Hydrogen bonding in the anhydrous 1:1 proton-transfer compounds of isonipecotamide with nitro-substituted benzoic acids: the salts of the three isomeric mononitro­benzoic acids and of 3,5-dinitro­benzoic acid

The structures of the anhydrous 1:1 proton-transfer com­pounds of isonipecotamide (piperidine-4-carboxamide) with the three isomeric mononitro-substituted benzoic acids and with 3,5-dinitro­benzoic acid, namely 4-carbamoylpiperidinium 2-nitro­benzoate, (I), 4-carbamoylpiperidinium 3-nitro­benz­oate, (II), and 4-carbamoylpiperidinium 4-nitro­benzoate, (III), all C₆H₁₃N₂O⁺·C₇H₄NO₄^-, and 4-carbamoylpiperidin­ium 3,5-dinitro­benzoate, C₆H₁₃N₂O₈⁺·C₇H₃N₂O₆^-, (IV), respectively, have been determined at 200 K. All the salts form hydrogen-bonded structures, viz. three-dimensional in (I), two-dimensional in (II) and (III), and one-dimensional in (IV). Featured in the hydrogen bonding of three of these [(I), (II) and (IV)] is the cyclic head-to-head amide-amide homodimer motif [graph set R₂²(8)] through a duplex N-H...O association, the dimer then giving structure extension via either piperidinium or amide H-atom donors and carboxyl­ate O-atom and, in some examples [(II) and (IV)], nitro O-atom acceptors. In (I), the centrosymmetric amide-amide homodimers are expanded laterally through N-H...O hydrogen bonds via cyclic R₄²(8) inter­actions, forming ribbons which extend along the c cell direction. These ribbons incorporate the 2-nitro­benzoate cations through centrosymmetric cyclic piperidine-carboxyl­ate N-H...O associations [graph set R₄⁴(12)], giving inter­connected sheets in the three-dimensional structure. In (II), in which no amide-amide homodimer is present, duplex piperidinium-amide N-H...O homomolecular hydrogen-bonding associations [graph set R₂²(14)] give centrosymmetric head-to-tail dimers. Structure extension occurs through hydrogen-bonding associations between both the amide H-atom donors and carboxyl­ate and nitro O-atom acceptors, as well as a three-centre piperidinium-carboxyl­ate N-H...O,O' cyclic R₁²(4) association, giving the two-dimensional network structure. In (III), the centrosymmetric amide-amide dimers are linked through the two carboxyl­ate O-atom acceptors of the anions via bridging piperidinium N-H...O,O'...H-N_amide hydrogen bonds, giving the two-dimensional sheet structure which features centrosymmetric cyclic R₄⁴(12) associations. In (IV), the amide-amide dimer is also centrosymmetric, with the dimers linked to the anions through amide-nitro N-H...O inter­actions. The piperidin­ium groups extend the structure into one-dimensional ribbons via N-H...O_{carboxyl­ate} hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation in mol­ecular assembly. They also highlight the efficacy of the cyclic R₂²(8) amide-amide hydrogen-bonding homodimer motif in this process and provide an additional homodimer motif type in the head-to-tail R₂²(14) association.

S1. Comment

The alicyclic amide 4-carbamoylpiperidine (isonipecotamide, INIPA) (O'Neil, 2001) or any of its compounds previously had no structural representation in the crystallographic literature, prompting our investigation of the possible use of this Lewis base for the formation of crystalline proton-transfer compounds with organic acids. We have recently reported the crystal structures and hydrogen-bonding features of the anhydrous 1:1 salts with both picric acid and 3,5-dinitrosalicylic acid (two polymorphs, both picrates) (Smith & Wermuth, 2010b), as well the acetate (Smith & Wermuth, 2010a) and the 2:1 salt with biphenyl-4,4'-disulfonic acid (Smith et al., 2010).

Among a number of 1:1 stoichiometric reactions of INIPA with aromatic acids in 50% aqueous ethanol, we also obtained good crystals of the anhydrous salts with the three isomeric mononitro-substituted benzoic acids and with 3,5-dinitrobenzoic acid, namely 4-carbamoylpiperidinium 2-nitrobenzoate, (I), 4-carbamoylpiperidinium 3-nitrobenzoate, (II), 4-carbamoylpiperidinium 4-nitrobenzoate, (III), and 4-carbamoylpiperidinium 3,5-dinitrobenzoate, (IV), and their structures and hydrogen-bonding modes are reported here. We have also recently determined the structures of a number of 1:1 proton-transfer salts of INIPA with aromatic dicarboxylic acids and heteroaromatic carboxylic acids (Smith & Wermuth, 2010c).

With the structures of (I)–(IV) (Figs. 1–4), proton transfer occurs to the hetero-N atom of the piperidine ring, and the resulting group is subsequently involved in both hydrogen-bonded cation–anion interactions [single in (I), (III) and (IV), but asymmetric bidentate in (III)]. Featured in the hydrogen bonding of three of these [(I), (II) and (IV)] is the head-to-head cyclic amide–amide homodimer motif [graph set R₂²(8) (Etter et al., 1990)], formed through a duplex N—H···O hydrogen-bonding association. Hydrogen-bonding extensions (Tables 1–4) result in structures which are three-dimensional in (I), two-dimensional in (II) and (III), and one-dimensional in (IV) (Figs. 5–8). The head-to-head amide hydrogen-bonding motif [the `cyclic amide motif' (motif 23) (Allen et al., 1998)] has a surprisingly low probability of formation among the total set of known amide structures, but when restricted to primary amides which have no competing functional substituent groups or other associative companion species such as molecules of solvation the probability is much higher. No amide–amide dimers were found in any of the phenolate structures (Smith & Wermuth, 2010c), but in the biphenyl-4,4'-disulfonate salt there are two separate examples of the dimer involving the three independent INIPA cations, one centrosymmetric and the other noncentrosymmetric (Smith et al., 2010).

In the structure of (I) (Fig. 1), the 2-nitrobenzoate salt, the centrosymmetric R₂²(8) INIPA cation amide–amide homodimers are extended laterally through N—H···O hydrogen bonds (Table 1). giving cyclic R₄²(8) interactions which are centred on crystallographic twofold rotation axes, forming ribbons which extend along the c cell direction at a = 0, 1/2 (Fig. 5). These ribbons incorporate the cations through centrosymmetric cyclic piperidine–carboxylate N—H···O associations [graph set R₄⁴(12)], giving interconnected sheets in the three-dimensional structure. The nitro group of the anion is unassociated, and both it and the carboxylate group are significantly rotated out of the plane of the benzene ring [torsion angles C1—C2—N2—O22 = -131.60 (13)° and C2—C1—C11—O11 = -138.95 (14)°].

With the structure of the 3-nitrobenzoate salt, (II) (Fig. 2), in which no INIPA amide–amide dimer is present, a different homomolecular head-to-tail cyclic dimer is present involving the R₂²(14) duplex piperidinium N—H···O_amide hydrogen-bonding association (Fig. 6). This dimer has precedence in a single example among the known INIPA structures in the picrate (Smith & Wermuth, 2010b). In (II), structure extension occurs through hydrogen-bonding associations between both amide H-atom donors and the carboxylate and nitro O-atom acceptors, and between the second piperidinium H-atom donor and the carboxylate O-atom acceptors of the anion, in an asymmetric three-centre cyclic R₁²(4) mode (Table 2). This results in the two-dimensional structure, which also features large cyclic rings [R₄⁴(30)]. The carboxylate group of the anion is approximately coplanar with the benzene ring, while the nitro group is rotated slightly out of the plane [torsion angles C2—C1—C11—O11 = -174.27 (16)° and C2—C3—N3—O32 = -167.65 (16)°].

In the structure of the 4-nitrobenzoate salt, (III) (Fig. 3), the centrosymmetric R₂²(8) amide–amide dimers are linked through the two carboxylate O-atom acceptors of the anions via bridging amide–carboxylate N—H···O and piperidinium–carboxylate N—H..O hydrogen bonds, giving the two-dimensional sheet structure. Within this structure are centrosymmetric R₄⁴(12) associations (Fig. 7). The nitro group is unassociated. Both the carboxylate and nitro groups of the anion in (III) are rotated slightly out of the plane of the benzene ring [torsion angles C2—C1—C11—O12 = -163.01 (12)° and C3—C4—N4—O41 = 169.40 (12)°].

In the 3,5-dinitrobenzoate salt, (IV), the amide–amide dimer is also centrosymmetric but with the dimers linked to the anions through amide N—H···O_nitro interactions (Table 4), the second nitro group (at C3) being unassociated. The piperidinium groups extend the structure into one-dimensional ribbons via N—H···O_carboxylate hydrogen bonds (Fig. 8). The carboxylate group of the anion in (IV) is approximately coplanar with the benzene ring [torsion angle C2—C1—C11—O11 = 175.83 (15)°], while the nitro groups are either close to coplanar [C2—C3—N3—O32 = -178.67 (16)°] or rotated slightly out of the plane [C4—C5—N5—O52 = 168.85 (16)°].

With the INIPA cations in (I)–(IV), the conformation of the amide group is variable [minimum torsion angle C3A/C5A—C4A—C41A—O41A = -15.24 (19)° in (I), 35.9 (2)° in (II), 14.2 (3)° in (III) and -27.3 (2)° in (IV)]. However, the largest value is associated with the structure of (II), where no amide–amide homodimer is formed.

The structures reported here demonstrate the utility of the INIPA cation as a synthon with previously unrecognized potential for structure-assembly applications, in many cases facilitated through the formation of the robust cyclic head-to-head amide–amide hydrogen-bonded dimer association.

S2. Experimental

The title compounds were synthesized by heating together for 10 min under reflux 4-carbamoylpiperidine (isonipecotamide) (1 mmol) with 2-nitrobenzoic acid (1 mmol) [for (I)], 3-nitrobenzoic acid (1 mmol) [for (II)], 4-nitrobenzic acid (1 mmol) [for (III)] or 3,5-dinitrobenzoic acid (1 mmol) [for (IV)] in 50% ethanol–water (50 ml). After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solutions gave colourless prisms of (I)–(III) [CIF states needle for (I) - please clarify] (m.p. 429, 452 and 537–539 K, respectively) and yellow plates of (IV) (m.p. 473–475 K).

S3. Refinement

H atoms involved in hydrogen-bonding interactions were located in difference electron-density maps and were freely refined. The other H atoms were included in calculated positions and refined using a riding model approximation, with C—H(aromatic) = 0.93 Å and C—H(aliphatic) = 0.97–0.98 Å, and with U_iso(H) = 1.2U_eq(C).

Computing details

For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular configuration and atom-naming scheme for the INIPA cation and 2-nitrobenzoate anion in (I). Displacement ellipsoids are drawn at the 50% probability level. The inter-ion hydrogen bond is shown as a dashed line.
	Fig. 2. The molecular configuration and atom-naming scheme for the INIPA cation and 3-nitrobenzoate anion in (II). Displacement ellipsoids are drawn at the 50% probability level. Inter-ion hydrogen bonds are shown as dashed lines.
	Fig. 3. The molecular configuration and atom-naming scheme for the INIPA cation and 4-nitrobenzoate anion in (III). Displacement ellipsoids are drawn at the 50% probability level. The inter-ion hydrogen bond is shown as a dashed line.
	Fig. 4. The molecular configuration and atom-naming scheme for the INIPA cation and 3,5-dinitrobenzoate anion in (IV). Displacement ellipsoids are drawn at the 50% probability level. The inter-ion hydrogen bond is shown as a dashed line.
	Fig. 5. A view of the partial unit cell of (I), viewed down the approximate b cell direction, showing the centrosymmetric R2^2(8) hydrogen-bonded INIPA amide–amide homodimers and their lateral extension into ribbon structures along c at a = 0, and their further extensions through the 2-nitrobenzoate anions. Hydrogen bonds are shown as dashed lines and non-associative H atoms have been omitted. (For symmetry codes, see Table 1.)
	Fig. 6. A perspective view of the two-dimensional hydrogen-bonded network structure of (II), showing the centrosymmetric head-to-tail cyclic R2^2(14) hydrogen-bonded piperidinium–amide associations in the INIPA cationic dimer and the structure extensions. Hydrogen bonds are shown as dashed lines and non-associative H atoms have been omitted. (For symmetry codes, see Table 2.)
	Fig. 7. The two-dimensional hydrogen-bonded network structure of (III), showing the centrosymmetric hydrogen-bonded amide–amide dimers and their extensions via the carboxylate groups of the anions, in a perspective view of the unit cell. Hydrogen bonds are shown as dashed lines and non-associative H atoms have been omitted. (For symmetry codes, see Table 3.)
	Fig. 8. A perspective view of the one-dimensional hydrogen-bonded ribbon structure of (IV), formed by extension of the INIPA amide–amide dimers through both amide and piperidinium N—H···O interactions. Hydrogen bonds are shown as dashed lines and non-associative H atoms have been omitted. (For symmetry codes, see Table 4.)

(I) 4-carbamoylpiperidinium 2-nitrobenzoate

Crystal data

C6H13N2O^+·C7H4NO4^−	F(000) = 1248
Mr = 295.30	Dx = 1.354 Mg m^−3
Monoclinic, C2/c	Melting point: 429 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 29.035 (3) Å	Cell parameters from 3737 reflections
b = 9.7660 (9) Å	θ = 3.9–27.1°
c = 10.5779 (12) Å	µ = 0.11 mm^−1
β = 105.020 (12)°	T = 200 K
V = 2897.0 (5) Å^3	Needle, colourless
Z = 8	0.50 × 0.26 × 0.12 mm

Data collection

Oxford Gemini-S Ultra CCD area-detector diffractometer	2832 independent reflections
Radiation source: Enhance (Mo) X-ray tube	2076 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.9°
ω scans	h = −35→34
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −12→12
Tmin = 0.940, Tmax = 0.980	l = −12→13
9784 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ^2(Fo^2) + (0.0528P)^2] where P = (Fo^2 + 2Fc^2)/3
2832 reflections	(Δ/σ)max = 0.001
206 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O41A	0.05495 (4)	0.52146 (13)	−0.05296 (10)	0.0523 (4)
N1A	0.21327 (5)	0.68599 (12)	0.11530 (12)	0.0316 (4)
N41A	0.04668 (5)	0.52323 (15)	0.15267 (13)	0.0445 (5)
C2A	0.20653 (5)	0.54186 (14)	0.06848 (13)	0.0339 (4)
C3A	0.15361 (5)	0.51160 (14)	0.01937 (13)	0.0302 (4)
C4A	0.12662 (4)	0.54143 (13)	0.12264 (12)	0.0282 (4)
C5A	0.13775 (5)	0.68601 (14)	0.17882 (13)	0.0313 (4)
C6A	0.19110 (5)	0.71037 (15)	0.22545 (13)	0.0328 (4)
C41A	0.07312 (5)	0.52602 (15)	0.06678 (13)	0.0351 (5)
O11	0.34239 (4)	0.65328 (10)	0.08264 (10)	0.0506 (4)
O12	0.30583 (3)	0.76968 (10)	0.20967 (9)	0.0359 (3)
O21	0.29603 (4)	0.52504 (10)	0.35102 (10)	0.0423 (3)
O22	0.30846 (4)	0.65247 (12)	0.52331 (12)	0.0608 (5)
N2	0.32150 (4)	0.59869 (12)	0.43449 (11)	0.0362 (4)
C1	0.37897 (5)	0.66222 (13)	0.30968 (13)	0.0320 (4)
C2	0.37084 (5)	0.62362 (13)	0.42810 (13)	0.0316 (4)
C3	0.40692 (6)	0.60594 (16)	0.54097 (15)	0.0473 (6)
C4	0.45340 (6)	0.6284 (2)	0.53539 (19)	0.0635 (7)
C5	0.46291 (6)	0.6659 (2)	0.4197 (2)	0.0656 (7)
C6	0.42626 (5)	0.68194 (17)	0.30750 (17)	0.0487 (6)
C11	0.33875 (5)	0.69610 (14)	0.19034 (13)	0.0321 (4)
H4A	0.13700	0.47550	0.19420	0.0340*
H11A	0.1983 (6)	0.7453 (17)	0.0468 (17)	0.052 (5)*
H12A	0.2461 (6)	0.7102 (15)	0.1426 (14)	0.043 (4)*
H21A	0.22090	0.48000	0.13940	0.0410*
H22A	0.22200	0.52810	−0.00160	0.0410*
H31A	0.14930	0.41600	−0.00600	0.0360*
H32A	0.14030	0.56670	−0.05770	0.0360*
H41A	0.0150 (7)	0.5153 (16)	0.1217 (17)	0.053 (5)*
H42A	0.0607 (5)	0.5226 (15)	0.2368 (16)	0.039 (4)*
H51A	0.12370	0.75290	0.11210	0.0380*
H52A	0.12350	0.69830	0.25150	0.0380*
H61A	0.19720	0.80370	0.25660	0.0390*
H62A	0.20500	0.64890	0.29730	0.0390*
H3	0.40020	0.57960	0.61870	0.0570*
H4	0.47830	0.61800	0.61040	0.0760*
H5	0.49430	0.68060	0.41680	0.0790*
H6	0.43330	0.70620	0.22950	0.0580*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O41A	0.0292 (6)	0.0985 (9)	0.0272 (6)	−0.0100 (5)	0.0039 (5)	0.0010 (5)
N1A	0.0273 (7)	0.0409 (7)	0.0264 (6)	−0.0066 (5)	0.0067 (5)	0.0000 (5)
N41A	0.0252 (7)	0.0793 (10)	0.0288 (7)	−0.0068 (6)	0.0067 (6)	0.0010 (6)
C2A	0.0290 (7)	0.0411 (8)	0.0320 (7)	0.0026 (6)	0.0085 (6)	−0.0033 (6)
C3A	0.0301 (7)	0.0305 (7)	0.0296 (7)	−0.0014 (6)	0.0069 (6)	−0.0034 (6)
C4A	0.0260 (7)	0.0336 (7)	0.0238 (7)	−0.0004 (6)	0.0043 (6)	0.0048 (6)
C5A	0.0326 (8)	0.0370 (8)	0.0259 (7)	0.0013 (6)	0.0106 (6)	−0.0002 (6)
C6A	0.0363 (8)	0.0392 (8)	0.0232 (7)	−0.0066 (6)	0.0084 (6)	−0.0022 (6)
C41A	0.0296 (8)	0.0455 (8)	0.0294 (8)	−0.0045 (6)	0.0064 (6)	0.0018 (6)
O11	0.0788 (8)	0.0450 (6)	0.0270 (6)	0.0085 (6)	0.0120 (5)	−0.0029 (5)
O12	0.0304 (5)	0.0385 (6)	0.0367 (6)	−0.0021 (4)	0.0048 (4)	0.0009 (4)
O21	0.0458 (6)	0.0399 (6)	0.0383 (6)	−0.0091 (5)	0.0059 (5)	−0.0013 (5)
O22	0.0752 (9)	0.0667 (8)	0.0533 (7)	−0.0077 (6)	0.0396 (7)	−0.0178 (6)
N2	0.0460 (8)	0.0345 (7)	0.0299 (6)	−0.0016 (6)	0.0129 (6)	0.0007 (5)
C1	0.0338 (8)	0.0286 (7)	0.0340 (8)	0.0011 (6)	0.0095 (6)	−0.0028 (6)
C2	0.0360 (8)	0.0277 (7)	0.0299 (7)	0.0011 (6)	0.0066 (6)	−0.0030 (6)
C3	0.0569 (11)	0.0434 (9)	0.0349 (9)	0.0038 (8)	−0.0003 (8)	0.0018 (7)
C4	0.0425 (11)	0.0709 (13)	0.0616 (12)	0.0057 (9)	−0.0146 (9)	0.0071 (10)
C5	0.0310 (9)	0.0795 (14)	0.0822 (15)	0.0030 (8)	0.0071 (10)	0.0072 (11)
C6	0.0389 (9)	0.0574 (11)	0.0524 (10)	0.0023 (7)	0.0167 (8)	0.0028 (8)
C11	0.0411 (9)	0.0270 (7)	0.0278 (7)	−0.0079 (6)	0.0080 (6)	0.0001 (6)

Geometric parameters (Å, º)

O41A—C41A	1.2403 (17)	C2A—H21A	0.9700
O11—C11	1.2435 (17)	C3A—H32A	0.9700
O12—C11	1.2542 (17)	C3A—H31A	0.9700
O21—N2	1.2269 (16)	C4A—H4A	0.9800
O22—N2	1.2191 (17)	C5A—H52A	0.9700
N1A—C2A	1.4882 (18)	C5A—H51A	0.9700
N1A—C6A	1.4891 (19)	C6A—H62A	0.9700
N41A—C41A	1.333 (2)	C6A—H61A	0.9700
N1A—H11A	0.941 (17)	C1—C2	1.3857 (19)
N1A—H12A	0.951 (18)	C1—C6	1.393 (2)
N41A—H42A	0.878 (16)	C1—C11	1.518 (2)
N41A—H41A	0.90 (2)	C2—C3	1.380 (2)
N2—C2	1.4719 (19)	C3—C4	1.384 (3)
C2A—C3A	1.518 (2)	C4—C5	1.372 (3)
C3A—C4A	1.5284 (19)	C5—C6	1.382 (3)
C4A—C5A	1.5335 (19)	C3—H3	0.9300
C4A—C41A	1.5196 (19)	C4—H4	0.9300
C5A—C6A	1.518 (2)	C5—H5	0.9300
C2A—H22A	0.9700	C6—H6	0.9300
C2A—N1A—C6A	111.43 (11)	C5A—C4A—H4A	108.00
H11A—N1A—H12A	107.9 (14)	C3A—C4A—H4A	108.00
C2A—N1A—H12A	111.8 (9)	C4A—C5A—H51A	109.00
C6A—N1A—H11A	107.3 (11)	C4A—C5A—H52A	109.00
C2A—N1A—H11A	109.3 (10)	C6A—C5A—H51A	109.00
C6A—N1A—H12A	109.0 (9)	C6A—C5A—H52A	109.00
C41A—N41A—H42A	119.6 (10)	H51A—C5A—H52A	108.00
H41A—N41A—H42A	122.2 (15)	N1A—C6A—H62A	110.00
C41A—N41A—H41A	118.1 (12)	H61A—C6A—H62A	108.00
O22—N2—C2	117.68 (12)	C5A—C6A—H61A	110.00
O21—N2—O22	123.88 (13)	C5A—C6A—H62A	110.00
O21—N2—C2	118.44 (11)	N1A—C6A—H61A	110.00
N1A—C2A—C3A	109.40 (12)	C2—C1—C6	116.89 (14)
C2A—C3A—C4A	112.29 (11)	C2—C1—C11	122.46 (13)
C3A—C4A—C41A	111.41 (11)	C6—C1—C11	120.37 (13)
C5A—C4A—C41A	109.48 (11)	N2—C2—C1	118.84 (12)
C3A—C4A—C5A	110.91 (11)	N2—C2—C3	117.99 (13)
C4A—C5A—C6A	111.41 (11)	C1—C2—C3	123.17 (14)
N1A—C6A—C5A	109.42 (11)	C2—C3—C4	118.26 (15)
O41A—C41A—C4A	121.47 (13)	C3—C4—C5	120.28 (17)
O41A—C41A—N41A	121.84 (14)	C4—C5—C6	120.52 (17)
N41A—C41A—C4A	116.63 (12)	C1—C6—C5	120.87 (16)
N1A—C2A—H21A	110.00	O11—C11—O12	126.25 (13)
H21A—C2A—H22A	108.00	O11—C11—C1	117.32 (13)
N1A—C2A—H22A	110.00	O12—C11—C1	116.36 (12)
C3A—C2A—H21A	110.00	C2—C3—H3	121.00
C3A—C2A—H22A	110.00	C4—C3—H3	121.00
C2A—C3A—H31A	109.00	C3—C4—H4	120.00
C2A—C3A—H32A	109.00	C5—C4—H4	120.00
C4A—C3A—H31A	109.00	C4—C5—H5	120.00
H31A—C3A—H32A	108.00	C6—C5—H5	120.00
C4A—C3A—H32A	109.00	C1—C6—H6	120.00
C41A—C4A—H4A	108.00	C5—C6—H6	120.00
C6A—N1A—C2A—C3A	60.90 (14)	C6—C1—C2—N2	−178.69 (12)
C2A—N1A—C6A—C5A	−61.94 (15)	C6—C1—C2—C3	0.7 (2)
O21—N2—C2—C1	48.67 (17)	C11—C1—C2—N2	7.42 (19)
O21—N2—C2—C3	−130.73 (14)	C11—C1—C2—C3	−173.22 (13)
O22—N2—C2—C1	−131.60 (13)	C2—C1—C6—C5	−1.2 (2)
O22—N2—C2—C3	49.00 (18)	C11—C1—C6—C5	172.83 (15)
N1A—C2A—C3A—C4A	−55.32 (14)	C2—C1—C11—O11	−138.93 (14)
C2A—C3A—C4A—C5A	51.32 (14)	C2—C1—C11—O12	43.84 (18)
C2A—C3A—C4A—C41A	173.54 (11)	C6—C1—C11—O11	47.39 (19)
C5A—C4A—C41A—O41A	107.81 (15)	C6—C1—C11—O12	−129.85 (15)
C5A—C4A—C41A—N41A	−69.58 (16)	N2—C2—C3—C4	179.61 (14)
C3A—C4A—C41A—O41A	−15.24 (19)	C1—C2—C3—C4	0.2 (2)
C3A—C4A—C5A—C6A	−51.84 (14)	C2—C3—C4—C5	−0.6 (3)
C41A—C4A—C5A—C6A	−175.18 (11)	C3—C4—C5—C6	0.1 (3)
C3A—C4A—C41A—N41A	167.38 (13)	C4—C5—C6—C1	0.8 (3)
C4A—C5A—C6A—N1A	56.75 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O11^i	0.941 (17)	1.848 (17)	2.7759 (17)	168.3 (17)
N1A—H12A···O12	0.951 (18)	1.792 (17)	2.7380 (17)	172.5 (13)
N41A—H41A···O41A^ii	0.90 (2)	2.00 (2)	2.8978 (19)	174.6 (15)
N41A—H42A···O41A^iii	0.878 (16)	2.313 (16)	3.0914 (17)	147.8 (13)
C6A—H61A···O21^iv	0.97	2.47	3.2240 (18)	134

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

(II) 4-carbamoylpiperidinium 3-nitrobenzoate

Crystal data

C6H13N2O^+·C7H4NO4^−	F(000) = 624
Mr = 295.30	Dx = 1.444 Mg m^−3
Monoclinic, P21/c	Melting point: 452 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.2504 (15) Å	Cell parameters from 3622 reflections
b = 6.8276 (5) Å	θ = 3.2–28.8°
c = 15.4580 (17) Å	µ = 0.11 mm^−1
β = 115.410 (13)°	T = 200 K
V = 1358.5 (2) Å^3	Prism, colourless
Z = 4	0.30 × 0.20 × 0.15 mm

Data collection

Oxford Gemini S Ultra CCD area-detector diffractometer	2669 independent reflections
Radiation source: Enhance (Mo) X-ray source	1982 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −17→17
Tmin = 0.948, Tmax = 0.980	k = −8→8
9250 measured reflections	l = −19→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 0.0538P] where P = (Fo^2 + 2Fc^2)/3
2669 reflections	(Δ/σ)max < 0.001
206 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O41A	0.45623 (8)	−0.33122 (16)	0.54658 (7)	0.0343 (3)
N1A	0.38389 (10)	0.13659 (19)	0.30335 (11)	0.0326 (4)
N41A	0.31271 (11)	−0.5030 (2)	0.45585 (11)	0.0324 (5)
C2A	0.28255 (12)	0.0745 (2)	0.29981 (11)	0.0295 (5)
C3A	0.29881 (11)	−0.0660 (2)	0.38042 (10)	0.0265 (5)
C4A	0.36431 (11)	−0.2434 (2)	0.37976 (10)	0.0230 (4)
C5A	0.46462 (11)	−0.1781 (2)	0.37580 (11)	0.0282 (5)
C6A	0.44431 (12)	−0.0342 (3)	0.29464 (11)	0.0341 (5)
C41A	0.38334 (11)	−0.3643 (2)	0.46824 (10)	0.0250 (5)
O11	0.31363 (8)	0.45491 (18)	0.18250 (8)	0.0401 (4)
O12	0.25353 (10)	0.19447 (18)	0.08824 (8)	0.0443 (4)
O31	−0.06945 (10)	0.2634 (2)	−0.20416 (9)	0.0513 (5)
O32	−0.11616 (10)	0.5492 (2)	−0.26766 (9)	0.0588 (5)
N3	−0.06099 (10)	0.4411 (2)	−0.20179 (9)	0.0368 (5)
C1	0.17035 (11)	0.5008 (2)	0.03219 (10)	0.0230 (4)
C2	0.09472 (11)	0.4156 (2)	−0.04977 (10)	0.0229 (4)
C3	0.01941 (11)	0.5338 (2)	−0.11617 (10)	0.0259 (4)
C4	0.01652 (13)	0.7342 (2)	−0.10502 (11)	0.0324 (5)
C5	0.09258 (13)	0.8171 (2)	−0.02317 (12)	0.0346 (5)
C6	0.16832 (12)	0.7015 (2)	0.04443 (11)	0.0284 (5)
C11	0.25286 (12)	0.3729 (2)	0.10671 (11)	0.0285 (5)
H4A	0.32430	−0.32240	0.32280	0.0280*
H11A	0.4258 (15)	0.203 (3)	0.3627 (14)	0.056 (6)*
H12A	0.3673 (17)	0.223 (4)	0.2523 (16)	0.074 (7)*
H21A	0.24150	0.01150	0.23890	0.0350*
H22A	0.24470	0.18850	0.30500	0.0350*
H31A	0.23180	−0.11080	0.37470	0.0320*
H32A	0.33310	0.00200	0.44110	0.0320*
H41A	0.2578 (14)	−0.502 (2)	0.4021 (13)	0.040 (5)*
H42A	0.3112 (14)	−0.564 (3)	0.5072 (14)	0.051 (6)*
H51A	0.50950	−0.11700	0.43610	0.0340*
H52A	0.50050	−0.29190	0.36720	0.0340*
H61A	0.50990	0.01050	0.29680	0.0410*
H62A	0.40580	−0.09890	0.23370	0.0410*
H2	0.09480	0.28130	−0.05980	0.0280*
H4	−0.03470	0.81080	−0.15090	0.0390*
H5	0.09270	0.95160	−0.01360	0.0410*
H6	0.21870	0.75950	0.09900	0.0340*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O41A	0.0332 (6)	0.0366 (6)	0.0222 (6)	−0.0043 (5)	0.0015 (5)	0.0007 (5)
N1A	0.0268 (7)	0.0304 (8)	0.0298 (8)	−0.0023 (6)	0.0018 (6)	0.0088 (6)
N41A	0.0272 (8)	0.0356 (8)	0.0266 (8)	−0.0060 (6)	0.0041 (6)	0.0058 (6)
C2A	0.0228 (8)	0.0278 (8)	0.0321 (9)	0.0047 (7)	0.0062 (6)	0.0009 (7)
C3A	0.0223 (8)	0.0314 (8)	0.0235 (8)	0.0028 (7)	0.0077 (6)	−0.0004 (7)
C4A	0.0224 (8)	0.0230 (7)	0.0199 (7)	0.0000 (6)	0.0055 (6)	−0.0032 (6)
C5A	0.0235 (8)	0.0318 (8)	0.0285 (8)	0.0056 (7)	0.0105 (6)	0.0026 (7)
C6A	0.0244 (8)	0.0466 (10)	0.0304 (9)	−0.0002 (8)	0.0110 (7)	0.0066 (8)
C41A	0.0232 (8)	0.0255 (8)	0.0241 (8)	0.0032 (6)	0.0080 (6)	−0.0013 (6)
O11	0.0340 (7)	0.0478 (7)	0.0261 (6)	−0.0036 (6)	0.0012 (5)	0.0020 (5)
O12	0.0611 (8)	0.0365 (7)	0.0306 (6)	0.0218 (6)	0.0153 (6)	0.0027 (5)
O31	0.0489 (8)	0.0543 (9)	0.0421 (8)	−0.0168 (7)	0.0114 (6)	−0.0188 (7)
O32	0.0358 (7)	0.0842 (10)	0.0344 (7)	0.0154 (7)	−0.0058 (6)	0.0003 (7)
N3	0.0242 (7)	0.0551 (10)	0.0286 (8)	−0.0021 (7)	0.0090 (6)	−0.0075 (7)
C1	0.0234 (8)	0.0269 (8)	0.0217 (7)	−0.0010 (6)	0.0125 (6)	0.0013 (6)
C2	0.0258 (8)	0.0212 (7)	0.0246 (8)	−0.0021 (6)	0.0135 (6)	−0.0006 (6)
C3	0.0204 (8)	0.0352 (8)	0.0210 (7)	−0.0026 (7)	0.0079 (6)	−0.0011 (7)
C4	0.0291 (9)	0.0348 (9)	0.0327 (9)	0.0086 (7)	0.0128 (7)	0.0102 (7)
C5	0.0419 (10)	0.0198 (8)	0.0441 (10)	−0.0003 (7)	0.0205 (8)	0.0020 (7)
C6	0.0283 (8)	0.0290 (8)	0.0270 (8)	−0.0071 (7)	0.0111 (6)	−0.0036 (7)
C11	0.0274 (8)	0.0381 (9)	0.0212 (8)	0.0032 (7)	0.0117 (6)	0.0041 (7)

Geometric parameters (Å, º)

O41A—C41A	1.2316 (18)	C2A—H21A	0.9700
O11—C11	1.2511 (19)	C3A—H32A	0.9700
O12—C11	1.2522 (19)	C3A—H31A	0.9700
O31—N3	1.2182 (19)	C4A—H4A	0.9800
O32—N3	1.2299 (19)	C5A—H52A	0.9700
N1A—C2A	1.483 (2)	C5A—H51A	0.9700
N1A—C6A	1.490 (2)	C6A—H62A	0.9700
N41A—C41A	1.335 (2)	C6A—H61A	0.9700
N1A—H11A	0.97 (2)	C1—C2	1.390 (2)
N1A—H12A	0.93 (2)	C1—C6	1.3853 (19)
N41A—H42A	0.91 (2)	C1—C11	1.520 (2)
N41A—H41A	0.863 (19)	C2—C3	1.383 (2)
N3—C3	1.471 (2)	C3—C4	1.3819 (19)
C2A—C3A	1.510 (2)	C4—C5	1.385 (2)
C3A—C4A	1.532 (2)	C5—C6	1.383 (2)
C4A—C5A	1.524 (2)	C2—H2	0.9300
C4A—C41A	1.519 (2)	C4—H4	0.9300
C5A—C6A	1.520 (2)	C5—H5	0.9300
C2A—H22A	0.9700	C6—H6	0.9300
C2A—N1A—C6A	111.36 (13)	C5A—C4A—H4A	109.00
H11A—N1A—H12A	110 (2)	C3A—C4A—H4A	109.00
C2A—N1A—H12A	105.1 (16)	C4A—C5A—H51A	109.00
C6A—N1A—H11A	107.9 (13)	C4A—C5A—H52A	109.00
C2A—N1A—H11A	111.4 (14)	C6A—C5A—H51A	109.00
C6A—N1A—H12A	111.5 (16)	C6A—C5A—H52A	109.00
C41A—N41A—H42A	120.1 (13)	H51A—C5A—H52A	108.00
H41A—N41A—H42A	119.7 (19)	N1A—C6A—H62A	110.00
C41A—N41A—H41A	116.7 (11)	H61A—C6A—H62A	108.00
O32—N3—C3	117.46 (13)	C5A—C6A—H61A	110.00
O31—N3—O32	123.57 (14)	C5A—C6A—H62A	110.00
O31—N3—C3	118.97 (13)	N1A—C6A—H61A	110.00
N1A—C2A—C3A	110.42 (14)	C2—C1—C6	119.00 (14)
C2A—C3A—C4A	112.03 (13)	C2—C1—C11	119.69 (12)
C3A—C4A—C41A	107.31 (12)	C6—C1—C11	121.30 (13)
C5A—C4A—C41A	112.78 (13)	C1—C2—C3	118.92 (13)
C3A—C4A—C5A	110.72 (12)	N3—C3—C2	118.27 (12)
C4A—C5A—C6A	111.88 (13)	N3—C3—C4	119.00 (13)
N1A—C6A—C5A	110.13 (14)	C2—C3—C4	122.72 (14)
O41A—C41A—C4A	122.35 (14)	C3—C4—C5	117.71 (14)
O41A—C41A—N41A	122.49 (14)	C4—C5—C6	120.54 (13)
N41A—C41A—C4A	115.10 (13)	C1—C6—C5	121.11 (14)
N1A—C2A—H21A	110.00	O11—C11—O12	125.38 (15)
H21A—C2A—H22A	108.00	O11—C11—C1	116.88 (13)
N1A—C2A—H22A	110.00	O12—C11—C1	117.73 (14)
C3A—C2A—H21A	110.00	C1—C2—H2	121.00
C3A—C2A—H22A	110.00	C3—C2—H2	121.00
C2A—C3A—H31A	109.00	C3—C4—H4	121.00
C2A—C3A—H32A	109.00	C5—C4—H4	121.00
C4A—C3A—H31A	109.00	C4—C5—H5	120.00
H31A—C3A—H32A	108.00	C6—C5—H5	120.00
C4A—C3A—H32A	109.00	C1—C6—H6	119.00
C41A—C4A—H4A	109.00	C5—C6—H6	119.00
C6A—N1A—C2A—C3A	59.73 (16)	C4A—C5A—C6A—N1A	55.67 (17)
C2A—N1A—C6A—C5A	−59.64 (17)	C6—C1—C2—C3	−0.5 (2)
O31—N3—C3—C2	12.2 (2)	C11—C1—C2—C3	179.11 (15)
O31—N3—C3—C4	−167.54 (17)	C2—C1—C6—C5	0.1 (3)
O32—N3—C3—C2	−167.65 (16)	C11—C1—C6—C5	−179.44 (17)
O32—N3—C3—C4	12.7 (2)	C2—C1—C11—O11	−174.27 (16)
N1A—C2A—C3A—C4A	−55.58 (16)	C2—C1—C11—O12	4.6 (2)
C2A—C3A—C4A—C5A	51.69 (16)	C6—C1—C11—O11	5.3 (2)
C2A—C3A—C4A—C41A	175.15 (13)	C6—C1—C11—O12	−175.90 (17)
C5A—C4A—C41A—O41A	35.9 (2)	C1—C2—C3—N3	−179.09 (15)
C5A—C4A—C41A—N41A	−147.04 (14)	C1—C2—C3—C4	0.6 (3)
C3A—C4A—C41A—O41A	−86.34 (18)	N3—C3—C4—C5	179.31 (16)
C3A—C4A—C5A—C6A	−51.69 (16)	C2—C3—C4—C5	−0.4 (3)
C41A—C4A—C5A—C6A	−171.94 (13)	C3—C4—C5—C6	0.0 (3)
C3A—C4A—C41A—N41A	90.77 (16)	C4—C5—C6—C1	0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O41A^i	0.97 (2)	1.88 (2)	2.7933 (19)	157 (2)
N1A—H12A···O11	0.93 (2)	1.88 (3)	2.7587 (19)	156 (2)
N1A—H12A···O12	0.93 (2)	2.36 (2)	3.0599 (19)	132 (2)
N41A—H41A···O32^ii	0.863 (19)	2.213 (19)	3.068 (2)	171.1 (13)
N41A—H42A···O12^iii	0.91 (2)	1.98 (2)	2.844 (2)	159 (2)
C2A—H22A···O32^iv	0.97	2.45	3.385 (2)	163
C6A—H61A···O11^v	0.97	2.42	3.314 (2)	152

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

(III) 4-carbamoylpiperidinium 4-nitrobenzoate

Crystal data

C6H13N2O^+·C7H4NO4^−	F(000) = 624
Mr = 295.30	Dx = 1.409 Mg m^−3
Monoclinic, P21/c	Melting point = 537–539 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.5371 (6) Å	Cell parameters from 4862 reflections
b = 12.4216 (12) Å	θ = 3.2–28.9°
c = 15.0911 (13) Å	µ = 0.11 mm^−1
β = 99.848 (7)°	T = 200 K
V = 1392.1 (2) Å^3	Prism, colourless
Z = 4	0.30 × 0.18 × 0.15 mm

Data collection

Oxford Gemini-S Ultra CCD area-detector diffractometer	2727 independent reflections
Radiation source: Enhance (Mo) X-ray source	2279 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −9→9
Tmin = 0.952, Tmax = 0.980	k = −15→15
14612 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 0.0719P] where P = (Fo^2 + 2Fc^2)/3
2727 reflections	(Δ/σ)max < 0.001
206 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O41A	0.02263 (15)	1.05263 (8)	0.11414 (7)	0.0380 (3)
N1A	0.09525 (15)	0.89654 (8)	0.41329 (8)	0.0234 (3)
N41A	0.14124 (17)	0.89959 (9)	0.06854 (8)	0.0308 (4)
C2A	0.21319 (19)	0.98633 (10)	0.39172 (9)	0.0282 (4)
C3A	0.15409 (18)	1.02313 (10)	0.29510 (9)	0.0249 (4)
C4A	0.16009 (17)	0.93024 (9)	0.22941 (8)	0.0217 (4)
C5A	0.04143 (18)	0.83686 (9)	0.25324 (8)	0.0233 (4)
C6A	0.09620 (18)	0.80295 (10)	0.35103 (9)	0.0243 (4)
C41A	0.10137 (17)	0.96574 (10)	0.13201 (9)	0.0239 (4)
O11	0.24349 (13)	0.99568 (7)	0.61984 (6)	0.0310 (3)
O12	0.26652 (14)	0.82492 (7)	0.57656 (6)	0.0353 (3)
O41	0.79560 (14)	0.72149 (8)	0.99299 (7)	0.0395 (3)
O42	0.66121 (16)	0.85260 (9)	1.04955 (7)	0.0476 (4)
N4	0.68785 (15)	0.79664 (9)	0.98578 (8)	0.0289 (3)
C1	0.39884 (16)	0.87176 (10)	0.72586 (8)	0.0210 (4)
C2	0.39457 (18)	0.94083 (10)	0.79822 (9)	0.0281 (4)
C3	0.48704 (18)	0.91611 (11)	0.88355 (9)	0.0304 (4)
C4	0.58553 (17)	0.82173 (10)	0.89532 (9)	0.0236 (4)
C5	0.59296 (16)	0.75004 (10)	0.82531 (9)	0.0222 (4)
C6	0.49811 (16)	0.77620 (9)	0.74027 (9)	0.0214 (4)
C11	0.29466 (16)	0.90024 (10)	0.63323 (9)	0.0225 (4)
H4A	0.28460	0.90450	0.23630	0.0260*
H11A	−0.022 (2)	0.9235 (12)	0.4094 (11)	0.038 (4)*
H12A	0.137 (2)	0.8721 (13)	0.4718 (12)	0.039 (4)*
H21A	0.33730	0.96210	0.40010	0.0340*
H22A	0.20620	1.04620	0.43230	0.0340*
H31A	0.23260	1.08050	0.28160	0.0300*
H32A	0.03250	1.05140	0.28790	0.0300*
H41A	0.098 (2)	0.9159 (13)	0.0072 (13)	0.047 (5)*
H42A	0.190 (2)	0.8355 (13)	0.0803 (10)	0.033 (4)*
H51A	−0.08370	0.85930	0.24280	0.0280*
H52A	0.05270	0.77590	0.21440	0.0280*
H61A	0.01360	0.74830	0.36530	0.0290*
H62A	0.21590	0.77170	0.35960	0.0290*
H2	0.32890	1.00440	0.78930	0.0340*
H3	0.48280	0.96210	0.93180	0.0370*
H5	0.65900	0.68660	0.83480	0.0270*
H6	0.50090	0.72940	0.69240	0.0260*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O41A	0.0629 (7)	0.0281 (5)	0.0214 (5)	0.0176 (5)	0.0024 (5)	0.0030 (4)
N1A	0.0288 (6)	0.0244 (6)	0.0161 (6)	0.0014 (5)	0.0011 (4)	0.0030 (4)
N41A	0.0482 (7)	0.0247 (6)	0.0189 (7)	0.0109 (5)	0.0037 (5)	0.0024 (5)
C2A	0.0356 (7)	0.0258 (7)	0.0215 (7)	−0.0073 (5)	0.0002 (5)	−0.0018 (5)
C3A	0.0332 (7)	0.0203 (6)	0.0213 (7)	−0.0047 (5)	0.0046 (5)	0.0007 (5)
C4A	0.0254 (6)	0.0209 (6)	0.0185 (7)	0.0026 (5)	0.0030 (5)	0.0030 (5)
C5A	0.0311 (7)	0.0186 (6)	0.0195 (7)	−0.0010 (5)	0.0027 (5)	−0.0002 (5)
C6A	0.0305 (7)	0.0191 (6)	0.0228 (7)	0.0013 (5)	0.0032 (5)	0.0023 (5)
C41A	0.0310 (7)	0.0213 (6)	0.0192 (7)	0.0013 (5)	0.0036 (5)	0.0020 (5)
O11	0.0365 (5)	0.0274 (5)	0.0269 (5)	0.0071 (4)	−0.0004 (4)	0.0061 (4)
O12	0.0538 (7)	0.0247 (5)	0.0218 (5)	−0.0050 (4)	−0.0097 (4)	0.0019 (4)
O41	0.0494 (6)	0.0317 (5)	0.0321 (6)	0.0128 (5)	−0.0081 (5)	0.0029 (4)
O42	0.0634 (8)	0.0534 (7)	0.0219 (6)	0.0176 (6)	−0.0040 (5)	−0.0085 (5)
N4	0.0346 (6)	0.0271 (6)	0.0225 (6)	0.0016 (5)	−0.0025 (5)	0.0000 (5)
C1	0.0202 (6)	0.0214 (6)	0.0208 (7)	−0.0026 (5)	0.0019 (5)	0.0022 (5)
C2	0.0318 (7)	0.0232 (6)	0.0270 (7)	0.0080 (5)	−0.0013 (6)	−0.0018 (5)
C3	0.0382 (8)	0.0279 (7)	0.0230 (8)	0.0073 (6)	−0.0009 (6)	−0.0066 (6)
C4	0.0246 (7)	0.0253 (6)	0.0188 (7)	−0.0005 (5)	−0.0019 (5)	0.0009 (5)
C5	0.0220 (6)	0.0191 (6)	0.0247 (7)	0.0012 (5)	0.0021 (5)	0.0006 (5)
C6	0.0248 (6)	0.0195 (6)	0.0199 (7)	−0.0026 (5)	0.0035 (5)	−0.0024 (5)
C11	0.0231 (6)	0.0229 (6)	0.0210 (7)	−0.0040 (5)	0.0022 (5)	0.0031 (5)

Geometric parameters (Å, º)

O41A—C41A	1.2390 (16)	C2A—H21A	0.9700
O11—C11	1.2524 (15)	C3A—H32A	0.9700
O12—C11	1.2608 (16)	C3A—H31A	0.9700
O41—N4	1.2299 (15)	C4A—H4A	0.9800
O42—N4	1.2312 (16)	C5A—H52A	0.9700
N1A—C2A	1.4964 (17)	C5A—H51A	0.9700
N1A—C6A	1.4955 (17)	C6A—H62A	0.9700
N41A—C41A	1.3347 (18)	C6A—H61A	0.9700
N1A—H11A	0.938 (15)	C1—C2	1.3934 (18)
N1A—H12A	0.936 (18)	C1—C6	1.4002 (17)
N41A—H42A	0.882 (16)	C1—C11	1.5233 (18)
N41A—H41A	0.949 (19)	C2—C3	1.3897 (19)
N4—C4	1.4817 (18)	C3—C4	1.3827 (19)
C2A—C3A	1.5203 (19)	C4—C5	1.3902 (18)
C3A—C4A	1.5269 (17)	C5—C6	1.3964 (19)
C4A—C5A	1.5442 (17)	C2—H2	0.9300
C4A—C41A	1.5259 (18)	C3—H3	0.9300
C5A—C6A	1.5223 (18)	C5—H5	0.9300
C2A—H22A	0.9700	C6—H6	0.9300
C2A—N1A—C6A	112.08 (10)	C5A—C4A—H4A	108.00
H11A—N1A—H12A	109.7 (14)	C3A—C4A—H4A	108.00
C2A—N1A—H12A	109.3 (10)	C4A—C5A—H51A	109.00
C6A—N1A—H11A	110.1 (10)	C4A—C5A—H52A	109.00
C2A—N1A—H11A	108.0 (9)	C6A—C5A—H51A	109.00
C6A—N1A—H12A	107.7 (10)	C6A—C5A—H52A	109.00
C41A—N41A—H42A	123.3 (10)	H51A—C5A—H52A	108.00
H41A—N41A—H42A	116.8 (14)	N1A—C6A—H62A	109.00
C41A—N41A—H41A	119.1 (10)	H61A—C6A—H62A	108.00
O42—N4—C4	118.21 (11)	C5A—C6A—H61A	109.00
O41—N4—O42	123.57 (12)	C5A—C6A—H62A	109.00
O41—N4—C4	118.23 (11)	N1A—C6A—H61A	109.00
N1A—C2A—C3A	110.20 (11)	C2—C1—C6	118.92 (11)
C2A—C3A—C4A	111.05 (10)	C2—C1—C11	119.92 (11)
C3A—C4A—C41A	111.78 (10)	C6—C1—C11	121.15 (11)
C5A—C4A—C41A	110.93 (10)	C1—C2—C3	121.00 (12)
C3A—C4A—C5A	109.50 (10)	C2—C3—C4	118.65 (12)
C4A—C5A—C6A	111.21 (10)	N4—C4—C3	118.69 (11)
N1A—C6A—C5A	111.37 (10)	N4—C4—C5	118.90 (11)
O41A—C41A—C4A	120.71 (12)	C3—C4—C5	122.41 (12)
O41A—C41A—N41A	122.57 (13)	C4—C5—C6	117.94 (11)
N41A—C41A—C4A	116.72 (11)	C1—C6—C5	121.07 (11)
N1A—C2A—H21A	110.00	O11—C11—O12	125.56 (12)
H21A—C2A—H22A	108.00	O11—C11—C1	117.65 (11)
N1A—C2A—H22A	110.00	O12—C11—C1	116.79 (11)
C3A—C2A—H21A	110.00	C1—C2—H2	120.00
C3A—C2A—H22A	110.00	C3—C2—H2	119.00
C2A—C3A—H31A	109.00	C2—C3—H3	121.00
C2A—C3A—H32A	109.00	C4—C3—H3	121.00
C4A—C3A—H31A	109.00	C4—C5—H5	121.00
H31A—C3A—H32A	108.00	C6—C5—H5	121.00
C4A—C3A—H32A	109.00	C1—C6—H6	119.00
C41A—C4A—H4A	108.00	C5—C6—H6	119.00
C6A—N1A—C2A—C3A	57.56 (14)	C4A—C5A—C6A—N1A	54.50 (14)
C2A—N1A—C6A—C5A	−56.10 (14)	C6—C1—C2—C3	0.08 (19)
O41—N4—C4—C3	−169.40 (12)	C11—C1—C2—C3	179.36 (12)
O41—N4—C4—C5	10.16 (18)	C2—C1—C6—C5	−0.48 (18)
O42—N4—C4—C3	10.14 (18)	C11—C1—C6—C5	−179.75 (11)
O42—N4—C4—C5	−170.29 (12)	C2—C1—C11—O11	16.61 (18)
N1A—C2A—C3A—C4A	−58.22 (14)	C2—C1—C11—O12	−163.01 (12)
C2A—C3A—C4A—C5A	56.72 (14)	C6—C1—C11—O11	−164.13 (12)
C2A—C3A—C4A—C41A	−179.93 (12)	C6—C1—C11—O12	16.26 (18)
C5A—C4A—C41A—O41A	107.96 (14)	C1—C2—C3—C4	0.7 (2)
C5A—C4A—C41A—N41A	−72.89 (15)	C2—C3—C4—N4	178.49 (12)
C3A—C4A—C41A—O41A	−14.57 (17)	C2—C3—C4—C5	−1.1 (2)
C3A—C4A—C5A—C6A	−54.70 (13)	N4—C4—C5—C6	−178.88 (11)
C41A—C4A—C5A—C6A	−178.55 (10)	C3—C4—C5—C6	0.67 (19)
C3A—C4A—C41A—N41A	164.58 (12)	C4—C5—C6—C1	0.12 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O11^i	0.938 (15)	1.933 (15)	2.8503 (15)	165.4 (14)
N1A—H12A···O12	0.936 (18)	1.808 (17)	2.7278 (15)	167.0 (14)
N41A—H41A···O41A^ii	0.949 (19)	1.940 (19)	2.8833 (16)	172.3 (14)
N41A—H42A···O12^iii	0.882 (16)	2.078 (16)	2.9401 (15)	165.5 (14)
C3—H3···O42^iv	0.93	2.58	3.3027 (18)	135
C5—H5···O11^v	0.93	2.54	3.4407 (16)	163
C2A—H22A···O41^vi	0.97	2.45	3.4064 (17)	167
C6A—H61A···O41A^vii	0.97	2.47	3.3027 (16)	144

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

(IV) 4-carbamoylpiperidinium 3,5-dinitrobenzoate

Crystal data

C6H13N2O^+·C7H3N2O6^−	Z = 2
Mr = 340.30	F(000) = 356
Triclinic, P1	Dx = 1.473 Mg m^−3
Hall symbol: -P 1	Melting point = 473–475 K
a = 5.7159 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.9970 (12) Å	Cell parameters from 3824 reflections
c = 12.6447 (10) Å	θ = 3.1–28.7°
α = 111.370 (8)°	µ = 0.12 mm^−1
β = 99.504 (7)°	T = 200 K
γ = 100.772 (8)°	Plate, yellow
V = 767.04 (14) Å^3	0.30 × 0.25 × 0.15 mm

Data collection

Oxford Gemini-S Ultra CCD area-detector diffractometer	2996 independent reflections
Radiation source: Enhance (Mo) X-ray source	2279 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −7→7
Tmin = 0.967, Tmax = 0.980	k = −14→14
9445 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0464P)^2 + 0.0623P] where P = (Fo^2 + 2Fc^2)/3
2996 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O41A	0.0238 (2)	0.94674 (11)	0.12385 (10)	0.0368 (4)
N1A	0.4414 (3)	0.69533 (13)	0.25966 (12)	0.0313 (5)
N41A	0.2169 (3)	0.91229 (13)	−0.02221 (12)	0.0304 (4)
C2A	0.4128 (3)	0.64556 (16)	0.13017 (14)	0.0359 (6)
C3A	0.2496 (3)	0.70614 (15)	0.07572 (14)	0.0304 (5)
C4A	0.3521 (3)	0.84774 (14)	0.13217 (13)	0.0273 (5)
C5A	0.3880 (3)	0.89615 (15)	0.26500 (13)	0.0334 (5)
C6A	0.5495 (3)	0.83224 (16)	0.31662 (14)	0.0356 (6)
C41A	0.1842 (3)	0.90734 (14)	0.07838 (13)	0.0269 (5)
O11	0.9403 (2)	0.58841 (12)	0.23351 (11)	0.0435 (4)
O12	0.6878 (2)	0.56279 (11)	0.34513 (10)	0.0371 (4)
O31	0.7183 (2)	0.25715 (13)	0.50782 (12)	0.0527 (5)
O32	0.9621 (3)	0.13842 (13)	0.47058 (13)	0.0593 (6)
O51	1.4706 (2)	0.16989 (12)	0.20496 (12)	0.0534 (5)
O52	1.4018 (2)	0.28118 (15)	0.10752 (12)	0.0605 (5)
N3	0.8779 (3)	0.22183 (14)	0.46136 (12)	0.0393 (5)
N5	1.3703 (2)	0.24465 (14)	0.18419 (13)	0.0416 (5)
C1	0.9562 (3)	0.43419 (14)	0.30805 (12)	0.0259 (4)
C2	0.8795 (3)	0.37918 (14)	0.38042 (12)	0.0263 (5)
C3	0.9707 (3)	0.28290 (15)	0.38908 (13)	0.0284 (5)
C4	1.1348 (3)	0.23763 (15)	0.32766 (14)	0.0319 (5)
C5	1.2050 (3)	0.29341 (15)	0.25593 (13)	0.0307 (5)
C6	1.1204 (3)	0.39006 (15)	0.24469 (13)	0.0294 (5)
C11	0.8538 (3)	0.53762 (15)	0.29406 (14)	0.0296 (5)
H4A	0.51320	0.86850	0.11650	0.0330*
H11A	0.283 (3)	0.6745 (16)	0.2719 (14)	0.034 (4)*
H12A	0.542 (4)	0.652 (2)	0.2898 (18)	0.062 (6)*
H21A	0.34100	0.55630	0.09560	0.0430*
H22A	0.57320	0.66170	0.11430	0.0430*
H31A	0.08530	0.68400	0.08590	0.0370*
H32A	0.23790	0.67560	−0.00790	0.0370*
H41A	0.332 (4)	0.8823 (18)	−0.0494 (17)	0.049 (6)*
H42A	0.135 (3)	0.9531 (17)	−0.0548 (15)	0.038 (5)*
H51A	0.46370	0.98510	0.30060	0.0400*
H52A	0.22910	0.88140	0.28250	0.0400*
H61A	0.71290	0.85250	0.30480	0.0430*
H62A	0.56460	0.86170	0.40040	0.0430*
H2	0.76780	0.40680	0.42270	0.0320*
H4	1.19480	0.17290	0.33430	0.0380*
H6	1.17280	0.42520	0.19520	0.0350*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O41A	0.0379 (6)	0.0498 (8)	0.0405 (7)	0.0247 (6)	0.0186 (5)	0.0282 (6)
N1A	0.0300 (8)	0.0401 (9)	0.0389 (8)	0.0169 (7)	0.0140 (6)	0.0271 (7)
N41A	0.0344 (8)	0.0368 (8)	0.0295 (7)	0.0181 (7)	0.0109 (6)	0.0188 (6)
C2A	0.0423 (10)	0.0375 (10)	0.0397 (9)	0.0194 (8)	0.0189 (8)	0.0210 (8)
C3A	0.0342 (9)	0.0319 (9)	0.0302 (8)	0.0118 (7)	0.0105 (7)	0.0158 (7)
C4A	0.0237 (8)	0.0314 (9)	0.0337 (9)	0.0096 (7)	0.0096 (6)	0.0190 (7)
C5A	0.0365 (9)	0.0328 (9)	0.0323 (9)	0.0112 (7)	0.0042 (7)	0.0160 (7)
C6A	0.0329 (9)	0.0422 (11)	0.0346 (9)	0.0088 (8)	0.0037 (7)	0.0217 (8)
C41A	0.0263 (8)	0.0256 (8)	0.0299 (8)	0.0063 (7)	0.0061 (6)	0.0133 (7)
O11	0.0359 (7)	0.0550 (8)	0.0597 (8)	0.0151 (6)	0.0160 (6)	0.0426 (7)
O12	0.0362 (6)	0.0428 (7)	0.0473 (7)	0.0214 (6)	0.0174 (5)	0.0270 (6)
O31	0.0591 (8)	0.0658 (10)	0.0547 (8)	0.0227 (7)	0.0310 (7)	0.0386 (7)
O32	0.0791 (10)	0.0515 (9)	0.0692 (10)	0.0283 (8)	0.0210 (8)	0.0429 (8)
O51	0.0371 (7)	0.0352 (8)	0.0740 (10)	0.0143 (6)	0.0190 (6)	0.0025 (7)
O52	0.0528 (8)	0.0812 (11)	0.0462 (8)	0.0190 (8)	0.0292 (7)	0.0171 (8)
N3	0.0452 (9)	0.0401 (9)	0.0371 (8)	0.0107 (7)	0.0097 (7)	0.0213 (7)
N5	0.0262 (8)	0.0396 (9)	0.0385 (9)	0.0022 (7)	0.0094 (6)	−0.0039 (7)
C1	0.0223 (8)	0.0278 (8)	0.0236 (7)	0.0044 (6)	0.0020 (6)	0.0087 (6)
C2	0.0240 (8)	0.0284 (9)	0.0238 (8)	0.0066 (7)	0.0058 (6)	0.0080 (6)
C3	0.0304 (8)	0.0278 (9)	0.0249 (8)	0.0066 (7)	0.0041 (6)	0.0103 (7)
C4	0.0306 (9)	0.0255 (9)	0.0337 (9)	0.0098 (7)	0.0017 (7)	0.0074 (7)
C5	0.0239 (8)	0.0317 (9)	0.0278 (8)	0.0066 (7)	0.0065 (6)	0.0030 (7)
C6	0.0252 (8)	0.0342 (9)	0.0243 (8)	0.0018 (7)	0.0054 (6)	0.0104 (7)
C11	0.0247 (8)	0.0333 (9)	0.0331 (9)	0.0066 (7)	0.0033 (7)	0.0184 (7)

Geometric parameters (Å, º)

O41A—C41A	1.238 (2)	C5A—C6A	1.515 (3)
O11—C11	1.247 (2)	C2A—H21A	0.9700
O12—C11	1.255 (2)	C2A—H22A	0.9700
O31—N3	1.224 (2)	C3A—H32A	0.9700
O32—N3	1.222 (2)	C3A—H31A	0.9700
O51—N5	1.231 (2)	C4A—H4A	0.9800
O52—N5	1.226 (2)	C5A—H51A	0.9700
N1A—C6A	1.487 (3)	C5A—H52A	0.9700
N1A—C2A	1.492 (2)	C6A—H61A	0.9700
N41A—C41A	1.336 (2)	C6A—H62A	0.9700
N1A—H12A	0.96 (2)	C1—C2	1.389 (2)
N1A—H11A	0.947 (18)	C1—C6	1.389 (2)
N41A—H42A	0.89 (2)	C1—C11	1.520 (3)
N41A—H41A	0.87 (2)	C2—C3	1.384 (3)
N3—C3	1.468 (2)	C3—C4	1.379 (2)
N5—C5	1.470 (2)	C4—C5	1.376 (3)
C2A—C3A	1.509 (3)	C5—C6	1.380 (3)
C3A—C4A	1.531 (3)	C2—H2	0.9300
C4A—C41A	1.513 (2)	C4—H4	0.9300
C4A—C5A	1.527 (2)	C6—H6	0.9300
C2A—N1A—C6A	111.66 (14)	C3A—C4A—H4A	108.00
H11A—N1A—H12A	108.3 (18)	C41A—C4A—H4A	108.00
C2A—N1A—H12A	107.0 (12)	C5A—C4A—H4A	108.00
C6A—N1A—H11A	110.2 (12)	C6A—C5A—H51A	109.00
C2A—N1A—H11A	107.3 (10)	C4A—C5A—H52A	109.00
C6A—N1A—H12A	112.1 (14)	C4A—C5A—H51A	109.00
C41A—N41A—H42A	120.4 (11)	C6A—C5A—H52A	109.00
H41A—N41A—H42A	121.8 (18)	H51A—C5A—H52A	108.00
C41A—N41A—H41A	117.4 (14)	H61A—C6A—H62A	108.00
O32—N3—C3	118.39 (16)	N1A—C6A—H61A	110.00
O31—N3—O32	124.01 (17)	N1A—C6A—H62A	110.00
O31—N3—C3	117.60 (16)	C5A—C6A—H61A	110.00
O51—N5—C5	118.14 (15)	C5A—C6A—H62A	110.00
O52—N5—C5	118.22 (15)	C2—C1—C6	119.13 (16)
O51—N5—O52	123.64 (14)	C2—C1—C11	120.61 (15)
N1A—C2A—C3A	110.18 (14)	C6—C1—C11	120.21 (15)
C2A—C3A—C4A	110.96 (14)	C1—C2—C3	119.41 (16)
C5A—C4A—C41A	111.63 (14)	N3—C3—C2	118.55 (15)
C3A—C4A—C41A	110.39 (14)	N3—C3—C4	118.65 (17)
C3A—C4A—C5A	110.00 (14)	C2—C3—C4	122.70 (16)
C4A—C5A—C6A	110.83 (14)	C3—C4—C5	116.36 (17)
N1A—C6A—C5A	110.25 (14)	N5—C5—C4	118.51 (16)
O41A—C41A—N41A	122.33 (16)	N5—C5—C6	118.27 (15)
O41A—C41A—C4A	121.88 (14)	C4—C5—C6	123.17 (16)
N41A—C41A—C4A	115.78 (15)	C1—C6—C5	119.23 (16)
N1A—C2A—H21A	110.00	O11—C11—O12	126.51 (18)
C3A—C2A—H22A	110.00	O11—C11—C1	117.67 (15)
N1A—C2A—H22A	110.00	O12—C11—C1	115.82 (16)
C3A—C2A—H21A	110.00	C1—C2—H2	120.00
H21A—C2A—H22A	108.00	C3—C2—H2	120.00
C4A—C3A—H31A	109.00	C3—C4—H4	122.00
C2A—C3A—H31A	109.00	C5—C4—H4	122.00
C2A—C3A—H32A	109.00	C1—C6—H6	120.00
H31A—C3A—H32A	108.00	C5—C6—H6	120.00
C4A—C3A—H32A	109.00
C6A—N1A—C2A—C3A	−58.9 (2)	C3A—C4A—C5A—C6A	55.18 (19)
C2A—N1A—C6A—C5A	58.87 (19)	C4A—C5A—C6A—N1A	−56.93 (19)
O31—N3—C3—C2	2.1 (2)	C6—C1—C2—C3	0.9 (2)
O31—N3—C3—C4	−174.46 (16)	C11—C1—C2—C3	178.26 (15)
O32—N3—C3—C2	−178.67 (16)	C2—C1—C6—C5	−0.6 (2)
O32—N3—C3—C4	4.8 (2)	C11—C1—C6—C5	−177.95 (15)
O52—N5—C5—C4	168.85 (16)	C2—C1—C11—O11	175.83 (15)
O52—N5—C5—C6	−8.8 (2)	C2—C1—C11—O12	−4.5 (2)
O51—N5—C5—C6	170.81 (15)	C6—C1—C11—O11	−6.8 (2)
O51—N5—C5—C4	−11.6 (2)	C6—C1—C11—O12	172.89 (15)
N1A—C2A—C3A—C4A	56.79 (19)	C1—C2—C3—N3	−176.96 (14)
C2A—C3A—C4A—C5A	−55.30 (18)	C1—C2—C3—C4	−0.6 (2)
C2A—C3A—C4A—C41A	−178.92 (14)	N3—C3—C4—C5	176.32 (15)
C41A—C4A—C5A—C6A	178.08 (15)	C2—C3—C4—C5	−0.1 (2)
C3A—C4A—C41A—O41A	95.34 (18)	C3—C4—C5—N5	−177.09 (15)
C3A—C4A—C41A—N41A	−83.34 (19)	C3—C4—C5—C6	0.4 (3)
C5A—C4A—C41A—O41A	−27.3 (2)	N5—C5—C6—C1	177.41 (14)
C5A—C4A—C41A—N41A	153.99 (16)	C4—C5—C6—C1	−0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O11^i	0.947 (18)	1.925 (18)	2.822 (2)	157.4 (15)
N1A—H12A···O12	0.96 (2)	1.74 (2)	2.696 (2)	173 (2)
N41A—H41A···O51^ii	0.87 (2)	2.37 (2)	3.141 (2)	147.5 (18)
N41A—H42A···O41A^iii	0.89 (2)	1.99 (2)	2.877 (2)	175.8 (17)

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