Zero-, one- and two-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of 4,5-dichloro­phthalic acid with the monocyclic heteroaromatic Lewis bases 2-amino­pyrimidine, nicotin­amide and isonicotinamide

The structures of the anhydrous 1:1 proton-transfer com­pounds of 4,5-dichloro­phthalic acid (DCPA) with the mono­cyclic heteroaromatic Lewis bases 2-amino­pyrimidine, 3-(am­ino­carb­onyl)pyridine (nicotinamide) and 4-(amino­carbon­yl)pyridine (isonicotinamide), namely 2-amino­pyrimidinium 2-carb­oxy-4,5-dichloro­benzoate, C₄H₆N₃⁺·C₈H₃Cl₂O₄⁻, (I), 3-(amino­carbon­yl)pyridinium 2-carb­oxy-4,5-dichloro­benzoate, C₆H₇N₂O⁺·C₈H₃Cl₂O₄⁻, (II), and the unusual salt adduct 4-(amino­carbon­yl)pyridinium 2-carb­oxy-4,5-dichloro­benzo­ate–­methyl 2-carb­oxy-4,5-dichloro­benzoate (1/1), C₆H₇N₂O⁺·C₈H₃Cl₂O₄⁻·C₉H₆Cl₂O₄, (III), have been determined at 130 K. Compound (I) forms discrete centrosymmetric hydrogen-bonded cyclic bis­(cation–anion) units having both R₂²(8) and R₁²(4) N—H...O inter­actions. In (II), the primary N—H...O-linked cation–anion units are extended into a two-dimensional sheet structure via amide–carboxyl and amide–carbonyl N—H...O inter­actions. The structure of (III) reveals the presence of an unusual and unexpected self-synthesized methyl monoester of the acid as an adduct mol­ecule, giving one-dimensional hydrogen-bonded chains. In all three structures, the hydrogen phthalate anions are essentially planar with short intra­molecular carboxyl–carboxylate O—H...O hydrogen bonds [O...O = 2.393 (8)–2.410 (2) Å]. This work provides examples of low-dimensional 1:1 hydrogen-bonded DCPA structure types, and includes the first example of a discrete cyclic `hetero­tetra­mer.' This low dimensionality in the structures of the 1:1 aromatic Lewis base salts of the parent acid is generally associated with the planar DCPA anion species.

S1. Comment

The 1:1 proton-transfer compounds of the acid salts of 4,5-dichlorophthalic acid (DCPA) with aromatic and heteroaromatic nitrogen Lewis bases generally show low-dimensional hydrogen-bonded structure types (Smith et al., 2008a), with the occurrence of three-dimensional structures limited to the compounds with the bifunctional examples 3- and 4-aminobenzoic acid (Smith et al., 2008b). In these two examples the primary hydrogen-bonded cation–anion `heterodimer' (Etter & Adsmond, 1990) is extended into sheet substructures through further anion–cation interactions, then into a three-dimensional framework via cyclic R₂²(8) cation carboxylic acid hydrogen bonds (Etter et al., 1990). In these examples the DCPA anions are non-planar whereas in the low-dimensional structure types the DCPA anion species are essentially planar with the planarity achieved through short intramolecular carboxylic acid O—H···O_carboxyl hydrogen bonds [typically 2.441 (3) in the brucinium DCPA compound (Smith et al., 2007)]. There is also a low incidence of hydrates among the structures of the (1:1) proton-transfer compounds of DCPA when prepared in aqueous alcohol solution, with the only three known examples limited to the salts with quinaldic acid (a monohydrate) (Smith et al., 2008a), 2-aminobenzoic acid (a dihydrate) (Smith et al., 2008b), hexamethylenetetramine (a monohydrate) (Smith et al., 2009) and the drug quinacrine (a tetrahydrate) (Smith & Wermuth, 2009).

The 1:1 stoichiometric reaction of DCPA with the substituted monocyclic heteroaromatic bases 2-aminopyrimidine, 3-(aminocarbonyl)pyridine (nicotinamide) and 4-(aminocarbonyl)pyridine (isonicotinamide) in methanol gave the anhydrous compounds 2-aminopyrimidinium 2-carboxy-4,5-dichlorobenzoate C₄H₆N₃⁺ C₈H₃Cl₂O₄^-, (I), 3-(aminocarbonyl)pyridinium 2-carboxy-4,5-dichlorobenzoate C₇H₈NO₂⁺ C₈H₃Cl₂O₄^-, (II), and the unusual adduct 4-(aminocarbonyl)pyridinium 2-carboxy-4,5-dichlorobenzoate 2-carboxymethyl-4,5-dichlorobenzoic acid (1/1/1) C₆H₇N₂O⁺ C₈H₃Cl₂O₄^-. C₉H₆Cl₂O₄, (III). This set of compounds shows examples of zero-, one- and two-dimensional hydrogen-bonded structures.

All three compounds have at least one direct hetero-ring N⁺—H···O_carboxyl hydrogen-bonding interaction (Figs. 1–3 and Tables 1–3), and all show low-dimensional hydrogen-bonded overall structures, two- in (II), one- in (III) and the first example of a cyclic zero-dimensional bis(cation–anion) species in (I) (Figs. 4–6). Associated with all of these DCPA structure types is the essentially planar monoanion species which is found in ca 50% of the known 1:1 acid salts of DCPA with aromatic Lewis bases (Smith et al., 2008a). However structures (I)–(III) are sufficiently different as to be described separately.

With compound (I), the primary cation–anion association is an asymmetric cyclic R₂²(8) pyrimidine hetero-N···O,O'_carboxyl association (Fig. 1). This is the high-probability Type 4 hydrogen-bonding structural motif described by Allen et al. (1998). The cation-anion pairs so formed repeat across inversion centres via cyclic three-centre R₁²(4) amine –N⁺—H···O,O'_carboxyl associations, enclosing R⁶₆(12) rings, giving discrete four-molecule 'heterotetramer' structural units (Fig. 4). Although other zero-dimensional structures are known among the DCPA proton-transfer compounds [others being discrete cation–anion `heterodimers' (Etter & Adsmond, 1990), with brucine (Smith et al., 2007), hexamethylenetetramine and 1,10-phenanthroline (Smith et al., 2009), the formation of this bis-(cation–anion) structure type is driven more by the interactive features of the 2-aminopyrimidine molecular synthon and finds a small incidence among its 1:1 salts with the aromatic acids, e.g. (3,4-dichlorophenoxy)acetic acid (Lynch et al., 1994) and phthalic acid (Smith et al., 1995).

With (II), the nicotinamide cations form chain structures through homomeric amide N31—H···O_carbonyl interactions. These chains are linked along the b cell direction by associations involving proton donors of both the amide N and the primary pyridinium groups to carboxyl O acceptors of the anions (Table 3), giving a sheet parallel to (100) (Fig. 5).

Compound (III) is an example of a (1:1:1) cation–anion adduct structure with the adduct molecule an unexpected methyl monoester of DCPA, arising from self-synthesis in the methanol solvent under the conditions of the reaction. This phenomenon has no precedence among the proton-transfer compounds prepared under similar conditions in our laboratory. In (III), the primary hetero N⁺—H···O_carboxyl hydrogen-bonded unit is extended into a zigzag chain along [101] via an amide N—H···O_carboxyl association (Fig. 6). The second amide N atom, together with the amide carbonyl O atom, is involved in an asymmetric cyclic R₂²(8) association with the peripherally linked DCPA methyl monoester adduct molecule (B).

There is an absence in (I)–(III) of short intermolecular Cl···Cl interactions such as has been found in the DCPA compounds with 3- and 4-aminobenzoic acids (Smith et al., 2008a; please check; this reference appears to be for different compounds). The occurrence of this phenomenon, particularly in dichloro-substituted aromatic compounds, has previously been described (Sarma & Desiraju, 1986). However, in all three structures there are short Cl···O_carboxyl associations [for (I), Cl4···O32ⁱⁱ = 3.0683 (14) Å; symmetry code: (ii) -x + 1, -y + 2, -z + 1; for (II), Cl4···O11ⁱⁱ = 3.1582 (15) Å; symmetry code: (iii) -x + 1, y + 1/2, -z + 5/2; for (III), Cl4···O22ⁱⁱⁱ = 2.982 (5) Å; symmetry code: (iii) x, -y + 1, z - 1/2.]

With the DCPA anions in this series the essential planarity is the result of the presence of short intramolecular hydrogen bonds between the carboxyl groups [2.393 (8) Å in (III)–2.410 (2) Å in (II)]. The torsion angles associated with these groups (C2—C1—C11—O11 and C1—C2—C21—O22) are, for (I), -170.16 (16) and -179.70 (16)°; for (II), -178.68 (19) and 172.58 (18)°; and, for (III), 173.0 (7) and -175.6</span><span style=" font-weight:600;">(6)° [-178.5 (7)?], respectively. The planarity also means that there are short intramolecular aromatic ring C—H···O_carboxyl interactions [typically C6—H6···O12 = 2.676 (2) Å and C3—H3···O22 = 2.643 (2) Å in (I)]. With the methyl ester adduct molecule in (III), the carboxylic acid group provides hydrogen-bonding links to the cation–anion chain structure rather than forming an intramolecular hydrogen bond and is therefore rotated out of the molecular plane [C2B—C1B—C11B—O11B = -151.6 (6)°].

This present series provides a set of low-dimensional hydrogen- bonded structure types in the series of 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with aromatic Lewis bases. This low dimensionality is largely associated with planarity in the internally hydrogen-bonded hydrogen phthalate anion species.

Related literature

For related literature, see: Allen et al. (1998); Etter & Adsmond (1990); Etter, MacDonald & Bernstein (1990); Flack (1983); Lynch et al. (1994); Sarma & Desiraju (1986); Smith & Wermuth (2009); Smith et al. (1995, 2007, 2008a, 2008b); Smith, Wermuth & White (2009).

S2. Experimental

Compounds (I)–(III) were synthesized by heating together for 10 min under reflux, 1 mmol quantities of 4,5-dichlorophthalic acid and, respectively, 2-aminopyrimidine, nicotinic acid and isonicotinic acid in 50 ml of methanol. All compounds were obtained as small colourless plates or prisms [`needles' in CIF?] [m.p. (I) 334 K; (II) 455–457 K; (III) 433–434 K], after partial room-temperature evaporation of solvent.

S3. Refinement

H atoms potentially involved in hydrogen-bonding interactions in all compounds were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included at calculated positions [C—H = 0.93 Å (0.96 Å for methyl H atoms)] and treated as riding [with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C)]. For compound (III), the correct orientation of the structure with respect to the polar axis directions was established by means of the Flack (1983) x parameter.

Computing details

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular configuration and atom-numbering scheme for the 2-aminopyrimidinium cation and the 2-carboxy-4,5-dichlorobenzoate anion in (I), showing the cyclic R2^2(8) inter-species hydrogen-bonding associations as dashed lines. Non-H atoms are shown as 50% probability displacement ellipsoids.
	Fig. 2. The molecular configuration and atom-numbering scheme for the 3-(aminocarbony)pyridinium cations and the 2-carboxy-4,5-dichlorobenzoate anion in (II). The dashed lines indicate the inter-species hydrogen bonds, while non-H atoms are shown as 50% probability displacement ellipsoids.
	Fig. 3. Molecular configuration and atom-numbering scheme for the 4-(aminocarbonyl)pyridinium cation, the 2-carboxy-4,5-dichlorobenzoate anion and the 2-(carboxymethyl)-4,5-dichlorobenzoic acid adduct molecule in (III). The dashed lines indicate the inter-species hydrogen bonds, while non-H atoms are shown as 50% probability displacement ellipsoids.
	Fig. 4. Hydrogen-bonding in the discrete cyclic centrosymmetric bis(cation–anion) `heterotetramer' structural units in (I), shown as dashed lines. Non-interactive H atoms ahave been omitted. (For symmetry code, see Table 1.)
	Fig. 5. The hydrogen-bonding in the homomeric cation chains and the peripheral cation–anion extensions in the sheet structure of in a perspective view of the unit cell of (II). Non-interactive H atoms have been omitted, and hydrogen bonds are shown as dashed lines. (For symmetry codes, see Table 2.)
	Fig. 6. The zigzag hydrogen-bonded chains formed by extension of the cation–anion pairs and the peripherally attached methyl monoester adduct B molecules, in the structure of (III), in a perspective view of the unit cell. Non-interactive H atoms have been omitted. [Symmetry code: (ii) x - 1/2, y + 3/2, z - 1/2. For symmetry code (i), see Table 3.]

(I) 2-aminopyrimidininium 2-carboxy-4,5-dichlorobenzoate

Crystal data

C4H6N3^+·C8H3Cl2O4^−	Z = 2
Mr = 330.12	F(000) = 336
Triclinic, P1	Dx = 1.685 Mg m^−3
Hall symbol: -P 1	Melting point: 337 K
a = 6.9738 (4) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.4413 (4) Å	Cell parameters from 3656 reflections
c = 10.8900 (7) Å	θ = 4.2–73.2°
α = 97.420 (4)°	µ = 4.70 mm^−1
β = 100.527 (5)°	T = 180 K
γ = 109.473 (5)°	Plate, colourless
V = 650.50 (7) Å^3	0.40 × 0.25 × 0.06 mm

Data collection

Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer	2542 independent reflections
Radiation source: Enhance (Cu) X-ray tube	2300 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω scans	θmax = 73.3°, θmin = 4.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.263, Tmax = 0.750	k = −11→9
4955 measured reflections	l = −13→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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0638P)^2 + 0.0923P] where P = (Fo^2 + 2Fc^2)/3
2542 reflections	(Δ/σ)max = 0.001
206 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.27 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
Cl4	0.45906 (6)	1.22867 (4)	0.51774 (4)	0.0267 (1)
Cl5	0.08646 (7)	1.35528 (4)	0.47231 (4)	0.0275 (1)
O11	−0.50174 (19)	0.92708 (14)	0.14526 (13)	0.0296 (4)
O12	−0.45627 (18)	0.70762 (13)	0.11433 (12)	0.0253 (4)
O21	−0.17727 (18)	0.61141 (13)	0.15572 (12)	0.0252 (3)
O22	0.15213 (18)	0.68947 (13)	0.26292 (12)	0.0265 (4)
C1	−0.1727 (2)	0.93013 (17)	0.25534 (15)	0.0182 (4)
C2	−0.0092 (2)	0.87302 (17)	0.27900 (15)	0.0169 (4)
C3	0.1830 (2)	0.97005 (18)	0.35952 (15)	0.0192 (4)
C4	0.2158 (2)	1.11762 (18)	0.41903 (15)	0.0196 (4)
C5	0.0539 (3)	1.17249 (17)	0.39877 (15)	0.0197 (4)
C6	−0.1366 (3)	1.07938 (18)	0.31709 (16)	0.0199 (4)
C11	−0.3912 (2)	0.85223 (19)	0.16635 (16)	0.0201 (5)
C21	−0.0111 (2)	0.71330 (18)	0.22830 (15)	0.0183 (4)
N1A	0.1949 (2)	0.42610 (15)	0.18145 (13)	0.0197 (4)
N3A	0.0629 (2)	0.17310 (15)	0.05974 (14)	0.0215 (4)
N21A	−0.1428 (2)	0.31986 (17)	0.05611 (15)	0.0259 (4)
C2A	0.0384 (3)	0.30646 (17)	0.09894 (15)	0.0192 (4)
C4A	0.2454 (3)	0.16388 (18)	0.10567 (16)	0.0215 (4)
C5A	0.4133 (3)	0.28319 (19)	0.19192 (17)	0.0234 (5)
C6A	0.3821 (3)	0.41541 (18)	0.22853 (15)	0.0211 (5)
H3	0.29270	0.93430	0.37360	0.0230*
H6	−0.24410	1.11730	0.30280	0.0240*
H12	−0.335 (5)	0.669 (3)	0.130 (3)	0.066 (9)*
H1A	0.180 (3)	0.512 (2)	0.209 (2)	0.023 (5)*
H4A	0.26420	0.07280	0.07940	0.0260*
H5A	0.54010	0.27240	0.22260	0.0280*
H6A	0.48860	0.49790	0.28550	0.0250*
H21A	−0.239 (4)	0.244 (3)	0.001 (2)	0.039 (6)*
H22A	−0.163 (4)	0.410 (3)	0.077 (2)	0.036 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0242 (2)	0.0172 (2)	0.0292 (2)	0.0047 (2)	−0.0041 (2)	−0.0049 (2)
Cl5	0.0369 (3)	0.0143 (2)	0.0309 (2)	0.0122 (2)	0.0066 (2)	−0.0023 (2)
O11	0.0238 (6)	0.0231 (6)	0.0394 (7)	0.0119 (5)	−0.0024 (5)	0.0033 (5)
O12	0.0192 (6)	0.0200 (6)	0.0316 (7)	0.0068 (5)	−0.0013 (5)	−0.0006 (5)
O21	0.0208 (6)	0.0143 (5)	0.0352 (7)	0.0067 (4)	−0.0005 (5)	−0.0039 (5)
O22	0.0236 (6)	0.0181 (6)	0.0343 (7)	0.0111 (5)	−0.0009 (5)	−0.0048 (5)
C1	0.0208 (8)	0.0153 (7)	0.0190 (7)	0.0070 (6)	0.0049 (6)	0.0045 (6)
C2	0.0204 (7)	0.0120 (7)	0.0173 (7)	0.0054 (6)	0.0042 (6)	0.0015 (5)
C3	0.0209 (8)	0.0160 (7)	0.0208 (8)	0.0086 (6)	0.0031 (6)	0.0019 (6)
C4	0.0211 (8)	0.0139 (7)	0.0191 (8)	0.0035 (6)	0.0012 (6)	0.0002 (6)
C5	0.0273 (8)	0.0122 (7)	0.0201 (8)	0.0081 (6)	0.0066 (6)	0.0013 (6)
C6	0.0223 (8)	0.0180 (7)	0.0235 (8)	0.0118 (6)	0.0063 (6)	0.0054 (6)
C11	0.0192 (8)	0.0195 (8)	0.0215 (8)	0.0074 (6)	0.0037 (6)	0.0047 (6)
C21	0.0193 (7)	0.0137 (7)	0.0209 (8)	0.0062 (6)	0.0046 (6)	0.0005 (6)
N1A	0.0218 (7)	0.0124 (6)	0.0231 (7)	0.0066 (5)	0.0034 (5)	−0.0001 (5)
N3A	0.0226 (7)	0.0143 (6)	0.0259 (7)	0.0072 (5)	0.0037 (5)	0.0001 (5)
N21A	0.0224 (7)	0.0189 (7)	0.0324 (8)	0.0098 (6)	−0.0011 (6)	−0.0038 (6)
C2A	0.0217 (8)	0.0152 (7)	0.0207 (8)	0.0071 (6)	0.0056 (6)	0.0018 (6)
C4A	0.0261 (8)	0.0157 (7)	0.0248 (8)	0.0105 (6)	0.0070 (7)	0.0027 (6)
C5A	0.0222 (8)	0.0210 (8)	0.0286 (9)	0.0102 (6)	0.0052 (7)	0.0055 (7)
C6A	0.0198 (8)	0.0181 (8)	0.0213 (8)	0.0045 (6)	0.0021 (6)	0.0010 (6)

Geometric parameters (Å, º)

Cl4—C4	1.7290 (16)	C1—C11	1.527 (2)
Cl5—C5	1.7282 (17)	C1—C2	1.413 (2)
O11—C11	1.219 (2)	C1—C6	1.399 (2)
O12—C11	1.298 (2)	C2—C3	1.396 (2)
O21—C21	1.272 (2)	C2—C21	1.532 (2)
O22—C21	1.235 (2)	C3—C4	1.383 (2)
O12—H12	1.02 (4)	C4—C5	1.386 (3)
N1A—C6A	1.354 (3)	C5—C6	1.384 (3)
N1A—C2A	1.354 (2)	C3—H3	0.9300
N3A—C4A	1.315 (3)	C6—H6	0.9300
N3A—C2A	1.352 (2)	C4A—C5A	1.403 (3)
N21A—C2A	1.318 (3)	C5A—C6A	1.360 (3)
N1A—H1A	0.87 (2)	C4A—H4A	0.9300
N21A—H21A	0.86 (2)	C5A—H5A	0.9300
N21A—H22A	0.92 (3)	C6A—H6A	0.9300
C11—O12—H12	109.9 (16)	O12—C11—C1	119.55 (14)
C21—O21—H12	111.1 (12)	O11—C11—O12	121.06 (15)
C2A—N1A—C6A	120.74 (15)	O11—C11—C1	119.39 (15)
C2A—N3A—C4A	117.20 (15)	O21—C21—C2	119.98 (14)
C6A—N1A—H1A	116.7 (14)	O22—C21—C2	117.05 (14)
C2A—N1A—H1A	122.5 (14)	O21—C21—O22	122.95 (15)
C2A—N21A—H22A	121.6 (17)	C4—C3—H3	119.00
C2A—N21A—H21A	118 (2)	C2—C3—H3	119.00
H21A—N21A—H22A	120 (3)	C5—C6—H6	119.00
C6—C1—C11	112.63 (15)	C1—C6—H6	119.00
C2—C1—C11	128.90 (14)	N1A—C2A—N3A	121.65 (18)
C2—C1—C6	118.45 (15)	N1A—C2A—N21A	119.26 (16)
C1—C2—C21	128.72 (14)	N3A—C2A—N21A	119.10 (16)
C1—C2—C3	118.39 (14)	N3A—C4A—C5A	123.95 (17)
C3—C2—C21	112.89 (13)	C4A—C5A—C6A	116.90 (19)
C2—C3—C4	122.20 (14)	N1A—C6A—C5A	119.56 (16)
Cl4—C4—C3	118.76 (12)	N3A—C4A—H4A	118.00
C3—C4—C5	119.53 (15)	C5A—C4A—H4A	118.00
Cl4—C4—C5	121.72 (13)	C4A—C5A—H5A	122.00
C4—C5—C6	119.23 (15)	C6A—C5A—H5A	122.00
Cl5—C5—C6	119.55 (16)	N1A—C6A—H6A	120.00
Cl5—C5—C4	121.22 (14)	C5A—C6A—H6A	120.00
C1—C6—C5	122.16 (18)
C2A—N1A—C6A—C5A	0.3 (2)	C3—C2—C21—O22	−0.2 (2)
C6A—N1A—C2A—N3A	−0.5 (2)	C3—C2—C21—O21	178.59 (15)
C6A—N1A—C2A—N21A	179.15 (16)	C1—C2—C3—C4	1.8 (2)
C4A—N3A—C2A—N1A	0.3 (2)	C21—C2—C3—C4	−177.74 (14)
C4A—N3A—C2A—N21A	−179.35 (16)	C1—C2—C21—O21	−0.9 (3)
C2A—N3A—C4A—C5A	0.1 (3)	C1—C2—C21—O22	−179.70 (16)
C6—C1—C2—C21	177.35 (15)	C2—C3—C4—Cl4	179.66 (12)
C2—C1—C11—O12	9.8 (3)	C2—C3—C4—C5	−0.1 (2)
C6—C1—C11—O11	8.2 (2)	Cl4—C4—C5—C6	178.95 (13)
C11—C1—C2—C3	176.19 (15)	Cl4—C4—C5—Cl5	−0.4 (2)
C11—C1—C2—C21	−4.3 (3)	C3—C4—C5—Cl5	179.31 (13)
C2—C1—C6—C5	0.8 (2)	C3—C4—C5—C6	−1.3 (2)
C11—C1—C6—C5	−177.79 (15)	C4—C5—C6—C1	1.0 (3)
C2—C1—C11—O11	−170.16 (16)	Cl5—C5—C6—C1	−179.66 (13)
C6—C1—C11—O12	−171.81 (15)	N3A—C4A—C5A—C6A	−0.2 (3)
C6—C1—C2—C3	−2.1 (2)	C4A—C5A—C6A—N1A	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O21	1.02 (4)	1.38 (3)	2.4037 (19)	177 (3)
N1A—H1A···O22	0.87 (2)	1.79 (2)	2.6609 (19)	178.8 (19)
N21A—H21A···O11^i	0.86 (2)	2.18 (3)	3.038 (2)	173 (3)
N21A—H21A···O12^i	0.86 (2)	2.47 (3)	2.971 (2)	117 (2)
N21A—H22A···O21	0.92 (3)	2.02 (3)	2.929 (2)	169.4 (19)
C3—H3···O22	0.93	2.26	2.643 (2)	104
C4A—H4A···O11^ii	0.93	2.53	3.301 (2)	141
C6—H6···O11	0.93	2.31	2.679 (2)	103

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

(II) 3-(aminocarbonyl)pyridinium 2-carboxy-4,5-dichlorobenzoate

Crystal data

C6H7N2O^+·C8H3Cl2O4^−	F(000) = 728
Mr = 357.14	Dx = 1.656 Mg m^−3
Monoclinic, P21/c	Melting point = 455–457 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54184 Å
a = 11.4303 (3) Å	Cell parameters from 3546 reflections
b = 13.7933 (3) Å	θ = 3.2–72.9°
c = 9.2082 (2) Å	µ = 4.36 mm^−1
β = 99.454 (2)°	T = 130 K
V = 1432.06 (6) Å^3	Plate, colourless
Z = 4	0.50 × 0.25 × 0.07 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	2798 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2237 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 72.9°, θmin = 3.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→12
Tmin = 0.340, Tmax = 0.740	k = −16→17
6939 measured reflections	l = −10→11

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 = 0.96	w = 1/[σ^2(Fo^2) + (0.0656P)^2] where P = (Fo^2 + 2Fc^2)/3
2798 reflections	(Δ/σ)max = 0.001
224 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

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
Cl4	0.41142 (4)	0.30096 (3)	1.33710 (5)	0.0255 (1)
Cl5	0.40646 (4)	0.06833 (3)	1.33348 (6)	0.0319 (2)
O11	0.72056 (13)	−0.02599 (10)	1.03383 (16)	0.0320 (4)
O12	0.82117 (14)	0.09368 (11)	0.96028 (18)	0.0394 (5)
O21	0.83088 (13)	0.26806 (10)	0.97448 (17)	0.0359 (5)
O22	0.72470 (13)	0.38895 (9)	1.03689 (17)	0.0324 (4)
C1	0.66260 (16)	0.13098 (13)	1.1000 (2)	0.0218 (5)
C2	0.66584 (15)	0.23339 (13)	1.1034 (2)	0.0209 (5)
C3	0.58640 (16)	0.28245 (14)	1.17702 (19)	0.0225 (5)
C4	0.50620 (15)	0.23418 (13)	1.2473 (2)	0.0219 (5)
C5	0.50315 (16)	0.13317 (13)	1.2450 (2)	0.0229 (5)
C6	0.58049 (16)	0.08316 (13)	1.17111 (19)	0.0232 (5)
C11	0.73836 (17)	0.06060 (13)	1.0264 (2)	0.0244 (5)
C21	0.74647 (16)	0.30070 (13)	1.0326 (2)	0.0239 (5)
O31A	0.87437 (12)	0.81161 (9)	0.71542 (14)	0.0246 (4)
N1A	0.85072 (13)	0.49722 (11)	0.89564 (17)	0.0235 (5)
N31A	0.82644 (15)	0.80007 (11)	0.94426 (18)	0.0264 (5)
C2A	0.82812 (16)	0.59268 (13)	0.9002 (2)	0.0223 (5)
C3A	0.89223 (16)	0.65743 (14)	0.83085 (19)	0.0210 (5)
C4A	0.98051 (16)	0.62190 (13)	0.7572 (2)	0.0231 (5)
C5A	1.00311 (17)	0.52280 (14)	0.7553 (2)	0.0260 (5)
C6A	0.93541 (17)	0.46186 (14)	0.8258 (2)	0.0248 (5)
C31A	0.86413 (15)	0.76412 (13)	0.8265 (2)	0.0216 (5)
H3	0.58760	0.35130	1.17880	0.0270*
H6	0.57750	0.01430	1.16880	0.0280*
H12	0.825 (4)	0.165 (3)	0.966 (4)	0.067 (9)*
H1A	0.804 (2)	0.4581 (18)	0.950 (4)	0.044 (7)*
H2A	0.76790	0.61550	0.95140	0.0270*
H4A	1.02530	0.66540	0.70820	0.0280*
H5A	1.06380	0.49790	0.70650	0.0310*
H6A	0.94890	0.39390	0.82500	0.0300*
H31A	0.833 (2)	0.7639 (16)	1.024 (3)	0.032 (6)*
H32A	0.806 (2)	0.8622 (19)	0.946 (3)	0.041 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0228 (2)	0.0248 (2)	0.0306 (3)	0.0026 (2)	0.0092 (2)	−0.0038 (2)
Cl5	0.0339 (3)	0.0256 (3)	0.0410 (3)	−0.0017 (2)	0.0202 (2)	0.0038 (2)
O11	0.0366 (8)	0.0203 (7)	0.0428 (8)	0.0021 (6)	0.0173 (6)	−0.0027 (6)
O12	0.0462 (9)	0.0261 (7)	0.0543 (10)	0.0027 (7)	0.0332 (8)	−0.0009 (7)
O21	0.0350 (8)	0.0275 (8)	0.0509 (10)	−0.0018 (6)	0.0244 (7)	0.0009 (6)
O22	0.0355 (7)	0.0217 (7)	0.0444 (9)	−0.0007 (6)	0.0199 (6)	0.0032 (6)
C1	0.0226 (8)	0.0206 (9)	0.0223 (9)	0.0018 (7)	0.0043 (7)	−0.0004 (7)
C2	0.0210 (8)	0.0206 (9)	0.0209 (9)	−0.0003 (7)	0.0028 (7)	0.0003 (7)
C3	0.0236 (9)	0.0203 (9)	0.0234 (9)	−0.0006 (7)	0.0030 (7)	−0.0011 (7)
C4	0.0218 (8)	0.0199 (9)	0.0241 (9)	0.0039 (7)	0.0038 (7)	−0.0024 (7)
C5	0.0243 (9)	0.0208 (9)	0.0246 (10)	−0.0024 (7)	0.0072 (8)	0.0027 (7)
C6	0.0272 (9)	0.0178 (9)	0.0254 (9)	−0.0001 (7)	0.0064 (8)	0.0010 (7)
C11	0.0260 (9)	0.0234 (9)	0.0242 (9)	0.0027 (8)	0.0056 (7)	−0.0006 (7)
C21	0.0231 (9)	0.0238 (10)	0.0251 (9)	−0.0029 (7)	0.0046 (7)	0.0001 (7)
O31A	0.0301 (7)	0.0207 (6)	0.0250 (7)	−0.0018 (5)	0.0101 (5)	0.0021 (5)
N1A	0.0251 (8)	0.0201 (8)	0.0256 (8)	−0.0018 (6)	0.0052 (6)	0.0015 (6)
N31A	0.0375 (9)	0.0204 (8)	0.0232 (8)	0.0025 (7)	0.0107 (7)	0.0010 (6)
C2A	0.0223 (9)	0.0221 (9)	0.0228 (9)	0.0010 (7)	0.0043 (7)	−0.0012 (7)
C3A	0.0236 (8)	0.0206 (9)	0.0184 (8)	−0.0009 (7)	0.0023 (7)	−0.0009 (7)
C4A	0.0242 (9)	0.0219 (9)	0.0243 (9)	−0.0001 (7)	0.0071 (7)	0.0013 (7)
C5A	0.0267 (9)	0.0247 (9)	0.0279 (10)	0.0043 (8)	0.0080 (8)	−0.0005 (8)
C6A	0.0279 (9)	0.0189 (9)	0.0271 (9)	0.0028 (7)	0.0035 (8)	−0.0009 (7)
C31A	0.0219 (9)	0.0185 (9)	0.0246 (9)	−0.0026 (7)	0.0045 (7)	−0.0014 (7)

Geometric parameters (Å, º)

Cl4—C4	1.7321 (18)	C2—C3	1.394 (3)
Cl5—C5	1.7265 (19)	C2—C21	1.528 (3)
O11—C11	1.215 (2)	C3—C4	1.377 (3)
O12—C11	1.290 (3)	C4—C5	1.394 (3)
O21—C21	1.261 (2)	C5—C6	1.385 (3)
O22—C21	1.244 (2)	C3—H3	0.9500
O12—H12	0.99 (4)	C6—H6	0.9500
O31A—C31A	1.236 (2)	C2A—C3A	1.377 (3)
N1A—C6A	1.339 (2)	C3A—C4A	1.394 (3)
N1A—C2A	1.344 (2)	C3A—C31A	1.505 (3)
N31A—C31A	1.327 (2)	C4A—C5A	1.392 (3)
N1A—H1A	0.96 (3)	C5A—C6A	1.375 (3)
N31A—H32A	0.89 (3)	C2A—H2A	0.9500
N31A—H31A	0.88 (3)	C4A—H4A	0.9500
C1—C2	1.413 (3)	C5A—H5A	0.9500
C1—C11	1.531 (3)	C6A—H6A	0.9500
C1—C6	1.395 (3)
C11—O12—H12	111 (3)	O21—C21—C2	121.43 (16)
C21—O21—H12	110.3 (18)	O22—C21—C2	116.31 (16)
C2A—N1A—C6A	121.99 (16)	O21—C21—O22	122.26 (17)
C6A—N1A—H1A	123.8 (15)	C4—C3—H3	119.00
C2A—N1A—H1A	114.2 (16)	C2—C3—H3	119.00
C31A—N31A—H32A	119.8 (17)	C1—C6—H6	119.00
H31A—N31A—H32A	121 (2)	C5—C6—H6	119.00
C31A—N31A—H31A	118.4 (15)	N1A—C2A—C3A	120.09 (17)
C2—C1—C11	128.97 (16)	C2A—C3A—C31A	121.26 (16)
C6—C1—C11	112.39 (15)	C2A—C3A—C4A	118.72 (17)
C2—C1—C6	118.64 (16)	C4A—C3A—C31A	119.94 (16)
C1—C2—C3	118.62 (16)	C3A—C4A—C5A	120.14 (17)
C3—C2—C21	113.53 (16)	C4A—C5A—C6A	118.31 (18)
C1—C2—C21	127.84 (16)	N1A—C6A—C5A	120.75 (18)
C2—C3—C4	122.05 (17)	O31A—C31A—C3A	119.42 (16)
C3—C4—C5	119.54 (17)	N31A—C31A—C3A	116.11 (16)
Cl4—C4—C3	118.94 (14)	O31A—C31A—N31A	124.45 (17)
Cl4—C4—C5	121.52 (14)	N1A—C2A—H2A	120.00
C4—C5—C6	119.27 (17)	C3A—C2A—H2A	120.00
Cl5—C5—C6	118.92 (14)	C3A—C4A—H4A	120.00
Cl5—C5—C4	121.80 (14)	C5A—C4A—H4A	120.00
C1—C6—C5	121.87 (17)	C4A—C5A—H5A	121.00
O11—C11—C1	119.08 (17)	C6A—C5A—H5A	121.00
O12—C11—C1	119.79 (16)	N1A—C6A—H6A	120.00
O11—C11—O12	121.11 (18)	C5A—C6A—H6A	120.00
C2A—N1A—C6A—C5A	0.0 (3)	C2—C3—C4—Cl4	179.58 (14)
C6A—N1A—C2A—C3A	0.5 (3)	C2—C3—C4—C5	−0.3 (3)
C6—C1—C2—C3	−0.3 (3)	Cl4—C4—C5—C6	179.73 (14)
C11—C1—C2—C21	0.4 (3)	Cl4—C4—C5—Cl5	−1.0 (2)
C6—C1—C2—C21	−179.28 (17)	C3—C4—C5—Cl5	178.91 (14)
C11—C1—C6—C5	179.91 (17)	C3—C4—C5—C6	−0.4 (3)
C2—C1—C11—O11	−178.73 (19)	C4—C5—C6—C1	0.7 (3)
C2—C1—C11—O12	2.6 (3)	Cl5—C5—C6—C1	−178.62 (14)
C6—C1—C11—O11	1.0 (2)	N1A—C2A—C3A—C31A	176.36 (16)
C11—C1—C2—C3	179.36 (17)	N1A—C2A—C3A—C4A	−0.3 (3)
C6—C1—C11—O12	−177.68 (17)	C2A—C3A—C4A—C5A	−0.4 (3)
C2—C1—C6—C5	−0.4 (3)	C2A—C3A—C31A—O31A	−144.00 (18)
C21—C2—C3—C4	179.74 (16)	C2A—C3A—C31A—N31A	34.3 (3)
C1—C2—C21—O21	−8.1 (3)	C4A—C3A—C31A—O31A	32.6 (3)
C3—C2—C21—O21	172.92 (17)	C4A—C3A—C31A—N31A	−149.07 (18)
C3—C2—C21—O22	−6.5 (2)	C31A—C3A—C4A—C5A	−177.07 (17)
C1—C2—C3—C4	0.7 (3)	C3A—C4A—C5A—C6A	0.8 (3)
C1—C2—C21—O22	172.53 (18)	C4A—C5A—C6A—N1A	−0.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O21	0.99 (4)	1.43 (4)	2.410 (2)	180 (6)
N1A—H1A···O22	0.96 (3)	1.62 (3)	2.571 (2)	178 (3)
N31A—H31A···O31A^i	0.88 (3)	2.04 (3)	2.908 (2)	171 (2)
N31A—H32A···O11^ii	0.89 (3)	2.06 (3)	2.869 (2)	151 (2)
C3—H3···O22	0.95	2.26	2.644 (2)	103
C5A—H5A···O12^iii	0.95	2.55	3.200 (3)	126
C6—H6···O11	0.95	2.28	2.663 (2)	103
C6A—H6A···O31A^iv	0.95	2.40	3.072 (2)	128

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

(III) 4-(aminocarbonyl)pyridinium 2-carboxy-4,5-dichlorobenzoate– methyl 2-carboxy-4,5-dichlorobenzoate (1/1)

Crystal data

C6H7N2O^+·C8H3Cl2O4^−·C9H6Cl2O4	F(000) = 1232
Mr = 606.18	Dx = 1.638 Mg m^−3
Monoclinic, Cc	Melting point = 433–434 K
Hall symbol: C -2yc	Cu Kα radiation, λ = 1.54178 Å
a = 11.9645 (4) Å	Cell parameters from 2767 reflections
b = 26.1393 (6) Å	θ = 3.4–72.5°
c = 9.3213 (3) Å	µ = 4.90 mm^−1
β = 122.509 (3)°	T = 130 K
V = 2458.39 (15) Å^3	Needle, colourless
Z = 4	0.56 × 0.14 × 0.07 mm

Data collection

Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer	3034 independent reflections
Radiation source: Enhance (Cu) X-ray source	2530 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 72.9°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→12
Tmin = 0.454, Tmax = 0.710	k = −31→31
6097 measured reflections	l = −11→11

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)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.128	CALC W = 1/[Σ^2(FO^2) + (0.0961P)^2] WHERE P = (FO^2 + 2FC^2)/3
S = 0.97	(Δ/σ)max = 0.002
3034 reflections	Δρmax = 0.32 e Å^−3
363 parameters	Δρmin = −0.43 e Å^−3
1 restraint	Absolute structure: Flack (1983); 576 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (2)

Special details

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
Cl4B	0.40099 (18)	0.87331 (8)	1.1063 (2)	0.0506 (6)
Cl5B	0.42914 (18)	0.97992 (7)	0.9639 (2)	0.0491 (5)
O11B	0.6757 (4)	0.92532 (14)	0.6596 (5)	0.0354 (16)
O12B	0.5878 (5)	0.84818 (15)	0.5513 (6)	0.0357 (14)
O21B	0.7299 (4)	0.78825 (14)	0.8452 (6)	0.0361 (14)
O22B	0.5392 (5)	0.74628 (17)	0.7536 (7)	0.0462 (16)
C1B	0.5708 (6)	0.8805 (2)	0.7768 (7)	0.0283 (17)
C2B	0.5599 (6)	0.8339 (2)	0.8391 (7)	0.0304 (17)
C3B	0.5061 (6)	0.8318 (3)	0.9413 (8)	0.0359 (17)
C4B	0.4665 (6)	0.8773 (3)	0.9803 (8)	0.037 (2)
C5B	0.4777 (6)	0.9236 (2)	0.9188 (8)	0.0331 (17)
C6B	0.5322 (6)	0.9249 (2)	0.8184 (8)	0.0319 (17)
C11B	0.6144 (6)	0.8825 (2)	0.6520 (8)	0.0279 (17)
C21B	0.6050 (6)	0.7844 (2)	0.8061 (8)	0.0322 (17)
C22B	0.7803 (8)	0.7459 (2)	0.7948 (10)	0.047 (3)
Cl4	0.65337 (16)	0.50963 (5)	−0.01060 (19)	0.0372 (4)
Cl5	0.76492 (14)	0.60359 (5)	−0.11578 (17)	0.0335 (4)
O11	0.7303 (5)	0.75401 (15)	0.2059 (6)	0.0416 (16)
O12	0.6159 (8)	0.73933 (17)	0.3181 (10)	0.082 (3)
O21	0.5251 (6)	0.66858 (16)	0.3856 (8)	0.062 (2)
O22	0.4967 (5)	0.58620 (14)	0.3436 (6)	0.0388 (15)
C1	0.6530 (6)	0.6691 (2)	0.1780 (7)	0.0280 (17)
C2	0.5978 (6)	0.62739 (18)	0.2173 (8)	0.0260 (16)
C3	0.6000 (6)	0.57945 (19)	0.1548 (8)	0.0273 (16)
C4	0.6546 (6)	0.5706 (2)	0.0582 (7)	0.0258 (16)
C5	0.7031 (6)	0.6118 (2)	0.0142 (7)	0.0264 (17)
C6	0.7032 (6)	0.6601 (2)	0.0753 (7)	0.0254 (16)
C11	0.6694 (7)	0.7242 (2)	0.2387 (9)	0.036 (2)
C21	0.5363 (6)	0.62770 (19)	0.3231 (8)	0.0304 (16)
O41A	0.7480 (4)	0.93127 (13)	0.4354 (5)	0.0325 (14)
N1A	0.9145 (5)	0.91166 (17)	0.0534 (6)	0.0271 (14)
N41A	0.7358 (5)	0.84580 (16)	0.3910 (6)	0.0319 (16)
C2A	0.8628 (6)	0.9520 (2)	0.0862 (7)	0.0285 (16)
C3A	0.8163 (6)	0.94673 (19)	0.1918 (7)	0.0268 (16)
C4A	0.8217 (5)	0.8986 (2)	0.2615 (6)	0.0237 (17)
C5A	0.8770 (6)	0.8581 (2)	0.2250 (7)	0.0279 (16)
C6A	0.9233 (6)	0.8655 (2)	0.1183 (8)	0.0268 (16)
C41A	0.7642 (6)	0.8926 (2)	0.3696 (7)	0.0242 (16)
H3B	0.49690	0.80000	0.98310	0.0430*
H6B	0.54270	0.95690	0.77830	0.0380*
H11B	0.705 (7)	0.927 (2)	0.594 (9)	0.042 (15)*
H22B	0.76470	0.71370	0.83520	0.0700*
H23B	0.87560	0.75040	0.84480	0.0700*
H24B	0.73450	0.74500	0.67050	0.0700*
H3	0.56240	0.55140	0.17930	0.0330*
H6	0.73850	0.68790	0.04640	0.0300*
H12	0.598 (8)	0.714 (3)	0.352 (9)	0.082 (15)*
H1A	0.945 (6)	0.917 (2)	−0.019 (8)	0.034 (14)*
H2A	0.85810	0.98420	0.03630	0.0350*
H3A	0.78100	0.97530	0.21730	0.0320*
H5A	0.88310	0.82530	0.27280	0.0330*
H6A	0.96100	0.83790	0.09210	0.0320*
H41A	0.694 (6)	0.841 (2)	0.438 (7)	0.051 (13)*
H42A	0.742 (8)	0.823 (3)	0.336 (9)	0.061 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4B	0.0431 (9)	0.0857 (13)	0.0363 (9)	0.0031 (9)	0.0301 (8)	0.0013 (8)
Cl5B	0.0485 (9)	0.0561 (9)	0.0511 (10)	0.0015 (8)	0.0323 (8)	−0.0179 (8)
O11B	0.049 (3)	0.031 (2)	0.041 (3)	−0.0035 (18)	0.034 (2)	−0.0061 (17)
O12B	0.048 (3)	0.033 (2)	0.038 (2)	−0.0038 (19)	0.031 (2)	−0.0064 (18)
O21B	0.038 (2)	0.0294 (19)	0.045 (3)	0.0034 (17)	0.025 (2)	−0.0007 (17)
O22B	0.055 (3)	0.037 (2)	0.057 (3)	−0.012 (2)	0.037 (3)	−0.010 (2)
C1B	0.024 (3)	0.037 (3)	0.023 (3)	−0.004 (2)	0.012 (3)	−0.002 (2)
C2B	0.026 (3)	0.035 (3)	0.028 (3)	−0.001 (2)	0.013 (3)	−0.003 (2)
C3B	0.029 (3)	0.049 (3)	0.031 (3)	0.000 (3)	0.017 (3)	0.006 (3)
C4B	0.033 (4)	0.058 (4)	0.029 (3)	0.001 (3)	0.023 (3)	−0.006 (3)
C5B	0.029 (3)	0.046 (3)	0.024 (3)	−0.003 (3)	0.014 (3)	−0.009 (3)
C6B	0.034 (3)	0.037 (3)	0.026 (3)	0.001 (3)	0.017 (3)	−0.001 (2)
C11B	0.031 (3)	0.028 (3)	0.028 (3)	0.003 (2)	0.018 (3)	−0.002 (2)
C21B	0.036 (3)	0.034 (3)	0.030 (3)	−0.005 (3)	0.020 (3)	0.001 (2)
C22B	0.064 (5)	0.036 (3)	0.057 (5)	0.003 (3)	0.044 (4)	−0.007 (3)
Cl4	0.0536 (9)	0.0247 (5)	0.0425 (8)	−0.0001 (6)	0.0320 (7)	−0.0062 (6)
Cl5	0.0405 (8)	0.0353 (6)	0.0356 (8)	0.0019 (6)	0.0277 (7)	−0.0019 (6)
O11	0.060 (3)	0.028 (2)	0.055 (3)	−0.009 (2)	0.043 (3)	−0.0082 (19)
O12	0.157 (7)	0.027 (2)	0.153 (7)	−0.017 (3)	0.143 (6)	−0.019 (3)
O21	0.113 (5)	0.029 (2)	0.101 (5)	−0.010 (3)	0.096 (4)	−0.011 (3)
O22	0.058 (3)	0.0252 (18)	0.053 (3)	−0.0009 (19)	0.043 (3)	−0.0009 (19)
C1	0.036 (3)	0.025 (3)	0.022 (3)	0.003 (2)	0.015 (3)	0.000 (2)
C2	0.032 (3)	0.022 (2)	0.024 (3)	0.004 (2)	0.015 (3)	0.010 (2)
C3	0.029 (3)	0.022 (2)	0.033 (3)	−0.002 (2)	0.018 (3)	−0.002 (2)
C4	0.029 (3)	0.021 (2)	0.024 (3)	0.004 (2)	0.012 (2)	0.002 (2)
C5	0.028 (3)	0.029 (3)	0.026 (3)	0.003 (2)	0.017 (3)	0.002 (2)
C6	0.031 (3)	0.023 (2)	0.024 (3)	0.000 (2)	0.016 (2)	−0.001 (2)
C11	0.054 (4)	0.023 (3)	0.045 (4)	0.000 (3)	0.036 (3)	0.002 (2)
C21	0.040 (3)	0.022 (2)	0.035 (3)	0.005 (2)	0.024 (3)	0.003 (2)
O41A	0.048 (3)	0.0232 (19)	0.037 (2)	−0.0045 (18)	0.030 (2)	−0.0042 (16)
N1A	0.030 (3)	0.028 (2)	0.025 (2)	−0.002 (2)	0.016 (2)	0.0011 (18)
N41A	0.046 (3)	0.023 (2)	0.039 (3)	−0.001 (2)	0.031 (3)	−0.002 (2)
C2A	0.033 (3)	0.023 (2)	0.033 (3)	−0.002 (2)	0.020 (3)	−0.001 (2)
C3A	0.036 (3)	0.019 (2)	0.028 (3)	0.000 (2)	0.019 (3)	0.001 (2)
C4A	0.029 (3)	0.023 (3)	0.018 (3)	−0.004 (2)	0.012 (2)	−0.0062 (19)
C5A	0.029 (3)	0.022 (2)	0.030 (3)	−0.002 (2)	0.014 (3)	0.000 (2)
C6A	0.030 (3)	0.026 (2)	0.027 (3)	−0.001 (2)	0.017 (3)	−0.008 (2)
C41A	0.029 (3)	0.024 (2)	0.025 (3)	0.001 (2)	0.018 (2)	−0.002 (2)

Geometric parameters (Å, º)

Cl4B—C4B	1.730 (8)	C3B—C4B	1.399 (11)
Cl5B—C5B	1.716 (6)	C4B—C5B	1.376 (10)
Cl4—C4	1.715 (6)	C5B—C6B	1.399 (11)
Cl5—C5	1.739 (7)	C3B—H3B	0.9500
O11B—C11B	1.319 (7)	C6B—H6B	0.9500
O12B—C11B	1.211 (7)	C22B—H24B	0.9800
O21B—C22B	1.454 (9)	C22B—H22B	0.9800
O21B—C21B	1.338 (10)	C22B—H23B	0.9800
O22B—C21B	1.199 (8)	C1—C11	1.521 (8)
O11B—H11B	0.85 (9)	C1—C6	1.397 (10)
O11—C11	1.213 (10)	C1—C2	1.421 (9)
O12—C11	1.274 (13)	C2—C3	1.388 (7)
O21—C21	1.258 (8)	C2—C21	1.515 (11)
O22—C21	1.239 (7)	C3—C4	1.387 (11)
O12—H12	0.81 (8)	C4—C5	1.386 (9)
O41A—C41A	1.250 (7)	C5—C6	1.385 (8)
N1A—C6A	1.328 (7)	C3—H3	0.9500
N1A—C2A	1.338 (8)	C6—H6	0.9500
N41A—C41A	1.313 (7)	C2A—C3A	1.373 (10)
N1A—H1A	0.93 (8)	C3A—C4A	1.401 (7)
N41A—H41A	0.83 (7)	C4A—C5A	1.384 (9)
N41A—H42A	0.82 (8)	C4A—C41A	1.503 (9)
C1B—C11B	1.510 (10)	C5A—C6A	1.388 (10)
C1B—C6B	1.380 (9)	C2A—H2A	0.9500
C1B—C2B	1.385 (8)	C3A—H3A	0.9500
C2B—C3B	1.409 (11)	C5A—H5A	0.9500
C2B—C21B	1.496 (8)	C6A—H6A	0.9500
C21B—O21B—C22B	116.8 (5)	C6—C1—C11	113.4 (6)
C11B—O11B—H11B	116 (4)	C1—C2—C21	128.3 (5)
C11—O12—H12	107 (7)	C3—C2—C21	113.8 (5)
C2A—N1A—C6A	123.0 (6)	C1—C2—C3	117.9 (7)
C2A—N1A—H1A	117 (3)	C2—C3—C4	123.0 (6)
C6A—N1A—H1A	120 (3)	C3—C4—C5	118.7 (5)
C41A—N41A—H42A	118 (6)	Cl4—C4—C3	119.0 (5)
H41A—N41A—H42A	120 (7)	Cl4—C4—C5	122.2 (5)
C41A—N41A—H41A	120 (4)	C4—C5—C6	119.7 (6)
C6B—C1B—C11B	119.6 (5)	Cl5—C5—C6	119.5 (5)
C2B—C1B—C11B	120.2 (5)	Cl5—C5—C4	120.9 (4)
C2B—C1B—C6B	120.1 (7)	C1—C6—C5	122.0 (6)
C3B—C2B—C21B	116.9 (6)	O11—C11—O12	120.3 (6)
C1B—C2B—C3B	119.9 (6)	O11—C11—C1	119.3 (7)
C1B—C2B—C21B	123.3 (6)	O12—C11—C1	120.4 (7)
C2B—C3B—C4B	119.0 (7)	O21—C21—O22	121.8 (7)
Cl4B—C4B—C5B	121.1 (6)	O21—C21—C2	121.1 (6)
Cl4B—C4B—C3B	117.7 (6)	O22—C21—C2	117.1 (5)
C3B—C4B—C5B	121.1 (7)	C4—C3—H3	118.00
C4B—C5B—C6B	119.0 (6)	C2—C3—H3	119.00
Cl5B—C5B—C6B	118.9 (4)	C1—C6—H6	119.00
Cl5B—C5B—C4B	122.1 (6)	C5—C6—H6	119.00
C1B—C6B—C5B	121.0 (5)	N1A—C2A—C3A	120.0 (5)
O11B—C11B—O12B	125.3 (7)	C2A—C3A—C4A	119.1 (6)
O12B—C11B—C1B	121.1 (6)	C3A—C4A—C5A	118.8 (6)
O11B—C11B—C1B	113.6 (5)	C5A—C4A—C41A	122.5 (5)
O21B—C21B—O22B	124.5 (6)	C3A—C4A—C41A	118.7 (5)
O21B—C21B—C2B	110.6 (5)	C4A—C5A—C6A	119.8 (5)
O22B—C21B—C2B	124.9 (8)	N1A—C6A—C5A	119.3 (6)
C4B—C3B—H3B	121.00	O41A—C41A—C4A	119.5 (5)
C2B—C3B—H3B	121.00	N41A—C41A—C4A	116.6 (5)
C1B—C6B—H6B	120.00	O41A—C41A—N41A	123.9 (7)
C5B—C6B—H6B	119.00	N1A—C2A—H2A	120.00
O21B—C22B—H24B	110.00	C3A—C2A—H2A	120.00
O21B—C22B—H23B	109.00	C2A—C3A—H3A	120.00
H22B—C22B—H23B	109.00	C4A—C3A—H3A	120.00
H23B—C22B—H24B	109.00	C4A—C5A—H5A	120.00
H22B—C22B—H24B	109.00	C6A—C5A—H5A	120.00
O21B—C22B—H22B	109.00	N1A—C6A—H6A	120.00
C2—C1—C6	118.6 (5)	C5A—C6A—H6A	120.00
C2—C1—C11	128.0 (6)
C22B—O21B—C21B—O22B	10.2 (9)	C11—C1—C6—C5	176.9 (6)
C22B—O21B—C21B—C2B	−170.6 (5)	C2—C1—C11—O11	173.0 (7)
C2A—N1A—C6A—C5A	0.1 (10)	C2—C1—C11—O12	−9.4 (12)
C6A—N1A—C2A—C3A	0.3 (10)	C6—C1—C11—O11	−5.1 (10)
C6B—C1B—C2B—C21B	−177.3 (6)	C11—C1—C2—C3	−176.3 (7)
C6B—C1B—C2B—C3B	1.7 (10)	C6—C1—C11—O12	172.5 (7)
C2B—C1B—C6B—C5B	−2.1 (10)	C2—C1—C6—C5	−1.4 (10)
C11B—C1B—C6B—C5B	173.0 (6)	C21—C2—C3—C4	−178.6 (6)
C11B—C1B—C2B—C21B	7.7 (10)	C1—C2—C21—O21	2.2 (11)
C2B—C1B—C11B—O12B	31.6 (10)	C3—C2—C21—O21	−178.6 (7)
C6B—C1B—C11B—O11B	33.3 (9)	C3—C2—C21—O22	0.7 (9)
C6B—C1B—C11B—O12B	−143.4 (7)	C1—C2—C3—C4	0.7 (10)
C11B—C1B—C2B—C3B	−173.4 (6)	C1—C2—C21—O22	−178.5 (7)
C2B—C1B—C11B—O11B	−151.7 (6)	C2—C3—C4—Cl4	179.3 (5)
C21B—C2B—C3B—C4B	178.0 (6)	C2—C3—C4—C5	−3.5 (10)
C1B—C2B—C21B—O21B	51.4 (8)	Cl4—C4—C5—C6	−179.2 (5)
C3B—C2B—C21B—O21B	−127.6 (6)	Cl4—C4—C5—Cl5	0.4 (8)
C3B—C2B—C21B—O22B	51.7 (9)	C3—C4—C5—Cl5	−176.7 (5)
C1B—C2B—C3B—C4B	−1.0 (10)	C3—C4—C5—C6	3.7 (10)
C1B—C2B—C21B—O22B	−129.3 (8)	C4—C5—C6—C1	−1.4 (10)
C2B—C3B—C4B—Cl4B	−179.9 (5)	Cl5—C5—C6—C1	179.0 (5)
C2B—C3B—C4B—C5B	0.9 (10)	N1A—C2A—C3A—C4A	−1.1 (9)
Cl4B—C4B—C5B—C6B	179.6 (5)	C2A—C3A—C4A—C5A	1.6 (9)
C3B—C4B—C5B—Cl5B	179.7 (6)	C2A—C3A—C4A—C41A	−176.9 (6)
C3B—C4B—C5B—C6B	−1.3 (11)	C41A—C4A—C5A—C6A	177.2 (6)
Cl4B—C4B—C5B—Cl5B	0.5 (9)	C3A—C4A—C41A—O41A	−20.4 (9)
Cl5B—C5B—C6B—C1B	−179.0 (5)	C3A—C4A—C41A—N41A	160.7 (6)
C4B—C5B—C6B—C1B	1.9 (10)	C5A—C4A—C41A—O41A	161.2 (6)
C6—C1—C2—C3	1.7 (9)	C5A—C4A—C41A—N41A	−17.7 (9)
C11—C1—C2—C21	2.8 (12)	C3A—C4A—C5A—C6A	−1.3 (9)
C6—C1—C2—C21	−179.2 (6)	C4A—C5A—C6A—N1A	0.4 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O22^i	0.93 (8)	1.70 (7)	2.620 (8)	169 (5)
O11B—H11B···O41A	0.85 (9)	1.81 (8)	2.661 (7)	174 (8)
O12—H12···O21	0.81 (8)	1.60 (9)	2.394 (10)	166 (11)
N41A—H41A···O12B	0.83 (7)	2.05 (8)	2.866 (9)	166 (5)
N41A—H42A···O11	0.82 (8)	2.14 (8)	2.935 (6)	167 (10)
C2A—H2A···O41A^ii	0.95	2.48	3.331 (6)	149
C3—H3···O22	0.95	2.25	2.645 (10)	104
C5A—H5A···O11	0.95	2.45	3.191 (8)	135
C6—H6···O11	0.95	2.32	2.681 (7)	102
C6A—H6A···O21^i	0.95	2.43	3.134 (10)	131
C6A—H6A···O22B^i	0.95	2.54	3.189 (7)	125

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