catena-Poly­[[[aqua­bis(1H-benz­imidazole-κN³)­cadmium(II)]-μ-phthalato-κ³O,O′:O′′] hemihydrate]

The title compound is a polymeric complex bridged by a phthalate dianion, {[Cd(C₈H₄O₄)(C₇H₆N₂)₂(H₂O)]·0.5H₂O}_n. The asymmetric unit contains two Cd complex units, and both Cd^II atoms have the same distorted octahedral coordination geometry. Each phthalate dianion bridges two Cd atoms through the two terminal carboxy groups, one in a monodentate fashion and the other in a chelating mode, thus forming zigzag polymeric chains; π–π stacking occurs between neighboring chains. The bond angle involving the chelating carboxy group is large, but the corresponding bond distance is normal. This implies the existence of an electrostatic interaction between the Cd^II atoms and the carboxy groups.

S1. Comment

The consequences of non-covalent interaction in chemistry and structural biology have stimulated interest in exploring a variety of intermolecular forces. The aromatic π–π stacking interaction is correlated with electron transfer in some biological systems (Deisenhofer & Michel, 1989), and several structure determinations have revealed that the π–π stacking interaction commonly occurs in metal complexes with aromatic heteropolycyclic ligands (Nie et al., 2001). We present here the structure of the polymeric Cd^II complex, (I), of benzimidazole, in which π–π stacking occurs between adjacent polymeric chains.

The asymmetric unit of (I) contains two complex Cd^II units and one lattice water molecule, as shown in Fig. 1. The two independent Cd atoms have the same distorted octahedral coordination geometry, formed by two benzimidazole groups (BZIM) in a cis configuration, a coordinated water molecule and two phthalate dianions. Each phthalate dianion coordinates to two independent Cd atoms with both terminal carboxy groups, one in a monodentate fashion and the other in a chelating mode.

In the Cd1 complex unit, the O2—Cd1—N13 and O2—Cd1—O9ⁱ [symmetry code: (i) −1 + x,y,1 + z] angles (Table 1) are close to expected values, implying significant overlap of the Cd1 and O2 atomic orbitals, whereas the O1—Cd1—O9ⁱ angle [122.66 (7)°] suggests poor overlap of the Cd1 and O1 atomic orbitals. However, the Cd1—O1 bond distance is essentially the same as the Cd1—O2 bond distance. Likewise, in the Cd2 complex unit, the O6—Cd2—N43 and O6—Cd2—O3 angles imply significant overlap of the Cd2 and O6 atomic orbitals, whereas the O7—Cd2—O3 angle [119.72 (7)°] suggests poor overlap of the Cd2 and O7 atomic orbitals. However, the Cd2—O7 bond is shorter than the Cd2—O6 bond. These facts imply the existence of electrostatic interaction between the Cd atom and the coordinated carboxy group.

The Cd1—O9ⁱ and Cd2—O3 bonds for monodentate carboxy groups are significantly shorter than the chelating Cd—O bonds. The uncoordinated carboxy atoms O4 and O8 are hydrogen bonded to the neighboring coordinated water molecules O10 and O5. In addition, lattice water molecules O1W and O1Wⁱⁱ interact with carboxy groups bonded to the Cd2 complex unit via hydrogen bonding (Fig. 1), but there are no lattice water interactions with carboxy groups bonded to the Cd1 complex unit. Thus the Cd1 and Cd2 complex units are distinctly different.

Carboxy atoms O1, O2 and O9ⁱ, and BZIM atom N13, form an equatorial coordination plane around atom Cd1, with a maximum atomic deviation of 0.0339 (10) Å (for O2), while atoms O6, O7, O3 and N43 form another equatorial coordination plane around atom Cd2, with a maximum atomic deviation of 0.0759 (12) Å (for O6). The C31 phthalate dianion bridging the two Cd complex units is nearly parallel to both equatorial planes, the dihedral angles being 4.71 (11) and 2.71 (11)°, respectively. Thus the two equatorial coordinate planes are also nearly parallel, the dihedral angle being 3.80 (14)°.

Phthalate dianions bridge the adjacent Cd atoms to form zigzag polymeric chains, as shown in Fig. 2, along the [10–1] direction. π–π stacking interactions occur between neighboring polymeric chains related by an inversion center. The parallel N43–BZIM and N43^iv–BZIM rings [symmetry code (iv): 1 − x,1 − y,1 − z] overlap one another, as do the parallel C62–phthalate and C62^vi–phthalate rings [symmetry code (vi): 2 − x,1 − y,-z], as shown in Fig. 2. The separations between the neighboring parallel aromatic rings are 3.427 (14) (BZIM rings) and 3.298 (19) Å (phthalate rings).

Besides the hydrogen bonding between the carboxy and water O atoms mentioned above, hydrogen bonding is also observed between the BZIM and water molecules and between the BZIM and carboxyl groups (Table 2).

S2. Experimental

An aqueous solution (20 ml) of benzimidazole (0.12 g, 1 mmol) and CdCl₂·2H₂O (0.22 g, 1 mmol) was mixed with an aqueous solution (15 ml) of phthalic acid (0.17 g, 1 mmol) and NaOH (0.08 g, 2 mmol) at room temperature. The mixture was refluxed for 3 h and filtered twice. Single crystals were obtained from the filtrate after four weeks.

S3. Refinement

H atoms on water molecules were located in a difference Fourier map and included with fixed positional and isotropic displacement parameters [U_iso(H) = 0.05 Ų]. Other H atoms were placed in calculated positions (C—H = 0.93 Å and N—H = 0.86 Å) and were included in the final cycles of refinement in riding mode, with U_iso(H) equal to 1.2U_eq of the bonded atoms.

Computing details

Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC and Rigaku Corporation, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids, dashed lines showing hydrogen bonding. [Symmetry codes: (i)x − 1,y,z + 1; (ii)1 − x,1 − y,-z; (iii)-x,1 − y,1 − z].
	Fig. 2. A diagram showing the zigzag polymeric chains and the overlapped arrangement of aromatic rings from adjacent chains. [Symmetry codes: (iv)1 − x,1 − y,1 − z; (vi)2 − x,1 − y,-z.]

catena-Poly[[[aquabis(1H-benzimidazole-κN³)cadmium(II)]-µ-phthalato- κ³O,O':O''] hemihydrate]

Crystal data

[Cd(C8H4O4)(C7H6N2)2(H2O)]·0.5H2O	Z = 2
Mr = 1079.62	F(000) = 1084
Triclinic, P1	Dx = 1.707 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.2779 (12) Å	Cell parameters from 7404 reflections
b = 13.9092 (12) Å	θ = 1.7–25.1°
c = 14.2565 (13) Å	µ = 1.09 mm^−1
α = 61.140 (1)°	T = 295 K
β = 80.629 (2)°	Prism, colorless
γ = 88.464 (1)°	0.32 × 0.21 × 0.11 mm
V = 2100.1 (3) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	7404 independent reflections
Radiation source: fine-focus sealed tube	6572 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 10.00 pixels mm^-1	θmax = 25.2°, θmin = 1.7°
ω scans	h = −14→14
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→16
Tmin = 0.702, Tmax = 0.895	l = −17→16
16098 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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.060	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0279P)^2 + 1.7003P] where P = (Fo^2 + 2Fc^2)/3
7404 reflections	(Δ/σ)max = 0.002
586 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.41 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
Cd1	−0.078142 (14)	0.307363 (16)	0.679410 (14)	0.03158 (6)
Cd2	0.550413 (14)	0.455306 (15)	0.192041 (14)	0.03038 (6)
O1	0.07370 (14)	0.32424 (15)	0.54107 (14)	0.0354 (4)
O2	−0.07428 (13)	0.22181 (15)	0.56940 (14)	0.0348 (4)
O3	0.38339 (15)	0.37370 (18)	0.24636 (17)	0.0464 (5)
O4	0.37898 (15)	0.28312 (16)	0.15442 (15)	0.0430 (5)
O5	−0.14597 (14)	0.45657 (15)	0.52653 (14)	0.0346 (4)
O6	0.71989 (15)	0.56487 (16)	0.09835 (15)	0.0411 (4)
O7	0.67126 (14)	0.44490 (16)	0.05169 (15)	0.0392 (4)
O8	1.06513 (17)	0.5184 (2)	−0.33076 (17)	0.0552 (6)
O9	0.90252 (18)	0.42500 (18)	−0.25629 (18)	0.0532 (5)
O10	0.47785 (14)	0.60802 (16)	0.04273 (14)	0.0395 (4)
N11	−0.40868 (19)	0.2290 (2)	0.87925 (19)	0.0446 (6)
H11	−0.4574	0.2460	0.9186	0.054*
N13	−0.24884 (17)	0.23122 (18)	0.78053 (17)	0.0353 (5)
N21	0.1323 (2)	0.1468 (3)	0.9335 (2)	0.0618 (8)
H21	0.1664	0.1505	0.9799	0.074*
N23	0.02512 (19)	0.1954 (2)	0.80876 (19)	0.0450 (6)
N41	0.38445 (17)	0.57871 (19)	0.40469 (18)	0.0367 (5)
H41	0.3230	0.5820	0.4415	0.044*
N43	0.50188 (16)	0.53318 (18)	0.29992 (17)	0.0336 (5)
N51	0.75440 (17)	0.24907 (19)	0.44032 (19)	0.0399 (5)
H51	0.7996	0.2453	0.4820	0.048*
N53	0.64488 (17)	0.32138 (18)	0.31696 (17)	0.0362 (5)
C12	−0.3060 (2)	0.2741 (2)	0.8363 (2)	0.0407 (6)
H12	−0.2776	0.3301	0.8448	0.049*
C14	−0.3062 (2)	0.0801 (2)	0.7454 (2)	0.0416 (6)
H14	−0.2388	0.0797	0.7049	0.050*
C15	−0.3942 (3)	0.0095 (3)	0.7654 (3)	0.0529 (8)
H15	−0.3861	−0.0395	0.7381	0.063*
C16	−0.4957 (3)	0.0106 (3)	0.8262 (3)	0.0584 (9)
H16	−0.5536	−0.0379	0.8382	0.070*
C17	−0.5121 (2)	0.0804 (3)	0.8683 (3)	0.0521 (8)
H17	−0.5799	0.0812	0.9079	0.063*
C18	−0.4226 (2)	0.1506 (2)	0.8494 (2)	0.0380 (6)
C19	−0.3214 (2)	0.1517 (2)	0.7877 (2)	0.0333 (5)
C22	0.0662 (3)	0.2209 (3)	0.8731 (3)	0.0621 (9)
H22	0.0509	0.2850	0.8766	0.075*
C24	0.0584 (4)	0.0308 (3)	0.7798 (3)	0.0758 (12)
H24	0.0143	0.0506	0.7268	0.091*
C25	0.1156 (5)	−0.0628 (3)	0.8126 (4)	0.1082 (19)
H25	0.1112	−0.1061	0.7799	0.130*
C26	0.1806 (4)	−0.0950 (3)	0.8942 (4)	0.0923 (15)
H26	0.2172	−0.1598	0.9155	0.111*
C27	0.1908 (3)	−0.0331 (3)	0.9427 (3)	0.0629 (9)
H27	0.2332	−0.0545	0.9972	0.075*
C28	0.1354 (2)	0.0639 (3)	0.9077 (2)	0.0469 (7)
C29	0.0686 (2)	0.0953 (2)	0.8285 (2)	0.0443 (7)
C31	0.02340 (19)	0.2608 (2)	0.52073 (19)	0.0281 (5)
C32	0.07841 (19)	0.22905 (19)	0.43898 (19)	0.0272 (5)
C33	0.0260 (2)	0.1509 (2)	0.4241 (2)	0.0318 (5)
H33	−0.0416	0.1165	0.4670	0.038*
C34	0.0743 (2)	0.1246 (2)	0.3458 (2)	0.0359 (6)
H34	0.0394	0.0721	0.3364	0.043*
C35	0.1745 (2)	0.1759 (2)	0.2809 (2)	0.0321 (5)
H35	0.2053	0.1594	0.2267	0.039*
C36	0.22907 (19)	0.25192 (19)	0.29632 (19)	0.0274 (5)
C37	0.18073 (19)	0.2776 (2)	0.37604 (19)	0.0280 (5)
H37	0.2172	0.3278	0.3874	0.034*
C38	0.33954 (19)	0.3072 (2)	0.2258 (2)	0.0317 (5)
C42	0.3999 (2)	0.5232 (2)	0.3497 (2)	0.0362 (6)
H42	0.3438	0.4815	0.3468	0.043*
C44	0.6698 (2)	0.6363 (2)	0.2983 (2)	0.0389 (6)
H44	0.7196	0.6177	0.2540	0.047*
C45	0.7029 (2)	0.7002 (3)	0.3386 (2)	0.0475 (7)
H45	0.7771	0.7236	0.3229	0.057*
C46	0.6278 (3)	0.7308 (3)	0.4028 (3)	0.0512 (8)
H46	0.6533	0.7752	0.4278	0.061*
C47	0.5178 (2)	0.6975 (2)	0.4302 (2)	0.0441 (7)
H47	0.4679	0.7190	0.4721	0.053*
C48	0.4846 (2)	0.6298 (2)	0.3920 (2)	0.0320 (5)
C49	0.55859 (19)	0.6003 (2)	0.32596 (19)	0.0294 (5)
C52	0.7130 (2)	0.3407 (2)	0.3692 (2)	0.0397 (6)
H52	0.7304	0.4105	0.3580	0.048*
C54	0.5867 (3)	0.1422 (3)	0.3293 (3)	0.0576 (9)
H54	0.5409	0.1718	0.2773	0.069*
C55	0.6014 (3)	0.0309 (3)	0.3830 (4)	0.0742 (12)
H55	0.5652	−0.0154	0.3665	0.089*
C56	0.6695 (3)	−0.0137 (3)	0.4615 (3)	0.0694 (10)
H56	0.6768	−0.0893	0.4964	0.083*
C57	0.7258 (3)	0.0496 (3)	0.4889 (3)	0.0542 (8)
H57	0.7713	0.0192	0.5411	0.065*
C58	0.7116 (2)	0.1625 (2)	0.4345 (2)	0.0392 (6)
C59	0.6430 (2)	0.2083 (2)	0.3562 (2)	0.0388 (6)
C61	0.7374 (2)	0.5185 (2)	0.0405 (2)	0.0326 (5)
C62	0.84094 (19)	0.5510 (2)	−0.04178 (19)	0.0287 (5)
C63	0.85983 (19)	0.5081 (2)	−0.11240 (19)	0.0301 (5)
H63	0.8070	0.4594	−0.1090	0.036*
C64	0.95627 (19)	0.5369 (2)	−0.18807 (19)	0.0293 (5)
C65	1.0354 (2)	0.6080 (2)	−0.1904 (2)	0.0360 (6)
H65	1.1009	0.6274	−0.2403	0.043*
C66	1.0179 (2)	0.6500 (2)	−0.1197 (2)	0.0384 (6)
H66	1.0717	0.6970	−0.1216	0.046*
C67	0.9209 (2)	0.6227 (2)	−0.0465 (2)	0.0349 (6)
H67	0.9088	0.6523	0.0001	0.042*
C68	0.9774 (2)	0.4903 (2)	−0.2658 (2)	0.0352 (6)
O1W	0.6857 (2)	0.7905 (2)	−0.0032 (2)	0.0737 (7)
H1A	0.7033	0.7153	0.0364	0.050*
H1B	0.6601	0.7889	−0.0602	0.050*
H5A	−0.1117	0.4654	0.4669	0.050*
H5B	−0.1315	0.5257	0.5249	0.050*
H10A	0.4224	0.5905	0.0216	0.050*
H10B	0.5209	0.6373	−0.0196	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.03025 (10)	0.04030 (11)	0.02969 (10)	−0.00030 (7)	−0.00138 (7)	−0.02227 (9)
Cd2	0.02589 (9)	0.03907 (11)	0.02827 (10)	−0.00062 (7)	0.00033 (7)	−0.01931 (9)
O1	0.0319 (9)	0.0441 (10)	0.0383 (10)	−0.0007 (8)	−0.0035 (7)	−0.0267 (9)
O2	0.0267 (9)	0.0457 (11)	0.0336 (10)	−0.0022 (7)	0.0026 (7)	−0.0228 (9)
O3	0.0304 (10)	0.0629 (13)	0.0539 (12)	−0.0141 (9)	0.0067 (8)	−0.0380 (11)
O4	0.0406 (10)	0.0516 (12)	0.0381 (11)	−0.0027 (9)	0.0077 (8)	−0.0269 (10)
O5	0.0329 (9)	0.0397 (10)	0.0308 (9)	−0.0009 (7)	0.0029 (7)	−0.0191 (8)
O6	0.0417 (10)	0.0524 (12)	0.0363 (10)	0.0016 (9)	0.0030 (8)	−0.0299 (10)
O7	0.0314 (9)	0.0527 (12)	0.0344 (10)	−0.0047 (8)	0.0028 (7)	−0.0239 (9)
O8	0.0448 (12)	0.0897 (17)	0.0446 (12)	0.0008 (11)	0.0057 (9)	−0.0469 (12)
O9	0.0587 (13)	0.0615 (14)	0.0544 (13)	−0.0111 (11)	0.0073 (10)	−0.0443 (12)
O10	0.0336 (9)	0.0564 (12)	0.0328 (10)	0.0019 (8)	−0.0044 (7)	−0.0254 (9)
N11	0.0439 (13)	0.0492 (14)	0.0377 (13)	0.0072 (11)	0.0048 (10)	−0.0225 (12)
N13	0.0357 (11)	0.0367 (12)	0.0307 (11)	0.0000 (9)	−0.0013 (9)	−0.0152 (10)
N21	0.0739 (19)	0.076 (2)	0.0512 (17)	0.0170 (15)	−0.0335 (14)	−0.0374 (16)
N23	0.0399 (13)	0.0604 (16)	0.0383 (13)	0.0057 (11)	−0.0089 (10)	−0.0262 (12)
N41	0.0280 (11)	0.0482 (13)	0.0370 (12)	0.0037 (9)	0.0012 (9)	−0.0251 (11)
N43	0.0298 (11)	0.0407 (12)	0.0336 (12)	−0.0013 (9)	−0.0013 (9)	−0.0217 (10)
N51	0.0310 (11)	0.0512 (14)	0.0408 (13)	0.0001 (10)	−0.0112 (9)	−0.0232 (12)
N53	0.0309 (11)	0.0425 (13)	0.0337 (12)	0.0045 (9)	−0.0044 (9)	−0.0176 (10)
C12	0.0486 (16)	0.0392 (15)	0.0349 (15)	0.0006 (12)	−0.0027 (12)	−0.0197 (13)
C14	0.0384 (15)	0.0457 (16)	0.0416 (16)	0.0018 (12)	−0.0028 (12)	−0.0229 (14)
C15	0.0543 (19)	0.0550 (19)	0.056 (2)	−0.0026 (15)	−0.0096 (15)	−0.0314 (17)
C16	0.0466 (18)	0.063 (2)	0.056 (2)	−0.0179 (15)	−0.0061 (15)	−0.0210 (18)
C17	0.0343 (15)	0.063 (2)	0.0452 (18)	−0.0055 (14)	0.0026 (12)	−0.0183 (16)
C18	0.0351 (14)	0.0442 (16)	0.0270 (13)	0.0054 (11)	−0.0043 (10)	−0.0117 (12)
C19	0.0303 (13)	0.0340 (14)	0.0296 (13)	0.0020 (10)	−0.0044 (10)	−0.0110 (11)
C22	0.077 (2)	0.078 (2)	0.055 (2)	0.0258 (19)	−0.0292 (18)	−0.046 (2)
C24	0.114 (3)	0.047 (2)	0.076 (3)	0.006 (2)	−0.057 (2)	−0.0250 (19)
C25	0.181 (5)	0.048 (2)	0.119 (4)	0.023 (3)	−0.093 (4)	−0.039 (3)
C26	0.130 (4)	0.046 (2)	0.103 (4)	0.019 (2)	−0.066 (3)	−0.025 (2)
C27	0.068 (2)	0.050 (2)	0.054 (2)	−0.0036 (16)	−0.0275 (17)	−0.0060 (17)
C28	0.0435 (16)	0.0514 (18)	0.0369 (16)	−0.0069 (13)	−0.0089 (12)	−0.0132 (14)
C29	0.0414 (15)	0.0437 (16)	0.0374 (16)	−0.0094 (12)	−0.0079 (12)	−0.0106 (13)
C31	0.0285 (12)	0.0298 (12)	0.0261 (12)	0.0036 (10)	−0.0049 (9)	−0.0137 (11)
C32	0.0263 (12)	0.0288 (12)	0.0237 (12)	0.0036 (9)	−0.0038 (9)	−0.0107 (10)
C33	0.0277 (12)	0.0314 (13)	0.0359 (14)	−0.0031 (10)	−0.0021 (10)	−0.0168 (11)
C34	0.0387 (14)	0.0337 (14)	0.0414 (15)	−0.0022 (11)	−0.0067 (11)	−0.0229 (12)
C35	0.0353 (13)	0.0351 (14)	0.0298 (13)	0.0058 (10)	−0.0047 (10)	−0.0192 (11)
C36	0.0267 (12)	0.0293 (12)	0.0259 (12)	0.0025 (9)	−0.0048 (9)	−0.0130 (10)
C37	0.0257 (12)	0.0299 (13)	0.0291 (13)	0.0005 (9)	−0.0047 (9)	−0.0148 (11)
C38	0.0278 (12)	0.0339 (14)	0.0303 (13)	0.0043 (10)	−0.0032 (10)	−0.0138 (11)
C42	0.0302 (13)	0.0443 (15)	0.0365 (15)	0.0002 (11)	−0.0040 (11)	−0.0219 (13)
C44	0.0328 (13)	0.0459 (16)	0.0381 (15)	−0.0015 (11)	0.0013 (11)	−0.0224 (13)
C45	0.0384 (15)	0.0539 (18)	0.0497 (18)	−0.0115 (13)	−0.0031 (13)	−0.0254 (15)
C46	0.0578 (19)	0.0544 (19)	0.0539 (19)	−0.0088 (15)	−0.0080 (15)	−0.0360 (16)
C47	0.0527 (17)	0.0468 (17)	0.0430 (16)	0.0035 (13)	−0.0028 (13)	−0.0315 (14)
C48	0.0312 (13)	0.0364 (14)	0.0273 (13)	0.0051 (10)	−0.0044 (10)	−0.0149 (11)
C49	0.0311 (12)	0.0303 (13)	0.0253 (12)	0.0021 (10)	−0.0036 (10)	−0.0128 (11)
C52	0.0284 (13)	0.0473 (16)	0.0415 (16)	−0.0011 (11)	−0.0023 (11)	−0.0210 (14)
C54	0.066 (2)	0.056 (2)	0.065 (2)	0.0171 (16)	−0.0385 (17)	−0.0326 (18)
C55	0.094 (3)	0.055 (2)	0.099 (3)	0.017 (2)	−0.056 (2)	−0.046 (2)
C56	0.090 (3)	0.0417 (19)	0.084 (3)	0.0165 (18)	−0.044 (2)	−0.0279 (19)
C57	0.0568 (19)	0.0510 (19)	0.0522 (19)	0.0139 (15)	−0.0266 (15)	−0.0184 (16)
C58	0.0316 (13)	0.0488 (16)	0.0363 (15)	0.0052 (11)	−0.0082 (11)	−0.0194 (13)
C59	0.0353 (14)	0.0458 (16)	0.0381 (15)	0.0074 (11)	−0.0096 (11)	−0.0218 (13)
C61	0.0312 (13)	0.0409 (15)	0.0248 (13)	0.0066 (11)	−0.0039 (10)	−0.0157 (11)
C62	0.0302 (12)	0.0320 (13)	0.0253 (12)	0.0035 (10)	−0.0045 (9)	−0.0152 (11)
C63	0.0299 (12)	0.0324 (13)	0.0285 (13)	0.0000 (10)	−0.0048 (10)	−0.0151 (11)
C64	0.0295 (12)	0.0338 (13)	0.0238 (12)	0.0037 (10)	−0.0031 (9)	−0.0140 (11)
C65	0.0314 (13)	0.0410 (15)	0.0308 (14)	−0.0020 (11)	0.0015 (10)	−0.0156 (12)
C66	0.0378 (14)	0.0367 (15)	0.0416 (15)	−0.0067 (11)	−0.0050 (11)	−0.0197 (13)
C67	0.0407 (14)	0.0378 (14)	0.0335 (14)	0.0031 (11)	−0.0062 (11)	−0.0231 (12)
C68	0.0360 (14)	0.0414 (15)	0.0271 (13)	0.0051 (11)	−0.0058 (11)	−0.0158 (12)
O1W	0.115 (2)	0.0642 (16)	0.0637 (16)	0.0202 (15)	−0.0428 (15)	−0.0403 (14)

Geometric parameters (Å, º)

Cd1—O1	2.4083 (17)	C24—C29	1.392 (5)
Cd1—O2	2.3774 (17)	C24—H24	0.9300
Cd1—O5	2.4255 (18)	C25—C26	1.404 (6)
Cd1—O9^i	2.2203 (19)	C25—H25	0.9300
Cd1—N13	2.292 (2)	C26—C27	1.358 (6)
Cd1—N23	2.306 (2)	C26—H26	0.9300
Cd2—O3	2.2028 (17)	C27—C28	1.394 (5)
Cd2—O6	2.3950 (19)	C27—H27	0.9300
Cd2—O7	2.3511 (17)	C28—C29	1.395 (4)
Cd2—O10	2.4471 (19)	C31—C32	1.495 (3)
Cd2—N43	2.273 (2)	C32—C37	1.390 (3)
Cd2—N53	2.311 (2)	C32—C33	1.395 (3)
O1—C31	1.256 (3)	C33—C34	1.378 (3)
O2—C31	1.271 (3)	C33—H33	0.9300
O3—C38	1.254 (3)	C34—C35	1.384 (4)
O4—C38	1.241 (3)	C34—H34	0.9300
O5—H5A	0.837	C35—C36	1.387 (3)
O5—H5B	0.9717	C35—H35	0.9300
O6—C61	1.261 (3)	C36—C37	1.390 (3)
O7—C61	1.257 (3)	C36—C38	1.519 (3)
O8—C68	1.232 (3)	C37—H37	0.9300
O9—C68	1.254 (3)	C42—H42	0.9300
O10—H10A	0.872	C44—C45	1.369 (4)
O10—H10B	0.863	C44—C49	1.393 (3)
N11—C12	1.333 (4)	C44—H44	0.9300
N11—C18	1.372 (4)	C45—C46	1.396 (4)
N11—H11	0.8600	C45—H45	0.9300
N13—C12	1.316 (3)	C46—C47	1.372 (4)
N13—C19	1.394 (3)	C46—H46	0.9300
N21—C22	1.338 (4)	C47—C48	1.390 (4)
N21—C28	1.368 (4)	C47—H47	0.9300
N21—H21	0.8600	C48—C49	1.399 (3)
N23—C22	1.302 (4)	C52—H52	0.9300
N23—C29	1.390 (4)	C54—C55	1.378 (5)
N41—C42	1.333 (3)	C54—C59	1.390 (4)
N41—C48	1.378 (3)	C54—H54	0.9300
N41—H41	0.8600	C55—C56	1.394 (5)
N43—C42	1.310 (3)	C55—H55	0.9300
N43—C49	1.396 (3)	C56—C57	1.363 (5)
N51—C52	1.340 (4)	C56—H56	0.9300
N51—C58	1.370 (4)	C57—C58	1.396 (4)
N51—H51	0.8600	C57—H57	0.9300
N53—C52	1.317 (3)	C58—C59	1.398 (4)
N53—C59	1.392 (4)	C61—C62	1.493 (3)
C12—H12	0.9300	C62—C63	1.385 (3)
C14—C15	1.378 (4)	C62—C67	1.389 (3)
C14—C19	1.387 (4)	C63—C64	1.385 (3)
C14—H14	0.9300	C63—H63	0.9300
C15—C16	1.401 (5)	C64—C65	1.390 (3)
C15—H15	0.9300	C64—C68	1.520 (3)
C16—C17	1.364 (5)	C65—C66	1.376 (4)
C16—H16	0.9300	C65—H65	0.9300
C17—C18	1.392 (4)	C66—C67	1.374 (4)
C17—H17	0.9300	C66—H66	0.9300
C18—C19	1.396 (3)	C67—H67	0.9300
C22—H22	0.9300	O1W—H1A	0.958
C24—C25	1.369 (6)	O1W—H1B	0.928
O1—Cd1—O2	54.72 (6)	C26—C27—H27	121.2
O1—Cd1—O5	82.97 (6)	C28—C27—H27	121.2
O1—Cd1—O9^i	122.66 (7)	N21—C28—C27	132.9 (3)
O1—Cd1—N13	150.05 (7)	N21—C28—C29	105.2 (3)
O1—Cd1—N23	88.60 (7)	C27—C28—C29	121.8 (3)
O2—Cd1—O5	81.87 (6)	N23—C29—C24	130.6 (3)
O2—Cd1—O9^i	164.37 (8)	N23—C29—C28	109.4 (3)
O2—Cd1—N13	95.42 (7)	C24—C29—C28	120.0 (3)
O2—Cd1—N23	102.75 (8)	O1—C31—O2	121.0 (2)
O5—Cd1—O9^i	82.50 (7)	O1—C31—C32	120.2 (2)
O5—Cd1—N13	96.00 (7)	O2—C31—C32	118.7 (2)
O5—Cd1—N23	165.58 (7)	C37—C32—C33	119.3 (2)
O9^i—Cd1—N13	86.59 (8)	C37—C32—C31	120.9 (2)
O9^i—Cd1—N23	92.34 (9)	C33—C32—C31	119.8 (2)
N13—Cd1—N23	97.13 (8)	C34—C33—C32	120.0 (2)
O3—Cd2—O6	168.42 (7)	C34—C33—H33	120.0
O3—Cd2—O7	119.72 (7)	C32—C33—H33	120.0
O3—Cd2—O10	87.49 (7)	C33—C34—C35	120.4 (2)
O3—Cd2—N43	88.68 (7)	C33—C34—H34	119.8
O3—Cd2—N53	100.62 (8)	C35—C34—H34	119.8
O6—Cd2—O7	55.21 (6)	C34—C35—C36	120.4 (2)
O6—Cd2—O10	81.70 (6)	C34—C35—H35	119.8
O6—Cd2—N43	95.52 (7)	C36—C35—H35	119.8
O6—Cd2—N53	89.99 (7)	C35—C36—C37	119.1 (2)
O7—Cd2—O10	84.10 (6)	C35—C36—C38	120.2 (2)
O7—Cd2—N43	150.69 (7)	C37—C36—C38	120.7 (2)
O7—Cd2—N53	89.20 (7)	C36—C37—C32	120.8 (2)
O10—Cd2—N43	90.56 (7)	C36—C37—H37	119.6
O10—Cd2—N53	171.35 (7)	C32—C37—H37	119.6
N43—Cd2—N53	92.62 (8)	O4—C38—O3	125.7 (2)
C31—O1—Cd1	91.57 (14)	O4—C38—C36	118.6 (2)
C31—O2—Cd1	92.62 (14)	O3—C38—C36	115.7 (2)
C38—O3—Cd2	131.75 (16)	N43—C42—N41	113.3 (2)
Cd1—O5—H5A	112.08	N43—C42—H42	123.4
Cd1—O5—H5B	109.64	N41—C42—H42	123.4
H5A—O5—H5B	104.10	C45—C44—C49	117.6 (2)
C61—O6—Cd2	90.45 (15)	C45—C44—H44	121.2
C61—O7—Cd2	92.60 (14)	C49—C44—H44	121.2
C68—O9—Cd1^ii	125.43 (18)	C44—C45—C46	121.5 (3)
Cd2—O10—H10A	115.50	C44—C45—H45	119.3
Cd2—O10—H10B	115.91	C46—C45—H45	119.3
H10A—O10—H10B	96.45	C47—C46—C45	122.0 (3)
C12—N11—C18	107.6 (2)	C47—C46—H46	119.0
C12—N11—H11	126.2	C45—C46—H46	119.0
C18—N11—H11	126.2	C46—C47—C48	116.6 (3)
C12—N13—C19	104.8 (2)	C46—C47—H47	121.7
C12—N13—Cd1	120.80 (18)	C48—C47—H47	121.7
C19—N13—Cd1	133.71 (17)	N41—C48—C47	133.2 (2)
C22—N21—C28	107.0 (3)	N41—C48—C49	104.9 (2)
C22—N21—H21	126.5	C47—C48—C49	121.9 (2)
C28—N21—H21	126.5	C44—C49—N43	130.6 (2)
C22—N23—C29	104.3 (3)	C44—C49—C48	120.4 (2)
C22—N23—Cd1	125.3 (2)	N43—C49—C48	109.0 (2)
C29—N23—Cd1	130.03 (19)	N53—C52—N51	112.9 (3)
C42—N41—C48	107.8 (2)	N53—C52—H52	123.6
C42—N41—H41	126.1	N51—C52—H52	123.6
C48—N41—H41	126.1	C55—C54—C59	117.3 (3)
C42—N43—C49	105.0 (2)	C55—C54—H54	121.4
C42—N43—Cd2	121.07 (17)	C59—C54—H54	121.4
C49—N43—Cd2	133.85 (16)	C54—C55—C56	121.5 (3)
C52—N51—C58	107.6 (2)	C54—C55—H55	119.3
C52—N51—H51	126.2	C56—C55—H55	119.3
C58—N51—H51	126.2	C57—C56—C55	122.2 (3)
C52—N53—C59	105.2 (2)	C57—C56—H56	118.9
C52—N53—Cd2	124.11 (19)	C55—C56—H56	118.9
C59—N53—Cd2	130.68 (17)	C56—C57—C58	116.6 (3)
N13—C12—N11	113.2 (2)	C56—C57—H57	121.7
N13—C12—H12	123.4	C58—C57—H57	121.7
N11—C12—H12	123.4	N51—C58—C57	132.6 (3)
C15—C14—C19	117.8 (3)	N51—C58—C59	105.6 (2)
C15—C14—H14	121.1	C57—C58—C59	121.8 (3)
C19—C14—H14	121.1	C54—C59—N53	130.6 (3)
C14—C15—C16	120.9 (3)	C54—C59—C58	120.6 (3)
C14—C15—H15	119.5	N53—C59—C58	108.8 (2)
C16—C15—H15	119.5	O7—C61—O6	121.7 (2)
C17—C16—C15	122.1 (3)	O7—C61—C62	119.5 (2)
C17—C16—H16	119.0	O6—C61—C62	118.7 (2)
C15—C16—H16	119.0	C63—C62—C67	119.1 (2)
C16—C17—C18	117.0 (3)	C63—C62—C61	120.6 (2)
C16—C17—H17	121.5	C67—C62—C61	120.2 (2)
C18—C17—H17	121.5	C62—C63—C64	120.9 (2)
N11—C18—C17	132.9 (3)	C62—C63—H63	119.5
N11—C18—C19	105.4 (2)	C64—C63—H63	119.5
C17—C18—C19	121.7 (3)	C63—C64—C65	118.7 (2)
C14—C19—N13	130.5 (2)	C63—C64—C68	121.2 (2)
C14—C19—C18	120.5 (2)	C65—C64—C68	120.1 (2)
N13—C19—C18	109.0 (2)	C66—C65—C64	120.7 (2)
N23—C22—N21	114.1 (3)	C66—C65—H65	119.6
N23—C22—H22	123.0	C64—C65—H65	119.6
N21—C22—H22	123.0	C67—C66—C65	120.0 (2)
C25—C24—C29	117.8 (3)	C67—C66—H66	120.0
C25—C24—H24	121.1	C65—C66—H66	120.0
C29—C24—H24	121.1	C66—C67—C62	120.4 (2)
C24—C25—C26	121.8 (4)	C66—C67—H67	119.8
C24—C25—H25	119.1	C62—C67—H67	119.8
C26—C25—H25	119.1	O8—C68—O9	126.2 (3)
C27—C26—C25	121.0 (4)	O8—C68—C64	118.1 (2)
C27—C26—H26	119.5	O9—C68—C64	115.7 (2)
C25—C26—H26	119.5	H1A—O1W—H1B	99.6
C26—C27—C28	117.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O6	0.96	1.86	2.804 (4)	169
O1W—H1B···O4^iii	0.93	2.14	3.010 (4)	156
O5—H5A···O8^iii	0.84	1.84	2.660 (3)	168
O5—H5B···O1^iv	0.97	1.93	2.836 (3)	155
O10—H10A···O7^iii	0.87	1.89	2.745 (3)	166
O10—H10B···O4^iii	0.86	1.92	2.776 (3)	173
N11—H11···O10^iv	0.86	2.34	3.020 (4)	136
N21—H21···O1W^v	0.86	2.15	2.899 (4)	145
N41—H41···O5^iv	0.86	2.17	2.907 (3)	143
N51—H51···O2^vi	0.86	2.07	2.915 (3)	170

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