One- and two-dimensional Cd^II coordination polymers constructed from 2-(2-methyl-1H-benzimidazol-1-yl)acetate ligands

The one- and two-dimensional polymorphic cadmium poly­carboxyl­ate coordination polymers, catena-poly[bis[μ₂-2-(2-methyl-1H-benzimidazol-1-yl)acetato-κ³N³:O,O′]cadmium(II)], [Cd(C₁₀H₉N₂O₂)₂]_n, and poly[bis[μ₂-2-(2-methyl-1H-benzimidazol-1-yl)acetato-κ³N³:O,O′]cadmium(II)], also [Cd(C₁₀H₉N₂O₂)₂]_n, were prepared under solvothermal conditions. In each structure, each Cd^II atom is coordinated by four O atoms and two N atoms from four different ligands. In the former structure, two crystallographically independent Cd^II atoms are located on twofold symmetry axes and doubly bridged in a μ₂-N:O,O′-mode by the ligands into correspondingly independent chains that run in the [100] and [010] directions. Chains containing crystallographically related Cd^II atoms are linked into sheets via π–π stacking inter­actions. Sheets containing one of the distinct types of Cd^II atom are stacked perpendicular to [001] and alternate with sheets containing the other type of Cd^II atom. The second complex is a two-dimensional homometallic Cd^II (4,4) net structure in which each Cd^II atom is singly bridged to four neighbouring Cd^II atoms by four ligands also acting in a μ₂-N:O,O′-mode. A square-grid network results and the three-dimensional supra­molecular framework is completed by π–π stacking inter­actions between the aromatic ring systems.

S1. Introduction

A great deal of attention has been paid to the crystal engineering of metal–organic coordination polymers in recent years, due to a conbination of their fascinating molecular structures and their potential applications as functional materials (Kahn & Martinez, 1998; Xiong et al., 2001; Batten et al., 2009; Liao et al., 2004). A series of cadmium coordination polymers containing carboxyl­ate ligands have been reported (Yang et al., 2009; Zheng et al., 2012; Zhou et al., 2011; Nie & Wang, 2011; Han et al., 2012; Wang et al., 2012). According to previous reports, asymmetric bridging ligands containing carb­oxy­lic acid and nitro­gen groups with a variety of properties are excellent candidates for the construction of highly connected topological frameworks. The structural topologies of these polymers are affected by the coordination geometries of both the organic ligands and the metal atoms. Bridging ligands with N- and O-donor atoms play an instrumental role in building coordination polymers. Among the various ligands, the versatile carb­oxy­lic acid ligands display diverse coordination modes. In particular, the aromatic carb­oxy­lic acids, such as benzene- and naphthalene-based derivatives, have been used and well documented in the preparation of numerous carboxyl­ate-containing coordination complexes. In order to explore new coordination polymers using rigid building blocks, we synthesized a novel benzimidazole-derivative ligand containing a carb­oxy­lic acid group, namely, (2-methyl­benzimidazol-l-yl)acetate, L, which is formed in situ from the corresponding cyano-substituted derivative under solvothermal conditions in the presence of Cd^II cations. We report here the crystal structure of two new `polymorphic' Cd^II coordination polymers based on this ligand, (I) and (II), which show some inter­esting structural features.

S2. Experimental

S2.1. Synthesis and crystallization

(2-Methyl­benzimidazol-1-yl)aceto­nitrile was prepared by an adaptation of the literature method of Ramla et al. (2006) for the synthesis of 2-(2-methyl-5-nitro-1H-benzimidazol-1-yl)aceto­nitrile. To a solution of 2-methyl­benzimidazole (7.48g, 56.6 mmol) and sodium hydride (1.5g, 56.6 mmol) in tetra­hydro­furan (30 ml), bromo­aceto­nitrile (3.96 ml, 56.6 mmol) was added dropwise. The reaction mixture was stirred for 8 h at room temperature and then poured onto iced water. The obtained precipitate was filtered off, dried and recrystallized from ethanol (yield 8.24 g, 85%).

For the synthesis of (I), a mixture of (2-methyl­benzimidazol-1-yl)aceto­nitrile (0.0274g, 0.16mmol), Cd(ClO₄)₂·6H₂O (0.0336g, 0.08 mmol) and pyridine (0.0312 g, 0.2 mmol) was dissolved in deionized water and stirred for 30 min in air. The mixture was sealed in a 25 ml Teflon-lined stainless steel vessel, heated at 453 K for 3 d under autogenous pressure and then cooled to room temperature. Highly pure and well shaped colourless block crystals of (I) were collected in 67% yield. During the reaction under solvothermal conditions, the nitrile group of (I) is hydrolysed to a carboxyl­ate group (Liu & Ye, 2013).

For the synthesis of (II), a mixture of Cd(CH₃COO)₂.2H₂O (0.053 g, 0.2 mmol), (2-methyl­benzimidazol-1-yl)aceto­nitrile (0.068 g, 0.4 mmol) and distilled water (9 ml) was stirred to homogeneity for 10 min in air. The mixture was then transferred to a 20 ml Teflon-lined steel autoclave and heated at 433 K for 5 d under autogenously controlled pressure, followed by slow cooling to room temperature. Colourless blocks of complex (II) were collected (yield ca 65%, based on Cd).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methyl­ene), and with U_iso(H) = 1.5U_eq(C) for methyl groups or 1.2U_eq(C) otherwise.

S3. Results and discussion

The asymmetric unit of complex (I) contains two independent Cd atoms located on twofold symmetry axes and (2-methyl­benzimidazol-l-yl)acetate ligands in general positions. In this context, the cyano group of (2-methyl­benzimidazol-1-yl)aceto­nitrile has been hydrolysed to a carboxyl­ate group under hydro­thermal conditions. As shown in Fig. 1, each of the central Cd atoms (Cd1 and Cd2) is six-coordinated by four O atoms from two L carboxyl­ate groups and two N atoms from imidazole rings of two further L ligands. Both Cd atoms adopt a distorted o­cta­hedral coordination geometry, brought about mainly by the small bite angles of the bidentate carboxyl­ate groups (Table 2). All the carboxyl­ate groups maintain approximate equivalence of their C—O bonds, with lengths in the range 1.23–1.27 Å. The ranges shown by the Cd—O and Cd—N bond lengths (Table 2) are in good agreement with those found in other Cd complexes with six-coordinated geometries (Dai et al., 2002). The O1—Cd1—O2 and O3—Cd2—O4 angles (Table 2) are similar to those reported in other cadmium polymers coordinated by two O atoms from a carboxyl­ate group (Luo et al., 2004).

Compound (I) is a new coordination polymer in which both of the six-coordinated Cd centres adopt a distorted o­cta­hedral coordination geometry. It displays a novel coordination architecture compared with a similar compound, {[Cd(H₂PIMDC)₂]}_n (Zhai et al., 2013), in which the central Cd^II cation is coordinated by only one O atom of one carboxyl­ate group of each of four 2-propyl-1H-imidazole-4,5-di­carboxyl­ate (H₂PIMDC) ligands, rather than two O atoms of a carboxyl­ate group, plus the N atoms from just two of these ligands. Compound (I) also differs from another Cd complex with H₂PIDMC, [Cd(H₂PIMDC)₂(H₂O)₂]·4H₂O (Deng et al., 2012), where the central Cd cation is again coordinated by one O atom of one carboxyl­ate group and an N atom of each of two H₂PIMDC ligands, plus two O atoms from two coordinated water molecules, resulting in a distorted o­cta­hedral geometry.

The (2-methyl­benzimidazol-l-yl)acetate ligand in (I) is tridentate and links two Cd centres in chelate and chelate-bridged (µ₃-N:O,O) modes to form one-dimensional chains, in which two L ligands bridge each Cd atom (Figs. 2 and 3). In our notation, the letters A, B, C, D and A', B', C', D' denote imidazole rings in adjacent parallel sets of one-dimensional chains involving atoms Cd1 and Cd2, respectively. Within the chains containing Cd1, the dihedral angles between the planes of A and B, and between the symmetry-related pair C and D, are 53.07 (14)°, whereas within the chains containing Cd2, the dihedral angles between the planes of A' and B', and between C' and D', are 57.98 (14)°. Planes B and C, which are in adjacent chains composed of Cd1 atoms, and planes B' and C' from adjacent chains composed of Cd2 atoms, are close to being parallel, with dihedral angles of 3.73 (14) and 6.30 (14)°, respectively. Thus, for each of the two independent polymeric chains, there are weak π–π stacking inter­actions between adjacent imidazole rings, which leads to stacks of chains containing just one of the independent types of Cd atom. They are characterized by ring B–C and B'–C' centroid-to-centroid distances of 3.8446 (14) and 3.9664 (15) Å, respectively. The perpendicular displacement from the ring centroid of plane B to the mean plane C is 3.7096 (10) Å, and the perpendicular distance from the ring centroid of plane B' to the mean plane C' is 3.4548 (10) Å. In addition, it is likely that the steric inter­action resulting from the optimization of this stacking inter­action may explain the difference in the dihedral angles between adjacent imidazole rings, and the effect of this inter­action is to link molecules related by translation into chains.

A noteworthy feature of this structure is that the chains containing the Cd1 atoms run perpendicular to those containing the Cd2 atoms (Figs. 2 and 3). The chains containing the Cd1 atoms run parallel to the [100] direction with an intra­chain Cd···Cd distance of 7.3521 (4) Å, while the chains containing the Cd2 atoms run parallel to the [010] direction with an intra­chain Cd···Cd distance of 7.0037 (4) Å. In both cases, the π–π inter­actions link the chains into layers which lie parallel to the (001) plane (Fig. 4), but the two types are turned through 90° in this plane with respect to each other. These layers containing atoms Cd1 then stack along the [001] direction in an alternating fashion with those containing atoms Cd2.

The asymmetric unit of complex (II) contains one Cd^II cation and one L ligand, both in general positions (Fig. 5). As shown in Fig. 6, the central Cd^II cation is coordinated by four O atoms from the carboxyl­ate group of two L ligands and two benzimidazole N atoms from another two L ligands, forming a highly distorted CdO₄N₂ o­cta­hedral coordination geometry. Each L ligand acts in a µ₃-N:O,O mode to bridge two Cd^II cations through one chelating carboxyl­ate group and one benzimidazole N atom.

The six-coordinate geometry of (II) is similar to that in other carboxyl­ate-containing Cd^II complexes, e.g. [Cd(4-pyridyl­acrylate)₂].H₂O (Evans & Lin, 2001) and [Cd(oba)(1,4-bix)] [oba = 4,4'-oxybis(benzoate) and 1,4-bix = 1,4-bis­(imidazol-1-yl­methyl)­benzene; Yang et al., 2009]. The Cd—O and Cd—N bond lengths (Table 3), with the bond angles around each Cd^II centre ranging from 54.39 (18) to 154.3 (2)°, are fundamentally consistent with those in the above-mentioned Cd^II complexes. In contrast, the crystal structure of {Cd[4-(4-pyridyl)­benzoate]₂}.H₂O exhibits two distinct metal-atom coordination geometries; one is o­cta­hedral and similar to that in (II), while the other is trigonal–bipyramidal, with one of the carboxyl­ate groups only coordinating in a monodentate fashion (Evans & Lin, 2001).

In contrast with the structure of (I), where double bridges of L exist between adjacent Cd atoms to give a chain structure, each Cd atom in (II) is singly bridged by four L ligands to four different Cd atoms, which generates a two-dimensional (4,4) net structure that extends parallel to the (001) plane (Fig. 7). This connectivity leads to square-grid sheets, with a Cd···Cd distance along each grid side of 8.173 (4) Å. In each grid of two-dimensional sheets there are two benzimidazole rings projecting above and two below the plane defined by the Cd atoms. These benzimidazole rings participate in π–π inter­actions with benzimidazole rings from adjacent layers, with an inter­planar spacing of 3.415 (3) Å and a centroid separation of 3.564 (5) Å. These weak π–π stacking inter­actions between symmetry-related benzimidazole rings complete the three-dimensional supra­molecular structure of (II) (Fig. 8). The cavities in the (4,4) grid apparent in Fig. 7 are occupied by the benzene rings of L ligands in the adjacent layers on either side.

In conclusion, to the best of our knowledge, complexes (I) and (II) are new one- and two-dimensional cadmium coordination polymers of a new (2-methyl­benzimidazol-l-yl)acetate ligand. The complexes are polymorphs which form under solvothermal conditions involving slightly different components; for (I), pyridine was included in the reaction mixure, whereas no pyridine was used for the synthesis of (II). This work suggests that this carboxyl­ate-based ligand will be a rich source of new coordination polymers.

Related literature

For related literature, see: Batten et al. (2009); Evans & Lin (2001); Han et al. (2012); Kahn & Martinez (1998); Liao et al. (2004); Nie & Wang (2011); Ramla et al. (2006); Wang et al. (2012); Xiong et al. (2001); Yang et al. (2009); Zheng et al. (2012); Zhou et al. (2011).

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. (a) The local coordination environment of Cd1 in (I), viewed down the b axis and showing the atom-numbering scheme. (b) The coordination environment of Cd2 in (I), viewed down the a axis. [Symmetry codes: (i) x - 1/2, -y + 1, z; (ii) -x + 1/2, y + 1/2, z; (iii) x - 1/2, y, -z + 1/2; (iv) x, y + 1/2, -z; (v) -x + 1/2, y, -z; (vi) x, -y + 1, -z + 1/2.]
	Fig. 2. The two-dimensional network layer in (I) lying perpendicular to [001], formed via π–π stacking interactions (dashed lines) between Cd1-based polymeric chains running in the [100] direction. H atoms have been omitted for clarity.
	Fig. 3. The two-dimensional network layer in (I) perpendicular to [001], formed via π–π stacking interactions (dashed lines) between Cd2-based polymeric chains running in the [010] direction. H atoms have been omitted for clarity.
	Fig. 4. (a) A packing view of (I), showing the mutually perpendicular coordination polymer chains. H atoms have been omitted for clarity. (b) A schematic view of the topology of (I). The orange rods represent one type of coordination polymer chain and the blue dots represent the other chain running into the page.
	Fig. 5. The asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted.
	Fig. 6. A view of complex (II), depicting the coordination environment around the Cd centre. H atoms have been omitted for clarity. [Symmetry codes: (i) 1/2 + x, -1/2 + y, z; (ii) 3/2 - x, -1/2 + y, 1/2 - z; (iii) 2 - x, y, 1/2 - z.]
	Fig. 7. The square grid-like structure of complex (II) formed by the Cd^II centres, viewed in the (001) plane.
	Fig. 8. An illustration of the three-dimensional supramolecular network of (II), formed by π–π stacking interactions (indicated by dashed lines) between benzimidazole rings of parallel sheets, viewed along (left) the [001] direction and (right) the [100] direction.

(I) catena-poly[bis[µ₃-(2-methylbenzimidazol-1-yl)acetato]cadmium(II)]

Crystal data

[Cd(C10H9N2O2)2]	F(000) = 3936
Mr = 490.79	Dx = 1.668 Mg m^−3
Orthorhombic, Ibca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2b 2c	Cell parameters from 26640 reflections
a = 14.7042 (4) Å	θ = 3.0–27.6°
b = 14.0074 (4) Å	µ = 1.15 mm^−1
c = 37.9500 (9) Å	T = 293 K
V = 7816.5 (4) Å^3	Block, colourless
Z = 16	0.38 × 0.34 × 0.3 mm

Data collection

Rigaku SCXmini diffractometer	3781 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
ω scans	h = −18→19
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
Tmin = 0.652, Tmax = 0.708	l = −48→43
29375 measured reflections	3 standard reflections every 180 reflections
4479 independent reflections	intensity decay: none

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.022P)^2 + 9.7962P] where P = (Fo^2 + 2Fc^2)/3
4479 reflections	(Δ/σ)max = 0.001
265 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.37 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	0.129398 (16)	0.5000	0.2500	0.03330 (8)
Cd2	0.2500	0.593964 (16)	0.0000	0.03393 (8)
O1	0.26067 (13)	0.46968 (13)	0.21094 (6)	0.0518 (5)
O2	0.17001 (13)	0.35199 (13)	0.22580 (6)	0.0506 (5)
O4	0.08714 (16)	0.56909 (13)	0.02627 (6)	0.0578 (6)
O3	0.20319 (14)	0.47327 (13)	0.03579 (5)	0.0520 (5)
N1	0.53243 (13)	0.41704 (14)	0.21568 (5)	0.0335 (4)
N2	0.40367 (14)	0.34711 (14)	0.19958 (5)	0.0329 (4)
N4	0.09618 (14)	0.32183 (13)	0.05082 (5)	0.0342 (4)
N3	0.16944 (15)	0.19040 (14)	0.03481 (5)	0.0356 (5)
C3	0.4919 (2)	0.3809 (2)	0.10906 (7)	0.0559 (8)
H3	0.4802	0.3721	0.0852	0.067*
C4	0.5733 (2)	0.4205 (2)	0.11924 (8)	0.0569 (8)
H4	0.6157	0.4363	0.1020	0.068*
C5	0.5944 (2)	0.4377 (2)	0.15400 (7)	0.0469 (7)
H5	0.6493	0.4656	0.1605	0.056*
C8	0.42830 (18)	0.36733 (19)	0.26423 (6)	0.0406 (6)
H8A	0.4810	0.3723	0.2790	0.061*
H8B	0.4004	0.3060	0.2676	0.061*
H8C	0.3857	0.4166	0.2703	0.061*
C7	0.45592 (15)	0.37813 (16)	0.22664 (6)	0.0307 (5)
C10	0.24304 (17)	0.38308 (18)	0.21353 (6)	0.0351 (5)
C2	0.4270 (2)	0.3537 (2)	0.13340 (7)	0.0472 (7)
H2	0.3720	0.3266	0.1266	0.057*
C9	0.31234 (16)	0.30858 (18)	0.20261 (7)	0.0374 (6)
H9A	0.3125	0.2574	0.2198	0.045*
H9B	0.2944	0.2816	0.1801	0.045*
C1	0.44851 (16)	0.36892 (17)	0.16840 (6)	0.0337 (5)
C6	0.52988 (17)	0.41136 (17)	0.17888 (6)	0.0342 (5)
C20	0.11966 (19)	0.49194 (17)	0.03585 (7)	0.0389 (6)
C15	0.1860 (2)	0.1231 (2)	0.09647 (8)	0.0506 (7)
H15	0.2130	0.0657	0.0899	0.061*
C14	0.1687 (2)	0.1439 (3)	0.13138 (8)	0.0587 (8)
H14	0.1840	0.0995	0.1486	0.070*
C19	0.05368 (18)	0.41504 (17)	0.04737 (7)	0.0394 (6)
H19A	0.0273	0.4330	0.0698	0.047*
H19B	0.0047	0.4109	0.0303	0.047*
C12	0.10187 (19)	0.2971 (2)	0.11700 (7)	0.0463 (7)
H12	0.0748	0.3543	0.1237	0.056*
C13	0.1286 (2)	0.2298 (3)	0.14133 (8)	0.0565 (8)
H13	0.1197	0.2421	0.1652	0.068*
C18	0.12148 (19)	0.29955 (18)	−0.01369 (7)	0.0413 (6)
H18A	0.1713	0.3410	−0.0195	0.062*
H18B	0.0651	0.3330	−0.0170	0.062*
H18C	0.1230	0.2444	−0.0287	0.062*
C11	0.11781 (16)	0.27448 (19)	0.08191 (7)	0.0357 (5)
C16	0.16161 (17)	0.19135 (18)	0.07157 (6)	0.0363 (5)
C17	0.12932 (16)	0.26905 (17)	0.02374 (6)	0.0326 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02637 (13)	0.03605 (14)	0.03748 (15)	0.000	0.000	−0.00250 (11)
Cd2	0.03733 (15)	0.02713 (12)	0.03732 (14)	0.000	0.00199 (11)	0.000
O1	0.0407 (11)	0.0396 (10)	0.0752 (14)	0.0031 (8)	0.0003 (10)	−0.0025 (10)
O2	0.0367 (11)	0.0500 (11)	0.0652 (14)	0.0004 (8)	0.0178 (10)	−0.0049 (9)
O4	0.0817 (16)	0.0354 (10)	0.0562 (13)	−0.0030 (10)	0.0024 (11)	0.0125 (9)
O3	0.0498 (13)	0.0408 (11)	0.0655 (14)	−0.0089 (9)	0.0116 (10)	0.0007 (9)
N1	0.0280 (11)	0.0419 (11)	0.0307 (11)	−0.0014 (9)	0.0012 (8)	0.0038 (9)
N2	0.0276 (10)	0.0370 (11)	0.0341 (11)	−0.0015 (8)	0.0030 (8)	−0.0029 (9)
N4	0.0387 (12)	0.0283 (10)	0.0355 (11)	−0.0012 (8)	0.0042 (9)	0.0006 (8)
N3	0.0424 (12)	0.0324 (10)	0.0320 (11)	0.0026 (9)	−0.0055 (9)	−0.0004 (9)
C3	0.067 (2)	0.072 (2)	0.0283 (15)	0.0027 (16)	0.0006 (14)	0.0008 (14)
C4	0.057 (2)	0.077 (2)	0.0364 (16)	−0.0037 (16)	0.0138 (14)	0.0127 (14)
C5	0.0411 (15)	0.0571 (17)	0.0424 (16)	−0.0062 (13)	0.0054 (12)	0.0096 (13)
C8	0.0410 (15)	0.0480 (15)	0.0327 (14)	−0.0059 (12)	0.0042 (11)	0.0022 (11)
C7	0.0272 (12)	0.0326 (12)	0.0324 (13)	0.0028 (9)	0.0018 (9)	0.0012 (10)
C10	0.0307 (13)	0.0411 (13)	0.0336 (13)	0.0007 (11)	−0.0040 (11)	−0.0037 (10)
C2	0.0464 (17)	0.0543 (17)	0.0409 (16)	−0.0009 (13)	−0.0051 (13)	−0.0064 (13)
C9	0.0303 (13)	0.0374 (13)	0.0445 (15)	−0.0030 (10)	0.0035 (11)	−0.0063 (11)
C1	0.0314 (13)	0.0363 (12)	0.0332 (13)	0.0047 (10)	0.0016 (10)	−0.0001 (10)
C6	0.0315 (13)	0.0378 (13)	0.0333 (13)	0.0024 (10)	0.0017 (10)	0.0028 (10)
C20	0.0562 (18)	0.0318 (13)	0.0287 (13)	−0.0073 (12)	0.0082 (11)	−0.0040 (10)
C15	0.0486 (17)	0.0564 (17)	0.0467 (18)	0.0098 (14)	−0.0077 (13)	0.0074 (14)
C14	0.055 (2)	0.082 (2)	0.0387 (17)	0.0079 (17)	−0.0069 (14)	0.0173 (15)
C19	0.0413 (15)	0.0320 (13)	0.0448 (15)	0.0039 (10)	0.0108 (12)	0.0012 (11)
C12	0.0467 (16)	0.0540 (17)	0.0382 (15)	−0.0086 (13)	0.0069 (12)	−0.0058 (13)
C13	0.0529 (19)	0.085 (2)	0.0311 (16)	−0.0061 (16)	−0.0006 (13)	−0.0007 (15)
C18	0.0507 (17)	0.0359 (14)	0.0373 (14)	0.0055 (12)	−0.0028 (12)	0.0026 (11)
C11	0.0315 (13)	0.0400 (13)	0.0356 (14)	−0.0083 (11)	−0.0002 (10)	−0.0006 (11)
C16	0.0351 (13)	0.0399 (13)	0.0340 (13)	−0.0028 (11)	−0.0028 (10)	0.0004 (11)
C17	0.0342 (13)	0.0305 (11)	0.0331 (13)	−0.0034 (10)	−0.0017 (10)	−0.0002 (10)

Geometric parameters (Å, º)

Cd1—N1^i	2.254 (2)	C3—H3	0.9300
Cd1—N1^ii	2.254 (2)	C4—C5	1.376 (4)
Cd1—O1^iii	2.471 (2)	C4—H4	0.9300
Cd1—O1	2.471 (2)	C5—C6	1.388 (3)
Cd1—O2^iii	2.3448 (19)	C5—H5	0.9300
Cd1—O2	2.3448 (19)	C8—C7	1.491 (3)
Cd1—C10^iii	2.718 (2)	C8—H8A	0.9600
Cd2—N3^iv	2.230 (2)	C8—H8B	0.9600
Cd2—N3^v	2.230 (2)	C8—H8C	0.9600
Cd2—O3^vi	2.2753 (19)	C10—C9	1.516 (3)
Cd2—O3	2.2753 (19)	C2—C1	1.382 (4)
Cd2—O4^vi	2.617 (2)	C2—H2	0.9300
Cd2—O4	2.617 (2)	C9—H9A	0.9700
Cd2—C20^vi	2.751 (3)	C9—H9B	0.9700
O1—C10	1.244 (3)	C1—C6	1.394 (3)
O2—C10	1.249 (3)	C20—C19	1.514 (3)
O4—C20	1.236 (3)	C15—C14	1.381 (4)
O3—C20	1.256 (3)	C15—C16	1.392 (4)
N1—C7	1.317 (3)	C15—H15	0.9300
N1—C6	1.400 (3)	C14—C13	1.392 (5)
N1—Cd1^vii	2.254 (2)	C14—H14	0.9300
N2—C7	1.354 (3)	C19—H19A	0.9700
N2—C1	1.389 (3)	C19—H19B	0.9700
N2—C9	1.452 (3)	C12—C13	1.377 (4)
N4—C17	1.356 (3)	C12—C11	1.389 (4)
N4—C11	1.390 (3)	C12—H12	0.9300
N4—C19	1.453 (3)	C13—H13	0.9300
N3—C17	1.318 (3)	C18—C17	1.488 (3)
N3—C16	1.400 (3)	C18—H18A	0.9600
N3—Cd2^viii	2.230 (2)	C18—H18B	0.9600
C3—C4	1.375 (5)	C18—H18C	0.9600
C3—C2	1.381 (4)	C11—C16	1.387 (4)
N1^i—Cd1—N1^ii	101.51 (10)	C4—C5—H5	121.6
N1^i—Cd1—O2^iii	86.07 (7)	C6—C5—H5	121.6
N1^ii—Cd1—O2^iii	113.00 (7)	C7—C8—H8A	109.5
N1^i—Cd1—O2	113.00 (7)	C7—C8—H8B	109.5
N1^ii—Cd1—O2	86.07 (7)	H8A—C8—H8B	109.5
O2^iii—Cd1—O2	150.49 (10)	C7—C8—H8C	109.5
N1^i—Cd1—O1^iii	138.79 (7)	H8A—C8—H8C	109.5
N1^ii—Cd1—O1^iii	103.66 (7)	H8B—C8—H8C	109.5
O2^iii—Cd1—O1^iii	54.13 (6)	N1—C7—N2	112.2 (2)
O2—Cd1—O1^iii	100.84 (7)	N1—C7—C8	125.2 (2)
N1^i—Cd1—O1	103.66 (7)	N2—C7—C8	122.6 (2)
N1^ii—Cd1—O1	138.79 (7)	O1—C10—O2	123.3 (2)
O2^iii—Cd1—O1	100.84 (7)	O1—C10—C9	120.6 (2)
O2—Cd1—O1	54.13 (6)	O2—C10—C9	116.1 (2)
O1^iii—Cd1—O1	77.24 (10)	C3—C2—C1	116.3 (3)
N1^i—Cd1—C10^iii	111.87 (7)	C3—C2—H2	121.9
N1^ii—Cd1—C10^iii	113.91 (7)	C1—C2—H2	121.9
O2^iii—Cd1—C10^iii	27.30 (7)	N2—C9—C10	112.8 (2)
O2—Cd1—C10^iii	125.13 (7)	N2—C9—H9A	109.0
O1^iii—Cd1—C10^iii	27.21 (7)	C10—C9—H9A	109.0
O1—Cd1—C10^iii	85.91 (7)	N2—C9—H9B	109.0
N3^iv—Cd2—N3^v	105.44 (10)	C10—C9—H9B	109.0
N3^iv—Cd2—O3^vi	130.02 (8)	H9A—C9—H9B	107.8
N3^v—Cd2—O3^vi	104.90 (7)	C2—C1—N2	132.6 (2)
N3^iv—Cd2—O3	104.90 (7)	C2—C1—C6	122.4 (2)
N3^v—Cd2—O3	130.02 (8)	N2—C1—C6	105.0 (2)
O3^vi—Cd2—O3	84.02 (10)	C5—C6—C1	120.4 (2)
N3^iv—Cd2—O4^vi	79.65 (7)	C5—C6—N1	130.2 (2)
N3^v—Cd2—O4^vi	109.94 (7)	C1—C6—N1	109.4 (2)
O3^vi—Cd2—O4^vi	52.90 (7)	O4—C20—O3	124.0 (2)
O3—Cd2—O4^vi	113.91 (7)	O4—C20—C19	117.3 (3)
N3^iv—Cd2—O4	109.94 (7)	O3—C20—C19	118.6 (2)
N3^v—Cd2—O4	79.65 (7)	C14—C15—C16	117.3 (3)
O3^vi—Cd2—O4	113.91 (7)	C14—C15—H15	121.3
O3—Cd2—O4	52.90 (7)	C16—C15—H15	121.3
O4^vi—Cd2—O4	164.70 (8)	C15—C14—C13	121.4 (3)
N3^iv—Cd2—C20^vi	103.75 (8)	C15—C14—H14	119.3
N3^v—Cd2—C20^vi	113.06 (7)	C13—C14—H14	119.3
O3^vi—Cd2—C20^vi	26.86 (7)	N4—C19—C20	112.9 (2)
O3—Cd2—C20^vi	96.90 (7)	N4—C19—H19A	109.0
O4^vi—Cd2—C20^vi	26.48 (7)	C20—C19—H19A	109.0
O4—Cd2—C20^vi	139.18 (7)	N4—C19—H19B	109.0
C10—O1—Cd1	87.56 (15)	C20—C19—H19B	109.0
C10—O2—Cd1	93.25 (15)	H19A—C19—H19B	107.8
C20—O4—Cd2	82.79 (17)	C13—C12—C11	116.0 (3)
C20—O3—Cd2	98.18 (16)	C13—C12—H12	122.0
C7—N1—C6	105.6 (2)	C11—C12—H12	122.0
C7—N1—Cd1^vii	124.82 (16)	C12—C13—C14	122.1 (3)
C6—N1—Cd1^vii	128.54 (15)	C12—C13—H13	119.0
C7—N2—C1	107.83 (19)	C14—C13—H13	119.0
C7—N2—C9	125.7 (2)	C17—C18—H18A	109.5
C1—N2—C9	126.0 (2)	C17—C18—H18B	109.5
C17—N4—C11	107.5 (2)	H18A—C18—H18B	109.5
C17—N4—C19	125.1 (2)	C17—C18—H18C	109.5
C11—N4—C19	127.1 (2)	H18A—C18—H18C	109.5
C17—N3—C16	105.8 (2)	H18B—C18—H18C	109.5
C17—N3—Cd2^viii	123.71 (17)	C16—C11—C12	122.8 (3)
C16—N3—Cd2^viii	129.78 (16)	C16—C11—N4	105.4 (2)
C4—C3—C2	121.6 (3)	C12—C11—N4	131.8 (3)
C4—C3—H3	119.2	C11—C16—C15	120.3 (2)
C2—C3—H3	119.2	C11—C16—N3	109.2 (2)
C3—C4—C5	122.4 (3)	C15—C16—N3	130.5 (2)
C3—C4—H4	118.8	N3—C17—N4	112.0 (2)
C5—C4—H4	118.8	N3—C17—C18	125.4 (2)
C4—C5—C6	116.8 (3)	N4—C17—C18	122.6 (2)
N1^i—Cd1—O1—C10	−116.07 (15)	C7—N2—C1—C6	1.6 (3)
N1^ii—Cd1—O1—C10	10.0 (2)	C9—N2—C1—C6	174.8 (2)
O2^iii—Cd1—O1—C10	155.38 (15)	C4—C5—C6—C1	0.6 (4)
O2—Cd1—O1—C10	−7.38 (14)	C4—C5—C6—N1	178.0 (3)
O1^iii—Cd1—O1—C10	106.30 (17)	C2—C1—C6—C5	−1.9 (4)
C10^iii—Cd1—O1—C10	132.41 (14)	N2—C1—C6—C5	176.4 (2)
N1^i—Cd1—O2—C10	97.92 (16)	C2—C1—C6—N1	−179.9 (2)
N1^ii—Cd1—O2—C10	−161.24 (16)	N2—C1—C6—N1	−1.5 (3)
O2^iii—Cd1—O2—C10	−28.88 (15)	C7—N1—C6—C5	−176.8 (3)
O1^iii—Cd1—O2—C10	−58.06 (16)	Cd1^vii—N1—C6—C5	14.6 (4)
O1—Cd1—O2—C10	7.36 (14)	C7—N1—C6—C1	0.8 (3)
C10^iii—Cd1—O2—C10	−44.6 (2)	Cd1^vii—N1—C6—C1	−167.70 (16)
N3^iv—Cd2—O4—C20	−101.91 (16)	Cd2—O4—C20—O3	14.0 (3)
N3^v—Cd2—O4—C20	155.28 (17)	Cd2—O4—C20—C19	−164.3 (2)
O3^vi—Cd2—O4—C20	53.46 (17)	Cd2—O3—C20—O4	−16.2 (3)
O3—Cd2—O4—C20	−7.98 (15)	Cd2—O3—C20—C19	162.1 (2)
O4^vi—Cd2—O4—C20	25.06 (15)	C16—C15—C14—C13	−0.2 (5)
C20^vi—Cd2—O4—C20	41.8 (2)	C17—N4—C19—C20	−67.7 (3)
N3^iv—Cd2—O3—C20	111.83 (16)	C11—N4—C19—C20	106.0 (3)
N3^v—Cd2—O3—C20	−13.8 (2)	O4—C20—C19—N4	167.6 (2)
O3^vi—Cd2—O3—C20	−118.29 (19)	O3—C20—C19—N4	−10.8 (4)
O4^vi—Cd2—O3—C20	−163.07 (15)	C11—C12—C13—C14	−0.4 (4)
O4—Cd2—O3—C20	7.88 (15)	C15—C14—C13—C12	1.9 (5)
C20^vi—Cd2—O3—C20	−141.91 (14)	C13—C12—C11—C16	−2.8 (4)
C2—C3—C4—C5	−1.6 (5)	C13—C12—C11—N4	176.3 (3)
C3—C4—C5—C6	1.2 (5)	C17—N4—C11—C16	−2.0 (3)
C6—N1—C7—N2	0.2 (3)	C19—N4—C11—C16	−176.6 (2)
Cd1^vii—N1—C7—N2	169.31 (15)	C17—N4—C11—C12	178.8 (3)
C6—N1—C7—C8	179.6 (2)	C19—N4—C11—C12	4.2 (4)
Cd1^vii—N1—C7—C8	−11.3 (3)	C12—C11—C16—C15	4.6 (4)
C1—N2—C7—N1	−1.2 (3)	N4—C11—C16—C15	−174.7 (2)
C9—N2—C7—N1	−174.4 (2)	C12—C11—C16—N3	−178.4 (2)
C1—N2—C7—C8	179.4 (2)	N4—C11—C16—N3	2.3 (3)
C9—N2—C7—C8	6.2 (4)	C14—C15—C16—C11	−2.9 (4)
Cd1—O1—C10—O2	13.5 (3)	C14—C15—C16—N3	−179.1 (3)
Cd1—O1—C10—C9	−164.6 (2)	C17—N3—C16—C11	−1.7 (3)
Cd1—O2—C10—O1	−14.3 (3)	Cd2^viii—N3—C16—C11	169.00 (17)
Cd1—O2—C10—C9	163.97 (19)	C17—N3—C16—C15	174.9 (3)
C4—C3—C2—C1	0.2 (5)	Cd2^viii—N3—C16—C15	−14.4 (4)
C7—N2—C9—C10	68.6 (3)	C16—N3—C17—N4	0.4 (3)
C1—N2—C9—C10	−103.4 (3)	Cd2^viii—N3—C17—N4	−171.01 (15)
O1—C10—C9—N2	17.0 (3)	C16—N3—C17—C18	179.3 (2)
O2—C10—C9—N2	−161.3 (2)	Cd2^viii—N3—C17—C18	7.9 (3)
C3—C2—C1—N2	−176.4 (3)	C11—N4—C17—N3	1.0 (3)
C3—C2—C1—C6	1.5 (4)	C19—N4—C17—N3	175.8 (2)
C7—N2—C1—C2	179.7 (3)	C11—N4—C17—C18	−177.9 (2)
C9—N2—C1—C2	−7.1 (4)	C19—N4—C17—C18	−3.2 (4)

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

(II) poly[bis[µ₃-(2-methylbenzimidazol-1-yl)acetato]cadmium(II)]

Crystal data

[Cd(C10H9N2O2)2]	F(000) = 984
Mr = 490.79	Dx = 1.735 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2201 reflections
a = 11.476 (7) Å	θ = 3.5–27.5°
b = 11.641 (7) Å	µ = 1.20 mm^−1
c = 14.064 (13) Å	T = 293 K
β = 90.701 (14)°	Block, colourless
V = 1879 (2) Å^3	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	2168 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.061
Graphite monochromator	θmax = 28.7°, θmin = 2.5°
ω scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
Tmin = 0.787, Tmax = 0.787	l = −18→19
9836 measured reflections	3 standard reflections every 180 reflections
2421 independent reflections	intensity decay: none

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.195	H-atom parameters constrained
S = 1.23	w = 1/[σ^2(Fo^2) + (0.0827P)^2 + 8.5997P] where P = (Fo^2 + 2Fc^2)/3
2421 reflections	(Δ/σ)max = 0.007
133 parameters	Δρmax = 0.90 e Å^−3
0 restraints	Δρmin = −1.42 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	1.0000	0.19978 (5)	0.2500	0.0358 (2)
O2	0.4757 (5)	0.5517 (5)	0.3602 (4)	0.0522 (13)
O1	0.6585 (5)	0.5978 (4)	0.3348 (4)	0.0504 (12)
N1	0.7357 (4)	0.3863 (5)	0.4092 (4)	0.0366 (11)
N3	0.8943 (5)	0.3183 (5)	0.3423 (4)	0.0362 (11)
C7	0.8174 (7)	0.4160 (6)	0.5756 (5)	0.0486 (16)
H7	0.7498	0.4423	0.6041	0.058*
C6	0.9206 (8)	0.4061 (7)	0.6259 (5)	0.0535 (18)
H6	0.9224	0.4257	0.6900	0.064*
C5	1.0228 (8)	0.3675 (7)	0.5834 (6)	0.0543 (19)
H5	1.0917	0.3658	0.6188	0.065*
C4	1.0234 (6)	0.3321 (6)	0.4900 (5)	0.0444 (15)
H4	1.0909	0.3032	0.4628	0.053*
C3A	0.9202 (5)	0.3407 (5)	0.4375 (5)	0.0359 (12)
C7A	0.8189 (6)	0.3852 (5)	0.4805 (4)	0.0363 (12)
C2	0.7836 (6)	0.3459 (5)	0.3291 (4)	0.0361 (13)
C8	0.6168 (6)	0.4225 (6)	0.4193 (5)	0.0450 (15)
H8A	0.6015	0.4330	0.4864	0.054*
H8B	0.5663	0.3613	0.3965	0.054*
C9	0.5842 (6)	0.5333 (6)	0.3667 (5)	0.0394 (13)
C10	0.7180 (7)	0.3343 (7)	0.2375 (5)	0.0496 (17)
H10A	0.7622	0.2882	0.1943	0.074*
H10B	0.7054	0.4090	0.2105	0.074*
H10C	0.6443	0.2981	0.2489	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0359 (4)	0.0343 (4)	0.0374 (4)	0.000	0.0061 (3)	0.000
O2	0.049 (3)	0.060 (3)	0.048 (3)	0.019 (2)	0.014 (2)	0.006 (2)
O1	0.058 (3)	0.040 (2)	0.054 (3)	−0.005 (2)	−0.001 (2)	0.010 (2)
N1	0.036 (3)	0.039 (3)	0.036 (3)	0.008 (2)	0.002 (2)	0.004 (2)
N3	0.039 (3)	0.037 (3)	0.033 (3)	0.007 (2)	0.001 (2)	−0.001 (2)
C7	0.063 (4)	0.043 (4)	0.040 (4)	0.007 (3)	0.008 (3)	0.001 (3)
C6	0.070 (5)	0.052 (4)	0.039 (4)	−0.001 (4)	0.002 (3)	0.005 (3)
C5	0.061 (5)	0.046 (4)	0.055 (4)	−0.004 (3)	−0.016 (4)	0.008 (3)
C4	0.043 (4)	0.043 (3)	0.047 (4)	−0.002 (3)	0.000 (3)	0.005 (3)
C3A	0.036 (3)	0.033 (3)	0.039 (3)	−0.002 (2)	0.000 (2)	0.003 (2)
C7A	0.042 (3)	0.033 (3)	0.034 (3)	0.000 (2)	0.002 (2)	0.005 (2)
C2	0.042 (3)	0.031 (3)	0.036 (3)	0.009 (2)	0.001 (2)	0.003 (2)
C8	0.040 (3)	0.040 (3)	0.055 (4)	0.004 (3)	0.013 (3)	0.008 (3)
C9	0.047 (4)	0.035 (3)	0.037 (3)	0.003 (3)	0.005 (3)	−0.004 (2)
C10	0.054 (4)	0.054 (4)	0.041 (4)	0.014 (3)	−0.006 (3)	0.001 (3)

Geometric parameters (Å, º)

Cd1—N3	2.258 (5)	C7—C6	1.377 (11)
Cd1—N3^i	2.258 (5)	C7—H7	0.9300
Cd1—O2^ii	2.337 (5)	C6—C5	1.397 (12)
Cd1—O1^ii	2.467 (5)	C6—H6	0.9300
Cd1—O1^iii	2.467 (5)	C5—C4	1.377 (11)
Cd1—O2^iii	2.337 (5)	C5—H5	0.9300
Cd1—C9^ii	2.710 (7)	C4—C3A	1.392 (9)
Cd1—C9^iii	2.710 (7)	C4—H4	0.9300
O2—C9	1.266 (8)	C3A—C7A	1.414 (9)
O2—Cd1^iv	2.337 (5)	C2—C10	1.489 (9)
O1—C9	1.224 (8)	C8—C9	1.532 (9)
O1—Cd1^iv	2.467 (5)	C8—H8A	0.9700
N1—C2	1.346 (8)	C8—H8B	0.9700
N1—C7A	1.376 (8)	C9—Cd1^iv	2.710 (7)
N1—C8	1.436 (8)	C10—H10A	0.9600
N3—C2	1.321 (8)	C10—H10B	0.9600
N3—C3A	1.394 (8)	C10—H10C	0.9600
C7—C7A	1.385 (9)
O2^ii—Cd1—N3^i	90.03 (19)	C6—C7—H7	121.5
O2^iii—Cd1—N3^i	154.3 (2)	C7—C6—C5	121.9 (7)
N3—Cd1—N3^i	104.7 (3)	C7—C6—H6	119.1
N3—Cd1—O2^ii	154.3 (2)	C5—C6—H6	119.1
N3—Cd1—O2^iii	90.03 (19)	C4—C5—C6	121.3 (7)
O2^ii—Cd1—O2^iii	84.9 (3)	C4—C5—H5	119.4
N3—Cd1—O1^ii	100.02 (19)	C6—C5—H5	119.4
N3^i—Cd1—O1^ii	114.47 (19)	C5—C4—C3A	118.0 (7)
O2^ii—Cd1—O1^ii	54.39 (18)	C5—C4—H4	121.0
O2^iii—Cd1—O1^ii	82.7 (2)	C3A—C4—H4	121.0
N3—Cd1—O1^iii	114.47 (19)	N3—C3A—C4	131.8 (6)
N3^i—Cd1—O1^iii	100.02 (19)	N3—C3A—C7A	108.2 (5)
O2^ii—Cd1—O1^iii	82.7 (2)	C4—C3A—C7A	119.9 (6)
O2^iii—Cd1—O1^iii	54.39 (18)	N1—C7A—C7	133.2 (6)
O1^ii—Cd1—O1^iii	122.5 (2)	N1—C7A—C3A	105.0 (5)
N3—Cd1—C9^ii	126.5 (2)	C7—C7A—C3A	121.8 (6)
N3^i—Cd1—C9^ii	106.2 (2)	N3—C2—N1	111.7 (6)
O2^ii—Cd1—C9^ii	27.82 (19)	N3—C2—C10	125.0 (6)
O2^iii—Cd1—C9^ii	80.2 (2)	N1—C2—C10	123.3 (6)
O1^ii—Cd1—C9^ii	26.84 (19)	N1—C8—C9	115.2 (6)
O1^iii—Cd1—C9^ii	101.8 (2)	N1—C8—H8A	108.5
N3—Cd1—C9^iii	106.2 (2)	C9—C8—H8A	108.5
N3^i—Cd1—C9^iii	126.5 (2)	N1—C8—H8B	108.5
O2^ii—Cd1—C9^iii	80.2 (2)	C9—C8—H8B	108.5
O2^iii—Cd1—C9^iii	27.82 (19)	H8A—C8—H8B	107.5
O1^ii—Cd1—C9^iii	101.8 (2)	O1—C9—O2	123.9 (7)
O1^iii—Cd1—C9^iii	26.84 (19)	O1—C9—C8	121.8 (6)
C9^ii—Cd1—C9^iii	88.7 (3)	O2—C9—C8	114.3 (6)
C9—O2—Cd1^iv	92.7 (4)	O1—C9—Cd1^iv	65.5 (4)
C9—O1—Cd1^iv	87.7 (4)	O2—C9—Cd1^iv	59.5 (4)
C2—N1—C7A	108.7 (5)	C8—C9—Cd1^iv	168.0 (5)
C2—N1—C8	125.7 (6)	C2—C10—H10A	109.5
C7A—N1—C8	125.6 (6)	C2—C10—H10B	109.5
C2—N3—C3A	106.4 (5)	H10A—C10—H10B	109.5
C2—N3—Cd1	126.2 (4)	C2—C10—H10C	109.5
C3A—N3—Cd1	123.9 (4)	H10A—C10—H10C	109.5
C7A—C7—C6	117.0 (7)	H10B—C10—H10C	109.5
C7A—C7—H7	121.5
N3^i—Cd1—N3—C2	100.6 (5)	C2—N1—C7A—C3A	−0.2 (7)
O2^ii—Cd1—N3—C2	−22.4 (8)	C8—N1—C7A—C3A	178.6 (6)
O2^iii—Cd1—N3—C2	−100.7 (5)	C6—C7—C7A—N1	−178.1 (7)
O1^ii—Cd1—N3—C2	−18.1 (6)	C6—C7—C7A—C3A	2.7 (10)
O1^iii—Cd1—N3—C2	−150.9 (5)	N3—C3A—C7A—N1	0.7 (7)
C9^ii—Cd1—N3—C2	−22.9 (6)	C4—C3A—C7A—N1	177.6 (6)
C9^iii—Cd1—N3—C2	−123.6 (5)	N3—C3A—C7A—C7	−179.9 (6)
N3^i—Cd1—N3—C3A	−103.5 (5)	C4—C3A—C7A—C7	−3.0 (10)
O2^ii—Cd1—N3—C3A	133.5 (5)	C3A—N3—C2—N1	0.8 (7)
O2^iii—Cd1—N3—C3A	55.2 (5)	Cd1—N3—C2—N1	160.1 (4)
O1^ii—Cd1—N3—C3A	137.7 (5)	C3A—N3—C2—C10	−179.1 (6)
O1^iii—Cd1—N3—C3A	4.9 (6)	Cd1—N3—C2—C10	−19.8 (9)
C9^ii—Cd1—N3—C3A	133.0 (5)	C7A—N1—C2—N3	−0.4 (7)
C9^iii—Cd1—N3—C3A	32.2 (5)	C8—N1—C2—N3	−179.2 (6)
C7A—C7—C6—C5	0.4 (11)	C7A—N1—C2—C10	179.5 (6)
C7—C6—C5—C4	−3.3 (12)	C8—N1—C2—C10	0.7 (10)
C6—C5—C4—C3A	2.9 (11)	C2—N1—C8—C9	−69.4 (9)
C2—N3—C3A—C4	−177.3 (7)	C7A—N1—C8—C9	112.0 (7)
Cd1—N3—C3A—C4	22.8 (10)	Cd1^iv—O1—C9—O2	−11.4 (7)
C2—N3—C3A—C7A	−0.9 (7)	Cd1^iv—O1—C9—C8	169.1 (6)
Cd1—N3—C3A—C7A	−160.8 (4)	Cd1^iv—O2—C9—O1	12.0 (7)
C5—C4—C3A—N3	176.2 (7)	Cd1^iv—O2—C9—C8	−168.4 (5)
C5—C4—C3A—C7A	0.2 (10)	N1—C8—C9—O1	−13.9 (10)
C2—N1—C7A—C7	−179.5 (7)	N1—C8—C9—O2	166.5 (6)
C8—N1—C7A—C7	−0.7 (11)	N1—C8—C9—Cd1^iv	110 (2)

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