Hydrogen bonding and π–π inter­actions in a laminar structure: benzene-1,3-dicarboxylic acid–4-methyl­pyridine (1/2)

The title complex, C₈H₆O₄·2C₆H₇N, consists of two crystallographically independent 1:2 clusters of benzene-1,3-­dicarboxylic acid and 4-methyl­pyridine. Each cluster, the components of which are linked by O—H...N hydrogen bonds, is almost planar by alignment of C—H...O hydrogen bonds. Herring-bone ribbons of clusters are formed by other C—H...O hydrogen bonds, and these ribbons are further packed to form a laminar structure by π–π inter­actions.

S1. Comment

Supramolecular aggregate design is an active field (Zaworotko, 2001; Bis & Zaworotko, 2005; Shattock et al., 2005; Turkington et al., 2005). Some cases have been reported using 1,3-benzenedicarboxylic acid (BDA) as a building block (Bielawski et al., 1998; Shan et al., 2002; Trivedi et al., 2003; Dale et al., 2004) to build supramolecular architectures. We have recently synthesized the title complex, (I), and describe here the cooperation of O—H···N and C—H···O hydrogen bonds and π–π interactions in forming the novel laminar structure.

There are two crystallographically independent 1:2 clusters of 1,3-benzenedicarboxylic acid (BDA) and 4-methylpyridine (MP) in the asymmetric unit (Fig. 1); one cluster is labelled A for the three molecules with atoms O1, N1 and N2 and the other is labelled B for the three molecules with atoms O5, N3 and N4.

The A cluster is built up by two nearly linear O2—H2···N1 and O4—H4···N2 hydrogen bonds (Table 1). The dihedral angles between the aromatic ring and the carboxyl groups of the BDA molecule are 3.0 (3) and 2.4 (4)° for the carboxyl groups with atoms O1 and O3, repectively. This conformation differs from those observed in a nickel 1,3-benzenedicarboxylate and a cobalt 1,3-benzenedicarboxylate (Bourne et al., 2001), where the phenyl rings are skewed at large angles with respect to the carboxylate groups. The carboxylic acid groups are almost coplanar with the MP rings, allowing weak C17—H17···O1 and C23—H23···O3 hydrogen bonds (Steiner & Desiraju, 1998). Furthermore, there are short C1—H1···O2, C1—H1···O4, C3—H3···O1 and C5—H5···O3 contacts, with H···O distances in the range 2.44–2.50 Å. The coplanar arrangment is different from the situation in a BDA–pyridine (1:1) complex (Dale et al., 2004), where the dihedral angle between the carboxylic acid group and the pyridine is large [28.6 (2)°] and allows no similar C—H···O hydrogen bonds. However, the coplanar arrangment in (I) resembles the situations observed in other BDA complexes, namely BDA and a pyridylamine derivative (Bielawski et al., 1998), and BDA:benzimidazole (1:1) (Trivedi et al., 2003). In a general view, therefore, the molecules in the A cluster of (I) are almost coplanar with one another, which is indicated by an r.m.s deviation of 0.119 (6) Å for the atoms from the plane of the A cluster.

The BDA molecule in the B cluster is less coplanar than that in the A cluster, as indicated by the two dihedral angles between the aromatic ring and the carboxyl groups of 4.9 (4) and 10.4 (4)° for the carboxyl groups with atoms O5 and O7, repectively. However, similar to what was observed in the A cluster, due to O—H···N and C—H···O hydrogen bonds (Table 1), the molecules in the B cluster are also almost coplanar, as indicated by an r.m.s deviation of 0.105 (7) Å for the atoms from the mean plane of the B cluster.

Viewed along the c axis (Fig. 2), the structure of (I) is characterized by layers of BDA and MP molecules, with a stratum equal to a quarter of the c axis. A ribbon of A-cluster molecules parallel to the (001) plane is formed by C21—H21···O1ⁱ and C27—H27···O3ⁱ hydrogen bonds [symmetry code: (i) x + 1, y, z]. The hydrogen-bonding patterns of this A-cluster ribbon can be described in graph-set terminolgy as C₂¹(6), C₂²(7), R₂²(7), R₄⁴(22) and R₄⁴(24) (Etter, 1990; Grell et al., 2000). Another similar ribbon for the B cluster parallel to the (001) plane is created by the C39—H39···O7ⁱⁱ hydrogen bond [symmetry code: (ii) x − 1, y, z]. [Please check added symmetry codes]

The A– and B-cluster ribbons between neighbouring layers are associated by a number of π–π interactions (Sharma et al., 1993; Pedireddi et al., 1996), the shortest of which has a distance of 3.683 (4) Å between the centroids of the MP molecule with atom N2 in cluster A and the MP molecule with atom N3 in cluster B at (1 + x, y, z); the angle between these two ring planes is 1.2°.

S2. Experimental

BDA (0.01 mol) and MP (0.04 mol) were mixed and heated to a temperature of 353 K, upon which a clear solution resulted. Single crystals of (I) were formed by gradual evaporation of excess MP in the resulting solution for a week at 293 K.

S3. Refinement

H atoms were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.82 (hydroxy), 0.93 (C—H aromatic) and 0.96 Å (methyl), with isotropic displacement parameters 1.2–1.5 times U_eq of their parent atoms. As the compound contains no heavy atoms, Friedel reflections were merged before the final refinement.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The formula unit of (I), with the atom-labelling scheme, showing 35% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are illustrated as dashed lines.
	Fig. 2. A view of the ribbons in (a) the A cluster and (b) the B cluster, extending along the a direction and viewed down the c axis. Intermolecular hydrogen bonds are shown as dashed lines. Atoms labelled with an asterisk (*) or hash (#) are at the symmetry positions (x + 1, y, z) and (x − 1, y, z), respectively.

Benzene-1,3-dicarboxylic acid–4-methylpyridine (1/2)

Crystal data

C8H6O4·2C6H7N	F(000) = 1488.0
Mr = 352.38	Dx = 1.269 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 239 reflections
a = 6.863 (6) Å	θ = 2.8–24.9°
b = 39.81 (3) Å	µ = 0.09 mm^−1
c = 13.527 (11) Å	T = 273 K
β = 93.276 (15)°	Sheet, colourless
V = 3690 (5) Å^3	0.30 × 0.25 × 0.20 mm
Z = 8

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3370 independent reflections
Radiation source: fine-focus sealed tube	2692 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 25.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS, Bruker, 2000)	h = −8→8
Tmin = 0.974, Tmax = 0.982	k = −48→22
9779 measured reflections	l = −16→16

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.173	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0929P)^2 + 1.2415P] where P = (Fo^2 + 2Fc^2)/3
3370 reflections	(Δ/σ)max < 0.001
476 parameters	Δρmax = 0.17 e Å^−3
2 restraints	Δρmin = −0.30 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	0.2147 (6)	0.33835 (9)	0.0019 (4)	0.1012 (14)
O2	0.4830 (5)	0.36691 (8)	−0.0152 (3)	0.0812 (10)
H2O	0.5275	0.3482	−0.0251	0.122*
O3	0.2247 (7)	0.51441 (9)	0.0713 (4)	0.1042 (14)
O4	0.4901 (6)	0.48775 (8)	0.0365 (3)	0.0899 (11)
H4O	0.5363	0.5067	0.0416	0.135*
C1	0.3002 (6)	0.42725 (10)	0.0228 (3)	0.0519 (10)
H1	0.4319	0.4279	0.0100	0.062*
C2	0.2020 (6)	0.39680 (11)	0.0198 (3)	0.0551 (10)
C3	0.0045 (7)	0.39670 (14)	0.0367 (4)	0.0713 (13)
H3	−0.0636	0.3765	0.0351	0.086*
C4	−0.0911 (8)	0.42577 (15)	0.0556 (4)	0.0784 (15)
H4	−0.2239	0.4254	0.0659	0.094*
C5	0.0076 (8)	0.45523 (13)	0.0593 (4)	0.0716 (14)
H5	−0.0585	0.4750	0.0721	0.086*
C6	0.2048 (7)	0.45638 (12)	0.0443 (3)	0.0590 (11)
C7	0.3056 (9)	0.48884 (13)	0.0515 (4)	0.0731 (14)
C8	0.2998 (7)	0.36443 (13)	0.0007 (4)	0.0672 (13)
O5	0.3772 (7)	0.66089 (9)	0.1996 (4)	0.1077 (15)
O6	0.1199 (6)	0.68873 (9)	0.2399 (3)	0.0911 (13)
H6O	0.0748	0.6697	0.2439	0.137*
O7	0.3832 (6)	0.83852 (10)	0.2210 (4)	0.1106 (16)
O8	0.1101 (5)	0.81067 (8)	0.2217 (3)	0.0807 (10)
H8O	0.0666	0.8296	0.2293	0.121*
C9	0.2976 (7)	0.74981 (10)	0.2137 (3)	0.0563 (11)
H9	0.1667	0.7497	0.2281	0.068*
C10	0.3968 (7)	0.72003 (12)	0.2036 (3)	0.0594 (11)
C11	0.5924 (7)	0.72041 (14)	0.1840 (4)	0.0716 (14)
H11	0.6597	0.7003	0.1791	0.086*
C12	0.6866 (8)	0.74981 (14)	0.1718 (4)	0.0778 (15)
H12	0.8174	0.7497	0.1572	0.093*
C13	0.5903 (7)	0.77967 (14)	0.1807 (4)	0.0711 (14)
H13	0.6555	0.7999	0.1725	0.085*
C14	0.3947 (7)	0.77966 (12)	0.2022 (3)	0.0592 (11)
C15	0.2970 (7)	0.81222 (13)	0.2159 (4)	0.0689 (13)
C16	0.2970 (8)	0.68695 (13)	0.2134 (4)	0.0709 (13)
N1	0.6286 (7)	0.30605 (10)	−0.0410 (3)	0.0731 (11)
C17	0.5080 (8)	0.28102 (14)	−0.0314 (4)	0.0767 (14)
H17	0.3792	0.2855	−0.0180	0.092*
C18	0.5683 (10)	0.24759 (14)	−0.0407 (5)	0.0828 (18)
H18	0.4802	0.2301	−0.0339	0.099*
C19	0.7606 (9)	0.24083 (13)	−0.0603 (4)	0.0707 (14)
C20	0.8765 (8)	0.26817 (14)	−0.0687 (4)	0.0739 (13)
H20	1.0071	0.2651	−0.0813	0.089*
C21	0.8092 (8)	0.29907 (14)	−0.0594 (4)	0.0774 (14)
H21	0.8953	0.3169	−0.0663	0.093*
C22	0.8317 (12)	0.20595 (15)	−0.0709 (5)	0.110 (2)
H22A	0.8604	0.2020	−0.1385	0.164*
H22B	0.7329	0.1905	−0.0521	0.164*
H22C	0.9477	0.2028	−0.0289	0.164*
N2	0.6291 (10)	0.55001 (13)	0.0338 (4)	0.0918 (14)
C23	0.5144 (8)	0.57432 (17)	0.0448 (4)	0.0846 (16)
H23	0.3867	0.5697	0.0600	0.102*
C24	0.5725 (12)	0.6087 (2)	0.0348 (5)	0.112 (3)
H24	0.4865	0.6264	0.0422	0.135*
C25	0.7725 (9)	0.61386 (13)	0.0127 (4)	0.0750 (14)
C26	0.8768 (9)	0.58590 (15)	0.0059 (5)	0.0856 (15)
H26	1.0082	0.5878	−0.0066	0.103*
C27	0.8035 (10)	0.55586 (17)	0.0161 (5)	0.0976 (18)
H27	0.8861	0.5376	0.0097	0.117*
C28	0.8604 (16)	0.64784 (17)	−0.0010 (6)	0.143 (4)
H28A	1.0001	0.6462	0.0056	0.214*
H28B	0.8162	0.6629	0.0484	0.214*
H28C	0.8215	0.6562	−0.0656	0.214*
N3	−0.0249 (7)	0.62792 (11)	0.2657 (3)	0.0777 (12)
C29	0.0890 (9)	0.60250 (16)	0.2555 (5)	0.0857 (16)
H29	0.2174	0.6064	0.2403	0.103*
C30	0.0269 (11)	0.56907 (16)	0.2665 (5)	0.0931 (19)
H30	0.1119	0.5512	0.2596	0.112*
C31	−0.1649 (9)	0.56391 (13)	0.2881 (4)	0.0784 (15)
C32	−0.2749 (10)	0.59173 (16)	0.2988 (5)	0.0855 (16)
C33	−0.2040 (9)	0.62238 (15)	0.2874 (5)	0.0866 (16)
H33	−0.2859	0.6407	0.2953	0.104*
C34	−0.2474 (13)	0.5293 (2)	0.3007 (7)	0.125 (3)
H34A	−0.3774	0.5310	0.3229	0.188*
H34B	−0.1669	0.5171	0.3487	0.188*
H34C	−0.2506	0.5176	0.2385	0.188*
N4	−0.0301 (7)	0.87121 (11)	0.2544 (3)	0.0757 (12)
C35	0.0856 (7)	0.89657 (15)	0.2559 (4)	0.0749 (14)
H35	0.2160	0.8927	0.2441	0.090*
C36	0.0285 (10)	0.92941 (15)	0.2739 (4)	0.0861 (18)
H36	0.1173	0.9471	0.2741	0.103*
C37	−0.1700 (9)	0.93494 (13)	0.2918 (3)	0.0740 (15)
C38	−0.2830 (8)	0.90716 (14)	0.2877 (4)	0.0735 (13)
H38	−0.4155	0.9091	0.2978	0.088*
C39	−0.2087 (9)	0.87673 (14)	0.2694 (4)	0.0812 (15)
H39	−0.2934	0.8585	0.2676	0.097*
C40	−0.2492 (15)	0.96900 (16)	0.3115 (5)	0.124 (3)
H40A	−0.2627	0.9814	0.2507	0.186*
H40B	−0.1614	0.9806	0.3575	0.186*
H40C	−0.3744	0.9669	0.3391	0.186*
H32	−0.404 (12)	0.589 (2)	0.315 (6)	0.148*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.081 (3)	0.057 (2)	0.166 (4)	−0.014 (2)	0.013 (2)	−0.010 (2)
O2	0.065 (2)	0.0588 (19)	0.122 (3)	−0.0002 (16)	0.0245 (19)	−0.0053 (19)
O3	0.128 (4)	0.054 (2)	0.133 (4)	0.013 (2)	0.026 (3)	−0.004 (2)
O4	0.092 (3)	0.056 (2)	0.122 (3)	−0.0162 (19)	0.011 (2)	−0.005 (2)
C1	0.047 (2)	0.057 (3)	0.051 (2)	−0.0004 (19)	−0.0002 (17)	−0.0019 (19)
C2	0.051 (2)	0.057 (3)	0.057 (2)	0.0005 (19)	0.0019 (18)	0.005 (2)
C3	0.057 (3)	0.079 (3)	0.078 (3)	−0.013 (3)	0.000 (2)	0.004 (3)
C4	0.052 (3)	0.098 (4)	0.085 (3)	0.007 (3)	0.005 (2)	0.008 (3)
C5	0.071 (3)	0.073 (3)	0.071 (3)	0.024 (3)	0.000 (2)	0.004 (2)
C6	0.058 (3)	0.066 (3)	0.053 (2)	0.004 (2)	0.0045 (19)	0.009 (2)
C7	0.094 (4)	0.056 (3)	0.069 (3)	−0.003 (3)	0.004 (3)	0.006 (2)
C8	0.066 (3)	0.065 (3)	0.071 (3)	−0.006 (2)	0.006 (2)	0.005 (2)
O5	0.100 (3)	0.057 (2)	0.169 (4)	0.009 (2)	0.032 (3)	−0.012 (2)
O6	0.081 (3)	0.054 (2)	0.141 (4)	−0.0035 (18)	0.035 (2)	−0.004 (2)
O7	0.089 (3)	0.063 (2)	0.182 (5)	−0.014 (2)	0.029 (3)	−0.015 (3)
O8	0.073 (2)	0.0539 (19)	0.116 (3)	0.0023 (17)	0.012 (2)	−0.0016 (18)
C9	0.049 (3)	0.058 (3)	0.063 (3)	0.002 (2)	0.0049 (19)	−0.001 (2)
C10	0.064 (3)	0.061 (3)	0.053 (2)	0.005 (2)	0.005 (2)	0.0013 (19)
C11	0.065 (3)	0.079 (4)	0.071 (3)	0.021 (3)	0.009 (2)	0.002 (2)
C12	0.050 (3)	0.101 (4)	0.083 (3)	0.002 (3)	0.011 (2)	0.006 (3)
C13	0.068 (3)	0.079 (4)	0.066 (3)	−0.017 (3)	0.003 (2)	0.002 (2)
C14	0.061 (3)	0.060 (3)	0.056 (3)	−0.005 (2)	0.004 (2)	0.0003 (19)
C15	0.063 (3)	0.067 (3)	0.078 (3)	−0.007 (2)	0.012 (2)	0.000 (2)
C16	0.075 (4)	0.062 (3)	0.076 (3)	0.007 (3)	0.009 (3)	−0.004 (2)
N1	0.082 (3)	0.059 (2)	0.078 (3)	−0.012 (2)	0.007 (2)	−0.006 (2)
C17	0.061 (3)	0.085 (4)	0.086 (3)	0.001 (3)	0.017 (2)	−0.004 (3)
C18	0.100 (5)	0.066 (3)	0.083 (4)	−0.026 (3)	0.009 (3)	0.001 (3)
C19	0.094 (4)	0.062 (3)	0.057 (3)	0.013 (3)	0.005 (2)	−0.006 (2)
C20	0.066 (3)	0.077 (4)	0.079 (3)	0.002 (3)	0.008 (2)	−0.006 (3)
C21	0.068 (3)	0.076 (3)	0.089 (4)	−0.015 (3)	0.011 (3)	−0.005 (3)
C22	0.164 (7)	0.071 (4)	0.095 (4)	0.029 (4)	0.020 (4)	−0.006 (3)
N2	0.111 (4)	0.081 (3)	0.083 (3)	−0.001 (3)	−0.004 (3)	−0.001 (3)
C23	0.065 (3)	0.102 (5)	0.088 (4)	−0.011 (3)	0.012 (3)	−0.008 (3)
C24	0.141 (7)	0.114 (5)	0.081 (4)	0.060 (5)	−0.001 (4)	−0.022 (4)
C25	0.102 (4)	0.056 (3)	0.067 (3)	−0.007 (3)	0.003 (3)	−0.002 (2)
C26	0.075 (3)	0.081 (4)	0.100 (4)	−0.007 (3)	−0.002 (3)	0.002 (3)
C27	0.086 (5)	0.085 (4)	0.120 (5)	−0.005 (4)	−0.009 (4)	0.003 (4)
C28	0.230 (11)	0.082 (5)	0.116 (6)	−0.058 (6)	0.002 (6)	0.006 (4)
N3	0.094 (3)	0.060 (2)	0.078 (3)	0.003 (2)	0.002 (2)	−0.004 (2)
C29	0.075 (4)	0.079 (4)	0.103 (4)	−0.002 (3)	0.007 (3)	−0.010 (3)
C30	0.115 (5)	0.070 (4)	0.095 (4)	0.027 (3)	0.008 (4)	−0.006 (3)
C31	0.096 (4)	0.059 (3)	0.080 (4)	−0.009 (3)	0.001 (3)	0.002 (2)
C32	0.087 (4)	0.081 (4)	0.089 (4)	−0.002 (3)	0.005 (3)	0.000 (3)
C33	0.084 (4)	0.067 (3)	0.109 (5)	0.005 (3)	0.006 (3)	−0.008 (3)
C34	0.125 (6)	0.125 (6)	0.125 (6)	0.000 (5)	0.007 (5)	0.000 (5)
N4	0.071 (3)	0.068 (3)	0.088 (3)	−0.003 (2)	0.005 (2)	0.006 (2)
C35	0.062 (3)	0.075 (4)	0.088 (4)	0.003 (3)	0.006 (2)	0.012 (3)
C36	0.099 (5)	0.077 (4)	0.080 (4)	−0.036 (3)	−0.012 (3)	0.011 (3)
C37	0.101 (4)	0.070 (3)	0.051 (3)	0.014 (3)	−0.005 (3)	−0.002 (2)
C38	0.067 (3)	0.076 (3)	0.077 (3)	−0.001 (3)	0.001 (2)	0.001 (3)
C39	0.081 (4)	0.063 (3)	0.099 (4)	−0.008 (3)	0.002 (3)	0.007 (3)
C40	0.202 (9)	0.080 (4)	0.088 (4)	0.033 (5)	−0.003 (4)	−0.011 (3)

Geometric parameters (Å, º)

O1—C8	1.192 (6)	C21—H21	0.9300
O2—C8	1.292 (6)	C22—H22A	0.9600
O2—H2O	0.8200	C22—H22B	0.9600
O3—C7	1.197 (6)	C22—H22C	0.9600
O4—C7	1.294 (7)	N2—C27	1.255 (8)
O4—H4O	0.8200	N2—C23	1.262 (8)
C1—C6	1.372 (6)	C23—C24	1.433 (10)
C1—C2	1.387 (6)	C23—H23	0.9300
C1—H1	0.9300	C24—C25	1.436 (10)
C2—C3	1.387 (7)	C24—H24	0.9300
C2—C8	1.482 (7)	C25—C26	1.330 (8)
C3—C4	1.362 (7)	C25—C28	1.497 (8)
C3—H3	0.9300	C26—C27	1.308 (8)
C4—C5	1.354 (7)	C26—H26	0.9300
C4—H4	0.9300	C27—H27	0.9300
C5—C6	1.381 (7)	C28—H28A	0.9600
C5—H5	0.9300	C28—H28B	0.9600
C6—C7	1.466 (7)	C28—H28C	0.9600
O5—C16	1.194 (6)	N3—C29	1.291 (7)
O6—C16	1.289 (6)	N3—C33	1.299 (8)
O6—H6O	0.8200	C29—C30	1.408 (9)
O7—C15	1.203 (6)	C29—H29	0.9300
O8—C15	1.291 (6)	C30—C31	1.380 (9)
O8—H8O	0.8200	C30—H30	0.9300
C9—C14	1.376 (6)	C31—C32	1.353 (8)
C9—C10	1.378 (6)	C31—C34	1.504 (9)
C9—H9	0.9300	C32—C33	1.326 (8)
C10—C11	1.383 (7)	C32—H32	0.93 (8)
C10—C16	1.494 (7)	C33—H33	0.9300
C11—C12	1.352 (7)	C34—H34A	0.9600
C11—H11	0.9300	C34—H34B	0.9600
C12—C13	1.369 (7)	C34—H34C	0.9600
C12—H12	0.9300	N4—C39	1.273 (7)
C13—C14	1.390 (7)	N4—C35	1.284 (7)
C13—H13	0.9300	C35—C36	1.390 (8)
C14—C15	1.476 (7)	C35—H35	0.9300
N1—C17	1.306 (6)	C36—C37	1.415 (9)
N1—C21	1.308 (7)	C36—H36	0.9300
C17—C18	1.402 (8)	C37—C38	1.350 (8)
C17—H17	0.9300	C37—C40	1.490 (8)
C18—C19	1.387 (9)	C38—C39	1.343 (8)
C18—H18	0.9300	C38—H38	0.9300
C19—C20	1.356 (8)	C39—H39	0.9300
C19—C22	1.481 (8)	C40—H40A	0.9600
C20—C21	1.322 (8)	C40—H40B	0.9600
C20—H20	0.9300	C40—H40C	0.9600
C8—O2—H2O	109.5	H22A—C22—H22B	109.5
C7—O4—H4O	109.5	C19—C22—H22C	109.5
C6—C1—C2	120.5 (4)	H22A—C22—H22C	109.5
C6—C1—H1	119.7	H22B—C22—H22C	109.5
C2—C1—H1	119.7	C27—N2—C23	119.2 (6)
C1—C2—C3	118.4 (4)	N2—C23—C24	122.8 (6)
C1—C2—C8	122.7 (4)	N2—C23—H23	118.6
C3—C2—C8	118.9 (4)	C24—C23—H23	118.6
C4—C3—C2	120.9 (5)	C23—C24—C25	115.5 (5)
C4—C3—H3	119.5	C23—C24—H24	122.2
C2—C3—H3	119.5	C25—C24—H24	122.2
C5—C4—C3	119.9 (5)	C26—C25—C24	114.8 (5)
C5—C4—H4	120.1	C26—C25—C28	121.7 (7)
C3—C4—H4	120.1	C24—C25—C28	123.5 (7)
C4—C5—C6	121.1 (5)	C27—C26—C25	123.1 (6)
C4—C5—H5	119.5	C27—C26—H26	118.4
C6—C5—H5	119.5	C25—C26—H26	118.4
C1—C6—C5	119.2 (5)	N2—C27—C26	124.5 (7)
C1—C6—C7	122.0 (4)	N2—C27—H27	117.7
C5—C6—C7	118.8 (5)	C26—C27—H27	117.7
O3—C7—O4	122.3 (5)	C25—C28—H28A	109.5
O3—C7—C6	122.8 (5)	C25—C28—H28B	109.5
O4—C7—C6	115.0 (5)	H28A—C28—H28B	109.5
O1—C8—O2	123.4 (5)	C25—C28—H28C	109.5
O1—C8—C2	121.9 (5)	H28A—C28—H28C	109.5
O2—C8—C2	114.7 (4)	H28B—C28—H28C	109.5
C16—O6—H6O	109.5	C29—N3—C33	118.5 (5)
C15—O8—H8O	109.5	N3—C29—C30	122.8 (5)
C14—C9—C10	119.1 (4)	N3—C29—H29	118.6
C14—C9—H9	120.4	C30—C29—H29	118.6
C10—C9—H9	120.4	C31—C30—C29	117.5 (5)
C9—C10—C11	120.0 (5)	C31—C30—H30	121.3
C9—C10—C16	121.2 (4)	C29—C30—H30	121.3
C11—C10—C16	118.8 (5)	C32—C31—C30	116.4 (5)
C12—C11—C10	120.6 (5)	C32—C31—C34	121.5 (6)
C12—C11—H11	119.7	C30—C31—C34	122.0 (6)
C10—C11—H11	119.7	C33—C32—C31	122.0 (6)
C11—C12—C13	120.3 (5)	C33—C32—H32	119 (5)
C11—C12—H12	119.8	C31—C32—H32	119 (5)
C13—C12—H12	119.8	N3—C33—C32	122.7 (6)
C12—C13—C14	119.7 (5)	N3—C33—H33	118.6
C12—C13—H13	120.2	C32—C33—H33	118.6
C14—C13—H13	120.2	C31—C34—H34A	109.5
C9—C14—C13	120.3 (5)	C31—C34—H34B	109.5
C9—C14—C15	121.2 (4)	H34A—C34—H34B	109.5
C13—C14—C15	118.5 (4)	C31—C34—H34C	109.5
O7—C15—O8	121.7 (5)	H34A—C34—H34C	109.5
O7—C15—C14	123.1 (5)	H34B—C34—H34C	109.5
O8—C15—C14	115.2 (4)	C39—N4—C35	117.5 (5)
O5—C16—O6	122.8 (5)	N4—C35—C36	124.2 (5)
O5—C16—C10	122.3 (5)	N4—C35—H35	117.9
O6—C16—C10	114.9 (4)	C36—C35—H35	117.9
C17—N1—C21	118.0 (5)	C35—C36—C37	117.4 (5)
N1—C17—C18	121.6 (5)	C35—C36—H36	121.3
N1—C17—H17	119.2	C37—C36—H36	121.3
C18—C17—H17	119.2	C38—C37—C36	115.0 (5)
C19—C18—C17	119.4 (5)	C38—C37—C40	122.6 (6)
C19—C18—H18	120.3	C36—C37—C40	122.4 (6)
C17—C18—H18	120.3	C39—C38—C37	121.6 (5)
C20—C19—C18	115.4 (5)	C39—C38—H38	119.2
C20—C19—C22	123.1 (6)	C37—C38—H38	119.2
C18—C19—C22	121.5 (6)	N4—C39—C38	124.4 (5)
C21—C20—C19	122.0 (5)	N4—C39—H39	117.8
C21—C20—H20	119.0	C38—C39—H39	117.8
C19—C20—H20	119.0	C37—C40—H40A	109.5
N1—C21—C20	123.7 (5)	C37—C40—H40B	109.5
N1—C21—H21	118.1	H40A—C40—H40B	109.5
C20—C21—H21	118.1	C37—C40—H40C	109.5
C19—C22—H22A	109.5	H40A—C40—H40C	109.5
C19—C22—H22B	109.5	H40B—C40—H40C	109.5
C6—C1—C2—C3	1.6 (6)	C9—C10—C16—O6	−5.7 (7)
C6—C1—C2—C8	−177.6 (4)	C11—C10—C16—O6	174.3 (4)
C1—C2—C3—C4	0.1 (7)	C21—N1—C17—C18	−0.3 (8)
C8—C2—C3—C4	179.3 (5)	N1—C17—C18—C19	0.2 (9)
C2—C3—C4—C5	−0.9 (8)	C17—C18—C19—C20	0.1 (8)
C3—C4—C5—C6	−0.1 (8)	C17—C18—C19—C22	180.0 (5)
C2—C1—C6—C5	−2.5 (6)	C18—C19—C20—C21	−0.5 (8)
C2—C1—C6—C7	177.8 (4)	C22—C19—C20—C21	179.7 (5)
C4—C5—C6—C1	1.8 (7)	C17—N1—C21—C20	0.0 (8)
C4—C5—C6—C7	−178.5 (5)	C19—C20—C21—N1	0.4 (9)
C1—C6—C7—O3	−179.2 (5)	C27—N2—C23—C24	2.1 (9)
C5—C6—C7—O3	1.1 (7)	N2—C23—C24—C25	−0.9 (9)
C1—C6—C7—O4	−0.3 (6)	C23—C24—C25—C26	−0.9 (8)
C5—C6—C7—O4	180.0 (4)	C23—C24—C25—C28	179.7 (6)
C1—C2—C8—O1	177.3 (5)	C24—C25—C26—C27	1.6 (9)
C3—C2—C8—O1	−1.9 (8)	C28—C25—C26—C27	−179.0 (7)
C1—C2—C8—O2	−1.5 (7)	C23—N2—C27—C26	−1.5 (11)
C3—C2—C8—O2	179.3 (4)	C25—C26—C27—N2	−0.5 (11)
C14—C9—C10—C11	1.2 (7)	C33—N3—C29—C30	0.3 (9)
C14—C9—C10—C16	−178.8 (4)	N3—C29—C30—C31	0.7 (9)
C9—C10—C11—C12	−1.9 (7)	C29—C30—C31—C32	−1.4 (8)
C16—C10—C11—C12	178.1 (5)	C29—C30—C31—C34	179.6 (6)
C10—C11—C12—C13	1.4 (8)	C30—C31—C32—C33	1.2 (9)
C11—C12—C13—C14	−0.2 (8)	C34—C31—C32—C33	−179.7 (6)
C10—C9—C14—C13	−0.1 (7)	C29—N3—C33—C32	−0.5 (9)
C10—C9—C14—C15	−177.7 (4)	C31—C32—C33—N3	−0.3 (10)
C12—C13—C14—C9	−0.4 (7)	C39—N4—C35—C36	0.8 (8)
C12—C13—C14—C15	177.3 (5)	N4—C35—C36—C37	0.2 (8)
C9—C14—C15—O7	168.6 (5)	C35—C36—C37—C38	−1.0 (7)
C13—C14—C15—O7	−9.1 (8)	C35—C36—C37—C40	−179.7 (5)
C9—C14—C15—O8	−11.6 (7)	C36—C37—C38—C39	1.1 (7)
C13—C14—C15—O8	170.7 (4)	C40—C37—C38—C39	179.7 (5)
C9—C10—C16—O5	175.8 (5)	C35—N4—C39—C38	−0.8 (9)
C11—C10—C16—O5	−4.1 (8)	C37—C38—C39—N4	−0.2 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···N1	0.82	1.83	2.652 (6)	177
O4—H4O···N2	0.82	1.84	2.657 (6)	172
O6—H6O···N3	0.82	1.83	2.648 (6)	175
O8—H8O···N4	0.82	1.82	2.642 (6)	176
C17—H17···O1	0.93	2.41	3.093 (7)	130
C21—H21···O1^i	0.93	2.48	3.258 (7)	141
C23—H23···O3	0.93	2.48	3.139 (8)	128
C27—H27···O3^i	0.93	2.59	3.375 (9)	142
C29—H29···O5	0.93	2.50	3.171 (8)	129
C35—H35···O7	0.93	2.47	3.138 (7)	129
C39—H39···O7^ii	0.93	2.41	3.221 (8)	146

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