A novel cadmium(II) coordination polymer with biphenyl-3,3′,4,4′-tetra­carboxylic acid and 4,4′-bipyridine

A novel cadmium(II) coordination polymer, poly[[[bis­(4,4′-bipyridine)cadmium(II)]-μ₃-4,4′-dicarboxy­biphenyl-3,3′-di­carboxyl­ato] 0.35-hydrate], {[Cd(C₁₆H₈O₈)(C₁₀H₈N₂)₂]·0.35H₂O}_n, was obtained by reaction of Cd(CH₃COO)₂·3H₂O, 4,4′-bipyridine (4,4′-bpy) and biphenyl-3,3′,4,4′-tetra­car­boxylic acid (H₄L) under hydro­thermal conditions. Each Cd^II atom lies at the centre of a distorted octa­hedron, coordinated by four O atoms from three H₂L²⁻ ligands and N atoms from two monodentate 4,4′-bpy ligands. Each H₂L²⁻ ligand coordinates to three Cd^II atoms through two carboxyl­ate groups, one acting as a bridging bidentate ligand and the other in a chelating bidentate fashion. Two Cd atoms, two H₂L²⁻ anions and four 4,4′-bpy ligands form a ring dimer node, which links into an extended broad zonal one-dimensional chain along the c axis.

S1. Comment

The metal carboxylate coordination polymers have emerged as an important family in the past few years (Rao et al., 2004). It is also well known that the incorporation of carboxylic acid groups into coordination compounds gives interesting supramolecular architectures (Puddephatt et al., 2002). Multifunctional carboxylates and related species provide an effective means of designing novel hybrid structures with porous and other properties (Yaghi et al., 2003; Kitagawa et al., 2004). In some of these structures, the carboxylate acts as a linker between two inorganic units. The biphenyl-3,3',4,4'-tetracarboxylic acid ligand (H₄L) has multifunctional possibilities: (a) it has four carboxyl groups that may be completely or partially deprotonated; (b) it can act not only as a hydrogen-bond acceptor but also as a hydrogen-bond donor, depending on the number of deprotonated carboxyl groups; (c) some of the carboxyl groups can be rotated out of the plane of the benzene ring upon complexation as a result of steric effects; thus the ligand may connect metal ions in three dimensions; (d) it is a flexible ligand. To the best of our knowledge, the crystal structure of a metal complex with the H₄L ligand has not been reported previously, although there are several crystal structures of complexes with analogous (but rigid) ligands, viz. terephthalic acid (Shi et al., 2005), benzene-1,3,5-tricarboxylic acid (Rosi et al., 2002; Li et al., 1999; Millange et al., 2002; Kepert & Rosseinsky, 1998), benzene-1,2,4,5-tetracarboxylic acid (Shi et al., 2001, 2005; Cao et al., 2002; Hou et al., 2004), biphenyl-4,4'-dicarboxylic acid (Shi et al., 2005; Pan et al., 2003; Dai et al., 2004; Mukherjee et al., 2004; Shiu et al., 2003) and its analogs. However, the H₄L coordination geometry is very different from those of the rigid ligands above because of the flexibility of its four carboxyl groups. We report here the preparation and crystal structure of a novel one-dimensional coordination polymer, formulated {[Cd(H₂L)(4,4'-bpy)₂]·0.35H₂O}_n (4,4'-bpy is 4,4'-bipyridine), (I).

Single-crystal X-ray diffraction reveals that (I) is an extended broad zonal one-dimensional chain based on ring dimer building blocks constructed from two Cd atoms, two H₂L²⁻ ligands and four 4,4'-bpy ligands. Each Cd^II atom is six-coordinate (Fig. 1), with two O atoms donated by one chelating bidentate H₂L²⁻ ligand, two from two separate bridging bidentate H₂L²⁻ ligands and two N atoms [Cd1—N2 = 2.312 (4) and Cd1—N3 = 2.404 (4) Å] from two 4,4'-bpy ligands, which, unusualy, act as monodentate (not bridging bidentate) ligands. The four Cd1—O_carboxyl distances fall in the range 2.206 (3)–2.466 (4) Å and the O—Cd1—O angles vary from 54.6 (1) to 85.1 (1)°. The bond lengths and angles of Cd—O_carboxyl are similar to those in other cadmium–carboxylate coordination polymers (Shi et al., 2005) with the Cd center displaying the typical distorted octahedral coordination geometry (Table 1). The H₂L²⁻ ligands exhibit an interesting connection mode with the metal ions, which is different from those in the other reported analogous ligands (Shi et al., 2001, 2005). As shown in the scheme and Fig. 1, three types of coordination modes of H₂L²⁻ ligands are present in the structure, viz. (a) two carboxylate groups (C13 and C16) are not deprotonated and remain free [C13—O2 = 1.180 (6) Å, C13—O1 = 1.330 (6) Å, C16—O8 = 1.208 (6) Å and C16—O7 = 1.310 (6) Å]; (b) one carboxylate group (C15) adopts a bidentate chelating mode, chelating one Cd^II atom; (c) another carboxylate group (C14) adopts a bidentate bridging mode, connecting two Cd^II atoms. Each H₂L²⁻ ligand acts as a tetradentate ligand coordinating to three Cd^II atoms. Two Cd atom, two H₂L²⁻ and four 4,4'-bpy ligands act as a ring dimer node (see Fig. 2). Nodes are connected through Cd1—O4ⁱ and O4—Cd1ⁱ bonds [symmetry code: (i) 2 − x, 1 − y, 2 − z] into an extended broad zonal one-dimensional chain along the c axis (see Fig. 3).

In the packing arrangement of (I) (see Fig. 4), adjacent one-dimensional chains are parallel to each other and associate into a two-dimensional supermolecular layer via hydrogen bonds between the N atoms of 4,4'-bpy and the free carboxyl groups of the H₂L²⁻ ligands (Table 2). Note that atom H1 bonded to carboxylic atom O1 could not be located in the final difference Fourier map and was instead included in an idealized position. The water molecule O9W was refined with a site occupancy of 0.35 and the H atoms attached to atom O9W were not located.

S2. Experimental

H₄L was purchased from TCI and used without further purification. Compound (I) was synthesized hydrothermally under autogenous pressure. A mixture of Cd(CH₃COO)₂·3H₂O (0.303 g, 1 mmol), H₄L (0.330 g, 1 mmol), 4,4'-bpy (0.312 g, 2 mmol) and NaOH (0.080 g, 2 mmol) was stirred for 20 min and then sealed in a Parr Teflon-lined stainless steel vessel, which was heated to 443 K for 72 h. After slow cooling to ambient temperature, colorless block-shaped crystals of (I) were separated mechanically from the powder and washed with distilled water (yield ca 70% based on Cd). The compound is insoluble in common organic solvents and water. Analysis found: C 57.3, H 3.3, N 7.5%; C₃₆H_24.70CdN₄O_8.35 requires: C 56.9, H 3.28, N 7.38%.

S3. Refinement

All H atoms on C and O atoms were positioned geometrically and refined as riding atoms [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C); O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O)]. The water molecule O9W was refined freely with a site occupancy of 0.35, and the attached H atoms were not located.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990).

Figures

	Fig. 1. View of the local coordination of the Cd^II atom, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted. [Symmetry codes: (i) 2 − x, 1 − y, 2 − z; (ii) x, y, z − 1.]
	Fig. 2. View of the dimer node, with displacement ellipsoids drawn at the 30% probability level. H atoms and water molecules have been omitted for clarity. [Symmetry code: (i) 2 − x, 1 − y, 2 − z.]
	Fig. 3. The one-dimensional chain-like fragment (along c) in (I). H atoms, 4,4'-bpy groups and water molecules have been omitted for clarity [Symmetry code: (i) 2 − x, 1 − y, 2 − z.]
	Fig. 4. The two-dimensional supermolecular hydrogen-bonded framework (along the ac plane) formed via O—H···N interactions.

poly[[bis(4,4'-bipyridine-κN)cadmium(II)]-µ₃-4,4'-dicarboxybiphenyl- 3,3'-dicarboxylato] 0.352-hydrate

Crystal data

[Cd(C16H8O8)(C10H8N2)2]·0.35H2O	F(000) = 1534
Mr = 759.34	Dx = 1.661 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 12.101 (5) Å	Cell parameters from 18569 reflections
b = 24.379 (5) Å	θ = 1.7–28.2°
c = 10.679 (5) Å	µ = 0.79 mm^−1
β = 105.413 (5)°	T = 298 K
V = 3037 (2) Å^3	BLOCK, colorless
Z = 4	0.35 × 0.26 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	7162 independent reflections
Radiation source: fine-focus sealed tube	3097 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
Detector resolution: 10.0 pixels mm^-1	θmax = 28.3°, θmin = 1.7°
ω scans	h = −7→15
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −32→32
Tmin = 0.784, Tmax = 0.828	l = −14→14
18797 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.036P)^2] where P = (Fo^2 + 2Fc^2)/3
7162 reflections	(Δ/σ)max = 0.074
454 parameters	Δρmax = 0.62 e Å^−3
0 restraints	Δρmin = −0.64 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	Occ. (<1)
Cd1	0.90990 (4)	0.548869 (16)	0.60887 (4)	0.03137 (14)
C1	1.0949 (5)	0.6760 (2)	1.4369 (5)	0.0304 (14)
C2	1.0549 (5)	0.7268 (2)	1.3886 (5)	0.0448 (18)
H2	1.0795	0.7578	1.4392	0.054*
C3	0.9787 (5)	0.7331 (2)	1.2663 (5)	0.0422 (17)
H3	0.9539	0.7680	1.2366	0.051*
C4	0.9392 (5)	0.6878 (2)	1.1881 (5)	0.0291 (14)
C5	0.9756 (5)	0.6367 (2)	1.2385 (5)	0.0324 (15)
H5	0.9482	0.6059	1.1884	0.039*
C6	1.0511 (4)	0.6291 (2)	1.3603 (5)	0.0274 (13)
C7	0.8585 (5)	0.6924 (2)	1.0572 (5)	0.0283 (14)
C8	0.7753 (5)	0.7341 (2)	1.0308 (5)	0.0327 (14)
H8	0.7734	0.7605	1.0932	0.039*
C9	0.6961 (5)	0.7353 (2)	0.9099 (5)	0.0333 (14)
H9	0.6398	0.7623	0.8931	0.040*
C10	0.6981 (4)	0.69732 (19)	0.8129 (4)	0.0221 (13)
C11	0.7827 (4)	0.65735 (19)	0.8388 (4)	0.0220 (12)
C12	0.8607 (4)	0.6557 (2)	0.9592 (5)	0.0268 (13)
H12	0.9171	0.6287	0.9752	0.032*
C13	1.1896 (5)	0.6733 (2)	1.5605 (6)	0.0377 (16)
C14	1.0722 (4)	0.5717 (2)	1.4110 (5)	0.0270 (14)
C15	0.8039 (5)	0.6169 (2)	0.7439 (5)	0.0270 (13)
C16	0.6056 (5)	0.7008 (2)	0.6875 (5)	0.0321 (14)
C17	0.7529 (5)	0.6151 (2)	0.3680 (5)	0.0369 (15)
H17	0.7763	0.6435	0.4274	0.044*
C18	0.6844 (5)	0.6275 (2)	0.2476 (5)	0.0356 (15)
H18	0.6615	0.6636	0.2276	0.043*
C19	0.6489 (4)	0.5873 (2)	0.1559 (5)	0.0296 (14)
C20	0.6880 (5)	0.5345 (2)	0.1924 (5)	0.0410 (16)
H20	0.6682	0.5058	0.1332	0.049*
C21	0.7553 (5)	0.5245 (2)	0.3145 (5)	0.0429 (17)
H21	0.7797	0.4888	0.3364	0.051*
C22	0.4290 (5)	0.6514 (2)	−0.1220 (6)	0.0413 (16)
H22	0.3800	0.6815	−0.1356	0.050*
C23	0.5006 (5)	0.6435 (2)	0.0005 (5)	0.0369 (15)
H23	0.4994	0.6680	0.0668	0.044*
C24	0.5742 (4)	0.5991 (2)	0.0249 (5)	0.0307 (14)
C25	0.5737 (5)	0.5661 (2)	−0.0790 (5)	0.0468 (18)
H25	0.6236	0.5365	−0.0686	0.056*
C26	0.4990 (6)	0.5767 (3)	−0.2002 (5)	0.0531 (19)
H26	0.5004	0.5536	−0.2690	0.064*
C27	1.1061 (5)	0.6123 (2)	0.8243 (5)	0.0387 (16)
H27	1.0912	0.6367	0.7550	0.046*
C28	1.1770 (5)	0.6288 (2)	0.9425 (5)	0.0404 (16)
H28	1.2088	0.6638	0.9508	0.049*
C29	1.2016 (5)	0.5933 (2)	1.0503 (5)	0.0346 (15)
C30	1.1529 (5)	0.5417 (2)	1.0296 (5)	0.0358 (15)
H30	1.1682	0.5162	1.0967	0.043*
C31	1.0820 (5)	0.5281 (2)	0.9106 (5)	0.0399 (16)
H31	1.0482	0.4935	0.9004	0.048*
C32	1.3739 (6)	0.6798 (3)	1.3239 (6)	0.0543 (19)
H32	1.3801	0.7167	1.3471	0.065*
C33	1.2930 (5)	0.6650 (2)	1.2125 (6)	0.0471 (18)
H33	1.2460	0.6915	1.1625	0.056*
C34	1.2818 (5)	0.6106 (2)	1.1748 (5)	0.0336 (15)
C35	1.3503 (5)	0.5734 (3)	1.2578 (6)	0.056 (2)
H35	1.3427	0.5360	1.2407	0.067*
C36	1.4301 (6)	0.5924 (3)	1.3663 (6)	0.064 (2)
H36	1.4776	0.5668	1.4191	0.077*
N1	0.4260 (4)	0.6184 (2)	−0.2217 (4)	0.0401 (13)
N2	0.7880 (4)	0.56398 (17)	0.4049 (4)	0.0336 (12)
N3	1.0585 (4)	0.56275 (19)	0.8063 (4)	0.0353 (13)
N4	1.4438 (4)	0.6443 (2)	1.4004 (5)	0.0520 (15)
O1	1.2580 (4)	0.63062 (17)	1.5593 (3)	0.0488 (12)
H1	1.2774	0.6169	1.6320	0.073*
O2	1.2042 (4)	0.70631 (16)	1.6440 (4)	0.0557 (13)
O3	1.0579 (3)	0.55962 (14)	1.5182 (3)	0.0407 (10)
O4	1.0988 (3)	0.53745 (14)	1.3326 (3)	0.0462 (11)
O5	0.7839 (3)	0.56738 (14)	0.7515 (3)	0.0367 (10)
O6	0.8586 (3)	0.63558 (13)	0.6660 (3)	0.0330 (9)
O7	0.6062 (3)	0.65876 (16)	0.6114 (4)	0.0406 (10)
H7	0.5494	0.6599	0.5492	0.061*
O8	0.5368 (3)	0.73779 (15)	0.6628 (3)	0.0471 (12)
O9W	0.3789 (16)	0.4901 (9)	0.4412 (19)	0.167 (12)	0.352 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0390 (3)	0.0299 (2)	0.0213 (2)	0.0065 (3)	0.00110 (17)	−0.0009 (2)
C1	0.037 (4)	0.023 (3)	0.025 (3)	−0.002 (3)	−0.003 (3)	−0.004 (2)
C2	0.057 (5)	0.028 (3)	0.037 (4)	−0.002 (3)	−0.009 (4)	−0.005 (3)
C3	0.067 (5)	0.016 (3)	0.032 (3)	0.004 (3)	−0.009 (3)	0.005 (3)
C4	0.034 (4)	0.027 (3)	0.023 (3)	0.000 (3)	0.000 (3)	0.000 (3)
C5	0.039 (4)	0.029 (3)	0.025 (3)	0.001 (3)	0.001 (3)	−0.007 (3)
C6	0.031 (3)	0.031 (3)	0.021 (3)	0.010 (3)	0.007 (3)	0.003 (2)
C7	0.034 (4)	0.019 (3)	0.025 (3)	0.004 (3)	−0.004 (3)	0.005 (2)
C8	0.047 (4)	0.030 (3)	0.021 (3)	0.004 (3)	0.009 (3)	−0.007 (2)
C9	0.035 (4)	0.028 (3)	0.034 (3)	0.013 (3)	0.003 (3)	0.007 (3)
C10	0.030 (3)	0.023 (3)	0.013 (3)	0.001 (3)	0.005 (3)	0.001 (2)
C11	0.029 (3)	0.018 (3)	0.020 (3)	0.001 (3)	0.010 (3)	−0.001 (2)
C12	0.034 (3)	0.027 (3)	0.021 (3)	0.013 (3)	0.010 (3)	−0.001 (2)
C13	0.042 (4)	0.034 (4)	0.033 (4)	0.002 (3)	0.003 (3)	0.014 (3)
C14	0.020 (3)	0.025 (3)	0.030 (3)	0.003 (2)	−0.002 (3)	0.001 (3)
C15	0.029 (3)	0.035 (4)	0.015 (3)	0.008 (3)	0.002 (3)	0.004 (2)
C16	0.031 (4)	0.041 (4)	0.020 (3)	−0.003 (3)	0.000 (3)	0.003 (3)
C17	0.046 (4)	0.034 (4)	0.027 (3)	−0.001 (3)	0.002 (3)	−0.002 (3)
C18	0.043 (4)	0.035 (3)	0.026 (3)	0.003 (3)	0.003 (3)	0.003 (3)
C19	0.022 (3)	0.041 (4)	0.023 (3)	−0.001 (3)	0.000 (3)	0.003 (3)
C20	0.046 (4)	0.037 (4)	0.031 (3)	0.005 (3)	−0.005 (3)	−0.009 (3)
C21	0.058 (5)	0.040 (4)	0.025 (3)	0.009 (3)	0.001 (3)	−0.003 (3)
C22	0.037 (4)	0.044 (4)	0.044 (4)	0.005 (3)	0.013 (3)	0.013 (3)
C23	0.033 (4)	0.042 (4)	0.033 (3)	−0.003 (3)	0.003 (3)	0.002 (3)
C24	0.026 (4)	0.034 (3)	0.028 (3)	−0.001 (3)	0.001 (3)	0.003 (3)
C25	0.045 (4)	0.055 (4)	0.035 (4)	0.014 (3)	−0.001 (3)	0.001 (3)
C26	0.069 (5)	0.054 (4)	0.024 (3)	−0.002 (4)	−0.009 (3)	−0.004 (3)
C27	0.039 (4)	0.038 (4)	0.032 (3)	0.001 (3)	−0.003 (3)	0.010 (3)
C28	0.038 (4)	0.030 (3)	0.044 (4)	−0.008 (3)	−0.006 (3)	0.002 (3)
C29	0.028 (4)	0.042 (4)	0.028 (3)	0.000 (3)	−0.003 (3)	−0.006 (3)
C30	0.040 (4)	0.037 (4)	0.024 (3)	0.001 (3)	−0.002 (3)	0.004 (3)
C31	0.041 (4)	0.033 (3)	0.039 (4)	−0.012 (3)	−0.001 (3)	−0.006 (3)
C32	0.058 (5)	0.056 (4)	0.045 (4)	−0.012 (4)	0.006 (4)	−0.024 (4)
C33	0.046 (4)	0.043 (4)	0.043 (4)	−0.003 (3)	−0.005 (3)	−0.012 (3)
C34	0.029 (4)	0.040 (4)	0.030 (3)	−0.003 (3)	0.004 (3)	−0.008 (3)
C35	0.063 (5)	0.046 (4)	0.042 (4)	0.010 (4)	−0.015 (4)	−0.016 (3)
C36	0.052 (5)	0.082 (6)	0.047 (5)	0.020 (4)	−0.009 (4)	−0.008 (4)
N1	0.037 (3)	0.049 (3)	0.027 (3)	0.002 (3)	−0.003 (2)	0.013 (2)
N2	0.040 (3)	0.030 (3)	0.026 (3)	0.009 (2)	0.002 (2)	0.004 (2)
N3	0.028 (3)	0.044 (3)	0.027 (3)	0.001 (2)	−0.004 (2)	0.000 (2)
N4	0.038 (4)	0.072 (4)	0.042 (3)	−0.004 (3)	0.004 (3)	−0.016 (3)
O1	0.051 (3)	0.056 (3)	0.027 (2)	0.005 (2)	−0.013 (2)	−0.001 (2)
O2	0.073 (3)	0.045 (3)	0.033 (3)	−0.001 (2)	−0.013 (2)	−0.017 (2)
O3	0.045 (3)	0.051 (3)	0.026 (2)	0.002 (2)	0.0086 (19)	0.0175 (19)
O4	0.070 (3)	0.026 (2)	0.035 (2)	0.011 (2)	0.003 (2)	−0.0014 (18)
O5	0.051 (3)	0.024 (2)	0.037 (2)	−0.0006 (19)	0.016 (2)	−0.0049 (17)
O6	0.040 (2)	0.030 (2)	0.028 (2)	0.0034 (19)	0.0047 (19)	−0.0062 (17)
O7	0.033 (3)	0.048 (3)	0.033 (2)	0.000 (2)	−0.0053 (19)	−0.008 (2)
O8	0.045 (3)	0.044 (3)	0.041 (2)	0.016 (2)	−0.009 (2)	0.004 (2)
O9W	0.143 (19)	0.22 (3)	0.14 (2)	−0.036 (16)	0.044 (15)	0.014 (16)

Geometric parameters (Å, º)

Cd1—O4^i	2.206 (3)	C19—C20	1.392 (7)
Cd1—O3^ii	2.266 (4)	C19—C24	1.477 (6)
Cd1—N2	2.312 (4)	C20—C21	1.363 (7)
Cd1—O6	2.330 (3)	C20—H20	0.9300
Cd1—N3	2.404 (4)	C21—N2	1.345 (6)
Cd1—O5	2.466 (4)	C21—H21	0.9300
C1—C2	1.378 (7)	C22—N1	1.327 (7)
C1—C6	1.424 (6)	C22—C23	1.377 (7)
C1—C13	1.503 (7)	C22—H22	0.9300
C2—C3	1.393 (7)	C23—C24	1.382 (7)
C2—H2	0.9300	C23—H23	0.9300
C3—C4	1.390 (6)	C24—C25	1.369 (7)
C3—H3	0.9300	C25—C26	1.391 (7)
C4—C5	1.384 (6)	C25—H25	0.9300
C4—C7	1.482 (6)	C26—N1	1.325 (7)
C5—C6	1.389 (6)	C26—H26	0.9300
C5—H5	0.9300	C27—N3	1.330 (6)
C6—C14	1.497 (7)	C27—C28	1.384 (7)
C7—C12	1.384 (6)	C27—H27	0.9300
C7—C8	1.405 (7)	C28—C29	1.407 (7)
C8—C9	1.389 (6)	C28—H28	0.9300
C8—H8	0.9300	C29—C30	1.382 (7)
C9—C10	1.395 (6)	C29—C34	1.484 (7)
C9—H9	0.9300	C30—C31	1.372 (6)
C10—C11	1.387 (6)	C30—H30	0.9300
C10—C16	1.502 (6)	C31—N3	1.366 (6)
C11—C12	1.378 (6)	C31—H31	0.9300
C11—C15	1.484 (7)	C32—N4	1.329 (7)
C12—H12	0.9300	C32—C33	1.373 (7)
C13—O2	1.180 (6)	C32—H32	0.9300
C13—O1	1.330 (6)	C33—C34	1.381 (7)
C14—O3	1.238 (6)	C33—H33	0.9300
C14—O4	1.284 (6)	C34—C35	1.381 (7)
C15—O5	1.238 (6)	C35—C36	1.377 (8)
C15—O6	1.277 (6)	C35—H35	0.9300
C16—O8	1.208 (6)	C36—N4	1.313 (8)
C16—O7	1.310 (6)	C36—H36	0.9300
C17—N2	1.343 (6)	O1—H1	0.8200
C17—C18	1.366 (6)	O3—Cd1^iii	2.266 (4)
C17—H17	0.9300	O4—Cd1^i	2.206 (3)
C18—C19	1.371 (7)	O7—H7	0.8200
C18—H18	0.9300
O4^i—Cd1—O3^ii	109.54 (14)	C18—C19—C20	116.3 (5)
O4^i—Cd1—N2	110.63 (14)	C18—C19—C24	122.3 (5)
O3^ii—Cd1—N2	87.58 (15)	C20—C19—C24	121.4 (5)
O4^i—Cd1—O6	139.04 (14)	C21—C20—C19	120.3 (5)
O3^ii—Cd1—O6	107.63 (13)	C21—C20—H20	119.9
N2—Cd1—O6	87.38 (13)	C19—C20—H20	119.9
O4^i—Cd1—N3	88.09 (15)	N2—C21—C20	123.1 (5)
O3^ii—Cd1—N3	82.34 (15)	N2—C21—H21	118.4
N2—Cd1—N3	160.90 (15)	C20—C21—H21	118.4
O6—Cd1—N3	80.33 (13)	N1—C22—C23	123.6 (6)
O4^i—Cd1—O5	85.14 (14)	N1—C22—H22	118.2
O3^ii—Cd1—O5	158.62 (12)	C23—C22—H22	118.2
N2—Cd1—O5	102.03 (15)	C24—C23—C22	120.0 (6)
O6—Cd1—O5	54.60 (12)	C24—C23—H23	120.0
N3—Cd1—O5	82.73 (14)	C22—C23—H23	120.0
C2—C1—C6	117.8 (5)	C25—C24—C23	116.3 (5)
C2—C1—C13	118.7 (5)	C25—C24—C19	121.6 (5)
C6—C1—C13	123.3 (5)	C23—C24—C19	122.1 (5)
C1—C2—C3	122.0 (5)	C24—C25—C26	120.5 (6)
C1—C2—H2	119.0	C24—C25—H25	119.8
C3—C2—H2	119.0	C26—C25—H25	119.8
C4—C3—C2	120.8 (5)	N1—C26—C25	122.8 (6)
C4—C3—H3	119.6	N1—C26—H26	118.6
C2—C3—H3	119.6	C25—C26—H26	118.6
C5—C4—C3	117.4 (5)	N3—C27—C28	122.4 (5)
C5—C4—C7	119.8 (5)	N3—C27—H27	118.8
C3—C4—C7	122.8 (5)	C28—C27—H27	118.8
C4—C5—C6	123.1 (5)	C27—C28—C29	120.7 (5)
C4—C5—H5	118.5	C27—C28—H28	119.6
C6—C5—H5	118.5	C29—C28—H28	119.6
C5—C6—C1	118.9 (5)	C30—C29—C28	116.2 (5)
C5—C6—C14	117.9 (5)	C30—C29—C34	123.5 (5)
C1—C6—C14	122.8 (4)	C28—C29—C34	120.2 (5)
C12—C7—C8	118.3 (5)	C31—C30—C29	120.2 (5)
C12—C7—C4	121.6 (5)	C31—C30—H30	119.9
C8—C7—C4	120.1 (5)	C29—C30—H30	119.9
C9—C8—C7	118.8 (5)	N3—C31—C30	123.2 (5)
C9—C8—H8	120.6	N3—C31—H31	118.4
C7—C8—H8	120.6	C30—C31—H31	118.4
C8—C9—C10	122.2 (5)	N4—C32—C33	123.5 (6)
C8—C9—H9	118.9	N4—C32—H32	118.2
C10—C9—H9	118.9	C33—C32—H32	118.2
C9—C10—C11	118.4 (4)	C32—C33—C34	119.8 (6)
C9—C10—C16	118.0 (5)	C32—C33—H33	120.1
C11—C10—C16	123.6 (5)	C34—C33—H33	120.1
C12—C11—C10	119.6 (4)	C35—C34—C33	116.6 (5)
C12—C11—C15	114.6 (4)	C35—C34—C29	121.7 (5)
C10—C11—C15	125.6 (4)	C33—C34—C29	121.6 (5)
C11—C12—C7	122.7 (5)	C36—C35—C34	119.1 (6)
C11—C12—H12	118.7	C36—C35—H35	120.5
C7—C12—H12	118.7	C34—C35—H35	120.5
O2—C13—O1	124.9 (6)	N4—C36—C35	124.5 (6)
O2—C13—C1	124.0 (6)	N4—C36—H36	117.8
O1—C13—C1	111.0 (5)	C35—C36—H36	117.8
O3—C14—O4	124.7 (5)	C26—N1—C22	116.8 (5)
O3—C14—C6	120.3 (5)	C17—N2—C21	116.3 (4)
O4—C14—C6	114.9 (5)	C17—N2—Cd1	119.8 (3)
O5—C15—O6	122.3 (5)	C21—N2—Cd1	123.7 (4)
O5—C15—C11	122.1 (5)	C27—N3—C31	117.1 (4)
O6—C15—C11	115.0 (5)	C27—N3—Cd1	116.7 (3)
O8—C16—O7	124.5 (5)	C31—N3—Cd1	124.9 (4)
O8—C16—C10	123.0 (5)	C36—N4—C32	116.4 (5)
O7—C16—C10	112.5 (5)	C13—O1—H1	109.5
N2—C17—C18	123.1 (5)	C14—O3—Cd1^iii	138.0 (3)
N2—C17—H17	118.4	C14—O4—Cd1^i	113.4 (3)
C18—C17—H17	118.4	C15—O5—Cd1	88.6 (3)
C17—C18—C19	120.8 (5)	C15—O6—Cd1	93.9 (3)
C17—C18—H18	119.6	C16—O7—H7	109.5
C19—C18—H18	119.6
C6—C1—C2—C3	−3.2 (9)	C27—C28—C29—C34	177.3 (5)
C13—C1—C2—C3	171.1 (6)	C28—C29—C30—C31	−2.1 (8)
C1—C2—C3—C4	0.4 (10)	C34—C29—C30—C31	−178.1 (5)
C2—C3—C4—C5	2.1 (9)	C29—C30—C31—N3	2.3 (9)
C2—C3—C4—C7	−179.8 (6)	N4—C32—C33—C34	−0.3 (10)
C3—C4—C5—C6	−1.9 (9)	C32—C33—C34—C35	3.5 (9)
C7—C4—C5—C6	−180.0 (5)	C32—C33—C34—C29	−175.4 (6)
C4—C5—C6—C1	−1.0 (9)	C30—C29—C34—C35	27.7 (9)
C4—C5—C6—C14	172.2 (5)	C28—C29—C34—C35	−148.2 (6)
C2—C1—C6—C5	3.5 (8)	C30—C29—C34—C33	−153.5 (6)
C13—C1—C6—C5	−170.6 (5)	C28—C29—C34—C33	30.6 (9)
C2—C1—C6—C14	−169.4 (5)	C33—C34—C35—C36	−4.5 (10)
C13—C1—C6—C14	16.5 (9)	C29—C34—C35—C36	174.4 (6)
C5—C4—C7—C12	−33.1 (8)	C34—C35—C36—N4	2.6 (11)
C3—C4—C7—C12	148.8 (6)	C25—C26—N1—C22	1.9 (9)
C5—C4—C7—C8	145.4 (6)	C23—C22—N1—C26	−1.8 (9)
C3—C4—C7—C8	−32.6 (8)	C18—C17—N2—C21	2.2 (9)
C12—C7—C8—C9	2.7 (8)	C18—C17—N2—Cd1	177.5 (4)
C4—C7—C8—C9	−175.9 (5)	C20—C21—N2—C17	−1.4 (9)
C7—C8—C9—C10	−1.6 (8)	C20—C21—N2—Cd1	−176.6 (4)
C8—C9—C10—C11	−0.3 (8)	O4^i—Cd1—N2—C17	159.2 (4)
C8—C9—C10—C16	177.6 (5)	O3^ii—Cd1—N2—C17	−90.9 (4)
C9—C10—C11—C12	1.0 (7)	O6—Cd1—N2—C17	16.9 (4)
C16—C10—C11—C12	−176.7 (5)	N3—Cd1—N2—C17	−32.8 (8)
C9—C10—C11—C15	−174.4 (5)	O5—Cd1—N2—C17	69.9 (4)
C16—C10—C11—C15	8.0 (8)	O4^i—Cd1—N2—C21	−25.8 (5)
C10—C11—C12—C7	0.2 (8)	O3^ii—Cd1—N2—C21	84.1 (5)
C15—C11—C12—C7	176.0 (5)	O6—Cd1—N2—C21	−168.1 (5)
C8—C7—C12—C11	−2.1 (8)	N3—Cd1—N2—C21	142.1 (5)
C4—C7—C12—C11	176.5 (5)	O5—Cd1—N2—C21	−115.1 (4)
C2—C1—C13—O2	29.8 (9)	C28—C27—N3—C31	0.3 (9)
C6—C1—C13—O2	−156.2 (6)	C28—C27—N3—Cd1	168.1 (4)
C2—C1—C13—O1	−146.5 (6)	C30—C31—N3—C27	−1.3 (9)
C6—C1—C13—O1	27.5 (8)	C30—C31—N3—Cd1	−168.0 (4)
C5—C6—C14—O3	−125.5 (6)	O4^i—Cd1—N3—C27	177.1 (4)
C1—C6—C14—O3	47.5 (8)	O3^ii—Cd1—N3—C27	67.1 (4)
C5—C6—C14—O4	50.9 (7)	N2—Cd1—N3—C27	8.3 (8)
C1—C6—C14—O4	−136.2 (5)	O6—Cd1—N3—C27	−42.4 (4)
C12—C11—C15—O5	73.8 (7)	O5—Cd1—N3—C27	−97.6 (4)
C10—C11—C15—O5	−110.6 (6)	O4^i—Cd1—N3—C31	−16.2 (5)
C12—C11—C15—O6	−96.8 (5)	O3^ii—Cd1—N3—C31	−126.2 (5)
C10—C11—C15—O6	78.8 (7)	N2—Cd1—N3—C31	175.1 (4)
C9—C10—C16—O8	7.1 (8)	O6—Cd1—N3—C31	124.4 (5)
C11—C10—C16—O8	−175.2 (5)	O5—Cd1—N3—C31	69.2 (5)
C9—C10—C16—O7	−170.8 (5)	C35—C36—N4—C32	0.7 (11)
C11—C10—C16—O7	6.9 (7)	C33—C32—N4—C36	−1.9 (10)
N2—C17—C18—C19	−1.0 (9)	O4—C14—O3—Cd1^iii	−105.3 (6)
C17—C18—C19—C20	−0.9 (8)	C6—C14—O3—Cd1^iii	70.7 (7)
C17—C18—C19—C24	179.6 (5)	O3—C14—O4—Cd1^i	9.4 (7)
C18—C19—C20—C21	1.6 (9)	C6—C14—O4—Cd1^i	−166.8 (3)
C24—C19—C20—C21	−178.9 (5)	O6—C15—O5—Cd1	8.3 (5)
C19—C20—C21—N2	−0.5 (10)	C11—C15—O5—Cd1	−161.6 (4)
N1—C22—C23—C24	−0.3 (9)	O4^i—Cd1—O5—C15	167.3 (3)
C22—C23—C24—C25	2.4 (8)	O3^ii—Cd1—O5—C15	32.5 (5)
C22—C23—C24—C19	−177.1 (5)	N2—Cd1—O5—C15	−82.6 (3)
C18—C19—C24—C25	154.9 (6)	O6—Cd1—O5—C15	−4.7 (3)
C20—C19—C24—C25	−24.5 (8)	N3—Cd1—O5—C15	78.6 (3)
C18—C19—C24—C23	−25.7 (8)	O5—C15—O6—Cd1	−8.8 (5)
C20—C19—C24—C23	154.9 (6)	C11—C15—O6—Cd1	161.8 (4)
C23—C24—C25—C26	−2.3 (9)	O4^i—Cd1—O6—C15	−7.7 (4)
C19—C24—C25—C26	177.2 (5)	O3^ii—Cd1—O6—C15	−162.1 (3)
C24—C25—C26—N1	0.2 (10)	N2—Cd1—O6—C15	111.3 (3)
N3—C27—C28—C29	−0.2 (9)	N3—Cd1—O6—C15	−83.4 (3)
C27—C28—C29—C30	1.1 (9)	O5—Cd1—O6—C15	4.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1^iv	0.82	2.04	2.677 (6)	134
O7—H7···N4^v	0.82	1.80	2.590 (6)	163

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