Two-dimensional hydrogen-bonded supra­molecular networks in the compounds of benzene-1,2,4,5-tetra­carb­oxy­lic acid (pyromellitic acid) with 2,2'-bi­imidazole and 4,4'-di­methyl-2,2'-bi­pyridine

Two products from the proton-transfer reactions of benzene-1,2,4,5-tetra­carb­oxy­lic acid (pyromellitic acid, PMA) with 2,2'-bi­imidazole and 4,4'-dimethyl-2,2'-bipyridine, namely 2,2'-bi­imidazole-3,3'-diium 2,5-di­carb­oxy­benzene-1,4-di­carboxyl­ate, C₆H₈N₄²⁺,C₁₀H₄O₈^2-, (I), and 4-methyl-2-(4-methyl­pyridin-2-yl)pyridinium 2,4,5-tri­carb­oxy­benzoate mono­hydrate, C₁₂H₁₃N₂⁺·C₁₀H₅O₈^-·H₂O, (II), have been prepared and their structures determined. Both compounds crystallize in the space group P. The asymmetric unit of (I) is composed of two independent ion pairs. Both the 2,2'-bi­imidazole-3,3'-diium dication and the PMA^2- anion are located on special positions (inversion centres). The protonated 2,2'-bi­imidazole-3,3'-diium ring H atoms are involved in hydrogen bonding with carboxyl­ate O atoms to form one-dimensional hydrogen-bonded chain structures. Adjacent chains are further linked via carbox­yl-carboxyl O-H...O hydrogen bonding, resulting in a two-dimensional supra­molecular sheet with the R₆⁵(34) motif extending in the (11) plane. In (II), classical O-H...O hydrogen-bond-linked anion-anion units are extended into a one-dimensional chain running parallel to the [100] direction, giving an R₂²(8)R₄⁴(30) motif. The chains are connected by water-carboxyl O-H...O hydrogen bonds to form a two-dimensional network parallel to the (01) plane. The 4-methyl-2-(4-methyl­pyridin-2-yl)pyridinium cations lie between the two-dimensional supra­molecular layers linked via N-H...O hydrogen-bonding inter­actions.

S1. Introduction

The supra­molecular assembly of metal–organic coordination frameworks has attracted increasing attention due to their fascinating structure, as well as their potential applications in materials science (Batten & Robson, 1998a; Pan et al., 2004; Zhang et al., 2010; Zhong et al., 2011). It is well established that hydrogen bonds play vital roles in molecular recognition and supra­molecular chemistry (Batten & Robson, 1998b; Juan et al., 2002; Qiu et al., 2008), owing to its moderately directional inter­molecular inter­action can effectively control short-range packing. Polycarboxyl­ate acids, such as benzene-1,2,4,5-tetra­carb­oxy­lic acid (Li et al., 2003; Oscar et al., 2008), benzene-1,3,5-tri­carb­oxy­lic acid (Pasdar et al., 2011) and benzene-1,2,3,4-tetra­carb­oxy­lic acid (pyromellitic acid, PMA; Zhang et al., 2010), have been widely applied in constructing inter­esting supra­molecule networks because they act not only as hydrogen-bond accepters but also as hydrogen-bond donors, depending upon the number of deprotonated carb­oxy­lic acid groups. Many transition metal complexes with benzene-1,2,4,5-tetra­carboxyl­ate have been previously synthesized and reported, such as the zinc (Rochon & Massarweh, 2000), nickel (Poleti et al., 1988; Murugavel et al., 2002), manganese (Hu et al., 2001), cobalt (Cheng et al., 2002), copper (Cao et al., 2002), silver (Jaber et al., 1997) and iron complexes (Chu et al., 2001). As far as we know, reports on benzene-1,2,4,5-tetra­carboxyl­ate salts with organic Lewis bases are few, e.g. guanidinium pyromellitate trihydrate monoperhydrate (Adams & Ramdas, 1978), 2,2'-bipyridinium hemi[benzene-1,2,4,5-tetra­carboxyl­ate(2-)] hemi(benzene-1,2,4,5-tetra­carb­oxy­lic acid) (Mrvos-Sermek et al., 1996), guanidinuium pyromellite (Sun et al., 2002a), imidazolium tri­hydrogen benzene-1,2,4,5-tetra­carboxyl­ate (Sun et al., 2002b), 6,21-di­aza-3,9,18,24-tetra­azoniatri­cyclo­[22.2.2.2^11,14]triaconta-11,13,24,26 (1),27,29-hexa­ene benzene-1,2,4,5-tetra­carboxyl­ate(4-) hexahydrate (Zhu et al., 2002), ethyl­enedi­ammonium bis­(tri­hydrogen benzene-1,2,4,5-tetra­carboxyl­ate) dehydrate (Li et al., 2006). Recently, we attempted to utilize polycarboxyl­ate acids and N-containing bidentate ligands as mixed ligands for the design of coordination networks. The title compounds, 2,2'-bi­imidazole and 4,4'-di­methyl-2,2'-bi­pyridine, namely 2,2'-bi­imidazole-3,3'-diium 2,5-di­carb­oxy­benzene-1,4-di­carboxyl­ate, (I), and 4-methyl-2-(4-methyl­pyridin-2-yl)pyridinium 2,4,5-tri­carb­oxy­benzoate monohydrate, (II), were obtained unintentionally during an attempt to synthesize mixed-ligand transition-metal complexes with PMA and N-containing ligands via a solvothermal reaction. Their crystal structures have not been reported previously.

S2. Experimental

S2.1. Synthesis and crystallization

2,2'-Bi­imidazole (0.1 mmol, 0.0134 g), benzene-1,2,4,5-tetra­carb­oxy­lic acid (0.1 mmol, 0.0254 g), ZnSO₄.7H₂O (0.1 mmol, 0.0287 g) and water (2.0 ml) were mixed and placed in a thick Pyrex tube, which was sealed and heated to 383 K for 72 h, whereupon colourless block-shaped crystals of (I) were obtained. Colourless block-shaped crystal of (II) were obtained by a procedure similar to that described previously, using 4,4'-di­methyl-2,2'-bi­pyridine instead of 2,2'-bi­imidazole.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bound to C, N and O atoms were were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C); N—H = 0.96 Å and U_iso(H) = 1.2U_eq(N), and O—H = 0.82 Å and U_iso(O) = 1.5U_eq(C). The H atoms of water molecules were located in difference Fourier maps and placed in calculated positions so as to form a reasonable hydrogen-bond network, as far as possible. Initially, their positions were refined with tight restraints on the O—H and H···H distance [0.82 (1) and 1.35 (1) Å, respectively] in order to ensure a reasonable geometry. They were then constrained to ride on their parent O atoms. with U_iso(H) = 1.5U_eq(C).

S3. Results and discussion

In both title compunds, (I) and (II), proton transfer has occurred. However, the differences between the structures are significant so the discussion considers each structure individually. Compound (I) crystallizes in the space group P\-1. Its asymmetric unit consists of two halves of the 2,2'-bi­imidazole­diium dication protonated at imidazole ring N atom and two halves of the benzene-1,2,4,5-tetra­carboxyl­icate dianion (PMA^2-) with two of the carb­oxy­lic acid groups deprotonated (Fig. 1). In (I), the two PMA^2- anions lie on crystallographic centres of symmetry at (0, 1/2, 1/2) and (1/2, 1/2, 0), respectively. They are connected by an O1—H1···O7 hydrogen bond (Table 2). The two 2,2'-bi­imidazole-3,3'-diium dications lie on crystallographic centres of symmetry at (1/2, 0, 0) and (0, 1/2, 0), respectively, and are linked by N3—H3A···O3, N4—H4B···O4ⁱⁱ, N1—H1B···O7^iv and N2—H2B···O8ⁱⁱⁱ hydrogen bonds with adjacent PMA^2- dianions (Fig. 1; see Table 2 for symmetry codes and geometric details). The environments of the two indepent 2,2'-bi­imidazole-3,3'-diium cations is similar. In contrast, both indepent PMA^2- anions are different in that only one anion has an intra­molecular O—H···O hydrogen bond (O6ⁱ—H6ⁱ···O8). The bond lengths and angles of the benzene-1,2,4,5-tetra­carboxyl­icate dianion are comparable with values reported previously in guanidinuium pyromellite (Sun et al., 2002a). The benzene rings of the two PMA^2- dianions are planar except for the carboxyl groups. The plane defined by the COO^- groups (C17/O7/O8 and C11/O3/O4) and the least-squares plane of the benzene ring subtend a dihedral angles of 32.2 (1) and 60.6 (1)°, respectively, while the plane defined by the COOH groups (C13/O5/O6 and C7/O1/O2) are oriented at 15.2 (1) and 25.4 (1)°, respectively. The two imidazole rings of the two 2,2'-bi­imidazole-3,3'-diium cations are almost coplanar, the mean deviations from the least-squares plane being 0.0126 (5) and 0.0055 (4) Å, respectively. The dihedral angle of the mean planes of the two 2,2'-bi­imidazole-3,3'-diium cations is 51.7 (1)°. The C—N and C—C bond lengths in the 2,2'-bi­imidazole-3,3'-diium cation are consistent with those usually found (Liu & Zhu, 2010). The dication inter­acts with two neighbouring PMA^2- anions via pairs of asymmetric inter­molecular N—H···O hydrogen bonds forming a primary cyclic R₂²(9) association (Bernstein et al., 1995) (Fig. 2). These aggregate units generate a one-dimensional supra­molecular chain. Adjacent chains are further linked via carboxyl–carboxyl O—H···O hydrogen bonds, resulting in a two-dimensional supra­molecular sheet extending parallel to the (121) plane. Within the sheet, the R₆⁵(34) motif can be discerned (Fig. 2).

The hydrate, (II), crystallize in the space group P1. The asymmetric unit of (II) is comprised of a 4-methyl-2-(4-methyl­pyridin-2-yl)pyridinium cation, a 2,4,5-tri­carb­oxy­benzoate anion and a water molecule (Fig. 3). Only one carboxyl group of the benzene-1,2,3,4-tetra­carb­oxy­lic acid molecule is deprotonated, which is different from that observed in the nonsubstituted 2,2'-bi­pyridine analogue (Mrvos-Sermek et al., 1996). Proton transfer from a carb­oxy­lic acid group of PMA to a ring N atom (N2) of 4,4'-di­methyl-2,2'-bi­pyridine is manifested in an increased inter­nal angle [C10—N2—C6 = 123.4 (2)°] of the pyridine ring, compared with that in unprotonated N1 atom of the pyridine ring [C1—N1—C5 = 116.7 (2)°]. Protonated atom N2 diminishing the steric effect of the lone pair of electrons is responsible for the slightly increased C10—N2—C6 angle (Fig. 3). The two rings of the cation are twisted slightly from away each other, forming a dihedral angle of 7.03 (8)°. The benzene ring of the PMA^- anion and the two pyridine rings (C1–C5/N1 and C6–C10/N2) of the cation are oriented at 6.22 (8) and 10.99 (9)°, respectively. The dihedral angles between the least-squares plane of the benzene ring of PMA^- and the carb­oxy­lic acid groups (COOH) are 13.35 (7) (O1/C21/O2), 31.20 (2) (O7/C20/O8) and 53.04 (9)° (O5/C19/O6). The O3/C22/O4 carboxyl­ate group (COO^-) is twisted by 16.22 (1)° with respect to the benzene ring, which is similar to the value found in a previously reported PMA^- compound (Sun et al., 2002b). The PMA^- anions form a one-dimensional chain along the [100] direction via O6^iv—H6ⁱⁱ···O3^v, O8—H8···O7^iv and O8^iv—H8^iv···O7 hydrogen bonds, enclosing R₂²(8)R₄⁴(30) rings (Fig. 4; see Table 3 for symmetry codes). Such chains are further joined together through water–carboxyl­ate O—H···O hydrogen bonds, viz O1Wⁱ—H1WAⁱ···O5 and O1Wⁱ—H1WBⁱ···O4^vii, to yield a two-dimensional supra­molecular layer extending in the (011) plane, involving R₄⁴(20) and R₆⁶(26) motifs (Fig. 4 and Table 3). The 4-methyl-2-(4-methyl­pyridin-2-yl)pyridinium cations are linked to the PMA^- anions through N2—H2···O3ⁱⁱ hydrogen bonds and lie between the above-mentioned two-dimensional supra­molecular layers (Table 3).

Related literature

For related literature, see: Adams & Ramdas (1978); Batten & Robson (1998a, 1998b); Cao et al. (2002); Cheng et al. (2002); Chu et al. (2001); Hu et al. (2001); Jaber et al. (1997); Juan et al. (2002); Li et al. (2003, 2006); Liu & Zhu (2010); Mrvos-Sermek et al. (1996); Murugavel et al. (2002); Oscar et al. (2008); Pan et al. (2004); Pasdar et al. (2011); Poleti et al. (1988); Qiu et al. (2008); Rochon & Massarweh (2000); Sun et al. (2002a, 2002b); Zhang et al. (2010); Zhong et al. (2011); Zhu et al. (2002).

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 35% probability level. The dashed lines represent O—H···O and N—H···O intra- and intermolecular interactions. H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+1, -y, -z; (v) -x+2, -y+1, -z+1; (vi) -x, -y+2, -z+1.]
	Fig. 2. A view of the two-dimensional hydrogen-bonded network of (I) along the b axis, showing the formation of R2^2(9) and R6^5(34) motifs. The dashed lines represent O—H···O interactions. [Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+1, -y, -z; (iii) -x, -y+1, -z+1; (v) -x+2, -y+1, -z+1; (vii) x, -y+1, z.]
	Fig. 3. The molecular structure of (II), showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level. The dashed lines represent O—H···O intramolecular interactions.
	Fig. 4. The two-dimensional hydrogen-bonded structure of (II), extending parallel to the (102) crystallographic plane, showing the formation of R2^2(8), R4^4(30), R4^4(20) and R6^6(26) motifs. Hydrogen bonds are represented by dotted lines. [Symmetry codes: (i) -x, -y+1, -z+1; (iv) -x+1, -y+1, -z; (v) -x+2, -y+1, -z; (vi) x+1, y, z; (vii) -x, -y+2, -z+1; (viii) x, y+1, z; (ix) -x+1, -y+2, -z+1; (x) -x+1, -y+1, -z+1.]

(I) 2-(Imidazol-1-ium-2-yl)imidazol-1-ium 2,5-dicarboxybenzene-1,4-dicarboxylate

Crystal data

C6H8N4^2+·C10H4O8^2^−	Z = 2
Mr = 388.30	F(000) = 400
Triclinic, P1	Dx = 1.614 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2246 (16) Å	Cell parameters from 3731 reflections
b = 8.7495 (17) Å	θ = 3.3–27.5°
c = 11.454 (2) Å	µ = 0.13 mm^−1
α = 100.67 (3)°	T = 223 K
β = 97.26 (3)°	Block, colourless
γ = 94.68 (3)°	0.40 × 0.27 × 0.20 mm
V = 798.8 (3) Å^3

Data collection

Rigaku Mercury CCD diffractometer	3595 independent reflections
Radiation source: fine-focus sealed tube	2808 reflections with I > σ(I)
Graphite Monochromator monochromator	Rint = 0.032
Detector resolution: 28.5714 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −10→10
Absorption correction: multi-scan (REQAB: Jacobson, 1998)	k = −11→9
Tmin = 0.720, Tmax = 1.000	l = −13→14
7722 measured 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)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.122	w = 1/[σ^2(Fo^2) + (0.072P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
3595 reflections	Δρmax = 0.35 e Å^−3
254 parameters	Δρmin = −0.57 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.074 (7)

Special details

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

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
O1	0.62669 (16)	0.47277 (17)	0.63757 (13)	0.0491 (4)
H1	0.5411	0.4294	0.6516	0.074*
O2	0.62998 (16)	0.24608 (15)	0.51284 (12)	0.0423 (4)
O3	0.65637 (14)	0.31690 (14)	0.27534 (11)	0.0352 (3)
O4	0.83769 (16)	0.14191 (15)	0.27634 (12)	0.0417 (3)
O5	0.82217 (15)	0.24782 (15)	0.95079 (12)	0.0384 (3)
O6	0.94434 (13)	0.42861 (15)	1.10085 (10)	0.0320 (3)
H6	0.9227	0.5087	1.1430	0.048*
O7	0.35869 (14)	0.30795 (14)	0.68918 (10)	0.0321 (3)
O8	0.13262 (13)	0.33080 (14)	0.77385 (10)	0.0312 (3)
N1	0.20074 (17)	1.10573 (16)	0.48835 (13)	0.0305 (3)
H1B	0.2289	1.1748	0.5533	0.037*
N2	0.06550 (17)	0.91666 (16)	0.35546 (12)	0.0285 (3)
H2B	−0.0088	0.8421	0.3198	0.034*
N3	0.43654 (16)	0.15350 (16)	0.11289 (12)	0.0272 (3)
H3A	0.5170	0.1808	0.1708	0.033*
N4	0.28846 (16)	0.03652 (16)	−0.05601 (12)	0.0268 (3)
H4B	0.2594	−0.0243	−0.1250	0.032*
C1	0.2026 (2)	0.9631 (2)	0.31045 (16)	0.0350 (4)
H1A	0.2319	0.9213	0.2363	0.042*
C2	0.2880 (2)	1.0814 (2)	0.39394 (16)	0.0373 (4)
H2A	0.3876	1.1361	0.3882	0.045*
C3	0.0645 (2)	1.00457 (18)	0.46313 (14)	0.0255 (4)
C4	0.2873 (2)	0.2127 (2)	0.10564 (16)	0.0308 (4)
H4A	0.2552	0.2900	0.1629	0.037*
C5	0.1944 (2)	0.1398 (2)	0.00105 (16)	0.0307 (4)
H5A	0.0874	0.1567	−0.0266	0.037*
C6	0.43411 (18)	0.04627 (18)	0.01405 (13)	0.0232 (3)
C7	0.68894 (19)	0.3774 (2)	0.55609 (14)	0.0274 (4)
C8	0.84615 (18)	0.44614 (18)	0.52423 (13)	0.0229 (3)
C9	0.89777 (18)	0.38360 (18)	0.41569 (13)	0.0226 (3)
C11	0.78931 (19)	0.26791 (19)	0.31646 (13)	0.0247 (4)
C12	1.05207 (18)	0.43707 (18)	0.39288 (14)	0.0242 (3)
H12A	1.0881	0.3944	0.3213	0.029*
C13	0.81518 (19)	0.36793 (19)	1.02148 (14)	0.0250 (4)
C14	0.65816 (18)	0.44640 (18)	1.01819 (13)	0.0208 (3)
C15	0.54537 (18)	0.38997 (18)	0.91379 (13)	0.0216 (3)
H15A	0.5764	0.3147	0.8546	0.026*
C16	0.39022 (18)	0.43945 (17)	0.89325 (13)	0.0202 (3)
C17	0.28687 (18)	0.35632 (18)	0.77638 (13)	0.0225 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0338 (7)	0.0558 (9)	0.0483 (8)	−0.0146 (6)	0.0210 (6)	−0.0158 (7)
O2	0.0370 (7)	0.0389 (8)	0.0459 (8)	−0.0106 (6)	0.0112 (6)	−0.0017 (6)
O3	0.0285 (6)	0.0337 (7)	0.0356 (7)	0.0065 (5)	−0.0115 (5)	−0.0039 (5)
O4	0.0375 (7)	0.0345 (7)	0.0419 (7)	0.0114 (6)	−0.0127 (6)	−0.0119 (6)
O5	0.0313 (7)	0.0376 (7)	0.0391 (7)	0.0124 (6)	−0.0024 (5)	−0.0098 (6)
O6	0.0236 (6)	0.0388 (7)	0.0281 (6)	0.0067 (5)	−0.0024 (5)	−0.0047 (5)
O7	0.0273 (6)	0.0420 (7)	0.0203 (6)	−0.0038 (5)	0.0038 (5)	−0.0078 (5)
O8	0.0209 (6)	0.0371 (7)	0.0287 (6)	−0.0036 (5)	0.0007 (5)	−0.0063 (5)
N1	0.0320 (8)	0.0297 (8)	0.0237 (7)	−0.0047 (6)	−0.0012 (6)	−0.0032 (6)
N2	0.0273 (7)	0.0273 (7)	0.0247 (7)	−0.0008 (6)	−0.0036 (6)	−0.0045 (6)
N3	0.0251 (7)	0.0318 (7)	0.0210 (6)	−0.0005 (6)	0.0003 (5)	−0.0005 (6)
N4	0.0218 (7)	0.0282 (7)	0.0264 (7)	0.0013 (6)	−0.0037 (5)	0.0005 (6)
C1	0.0330 (9)	0.0418 (10)	0.0257 (8)	0.0001 (8)	0.0026 (7)	−0.0019 (8)
C2	0.0349 (10)	0.0407 (10)	0.0313 (9)	−0.0055 (8)	0.0042 (8)	−0.0013 (8)
C3	0.0275 (8)	0.0230 (8)	0.0227 (7)	0.0004 (6)	−0.0034 (6)	0.0015 (6)
C4	0.0287 (9)	0.0331 (9)	0.0303 (9)	0.0051 (7)	0.0079 (7)	0.0019 (7)
C5	0.0230 (8)	0.0332 (9)	0.0361 (9)	0.0052 (7)	0.0024 (7)	0.0074 (7)
C6	0.0220 (8)	0.0227 (8)	0.0227 (7)	−0.0015 (6)	0.0003 (6)	0.0025 (6)
C7	0.0222 (8)	0.0361 (9)	0.0211 (7)	−0.0015 (7)	0.0000 (6)	0.0029 (7)
C8	0.0197 (7)	0.0270 (8)	0.0208 (7)	0.0025 (6)	0.0006 (6)	0.0029 (6)
C9	0.0210 (8)	0.0237 (8)	0.0209 (7)	0.0014 (6)	−0.0012 (6)	0.0024 (6)
C11	0.0233 (8)	0.0268 (9)	0.0211 (7)	−0.0007 (7)	0.0009 (6)	0.0007 (6)
C12	0.0232 (8)	0.0282 (8)	0.0192 (7)	0.0022 (7)	0.0023 (6)	0.0002 (6)
C13	0.0241 (8)	0.0289 (9)	0.0216 (7)	0.0031 (7)	0.0030 (6)	0.0035 (7)
C14	0.0199 (7)	0.0225 (7)	0.0194 (7)	−0.0002 (6)	0.0035 (6)	0.0034 (6)
C15	0.0223 (8)	0.0225 (8)	0.0182 (7)	0.0005 (6)	0.0041 (6)	−0.0002 (6)
C16	0.0213 (7)	0.0203 (7)	0.0174 (7)	−0.0022 (6)	0.0028 (6)	0.0012 (6)
C17	0.0220 (8)	0.0241 (8)	0.0194 (7)	−0.0002 (6)	0.0014 (6)	0.0011 (6)

Geometric parameters (Å, º)

O1—C7	1.316 (2)	C1—C2	1.351 (2)
O1—H1	0.8200	C1—H1A	0.9300
O2—C7	1.199 (2)	C2—H2A	0.9300
O3—C11	1.274 (2)	C3—C3^i	1.443 (3)
O4—C11	1.231 (2)	C4—C5	1.354 (2)
O5—C13	1.212 (2)	C4—H4A	0.9300
O6—C13	1.312 (2)	C5—H5A	0.9300
O6—H6	0.8200	C6—C6^ii	1.438 (3)
O7—C17	1.2485 (18)	C7—C8	1.497 (2)
O8—C17	1.2658 (18)	C8—C9	1.394 (2)
N1—C3	1.336 (2)	C8—C12^iii	1.395 (2)
N1—C2	1.366 (2)	C9—C12	1.389 (2)
N1—H1B	0.8600	C9—C11	1.511 (2)
N2—C3	1.329 (2)	C12—C8^iii	1.395 (2)
N2—C1	1.361 (2)	C12—H12A	0.9300
N2—H2B	0.8600	C13—C14	1.511 (2)
N3—C6	1.327 (2)	C14—C15	1.400 (2)
N3—C4	1.370 (2)	C14—C16^iv	1.406 (2)
N3—H3A	0.8600	C15—C16	1.387 (2)
N4—C6	1.342 (2)	C15—H15A	0.9300
N4—C5	1.366 (2)	C16—C14^iv	1.406 (2)
N4—H4B	0.8600	C16—C17	1.515 (2)
C7—O1—H1	109.5	N4—C6—C6^ii	124.99 (17)
C13—O6—H6	109.5	O2—C7—O1	124.22 (15)
C3—N1—C2	108.77 (14)	O2—C7—C8	122.18 (16)
C3—N1—H1B	125.6	O1—C7—C8	113.57 (14)
C2—N1—H1B	125.6	C9—C8—C12^iii	119.91 (13)
C3—N2—C1	109.35 (14)	C9—C8—C7	119.72 (14)
C3—N2—H2B	125.3	C12^iii—C8—C7	120.13 (14)
C1—N2—H2B	125.3	C12—C9—C8	119.12 (14)
C6—N3—C4	107.37 (14)	C12—C9—C11	117.45 (13)
C6—N3—H3A	126.3	C8—C9—C11	123.28 (13)
C4—N3—H3A	126.3	O4—C11—O3	125.17 (15)
C6—N4—C5	108.23 (14)	O4—C11—C9	119.76 (14)
C6—N4—H4B	125.9	O3—C11—C9	114.88 (14)
C5—N4—H4B	125.9	C9—C12—C8^iii	120.96 (14)
C2—C1—N2	107.01 (16)	C9—C12—H12A	119.5
C2—C1—H1A	126.5	C8^iii—C12—H12A	119.5
N2—C1—H1A	126.5	O5—C13—O6	119.60 (15)
C1—C2—N1	107.15 (15)	O5—C13—C14	119.99 (14)
C1—C2—H2A	126.4	O6—C13—C14	120.41 (14)
N1—C2—H2A	126.4	C15—C14—C16^iv	117.36 (14)
N2—C3—N1	107.72 (14)	C15—C14—C13	113.78 (13)
N2—C3—C3^i	125.75 (18)	C16^iv—C14—C13	128.79 (14)
N1—C3—C3^i	126.50 (18)	C16—C15—C14	124.03 (14)
C5—C4—N3	108.43 (15)	C16—C15—H15A	118.0
C5—C4—H4A	125.8	C14—C15—H15A	118.0
N3—C4—H4A	125.8	C15—C16—C14^iv	118.61 (14)
C4—C5—N4	106.62 (15)	C15—C16—C17	114.57 (13)
C4—C5—H5A	126.7	C14^iv—C16—C17	126.77 (14)
N4—C5—H5A	126.7	O7—C17—O8	122.99 (14)
N3—C6—N4	109.35 (14)	O7—C17—C16	118.47 (13)
N3—C6—C6^ii	125.66 (18)	O8—C17—C16	118.39 (13)
C3—N2—C1—C2	0.7 (2)	C12^iii—C8—C9—C11	−174.20 (15)
N2—C1—C2—N1	−0.4 (2)	C7—C8—C9—C11	11.4 (2)
C3—N1—C2—C1	−0.1 (2)	C12—C9—C11—O4	59.3 (2)
C1—N2—C3—N1	−0.79 (19)	C8—C9—C11—O4	−125.24 (18)
C1—N2—C3—C3^i	177.1 (2)	C12—C9—C11—O3	−115.92 (17)
C2—N1—C3—N2	0.6 (2)	C8—C9—C11—O3	59.6 (2)
C2—N1—C3—C3^i	−177.3 (2)	C8—C9—C12—C8^iii	−1.2 (3)
C6—N3—C4—C5	0.05 (18)	C11—C9—C12—C8^iii	174.46 (15)
N3—C4—C5—N4	−0.51 (18)	O5—C13—C14—C15	−14.0 (2)
C6—N4—C5—C4	0.79 (18)	O6—C13—C14—C15	166.32 (13)
C4—N3—C6—N4	0.45 (17)	O5—C13—C14—C16^iv	162.91 (15)
C4—N3—C6—C6^ii	−179.20 (19)	O6—C13—C14—C16^iv	−16.8 (2)
C5—N4—C6—N3	−0.78 (17)	C16^iv—C14—C15—C16	−0.2 (2)
C5—N4—C6—C6^ii	178.87 (19)	C13—C14—C15—C16	177.05 (14)
O2—C7—C8—C9	22.7 (3)	C14—C15—C16—C14^iv	0.2 (2)
O1—C7—C8—C9	−159.27 (16)	C14—C15—C16—C17	−177.27 (13)
O2—C7—C8—C12^iii	−151.64 (17)	C15—C16—C17—O7	−30.5 (2)
O1—C7—C8—C12^iii	26.4 (2)	C14^iv—C16—C17—O7	152.22 (15)
C12^iii—C8—C9—C12	1.2 (3)	C15—C16—C17—O8	145.24 (15)
C7—C8—C9—C12	−173.14 (15)	C14^iv—C16—C17—O8	−32.0 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O8^iv	0.82	1.67	2.4939 (18)	177
O1—H1···O7	0.82	1.91	2.7228 (18)	173
N3—H3A···O3	0.86	1.75	2.553 (2)	154
N4—H4B···O4^ii	0.86	1.89	2.738 (2)	170
N2—H2B···O8^v	0.86	1.83	2.676 (2)	168
N1—H1B···O7^vi	0.86	1.90	2.733 (2)	162

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

(II) 4-Methyl-2-(4-methylpyridin-2-yl)pyridinium 2,4,5-tricarboxybenzoate monohydrate

Crystal data

C12H13N2^+·C10H5O8^−·H2O	Z = 2
Mr = 456.40	F(000) = 476
Triclinic, P1	Dx = 1.514 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5166 (7) Å	Cell parameters from 2637 reflections
b = 9.9970 (8) Å	θ = 3.5–29.2°
c = 12.4106 (8) Å	µ = 0.12 mm^−1
α = 77.979 (6)°	T = 223 K
β = 73.421 (6)°	Block, colourless
γ = 62.655 (8)°	0.30 × 0.22 × 0.10 mm
V = 1001.03 (13) Å^3

Data collection

Rigaku Mercury CCD diffractometer	3516 independent reflections
Radiation source: fine-focus sealed tube	2681 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.041
Detector resolution: 28.5714 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ω scans	h = −11→11
Absorption correction: multi-scan (REQAB: Jacobson, 1998)	k = −11→11
Tmin = 0.997, Tmax = 1.000	l = −14→14
9371 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0474P)^2 + 0.9963P] where P = (Fo^2 + 2Fc^2)/3
3516 reflections	(Δ/σ)max < 0.001
304 parameters	Δρmax = 0.39 e Å^−3
3 restraints	Δρmin = −0.40 e Å^−3

Special details

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

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
O1	0.8114 (2)	0.8651 (2)	0.10369 (15)	0.0220 (4)
O1W	0.2492 (3)	0.2056 (3)	0.59885 (18)	0.0538 (7)
H1WA	0.181 (3)	0.182 (4)	0.6447 (18)	0.065*
H1WB	0.239 (4)	0.211 (5)	0.5345 (9)	0.065*
O2	0.6903 (2)	1.0820 (2)	0.17697 (16)	0.0279 (5)
H2	0.5980	1.1416	0.2037	0.042*
O3	0.4308 (2)	1.2318 (2)	0.28801 (16)	0.0265 (5)
O4	0.2056 (2)	1.2092 (2)	0.37778 (15)	0.0257 (5)
O5	0.0197 (2)	0.8706 (2)	0.28052 (15)	0.0262 (5)
O6	0.0740 (2)	0.8953 (2)	0.09100 (14)	0.0203 (4)
H6	−0.0092	0.8848	0.0999	0.030*
O7	0.3591 (2)	0.60899 (19)	0.10235 (15)	0.0206 (4)
O8	0.5562 (2)	0.6521 (2)	−0.02698 (15)	0.0246 (5)
H8	0.5667	0.5778	−0.0525	0.037*
N1	0.6780 (3)	0.3858 (2)	0.20738 (17)	0.0204 (5)
N2	0.3984 (2)	0.4962 (2)	0.35502 (17)	0.0183 (5)
H2B	0.4307	0.4206	0.3172	0.022*
C1	0.8219 (3)	0.3208 (3)	0.1372 (2)	0.0243 (6)
H1A	0.8372	0.2467	0.0950	0.029*
C2	0.9488 (3)	0.3587 (3)	0.1244 (2)	0.0232 (6)
H2A	1.0465	0.3104	0.0744	0.028*
C3	0.9308 (3)	0.4685 (3)	0.1860 (2)	0.0207 (6)
C4	0.7813 (3)	0.5371 (3)	0.2584 (2)	0.0188 (6)
H4A	0.7627	0.6122	0.3011	0.023*
C5	0.6601 (3)	0.4928 (3)	0.2665 (2)	0.0170 (6)
C6	0.5001 (3)	0.5601 (3)	0.3440 (2)	0.0171 (5)
C7	0.4475 (3)	0.6811 (3)	0.4059 (2)	0.0191 (6)
H7A	0.5156	0.7266	0.4003	0.023*
C8	0.2937 (3)	0.7353 (3)	0.4764 (2)	0.0213 (6)
C9	0.1945 (3)	0.6648 (3)	0.4831 (2)	0.0232 (6)
H9A	0.0910	0.6993	0.5291	0.028*
C10	0.2502 (3)	0.5444 (3)	0.4216 (2)	0.0225 (6)
H10A	0.1848	0.4963	0.4263	0.027*
C11	0.2372 (4)	0.8670 (3)	0.5426 (2)	0.0325 (7)
H11A	0.1293	0.8893	0.5864	0.049*
H11B	0.2375	0.9536	0.4917	0.049*
H11C	0.3087	0.8425	0.5921	0.049*
C12	1.0654 (3)	0.5124 (3)	0.1764 (2)	0.0278 (7)
H12A	1.1590	0.4539	0.1230	0.042*
H12B	1.0921	0.4933	0.2488	0.042*
H12C	1.0311	0.6180	0.1515	0.042*
C13	0.2554 (3)	0.9052 (3)	0.1798 (2)	0.0150 (5)
C14	0.4064 (3)	0.8186 (3)	0.1140 (2)	0.0144 (5)
C15	0.5373 (3)	0.8476 (3)	0.10869 (19)	0.0143 (5)
H15A	0.6373	0.7901	0.0648	0.017*
C16	0.5258 (3)	0.9592 (3)	0.1662 (2)	0.0142 (5)
C17	0.3742 (3)	1.0455 (3)	0.2337 (2)	0.0158 (5)
C18	0.2436 (3)	1.0146 (3)	0.2380 (2)	0.0160 (5)
H18A	0.1435	1.0708	0.2824	0.019*
C19	0.1040 (3)	0.8861 (3)	0.1895 (2)	0.0160 (5)
C20	0.4367 (3)	0.6847 (3)	0.0611 (2)	0.0152 (5)
C21	0.6861 (3)	0.9682 (3)	0.1483 (2)	0.0167 (6)
C22	0.3332 (3)	1.1702 (3)	0.3060 (2)	0.0177 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0129 (9)	0.0237 (10)	0.0311 (11)	−0.0078 (8)	−0.0013 (8)	−0.0110 (8)
O1W	0.0750 (18)	0.090 (2)	0.0300 (12)	−0.0689 (17)	0.0080 (13)	−0.0186 (14)
O2	0.0159 (9)	0.0246 (11)	0.0477 (12)	−0.0107 (9)	0.0012 (9)	−0.0188 (9)
O3	0.0236 (10)	0.0261 (10)	0.0360 (11)	−0.0155 (9)	0.0012 (9)	−0.0148 (9)
O4	0.0236 (10)	0.0294 (11)	0.0246 (10)	−0.0130 (9)	0.0052 (8)	−0.0143 (8)
O5	0.0220 (10)	0.0417 (12)	0.0200 (10)	−0.0207 (10)	0.0011 (8)	−0.0040 (9)
O6	0.0133 (9)	0.0315 (11)	0.0221 (10)	−0.0136 (8)	−0.0034 (7)	−0.0052 (8)
O7	0.0180 (9)	0.0198 (10)	0.0267 (10)	−0.0110 (8)	0.0007 (8)	−0.0083 (8)
O8	0.0249 (10)	0.0276 (11)	0.0256 (10)	−0.0169 (9)	0.0064 (8)	−0.0142 (8)
N1	0.0201 (12)	0.0203 (12)	0.0211 (12)	−0.0098 (10)	−0.0004 (10)	−0.0053 (9)
N2	0.0186 (11)	0.0181 (11)	0.0191 (11)	−0.0074 (10)	−0.0033 (9)	−0.0055 (9)
C1	0.0246 (15)	0.0211 (14)	0.0247 (15)	−0.0086 (13)	0.0004 (12)	−0.0080 (12)
C2	0.0195 (14)	0.0217 (15)	0.0212 (14)	−0.0054 (12)	0.0015 (11)	−0.0042 (11)
C3	0.0182 (13)	0.0216 (14)	0.0202 (14)	−0.0087 (12)	−0.0047 (11)	0.0033 (11)
C4	0.0202 (13)	0.0180 (14)	0.0194 (13)	−0.0080 (12)	−0.0069 (11)	−0.0006 (11)
C5	0.0189 (13)	0.0145 (13)	0.0162 (13)	−0.0069 (11)	−0.0032 (10)	0.0001 (10)
C6	0.0209 (13)	0.0170 (13)	0.0154 (12)	−0.0092 (12)	−0.0064 (11)	0.0003 (10)
C7	0.0210 (13)	0.0176 (13)	0.0196 (13)	−0.0100 (12)	−0.0036 (11)	−0.0004 (11)
C8	0.0265 (14)	0.0163 (14)	0.0169 (13)	−0.0062 (12)	−0.0046 (11)	−0.0001 (11)
C9	0.0159 (13)	0.0262 (15)	0.0193 (14)	−0.0046 (12)	0.0006 (11)	−0.0020 (12)
C10	0.0184 (14)	0.0281 (15)	0.0221 (14)	−0.0124 (13)	−0.0011 (11)	−0.0026 (12)
C11	0.0351 (17)	0.0279 (16)	0.0278 (16)	−0.0099 (14)	0.0026 (13)	−0.0108 (13)
C12	0.0211 (14)	0.0308 (16)	0.0317 (16)	−0.0123 (13)	−0.0043 (12)	−0.0027 (13)
C13	0.0143 (12)	0.0171 (13)	0.0154 (12)	−0.0076 (11)	−0.0051 (10)	−0.0001 (10)
C14	0.0146 (12)	0.0142 (13)	0.0145 (12)	−0.0064 (11)	−0.0036 (10)	−0.0004 (10)
C15	0.0114 (12)	0.0153 (13)	0.0140 (12)	−0.0041 (11)	−0.0015 (10)	−0.0020 (10)
C16	0.0134 (12)	0.0141 (13)	0.0164 (13)	−0.0063 (11)	−0.0043 (10)	−0.0011 (10)
C17	0.0177 (13)	0.0159 (13)	0.0151 (12)	−0.0078 (11)	−0.0056 (10)	0.0000 (10)
C18	0.0120 (12)	0.0171 (13)	0.0179 (13)	−0.0051 (11)	−0.0020 (10)	−0.0041 (10)
C19	0.0145 (12)	0.0132 (13)	0.0201 (14)	−0.0044 (11)	−0.0031 (11)	−0.0056 (10)
C20	0.0112 (12)	0.0173 (13)	0.0177 (13)	−0.0048 (11)	−0.0049 (10)	−0.0036 (10)
C21	0.0162 (13)	0.0196 (14)	0.0162 (13)	−0.0086 (12)	−0.0041 (11)	−0.0025 (11)
C22	0.0184 (13)	0.0163 (13)	0.0200 (13)	−0.0073 (12)	−0.0066 (11)	−0.0019 (11)

Geometric parameters (Å, º)

O1—C21	1.234 (3)	C6—C7	1.383 (4)
O1W—H1WA	0.8201 (10)	C7—C8	1.393 (4)
O1W—H1WB	0.8201 (10)	C7—H7A	0.9300
O2—C21	1.281 (3)	C8—C9	1.391 (4)
O2—H2	0.8200	C8—C11	1.499 (4)
O3—C22	1.281 (3)	C9—C10	1.371 (4)
O4—C22	1.230 (3)	C9—H9A	0.9300
O5—C19	1.212 (3)	C10—H10A	0.9300
O6—C19	1.308 (3)	C11—H11A	0.9600
O6—H6	0.8200	C11—H11B	0.9600
O7—C20	1.231 (3)	C11—H11C	0.9600
O8—C20	1.301 (3)	C12—H12A	0.9600
O8—H8	0.8200	C12—H12B	0.9600
N1—C1	1.339 (3)	C12—H12C	0.9600
N1—C5	1.342 (3)	C13—C18	1.379 (3)
N2—C10	1.334 (3)	C13—C14	1.401 (3)
N2—C6	1.348 (3)	C13—C19	1.507 (3)
N2—H2B	0.8600	C14—C15	1.385 (3)
C1—C2	1.383 (4)	C14—C20	1.487 (3)
C1—H1A	0.9300	C15—C16	1.393 (3)
C2—C3	1.386 (4)	C15—H15A	0.9300
C2—H2A	0.9300	C16—C17	1.413 (3)
C3—C4	1.390 (4)	C16—C21	1.519 (3)
C3—C12	1.502 (4)	C17—C18	1.397 (3)
C4—C5	1.386 (3)	C17—C22	1.527 (3)
C4—H4A	0.9300	C18—H18A	0.9300
C5—C6	1.479 (3)
H1WA—O1W—H1WB	110.2 (12)	H11A—C11—H11B	109.5
C21—O2—H2	109.5	C8—C11—H11C	109.5
C19—O6—H6	109.5	H11A—C11—H11C	109.5
C20—O8—H8	109.5	H11B—C11—H11C	109.5
C1—N1—C5	116.7 (2)	C3—C12—H12A	109.5
C10—N2—C6	123.4 (2)	C3—C12—H12B	109.5
C10—N2—H2B	118.3	H12A—C12—H12B	109.5
C6—N2—H2B	118.3	C3—C12—H12C	109.5
N1—C1—C2	123.2 (2)	H12A—C12—H12C	109.5
N1—C1—H1A	118.4	H12B—C12—H12C	109.5
C2—C1—H1A	118.4	C18—C13—C14	118.6 (2)
C1—C2—C3	120.1 (2)	C18—C13—C19	118.0 (2)
C1—C2—H2A	120.0	C14—C13—C19	123.3 (2)
C3—C2—H2A	120.0	C15—C14—C13	118.8 (2)
C2—C3—C4	116.9 (2)	C15—C14—C20	118.2 (2)
C2—C3—C12	122.2 (2)	C13—C14—C20	122.6 (2)
C4—C3—C12	120.8 (2)	C14—C15—C16	122.9 (2)
C5—C4—C3	119.5 (2)	C14—C15—H15A	118.6
C5—C4—H4A	120.3	C16—C15—H15A	118.6
C3—C4—H4A	120.3	C15—C16—C17	118.5 (2)
N1—C5—C4	123.5 (2)	C15—C16—C21	113.1 (2)
N1—C5—C6	114.9 (2)	C17—C16—C21	128.4 (2)
C4—C5—C6	121.6 (2)	C18—C17—C16	117.8 (2)
N2—C6—C7	117.9 (2)	C18—C17—C22	114.3 (2)
N2—C6—C5	116.5 (2)	C16—C17—C22	127.9 (2)
C7—C6—C5	125.6 (2)	C13—C18—C17	123.4 (2)
C6—C7—C8	120.7 (2)	C13—C18—H18A	118.3
C6—C7—H7A	119.7	C17—C18—H18A	118.3
C8—C7—H7A	119.7	O5—C19—O6	126.0 (2)
C9—C8—C7	118.4 (2)	O5—C19—C13	121.4 (2)
C9—C8—C11	121.2 (2)	O6—C19—C13	112.5 (2)
C7—C8—C11	120.4 (2)	O7—C20—O8	124.4 (2)
C10—C9—C8	119.7 (2)	O7—C20—C14	121.6 (2)
C10—C9—H9A	120.2	O8—C20—C14	114.0 (2)
C8—C9—H9A	120.2	O1—C21—O2	120.8 (2)
N2—C10—C9	119.9 (2)	O1—C21—C16	118.6 (2)
N2—C10—H10A	120.0	O2—C21—C16	120.5 (2)
C9—C10—H10A	120.0	O4—C22—O3	122.9 (2)
C8—C11—H11A	109.5	O4—C22—C17	118.2 (2)
C8—C11—H11B	109.5	O3—C22—C17	118.9 (2)
C5—N1—C1—C2	0.3 (4)	C13—C14—C15—C16	0.2 (4)
N1—C1—C2—C3	0.1 (4)	C20—C14—C15—C16	−172.5 (2)
C1—C2—C3—C4	−0.6 (4)	C14—C15—C16—C17	0.6 (4)
C1—C2—C3—C12	179.2 (2)	C14—C15—C16—C21	179.3 (2)
C2—C3—C4—C5	0.6 (4)	C15—C16—C17—C18	−0.6 (4)
C12—C3—C4—C5	−179.2 (2)	C21—C16—C17—C18	−179.1 (2)
C1—N1—C5—C4	−0.3 (4)	C15—C16—C17—C22	178.5 (2)
C1—N1—C5—C6	−179.3 (2)	C21—C16—C17—C22	0.0 (4)
C3—C4—C5—N1	−0.2 (4)	C14—C13—C18—C17	0.9 (4)
C3—C4—C5—C6	178.7 (2)	C19—C13—C18—C17	−178.5 (2)
C10—N2—C6—C7	0.5 (4)	C16—C17—C18—C13	−0.1 (4)
C10—N2—C6—C5	−180.0 (2)	C22—C17—C18—C13	−179.3 (2)
N1—C5—C6—N2	6.7 (3)	C18—C13—C19—O5	−51.5 (3)
C4—C5—C6—N2	−172.3 (2)	C14—C13—C19—O5	129.2 (3)
N1—C5—C6—C7	−173.8 (2)	C18—C13—C19—O6	125.7 (2)
C4—C5—C6—C7	7.2 (4)	C14—C13—C19—O6	−53.7 (3)
N2—C6—C7—C8	−0.5 (4)	C15—C14—C20—O7	144.7 (2)
C5—C6—C7—C8	180.0 (2)	C13—C14—C20—O7	−27.6 (4)
C6—C7—C8—C9	0.1 (4)	C15—C14—C20—O8	−31.7 (3)
C6—C7—C8—C11	−179.6 (2)	C13—C14—C20—O8	156.0 (2)
C7—C8—C9—C10	0.5 (4)	C15—C16—C21—O1	−12.1 (3)
C11—C8—C9—C10	−179.8 (3)	C17—C16—C21—O1	166.4 (2)
C6—N2—C10—C9	0.1 (4)	C15—C16—C21—O2	166.5 (2)
C8—C9—C10—N2	−0.6 (4)	C17—C16—C21—O2	−14.9 (4)
C18—C13—C14—C15	−0.9 (4)	C18—C17—C22—O4	15.0 (3)
C19—C13—C14—C15	178.4 (2)	C16—C17—C22—O4	−164.1 (3)
C18—C13—C14—C20	171.4 (2)	C18—C17—C22—O3	−163.5 (2)
C19—C13—C14—C20	−9.3 (4)	C16—C17—C22—O3	17.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O5^i	0.82 (1)	2.12 (1)	2.916 (3)	163 (3)
O1W—H1WB···O4^ii	0.82 (1)	2.06 (1)	2.880 (3)	175 (3)
N2—H2B···O3^ii	0.86	1.99	2.792 (3)	154
O6—H6···O1^iii	0.82	1.79	2.609 (2)	174
O8—H8···O7^iv	0.82	1.84	2.644 (2)	166

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