—C12—C13	109.3 (2)
C1A—C2A—C3A	120.0	C11—C12—C13	110.2 (2)
C1A—C2A—H2A	120.0	O3—C12—H12	108.5
C3A—C2A—H2A	120.0	C11—C12—H12	108.5
C4A—C3A—C2A	120.0	C13—C12—H12	108.5
C4A—C3A—H3A	120.0	O4—C13—C14	112.1 (2)
C2A—C3A—H3A	120.0	O4—C13—C12	110.9 (2)
C3A—C4A—C5A	120.0	C14—C13—C12	109.7 (2)
C3A—C4A—H4A	120.0	O4—C13—H13	108.0
C5A—C4A—H4A	120.0	C14—C13—H13	108.0
C4A—C5A—C6A	120.0	C12—C13—H13	108.0
C4A—C5A—H5A	120.0	O5—C14—O6	124.9 (3)
C6A—C5A—H5A	120.0	O5—C14—C13	123.3 (2)
C5A—C6A—C1A	120.0	O6—C14—C13	111.8 (2)
C5A—C6A—H6A	120.0	H71O—O7—H72O	105 (4)
C1A—C6A—H6A	120.0
C10—N1—C1—C2	3.8 (6)	N1—C1A—C6A—C5A	178.6 (8)
C7—N1—C1—C2	136.3 (5)	C1—N1—C7—C8	166.9 (4)
C10—N1—C1—C6	178.1 (4)	C1A—N1—C7—C8	160.3 (5)
C7—N1—C1—C6	−49.5 (5)	C10—N1—C7—C8	−58.0 (4)
C6—C1—C2—C3	0.0	C9—N2—C8—C7	−54.9 (5)
N1—C1—C2—C3	174.0 (5)	N1—C7—C8—N2	56.7 (5)
C1—C2—C3—C4	0.0	C8—N2—C9—C10	54.9 (5)
C2—C3—C4—C5	0.0	C1—N1—C10—C9	−168.4 (4)
C3—C4—C5—C6	0.0	C1A—N1—C10—C9	−161.7 (5)
C4—C5—C6—C1	0.0	C7—N1—C10—C9	56.8 (4)
C2—C1—C6—C5	0.0	N2—C9—C10—N1	−55.5 (4)
N1—C1—C6—C5	−174.4 (5)	O2—C11—C12—O3	6.3 (3)
C10—N1—C1A—C2A	23.7 (8)	O1—C11—C12—O3	−173.2 (2)
C7—N1—C1A—C2A	162.3 (6)	O2—C11—C12—C13	−115.4 (3)
C10—N1—C1A—C6A	−154.9 (6)	O1—C11—C12—C13	65.1 (3)
C7—N1—C1A—C6A	−16.3 (9)	O3—C12—C13—O4	−66.8 (3)
C6A—C1A—C2A—C3A	0.0	C11—C12—C13—O4	56.4 (3)
N1—C1A—C2A—C3A	−178.6 (8)	O3—C12—C13—C14	57.7 (3)
C1A—C2A—C3A—C4A	0.0	C11—C12—C13—C14	−179.2 (2)
C2A—C3A—C4A—C5A	0.0	O4—C13—C14—O5	0.4 (4)
C3A—C4A—C5A—C6A	0.0	C12—C13—C14—O5	−123.3 (3)
C4A—C5A—C6A—C1A	0.0	O4—C13—C14—O6	179.5 (2)
C2A—C1A—C6A—C5A	0.0	C12—C13—C14—O6	55.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O7^i	0.88 (2)	1.95 (2)	2.808 (5)	164 (4)
N2—H22···O1^ii	0.86 (2)	2.52 (3)	3.069 (4)	122 (3)
N2—H22···O5	0.86 (2)	2.22 (3)	2.820 (3)	127 (3)
N2—H22···O6^iii	0.86 (2)	2.41 (3)	2.992 (3)	125 (3)
C9—H9B···O2^iv	0.97	2.61	3.276 (4)	126
O3—H3O···O2	0.83 (2)	2.17 (3)	2.614 (3)	114 (3)
O3—H3O···O4^ii	0.83 (2)	2.04 (2)	2.789 (3)	150 (3)
O4—H4O···O1^ii	0.79 (2)	2.06 (3)	2.773 (3)	151 (3)
O6—H6O···O2^v	0.83 (2)	1.67 (2)	2.501 (3)	174 (3)
O7—H71O···O3	0.84 (2)	1.95 (2)	2.780 (3)	171 (4)
O7—H72O···O1^vi	0.85 (2)	1.97 (2)	2.821 (3)	178 (4)

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) x−1/2, −y+1/2, −z+1; (iv) x+1/2, −y+3/2, −z+1; (v) x, y−1, z; (vi) x−1, y, z.

4-Phenylpiperazin-1-ium fumarate (12)

Crystal data

C10H15N2^+·C4H3O4^−	Dx = 1.287 Mg m^−3
Mr = 278.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 6248 reflections
a = 26.702 (1) Å	θ = 2.7–27.8°
b = 7.9626 (3) Å	µ = 0.10 mm^−1
c = 6.7571 (3) Å	T = 293 K
V = 1436.68 (10) Å^3	Prism, light brown
Z = 4	0.48 × 0.44 × 0.40 mm
F(000) = 592

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD diffractometer	2770 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.018
Rotation method data acquisition using ω scans.	θmax = 27.9°, θmin = 3.0°
Absorption correction: multi-scan (CrysalisRED; Oxford Diffraction, 2007)	h = −33→33
Tmin = 0.894, Tmax = 1.000	k = −10→5
9534 measured reflections	l = −8→8
3127 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0296P)^2 + 0.3161P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.077	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.17 e Å^−3
3127 reflections	Δρmin = −0.13 e Å^−3
191 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.024 (5)
Primary atom site location: dual	Absolute structure: Flack x determined using 1130 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.3 (3)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.07139 (6)	0.0974 (2)	0.4560 (3)	0.0396 (4)
N2	0.15289 (7)	0.1889 (2)	0.2018 (3)	0.0359 (4)
H21	0.1639 (9)	0.258 (3)	0.111 (3)	0.043*
H22	0.1758 (8)	0.112 (3)	0.231 (4)	0.043*
C1	0.02675 (7)	0.1920 (3)	0.4495 (3)	0.0341 (5)
C2	−0.01118 (8)	0.1565 (3)	0.3155 (4)	0.0460 (5)
H2	−0.006524	0.072842	0.221209	0.055*
C3	−0.05581 (9)	0.2442 (3)	0.3210 (5)	0.0554 (6)
H3	−0.080837	0.217775	0.230469	0.066*
C4	−0.06407 (10)	0.3685 (3)	0.4555 (5)	0.0581 (8)
H4	−0.094144	0.427343	0.457231	0.070*
C5	−0.02681 (11)	0.4041 (4)	0.5880 (5)	0.0605 (8)
H5	−0.031873	0.488166	0.681492	0.073*
C6	0.01794 (9)	0.3187 (3)	0.5862 (4)	0.0493 (6)
H6	0.042619	0.346194	0.677785	0.059*
C7	0.11662 (9)	0.1763 (4)	0.5335 (4)	0.0516 (7)
H7A	0.140074	0.089729	0.573846	0.062*
H7B	0.108145	0.242129	0.649545	0.062*
C8	0.14116 (9)	0.2881 (3)	0.3825 (4)	0.0453 (6)
H8A	0.118887	0.380029	0.348976	0.054*
H8B	0.171722	0.335098	0.436782	0.054*
C9	0.10846 (8)	0.0982 (3)	0.1241 (3)	0.0406 (5)
H9A	0.118462	0.025512	0.015935	0.049*
H9B	0.084244	0.178364	0.073747	0.049*
C10	0.08503 (8)	−0.0048 (3)	0.2859 (4)	0.0458 (6)
H10A	0.055321	−0.060037	0.234969	0.055*
H10B	0.108400	−0.091175	0.327448	0.055*
O1	0.28279 (5)	0.92767 (16)	−0.2019 (3)	0.0457 (4)
O2	0.20615 (5)	1.03469 (16)	−0.1699 (3)	0.0403 (4)
H2O	0.2217 (8)	1.136 (3)	−0.190 (4)	0.048*
O3	0.24248 (5)	0.31442 (15)	−0.2281 (3)	0.0395 (4)
O4	0.17409 (5)	0.41963 (17)	−0.0874 (3)	0.0411 (4)
C11	0.23766 (7)	0.9127 (2)	−0.1764 (3)	0.0298 (4)
C12	0.21444 (7)	0.7446 (2)	−0.1522 (4)	0.0324 (5)
H12	0.181218	0.738436	−0.111463	0.039*
C13	0.23863 (7)	0.6049 (2)	−0.1857 (3)	0.0297 (4)
H13	0.271921	0.611739	−0.225248	0.036*
C14	0.21578 (7)	0.4351 (2)	−0.1639 (3)	0.0283 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0316 (9)	0.0426 (10)	0.0447 (11)	0.0009 (8)	0.0062 (8)	0.0066 (9)
N2	0.0258 (9)	0.0317 (9)	0.0504 (12)	0.0015 (7)	0.0070 (8)	0.0071 (9)
C1	0.0292 (10)	0.0343 (10)	0.0389 (11)	−0.0044 (8)	0.0063 (9)	0.0047 (10)
C2	0.0385 (11)	0.0495 (12)	0.0502 (14)	−0.0029 (10)	0.0001 (12)	−0.0091 (13)
C3	0.0355 (11)	0.0636 (15)	0.0670 (17)	−0.0042 (11)	−0.0095 (14)	0.0038 (16)
C4	0.0364 (13)	0.0466 (14)	0.091 (2)	0.0085 (11)	0.0081 (15)	0.0066 (16)
C5	0.0538 (16)	0.0474 (15)	0.080 (2)	0.0057 (12)	0.0095 (15)	−0.0165 (15)
C6	0.0423 (13)	0.0489 (14)	0.0567 (16)	−0.0027 (11)	−0.0030 (12)	−0.0138 (13)
C7	0.0339 (13)	0.0817 (19)	0.0391 (13)	0.0062 (13)	−0.0057 (10)	0.0027 (14)
C8	0.0279 (10)	0.0477 (13)	0.0604 (16)	−0.0049 (10)	−0.0010 (10)	−0.0136 (12)
C9	0.0338 (12)	0.0459 (13)	0.0419 (13)	−0.0004 (10)	0.0034 (10)	−0.0075 (11)
C10	0.0368 (11)	0.0295 (10)	0.0709 (17)	−0.0033 (9)	0.0130 (12)	−0.0028 (12)
O1	0.0309 (7)	0.0259 (7)	0.0802 (13)	−0.0035 (6)	0.0087 (9)	0.0026 (9)
O2	0.0367 (7)	0.0188 (6)	0.0654 (11)	0.0011 (6)	0.0051 (8)	0.0038 (8)
O3	0.0374 (8)	0.0208 (6)	0.0604 (11)	0.0016 (6)	0.0103 (7)	−0.0015 (7)
O4	0.0305 (8)	0.0258 (7)	0.0671 (11)	0.0008 (6)	0.0107 (7)	0.0088 (7)
C11	0.0332 (10)	0.0224 (9)	0.0338 (11)	−0.0009 (7)	0.0011 (9)	0.0004 (9)
C12	0.0297 (9)	0.0231 (8)	0.0443 (12)	−0.0037 (8)	0.0045 (9)	0.0019 (9)
C13	0.0297 (9)	0.0224 (8)	0.0369 (11)	−0.0028 (7)	0.0024 (9)	0.0029 (9)
C14	0.0283 (9)	0.0201 (8)	0.0365 (10)	0.0003 (7)	−0.0024 (9)	0.0033 (9)

Geometric parameters (Å, º)

N1—C1	1.411 (3)	C7—H7A	0.9700
N1—C10	1.455 (3)	C7—H7B	0.9700
N1—C7	1.459 (3)	C8—H8A	0.9700
N2—C9	1.485 (3)	C8—H8B	0.9700
N2—C8	1.487 (3)	C9—C10	1.504 (3)
N2—H21	0.87 (2)	C9—H9A	0.9700
N2—H22	0.89 (2)	C9—H9B	0.9700
C1—C2	1.388 (3)	C10—H10A	0.9700
C1—C6	1.388 (3)	C10—H10B	0.9700
C2—C3	1.382 (3)	O1—C11	1.223 (2)
C2—H2	0.9300	O2—C11	1.286 (2)
C3—C4	1.361 (4)	O2—H2O	0.921 (19)
C3—H3	0.9300	O3—C14	1.273 (2)
C4—C5	1.368 (4)	O4—C14	1.234 (2)
C4—H4	0.9300	C11—C12	1.485 (2)
C5—C6	1.375 (4)	C12—C13	1.306 (3)
C5—H5	0.9300	C12—H12	0.9300
C6—H6	0.9300	C13—C14	1.490 (2)
C7—C8	1.505 (4)	C13—H13	0.9300
C1—N1—C10	119.1 (2)	H7A—C7—H7B	107.9
C1—N1—C7	118.8 (2)	N2—C8—C7	109.53 (19)
C10—N1—C7	108.50 (18)	N2—C8—H8A	109.8
C9—N2—C8	112.35 (16)	C7—C8—H8A	109.8
C9—N2—H21	109.1 (17)	N2—C8—H8B	109.8
C8—N2—H21	108.3 (17)	C7—C8—H8B	109.8
C9—N2—H22	107.1 (16)	H8A—C8—H8B	108.2
C8—N2—H22	109.1 (17)	N2—C9—C10	109.9 (2)
H21—N2—H22	111 (2)	N2—C9—H9A	109.7
C2—C1—C6	117.3 (2)	C10—C9—H9A	109.7
C2—C1—N1	121.9 (2)	N2—C9—H9B	109.7
C6—C1—N1	120.7 (2)	C10—C9—H9B	109.7
C3—C2—C1	120.6 (2)	H9A—C9—H9B	108.2
C3—C2—H2	119.7	N1—C10—C9	111.91 (17)
C1—C2—H2	119.7	N1—C10—H10A	109.2
C4—C3—C2	121.7 (3)	C9—C10—H10A	109.2
C4—C3—H3	119.2	N1—C10—H10B	109.2
C2—C3—H3	119.2	C9—C10—H10B	109.2
C3—C4—C5	118.0 (2)	H10A—C10—H10B	107.9
C3—C4—H4	121.0	C11—O2—H2O	111.3 (14)
C5—C4—H4	121.0	O1—C11—O2	125.17 (17)
C4—C5—C6	121.6 (3)	O1—C11—C12	120.99 (17)
C4—C5—H5	119.2	O2—C11—C12	113.83 (16)
C6—C5—H5	119.2	C13—C12—C11	122.85 (17)
C5—C6—C1	120.8 (2)	C13—C12—H12	118.6
C5—C6—H6	119.6	C11—C12—H12	118.6
C1—C6—H6	119.6	C12—C13—C14	123.57 (17)
N1—C7—C8	111.8 (2)	C12—C13—H13	118.2
N1—C7—H7A	109.3	C14—C13—H13	118.2
C8—C7—H7A	109.3	O4—C14—O3	124.92 (16)
N1—C7—H7B	109.3	O4—C14—C13	120.10 (17)
C8—C7—H7B	109.3	O3—C14—C13	114.97 (16)
C10—N1—C1—C2	18.6 (3)	C10—N1—C7—C8	60.7 (3)
C7—N1—C1—C2	154.6 (2)	C9—N2—C8—C7	53.1 (3)
C10—N1—C1—C6	−165.3 (2)	N1—C7—C8—N2	−57.3 (3)
C7—N1—C1—C6	−29.3 (3)	C8—N2—C9—C10	−52.9 (2)
C6—C1—C2—C3	−0.4 (4)	C1—N1—C10—C9	79.8 (2)
N1—C1—C2—C3	175.8 (2)	C7—N1—C10—C9	−60.2 (3)
C1—C2—C3—C4	0.5 (4)	N2—C9—C10—N1	56.7 (2)
C2—C3—C4—C5	−0.5 (4)	O1—C11—C12—C13	−10.5 (4)
C3—C4—C5—C6	0.4 (5)	O2—C11—C12—C13	168.7 (2)
C4—C5—C6—C1	−0.3 (5)	C11—C12—C13—C14	−179.4 (2)
C2—C1—C6—C5	0.3 (4)	C12—C13—C14—O4	−9.5 (3)
N1—C1—C6—C5	−176.0 (3)	C12—C13—C14—O3	170.9 (2)
C1—N1—C7—C8	−79.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O4	0.87 (2)	1.88 (2)	2.741 (2)	168 (2)
N2—H22···O1^i	0.89 (2)	1.89 (2)	2.775 (2)	172 (2)
C7—H7A···O2^ii	0.97	2.51	3.317 (3)	141
C8—H8B···O3^iii	0.97	2.55	3.203 (3)	124
C9—H9A···O2^iv	0.97	2.66	3.318 (3)	126
O2—H2O···O3^v	0.92 (2)	1.54 (2)	2.4610 (18)	174 (2)

Symmetry codes: (i) −x+1/2, y−1, z+1/2; (ii) x, y−1, z+1; (iii) −x+1/2, y, z+1/2; (iv) x, y−1, z; (v) x, y+1, z.