Poly[[([mu]₂-biphenyl-2,4'-dicarboxyl­ato)[[mu]₂-1,4-bis­(imidazol-1-yl­methyl)­benzene]cadmium(II)] 0.15-hydrate]

The asymmetric unit of the title two-dimensional coordination polymer, {[Cd(C₁₄H₈O₄)(C₁₄H₁₄N₄)]·0.15H₂O}_n, is composed of one Cd^II cation, one biphenyl-2,4'-dicarboxyl­ate (bpdc) anion, one 1,4-bis­(imidazol-1-yl­methyl)­benzene (bix) ligand and 0.15 solvent water mol­ecules. The coordination environment of the Cd^II cation is defined by four carboxyl­ate O atoms from two different bpdc anions in a chelating mode and two N atoms from two distinct bix ligands, constructing a distorted trigonal prism polyhedron. Two inversion-related Cd^II cations are bridged together by two positionally disordered bpdc anions, forming a 22-membered ring with a Cd...Cd distance of 9.1966 (9) Å. These rings are then further linked by two bix ligands, extending into a two-dimensional layer along (102) with 6³ topology.

S1. Comment

Currently, the rational design and synthesis of metal–organic frameworks (MOFs) have attracted considerable attention due to the diversity in their architectures and topologies (Lu, 2003). Selection of suitable organic bridging ligands plays a key role in the construction of MOFs. During the past decade many MOFs in which polycarboxylates are used as the bridging ligands to assemble coordination polymers have been successfully synthesized and reported (Duan et al., 2007; Liu et al., 2008; Ghosh et al., 2009; Jiang et al., 2009; Xu et al., 2009; Li et al., 2009).

2,4,-Biphenyldicarboxylic acid (H₂bpdc) is a flexible ligand coordinating to transition metals, with two carboxyl groups that can supply four potential O donor atoms. Moreover, the two phenyl rings in H₂bpdc can be rotated around the bridging C—C single bond and the two carboxyl groups are located at asymmetric positions, which makes it a good candidate for constructing various MOFs. However, to the best of our knowledge, coordination polymers involving (H₂bpdc) have rarely been reported (Liu et al., 2010). Here, we present the title coordination polymer, (I).

As shown in Fig. 1, the asymmetric unit of (I) consists of one Cd^II cation, one 2,4-biphenyldicarboxylate (bpdc) anion which is positionally disordered, one 1,4-bis(imidazol-1-ylmethyl)benzene (bix) ligand and 0.15 solvent water molecules. The Cd^II cation is coordinated by four carboxylate O atoms [O1, O2, O3A and O4A; symmetry code: (A) -x + 1, -y + 1, -z] from two different bpdc anions and two N atoms [N1 and N4B; symmetry code: (B) -x, y - 1/2, -z + 1/2] from two distinct bix ligands, constructing a distorted CdO₄N₂ triprism polyhedron [Please check added symmetry codes]. The four Cd—O bond lengths range from 2.288 (12) to 2.421 (12) Å, and the Cd—N distances are 2.256 (5) and 2.275 (5) Å (Table 1). In the CdO₄N₂ triprism atoms O1, N1, O4A and O2 occupy the equatorial plane, while atoms O3A and N4B are in axial positions.

For the bix ligand, the two terminal imidazole groups (N1/N2/C1–C3 and N3/N4/C12–C14) assume an anti conformation and their planes are steeply tilted, by 71.8 (4) and 75.7 (4)°, respectively, with respect to the mean plane of the phenyl ring (C5–C10). The angles N2—C4—C5 and N3—C11—C8 are 113.1 (5) and 113.6 (6)°, respectively (atoms N2 and N3 are from two imidazole groups; atoms C5 and C8 are from the CH₂ groups between the phenyl ring and the imidazole group).

Two inversion-related Cd^II cations are bridged by two disordered bpdc anions, forming a 22-membered ring with a Cd···Cdⁱ distance of 9.1979 Å [Fig. 2; symmetry code: (i) -x + 1, -y + 1, -z]. Each Cd^II cation is then linked by two bix ligands so that these rings are further extended into a two-dimensional layer along (102) (Fig. 3). Overall, each Cd^II cation is linked to three neighbouring Cd^II cations through one pair of bptc anions and two bix ligands. For bpdc, both carboxyl groups coordinate to one Cd^II cation in a chelating mode, with dihedral angles of 46.8 (7)° between the two phenyl rings of the major component (C15–C20 and C22–C27) and 41.5 (9)° between those of the minor disordered component (C15'–C20' and C22'–C27').

A pair of bpdc anions and bix ligands can be considered as a 2-connector, while the Cd^II cation can be considered as a 3-connected node, so that the structure of (I) is further simplified into a 6³ topological network (Blatov et al., 2000) (Fig. 4) in which each node links neighbouring 3-connected nodes, corresponding to Cd···Cd distances of 9.198, 13.400 and 13.400 Å, respectively.

To the best of our knowledge, compounds related to 2,4'-bpdc have rarely been reported (Liu et al., 2010). In [Co(2,4'-bpdc)(bix)] (Liu et al., 2010), which is different to the arrangement in (I), the bpdc anion has two coordination modes connecting two Co centres: a 2-carboxyl group coordinates to one Co^II cation as a monodentate ligand, while the other 4'-carboxyl group coordinates to one Co^II cation in a chelating mode. Alternate Co^II cations and bpdc anions construct an infinite chain propagating along [010]. Adjacent chains are further pillared by bix ligands to form a two-dimensional wave-like network with (4,4) topology. The coordination environment of the Co^II cation in this structure is defined by three O atoms from two bpdc anions and two N atoms from two bix ligands, affording a distorted trigonal bipyramid. Compound (I) is also entirely different from another related compound, [Co(2,4'-bpdc)(bix)_0.25].0.25H₂O (Liu et al., 2010). In that structure, although the bpdc ligand also assumes two coordination modes, it coordinates to three Co^II cations: the 2-carboxyl group coordinates to two Co^II cations in a bidentate bridging mode, while the other 4'-carboxyl group coordinates to one Co^II cation in a monodentate mode. The 2,4'-bpdc ligands and the Co^II cations construct two-dimensional sheets, which are linked by bix ligands into a three-dimensional network with (6³).(6³.10³) topology.

S2. Experimental

A mixture of CdSO₄.8H₂O (0.17 mmol, 0.13 g), H₂bpdc (0.5 mmol, 0.17 g), bix (0.5 mmol, 0.10 g), NaOH (1 mmol, 0.04 g) and H₂O (15 ml) was placed in a Parr Teflon-lined stainless steel vessel (23 ml), which was then sealed and heated at 403 K for 3 d. After the mixture had slowly cooled to room temperature, a large quantity of colourless block-like crystals of (I) were obtained.

S3. Refinement

In the initial refinement, the whole bpdc molecule was found to be disordered over two positions. The coordinates and bond distances of this bpdc molecule were then refined using the commands SAME and ISOR (SHELXL97; Sheldrick, 2008). The most satisfactory occupancies for the disordered major (C15–C20 and C22–C27) and minor (C15'–C20' and C22'–C27') components were found to be 0.55 and 0.45, respectively. Atom O1W was assigned from a crystallographic point of view, with an occupancy of only 0.15. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 (aromatic) or 0.97 Å (methylene), and with U_iso(H) = 1.2U_eq(C). The coordinates of the O1W H atoms were calculated using the program PLATON (CAL-OH command; Spek, 2009) and they were refined with the O1W—H distances fixed at 0.82 Å and U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: TOPOS (Blatov et al., 2000) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (A) -x + 1, -y + 1, -z; (B) -x, y - 1/2, -z + 1/2.]
	Fig. 2. A view of the two inversion-related Cd^II cations bridged by two bpdc anions to form a 22-membered ring. H atoms have been omitted for clarity. [Symmetry code: (A) -x + 1, -y + 1, -z.]
	Fig. 3. A view of the crystal packing in (I), illustrating the formation of the two-dimensional network in (102). H atoms have been omitted for clarity.
	Fig. 4. A view of the 6^3 net (node: Cd) in the crystal structure of (I).

Poly[[(µ₂-biphenyl-2,4'-dicarboxylate- κ⁴O²,O^2':O⁴,O^4')[µ₂-1,4- bis(imidazol-1-ylmethyl)benzene-κ²N³:N^3']cadmium(II)] 0.15-hydrate]

Crystal data

[Cd(C14H8O4)(C14H14N4)]·0.15H2O	F(000) = 1198.0
Mr = 593.61	Dx = 1.504 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1463 reflections
a = 11.0099 (9) Å	θ = 2.6–17.8°
b = 12.558 (1) Å	µ = 0.87 mm^−1
c = 19.2362 (15) Å	T = 298 K
β = 99.635 (2)°	Block, colourless
V = 2622.1 (4) Å^3	0.15 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5157 independent reflections
Radiation source: fine-focus sealed tube	3405 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.083
0.3° wide ω exposures scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.870, Tmax = 0.918	k = −15→15
17539 measured reflections	l = −19→23

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0507P)^2 + 0.326P] where P = (Fo^2 + 2Fc^2)/3
5157 reflections	(Δ/σ)max < 0.001
458 parameters	Δρmax = 0.56 e Å^−3
45 restraints	Δρmin = −0.71 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	0.48950 (4)	0.76870 (3)	0.16128 (2)	0.04401 (18)
C1	0.4151 (6)	0.9738 (5)	0.0717 (3)	0.0539 (18)
H1	0.4536	0.9409	0.0380	0.065*
C2	0.3539 (6)	1.0659 (5)	0.0629 (3)	0.0552 (18)
H2	0.3406	1.1074	0.0222	0.066*
C3	0.3533 (5)	1.0068 (5)	0.1674 (3)	0.0472 (16)
H3	0.3395	1.0017	0.2137	0.057*
C4	0.2428 (6)	1.1802 (5)	0.1389 (4)	0.0538 (17)
H4A	0.2569	1.2369	0.1069	0.065*
H4B	0.2715	1.2048	0.1866	0.065*
C5	0.1055 (6)	1.1581 (5)	0.1301 (4)	0.0502 (17)
C6	0.0360 (7)	1.1344 (6)	0.0670 (4)	0.067 (2)
H6	0.0735	1.1291	0.0273	0.080*
C7	−0.0893 (6)	1.1178 (6)	0.0605 (4)	0.070 (2)
H7	−0.1346	1.1009	0.0166	0.084*
C8	−0.1467 (6)	1.1260 (6)	0.1168 (4)	0.075 (2)
C9	−0.0788 (8)	1.1498 (7)	0.1802 (5)	0.096 (3)
H9	−0.1172	1.1563	0.2196	0.115*
C10	0.0484 (7)	1.1647 (6)	0.1871 (4)	0.078 (2)
H10	0.0943	1.1793	0.2312	0.094*
C11	−0.2855 (7)	1.1040 (7)	0.1092 (5)	0.101 (3)
H11A	−0.3213	1.1059	0.0596	0.121*
H11B	−0.2974	1.0328	0.1265	0.121*
C12	−0.3779 (6)	1.1691 (6)	0.2114 (4)	0.063 (2)
H12	−0.3577	1.1094	0.2396	0.075*
C13	−0.4486 (7)	1.3191 (7)	0.1753 (4)	0.072 (2)
H13	−0.4866	1.3854	0.1733	0.086*
C14	−0.3966 (9)	1.2748 (8)	0.1227 (5)	0.094 (3)
H14	−0.3933	1.3043	0.0787	0.113*
N1	0.4127 (5)	0.9354 (4)	0.1376 (3)	0.0484 (13)
N2	0.3144 (4)	1.0875 (4)	0.1253 (3)	0.0400 (12)
N3	−0.3505 (5)	1.1795 (6)	0.1471 (4)	0.077 (2)
N4	−0.4364 (5)	1.2516 (4)	0.2309 (3)	0.0556 (15)
C15	0.8610 (9)	0.7788 (14)	0.1395 (10)	0.041 (10)	0.55
C16	0.9314 (14)	0.8647 (14)	0.1686 (12)	0.047 (6)	0.55
H16	0.8943	0.9206	0.1888	0.057*	0.55
C17	1.0573 (14)	0.8669 (14)	0.1675 (13)	0.058 (8)	0.55
H17	1.1044	0.9243	0.1869	0.069*	0.55
C18	1.1127 (9)	0.7833 (14)	0.1373 (12)	0.048 (7)	0.55
H18	1.1970	0.7847	0.1365	0.057*	0.55
C19	1.0423 (11)	0.6974 (11)	0.1082 (9)	0.057 (6)	0.55
H19	1.0794	0.6414	0.0879	0.068*	0.55
C20	0.9164 (10)	0.6952 (10)	0.1093 (8)	0.034 (5)	0.55
C21	0.7271 (14)	0.779 (3)	0.1468 (15)	0.046 (13)	0.55
O1	0.6597 (10)	0.8518 (9)	0.1170 (8)	0.083 (4)	0.55
O2	0.6877 (11)	0.7066 (8)	0.1813 (7)	0.060 (4)	0.55
C22	0.8373 (7)	0.6100 (6)	0.0663 (4)	0.041 (4)	0.55
C23	0.7331 (8)	0.6406 (5)	0.0194 (4)	0.050 (3)	0.55
H23	0.7081	0.7114	0.0173	0.061*	0.55
C24	0.6662 (6)	0.5654 (6)	−0.0242 (4)	0.045 (3)	0.55
H24	0.5964	0.5858	−0.0555	0.054*	0.55
C25	0.7036 (7)	0.4595 (6)	−0.0209 (4)	0.047 (5)	0.55
C26	0.8078 (7)	0.4289 (5)	0.0260 (5)	0.055 (3)	0.55
H26	0.8328	0.3580	0.0281	0.066*	0.55
C27	0.8747 (6)	0.5041 (7)	0.0696 (4)	0.049 (3)	0.55
H27	0.9445	0.4836	0.1009	0.059*	0.55
C28	0.638 (4)	0.3794 (16)	−0.0734 (13)	0.048 (11)	0.55
O3	0.5664 (12)	0.4125 (11)	−0.1272 (7)	0.066 (4)	0.55
O4	0.6481 (11)	0.2828 (9)	−0.0564 (7)	0.059 (3)	0.55
C15'	0.8632 (13)	0.7777 (18)	0.1340 (11)	0.050 (13)	0.45
C16'	0.939 (2)	0.8458 (19)	0.1786 (13)	0.056 (9)	0.45
H16'	0.9060	0.8902	0.2093	0.068*	0.45
C17'	1.065 (2)	0.848 (2)	0.1775 (16)	0.063 (10)	0.45
H17'	1.1160	0.8934	0.2073	0.076*	0.45
C18'	1.1149 (12)	0.782 (2)	0.1316 (16)	0.12 (2)	0.45
H18'	1.1991	0.7828	0.1308	0.146*	0.45
C19'	1.0388 (15)	0.7134 (18)	0.0869 (12)	0.067 (8)	0.45
H19'	1.0722	0.6690	0.0563	0.081*	0.45
C20'	0.9130 (14)	0.7114 (14)	0.0881 (9)	0.038 (6)	0.45
C21'	0.7274 (17)	0.782 (3)	0.1377 (16)	0.046 (16)	0.45
O1'	0.6485 (12)	0.8009 (10)	0.0837 (6)	0.052 (3)	0.45
O2'	0.6970 (14)	0.7672 (12)	0.1971 (7)	0.059 (4)	0.45
C22'	0.8391 (9)	0.6268 (7)	0.0440 (5)	0.037 (5)	0.45
C23'	0.7519 (9)	0.5676 (8)	0.0718 (4)	0.051 (4)	0.45
H23'	0.7392	0.5799	0.1177	0.061*	0.45
C24'	0.6838 (8)	0.4900 (7)	0.0310 (6)	0.055 (4)	0.45
H24'	0.6255	0.4504	0.0496	0.066*	0.45
C25'	0.7028 (9)	0.4716 (7)	−0.0376 (5)	0.038 (6)	0.45
C26'	0.7900 (9)	0.5308 (8)	−0.0655 (4)	0.056 (4)	0.45
H26'	0.8027	0.5185	−0.1114	0.067*	0.45
C27'	0.8581 (8)	0.6084 (7)	−0.0247 (5)	0.053 (4)	0.45
H27'	0.9165	0.6480	−0.0433	0.063*	0.45
C28'	0.623 (4)	0.390 (2)	−0.0823 (10)	0.051 (13)	0.45
O3'	0.6179 (15)	0.3926 (13)	−0.1483 (8)	0.078 (5)	0.45
O4'	0.5864 (12)	0.3096 (11)	−0.0530 (8)	0.066 (4)	0.45
O1W	0.751 (3)	0.948 (2)	0.3017 (16)	0.069 (9)	0.15
H1W1	0.7375	0.8986	0.2736	0.082*	0.15
H1W2	0.7124	0.9959	0.3170	0.082*	0.15

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0342 (3)	0.0500 (3)	0.0492 (3)	0.0013 (2)	0.0112 (2)	0.0014 (2)
C1	0.057 (4)	0.068 (5)	0.038 (4)	0.013 (4)	0.012 (4)	0.001 (3)
C2	0.056 (4)	0.066 (5)	0.043 (4)	0.010 (4)	0.010 (4)	0.016 (3)
C3	0.043 (4)	0.061 (4)	0.041 (4)	0.005 (3)	0.015 (3)	0.002 (3)
C4	0.046 (4)	0.049 (4)	0.064 (5)	−0.003 (3)	0.005 (4)	−0.008 (3)
C5	0.049 (4)	0.048 (4)	0.057 (5)	0.002 (3)	0.018 (4)	−0.009 (3)
C6	0.055 (5)	0.097 (6)	0.053 (5)	−0.004 (4)	0.024 (4)	−0.019 (4)
C7	0.046 (5)	0.112 (6)	0.053 (5)	0.000 (4)	0.012 (4)	−0.026 (4)
C8	0.038 (4)	0.110 (6)	0.075 (6)	−0.005 (4)	0.006 (4)	−0.062 (5)
C9	0.071 (6)	0.142 (8)	0.084 (7)	−0.021 (5)	0.041 (5)	−0.049 (6)
C10	0.059 (5)	0.112 (7)	0.061 (5)	−0.015 (5)	0.005 (4)	−0.037 (5)
C11	0.068 (6)	0.136 (8)	0.103 (7)	−0.007 (5)	0.028 (5)	−0.071 (6)
C12	0.042 (4)	0.070 (5)	0.075 (6)	−0.011 (4)	0.008 (4)	−0.022 (4)
C13	0.066 (5)	0.091 (6)	0.061 (5)	0.000 (4)	0.024 (4)	−0.013 (5)
C14	0.087 (7)	0.124 (8)	0.078 (7)	−0.007 (6)	0.034 (6)	−0.011 (6)
N1	0.045 (3)	0.056 (3)	0.045 (4)	0.007 (3)	0.012 (3)	0.000 (3)
N2	0.030 (3)	0.047 (3)	0.043 (3)	0.002 (2)	0.008 (3)	−0.004 (2)
N3	0.036 (4)	0.125 (6)	0.071 (5)	−0.017 (4)	0.018 (3)	−0.052 (4)
N4	0.046 (3)	0.055 (4)	0.073 (4)	−0.005 (3)	0.027 (3)	−0.008 (3)
C15	0.05 (2)	0.05 (2)	0.027 (12)	0.005 (15)	−0.005 (11)	−0.014 (12)
C16	0.040 (13)	0.047 (10)	0.053 (13)	−0.008 (9)	0.005 (10)	0.007 (10)
C17	0.049 (15)	0.055 (12)	0.067 (16)	−0.009 (10)	0.002 (11)	0.010 (12)
C18	0.015 (10)	0.059 (18)	0.073 (19)	−0.003 (10)	0.016 (11)	−0.007 (14)
C19	0.027 (9)	0.087 (15)	0.057 (11)	−0.003 (9)	0.007 (7)	0.004 (10)
C20	0.032 (8)	0.035 (7)	0.035 (10)	0.001 (6)	0.006 (7)	0.017 (7)
C21	0.03 (2)	0.06 (3)	0.05 (2)	−0.005 (18)	0.004 (14)	−0.010 (16)
O1	0.034 (6)	0.073 (9)	0.142 (14)	0.009 (6)	0.015 (7)	0.019 (8)
O2	0.033 (5)	0.085 (9)	0.062 (8)	0.001 (6)	0.013 (5)	0.011 (7)
C22	0.032 (9)	0.061 (10)	0.037 (8)	−0.002 (7)	0.024 (7)	0.007 (7)
C23	0.051 (8)	0.051 (7)	0.048 (8)	0.014 (6)	0.007 (7)	0.000 (6)
C24	0.041 (7)	0.053 (7)	0.033 (7)	0.005 (6)	−0.012 (6)	0.002 (6)
C25	0.042 (12)	0.058 (12)	0.044 (10)	−0.011 (9)	0.017 (8)	0.008 (9)
C26	0.046 (8)	0.059 (8)	0.059 (9)	0.016 (6)	0.007 (7)	0.001 (7)
C27	0.040 (7)	0.069 (8)	0.034 (7)	0.020 (6)	−0.007 (6)	−0.003 (6)
C28	0.044 (18)	0.052 (18)	0.050 (19)	0.003 (12)	0.012 (12)	−0.003 (13)
O3	0.075 (10)	0.080 (8)	0.033 (8)	−0.010 (7)	−0.016 (7)	−0.004 (6)
O4	0.060 (8)	0.055 (7)	0.056 (6)	0.013 (6)	−0.005 (6)	−0.004 (5)
C15'	0.02 (2)	0.04 (2)	0.09 (2)	−0.003 (17)	0.026 (17)	0.021 (18)
C16'	0.051 (18)	0.052 (13)	0.07 (2)	0.002 (12)	0.007 (14)	0.005 (14)
C17'	0.055 (19)	0.059 (14)	0.07 (2)	−0.005 (13)	0.002 (16)	0.010 (15)
C18'	0.11 (4)	0.12 (5)	0.13 (5)	0.00 (3)	0.02 (3)	0.00 (4)
C19'	0.062 (16)	0.048 (12)	0.10 (2)	0.005 (11)	0.028 (13)	−0.015 (13)
C20'	0.032 (10)	0.045 (11)	0.037 (13)	0.008 (8)	0.004 (8)	0.014 (10)
C21'	0.03 (3)	0.06 (3)	0.05 (2)	0.00 (2)	0.004 (17)	−0.010 (18)
O1'	0.044 (7)	0.067 (9)	0.045 (8)	0.010 (6)	0.009 (6)	0.012 (6)
O2'	0.049 (7)	0.092 (11)	0.037 (8)	0.001 (9)	0.012 (6)	0.017 (8)
C22'	0.028 (10)	0.016 (7)	0.072 (13)	0.001 (6)	0.021 (9)	0.001 (8)
C23'	0.059 (10)	0.056 (9)	0.041 (9)	−0.012 (8)	0.017 (8)	−0.009 (7)
C24'	0.070 (11)	0.045 (9)	0.054 (11)	−0.002 (8)	0.019 (9)	−0.005 (8)
C25'	0.049 (14)	0.038 (11)	0.028 (9)	0.006 (9)	0.009 (8)	−0.003 (8)
C26'	0.067 (11)	0.054 (9)	0.046 (10)	0.013 (8)	0.011 (8)	0.001 (7)
C27'	0.049 (9)	0.060 (9)	0.049 (10)	−0.004 (7)	0.008 (8)	−0.005 (7)
C28'	0.04 (2)	0.06 (2)	0.07 (3)	−0.001 (16)	0.023 (19)	−0.035 (19)
O3'	0.089 (12)	0.080 (9)	0.072 (12)	−0.007 (8)	0.036 (9)	−0.018 (8)
O4'	0.061 (10)	0.050 (8)	0.079 (10)	−0.012 (7)	−0.011 (9)	−0.007 (7)
O1W	0.08 (2)	0.060 (19)	0.07 (2)	0.007 (17)	0.018 (19)	0.003 (16)

Geometric parameters (Å, º)

Cd1—N4^i	2.256 (6)	C18—H18	0.9300
Cd1—O2'	2.273 (15)	C19—C20	1.3900
Cd1—N1	2.275 (5)	C19—H19	0.9300
Cd1—O2	2.288 (12)	C20—C22	1.531 (8)
Cd1—O4'^ii	2.328 (15)	C21—O2	1.25 (2)
Cd1—O3'^ii	2.338 (16)	C21—O1	1.251 (19)
Cd1—O4^ii	2.400 (12)	C22—C23	1.3900
Cd1—O3^ii	2.420 (13)	C22—C27	1.3900
Cd1—O1	2.421 (12)	C23—C24	1.3900
Cd1—O1'	2.516 (12)	C23—H23	0.9300
Cd1—C21	2.679 (15)	C24—C25	1.3900
Cd1—C28'^ii	2.680 (13)	C24—H24	0.9300
C1—C2	1.335 (8)	C25—C26	1.3900
C1—N1	1.360 (7)	C25—C28	1.520 (14)
C1—H1	0.9300	C26—C27	1.3900
C2—N2	1.370 (7)	C26—H26	0.9300
C2—H2	0.9300	C27—H27	0.9300
C3—N1	1.299 (7)	C28—O4	1.257 (18)
C3—N2	1.324 (7)	C28—O3	1.260 (19)
C3—H3	0.9300	C28—Cd1^ii	2.737 (14)
C4—N2	1.454 (7)	O3—Cd1^ii	2.420 (13)
C4—C5	1.518 (8)	O4—Cd1^ii	2.400 (12)
C4—H4A	0.9700	C15'—C16'	1.3900
C4—H4B	0.9700	C15'—C20'	1.3900
C5—C10	1.355 (9)	C15'—C21'	1.510 (13)
C5—C6	1.355 (9)	C16'—C17'	1.3900
C6—C7	1.379 (9)	C16'—H16'	0.9300
C6—H6	0.9300	C17'—C18'	1.3900
C7—C8	1.346 (9)	C17'—H17'	0.9300
C7—H7	0.9300	C18'—C19'	1.3900
C8—C9	1.354 (10)	C18'—H18'	0.9300
C8—C11	1.536 (9)	C19'—C20'	1.3900
C9—C10	1.397 (10)	C19'—H19'	0.9300
C9—H9	0.9300	C20'—C22'	1.510 (10)
C10—H10	0.9300	C21'—O2'	1.26 (2)
C11—N3	1.455 (9)	C21'—O1'	1.26 (2)
C11—H11A	0.9700	C22'—C23'	1.3900
C11—H11B	0.9700	C22'—C27'	1.3900
C12—N4	1.308 (8)	C23'—C24'	1.3900
C12—N3	1.328 (9)	C23'—H23'	0.9300
C12—H12	0.9300	C24'—C25'	1.3900
C13—N4	1.354 (9)	C24'—H24'	0.9300
C13—C14	1.362 (10)	C25'—C26'	1.3900
C13—H13	0.9300	C25'—C28'	1.518 (15)
C14—N3	1.353 (10)	C26'—C27'	1.3900
C14—H14	0.9300	C26'—H26'	0.9300
N4—Cd1^iii	2.256 (6)	C27'—H27'	0.9300
C15—C16	1.3900	C28'—O4'	1.255 (18)
C15—C20	1.3900	C28'—O3'	1.26 (2)
C15—C21	1.504 (12)	C28'—Cd1^ii	2.680 (13)
C16—C17	1.3900	O3'—Cd1^ii	2.338 (16)
C16—H16	0.9300	O4'—Cd1^ii	2.328 (15)
C17—C18	1.3900	O1W—H1W1	0.8201
C17—H17	0.9300	O1W—H1W2	0.8200
C18—C19	1.3900
N4^i—Cd1—O2'	97.0 (4)	C1—N1—Cd1	116.6 (4)
N4^i—Cd1—N1	97.27 (18)	C3—N2—C2	105.5 (5)
O2'—Cd1—N1	112.9 (4)	C3—N2—C4	129.2 (5)
N4^i—Cd1—O2	101.5 (4)	C2—N2—C4	125.3 (5)
O2'—Cd1—O2	20.7 (4)	C12—N3—C14	106.2 (7)
N1—Cd1—O2	131.2 (3)	C12—N3—C11	127.6 (9)
N4^i—Cd1—O4'^ii	132.2 (4)	C14—N3—C11	126.2 (8)
O2'—Cd1—O4'^ii	117.4 (5)	C12—N4—C13	104.9 (6)
N1—Cd1—O4'^ii	98.3 (4)	C12—N4—Cd1^iii	123.7 (5)
O2—Cd1—O4'^ii	101.3 (5)	C13—N4—Cd1^iii	131.3 (5)
N4^i—Cd1—O3'^ii	79.2 (3)	C16—C15—C20	120.0
O2'—Cd1—O3'^ii	119.3 (6)	C16—C15—C21	116.7 (12)
N1—Cd1—O3'^ii	127.7 (5)	C20—C15—C21	123.2 (12)
O2—Cd1—O3'^ii	100.0 (5)	C15—C16—C17	120.0
O4'^ii—Cd1—O3'^ii	55.9 (4)	C15—C16—H16	120.0
N4^i—Cd1—O4^ii	121.5 (3)	C17—C16—H16	120.0
O2'—Cd1—O4^ii	135.5 (4)	C18—C17—C16	120.0
N1—Cd1—O4^ii	85.3 (3)	C18—C17—H17	120.0
O2—Cd1—O4^ii	120.0 (4)	C16—C17—H17	120.0
O4'^ii—Cd1—O4^ii	18.6 (3)	C17—C18—C19	120.0
O3'^ii—Cd1—O4^ii	56.0 (5)	C17—C18—H18	120.0
N4^i—Cd1—O3^ii	93.8 (4)	C19—C18—H18	120.0
O2'—Cd1—O3^ii	105.8 (5)	C20—C19—C18	120.0
N1—Cd1—O3^ii	137.9 (3)	C20—C19—H19	120.0
O2—Cd1—O3^ii	85.3 (4)	C18—C19—H19	120.0
O4'^ii—Cd1—O3^ii	47.4 (5)	C19—C20—C15	120.0
O3'^ii—Cd1—O3^ii	19.0 (4)	C19—C20—C22	118.9 (9)
O4^ii—Cd1—O3^ii	54.7 (3)	C15—C20—C22	120.3 (9)
N4^i—Cd1—O1	134.3 (4)	O2—C21—O1	123.0 (13)
O2'—Cd1—O1	46.6 (6)	O2—C21—C15	118.7 (16)
N1—Cd1—O1	79.4 (3)	O1—C21—C15	118.4 (17)
O2—Cd1—O1	55.5 (3)	O2—C21—Cd1	58.4 (8)
O4'^ii—Cd1—O1	92.9 (5)	O1—C21—Cd1	64.5 (8)
O3'^ii—Cd1—O1	138.0 (4)	C15—C21—Cd1	176.8 (17)
O4^ii—Cd1—O1	103.7 (5)	C21—O1—Cd1	87.7 (10)
O3^ii—Cd1—O1	119.2 (4)	C21—O2—Cd1	93.9 (9)
N4^i—Cd1—O1'	150.8 (3)	C23—C22—C27	120.0
O2'—Cd1—O1'	54.4 (4)	C23—C22—C20	119.3 (8)
N1—Cd1—O1'	90.3 (3)	C27—C22—C20	120.4 (8)
O2—Cd1—O1'	54.2 (5)	C22—C23—C24	120.0
O4'^ii—Cd1—O1'	73.7 (4)	C22—C23—H23	120.0
O3'^ii—Cd1—O1'	117.8 (4)	C24—C23—H23	120.0
O4^ii—Cd1—O1'	87.1 (4)	C25—C24—C23	120.0
O3^ii—Cd1—O1'	99.3 (4)	C25—C24—H24	120.0
O1—Cd1—O1'	20.9 (3)	C23—C24—H24	120.0
N4^i—Cd1—C21	120.5 (6)	C24—C25—C26	120.0
O2'—Cd1—C21	23.5 (6)	C24—C25—C28	119.9 (11)
N1—Cd1—C21	105.6 (6)	C26—C25—C28	119.8 (12)
O2—Cd1—C21	27.7 (5)	C25—C26—C27	120.0
O4'^ii—Cd1—C21	98.0 (8)	C25—C26—H26	120.0
O3'^ii—Cd1—C21	121.1 (9)	C27—C26—H26	120.0
O4^ii—Cd1—C21	114.6 (8)	C26—C27—C22	120.0
O3^ii—Cd1—C21	103.1 (9)	C26—C27—H27	120.0
O1—Cd1—C21	27.8 (5)	C22—C27—H27	120.0
O1'—Cd1—C21	30.9 (6)	O4—C28—O3	123.3 (14)
N4^i—Cd1—C28'^ii	106.5 (6)	O4—C28—C25	117.0 (15)
O2'—Cd1—C28'^ii	120.9 (12)	O3—C28—C25	119.3 (17)
N1—Cd1—C28'^ii	116.7 (9)	O4—C28—Cd1^ii	61.3 (8)
O2—Cd1—C28'^ii	100.4 (12)	O3—C28—Cd1^ii	62.1 (9)
O4'^ii—Cd1—C28'^ii	27.9 (5)	C25—C28—Cd1^ii	176 (2)
O3'^ii—Cd1—C28'^ii	28.0 (5)	C28—O3—Cd1^ii	90.4 (11)
O4^ii—Cd1—C28'^ii	32.4 (8)	C28—O4—Cd1^ii	91.4 (9)
O3^ii—Cd1—C28'^ii	22.3 (7)	C16'—C15'—C20'	120.0
O1—Cd1—C28'^ii	115.7 (9)	C16'—C15'—C21'	116.6 (14)
O1'—Cd1—C28'^ii	95.0 (9)	C20'—C15'—C21'	123.4 (14)
C21—Cd1—C28'^ii	110.3 (14)	C17'—C16'—C15'	120.0
C2—C1—N1	109.8 (6)	C17'—C16'—H16'	120.0
C2—C1—H1	125.1	C15'—C16'—H16'	120.0
N1—C1—H1	125.1	C18'—C17'—C16'	120.0
C1—C2—N2	106.7 (6)	C18'—C17'—H17'	120.0
C1—C2—H2	126.7	C16'—C17'—H17'	120.0
N2—C2—H2	126.7	C19'—C18'—C17'	120.0
N1—C3—N2	113.1 (6)	C19'—C18'—H18'	120.0
N1—C3—H3	123.4	C17'—C18'—H18'	120.0
N2—C3—H3	123.4	C18'—C19'—C20'	120.0
N2—C4—C5	113.1 (5)	C18'—C19'—H19'	120.0
N2—C4—H4A	108.9	C20'—C19'—H19'	120.0
C5—C4—H4A	108.9	C19'—C20'—C15'	120.0
N2—C4—H4B	108.9	C19'—C20'—C22'	116.6 (12)
C5—C4—H4B	108.9	C15'—C20'—C22'	123.1 (12)
H4A—C4—H4B	107.8	O2'—C21'—O1'	121.8 (15)
C10—C5—C6	117.9 (7)	O2'—C21'—C15'	117.1 (18)
C10—C5—C4	119.1 (7)	O1'—C21'—C15'	121.2 (19)
C6—C5—C4	122.9 (6)	O2'—C21'—Cd1	55.5 (9)
C5—C6—C7	121.4 (7)	O1'—C21'—Cd1	66.5 (9)
C5—C6—H6	119.3	C15'—C21'—Cd1	171.3 (15)
C7—C6—H6	119.3	C21'—O1'—Cd1	86.1 (10)
C8—C7—C6	120.8 (7)	C21'—O2'—Cd1	97.5 (12)
C8—C7—H7	119.6	C23'—C22'—C27'	120.0
C6—C7—H7	119.6	C23'—C22'—C20'	120.1 (9)
C7—C8—C9	118.7 (7)	C27'—C22'—C20'	119.9 (9)
C7—C8—C11	120.2 (7)	C24'—C23'—C22'	120.0
C9—C8—C11	121.0 (7)	C24'—C23'—H23'	120.0
C8—C9—C10	120.5 (7)	C22'—C23'—H23'	120.0
C8—C9—H9	119.7	C25'—C24'—C23'	120.0
C10—C9—H9	119.7	C25'—C24'—H24'	120.0
C5—C10—C9	120.7 (7)	C23'—C24'—H24'	120.0
C5—C10—H10	119.7	C26'—C25'—C24'	120.0
C9—C10—H10	119.7	C26'—C25'—C28'	120.9 (12)
N3—C11—C8	113.6 (6)	C24'—C25'—C28'	119.1 (13)
N3—C11—H11A	108.8	C27'—C26'—C25'	120.0
C8—C11—H11A	108.8	C27'—C26'—H26'	120.0
N3—C11—H11B	108.8	C25'—C26'—H26'	120.0
C8—C11—H11B	108.8	C26'—C27'—C22'	120.0
H11A—C11—H11B	107.7	C26'—C27'—H27'	120.0
N4—C12—N3	112.9 (7)	C22'—C27'—H27'	120.0
N4—C12—H12	123.5	O4'—C28'—O3'	120.6 (15)
N3—C12—H12	123.5	O4'—C28'—C25'	119.2 (16)
N4—C13—C14	109.5 (8)	O3'—C28'—C25'	118.5 (18)
N4—C13—H13	125.3	O4'—C28'—Cd1^ii	60.2 (9)
C14—C13—H13	125.3	O3'—C28'—Cd1^ii	60.7 (9)
N3—C14—C13	106.5 (8)	C25'—C28'—Cd1^ii	173 (3)
N3—C14—H14	126.8	C28'—O3'—Cd1^ii	91.3 (10)
C13—C14—H14	126.8	C28'—O4'—Cd1^ii	91.9 (11)
C3—N1—C1	104.9 (5)	H1W1—O1W—H1W2	138.0
C3—N1—Cd1	138.1 (4)
N1—C1—C2—N2	1.5 (8)	O3^ii—Cd1—C21—O2	−51.1 (18)
N2—C4—C5—C10	115.2 (7)	C28'^ii—Cd1—C21—O2	−73.2 (19)
N2—C4—C5—C6	−66.4 (9)	N4^i—Cd1—C21—O1	−128.4 (14)
C10—C5—C6—C7	0.4 (11)	O2'—Cd1—C21—O1	−132 (4)
C4—C5—C6—C7	−178.0 (6)	N1—Cd1—C21—O1	−19.9 (19)
C5—C6—C7—C8	0.7 (12)	O2—Cd1—C21—O1	−180 (3)
C6—C7—C8—C9	−0.6 (13)	O4'^ii—Cd1—C21—O1	81.0 (18)
C6—C7—C8—C11	−178.1 (8)	O3'^ii—Cd1—C21—O1	135.8 (16)
C7—C8—C9—C10	−0.6 (14)	O4^ii—Cd1—C21—O1	72 (2)
C11—C8—C9—C10	176.9 (8)	O3^ii—Cd1—C21—O1	129.0 (17)
C6—C5—C10—C9	−1.5 (12)	O1'—Cd1—C21—O1	42.9 (9)
C4—C5—C10—C9	177.0 (7)	C28'^ii—Cd1—C21—O1	107.0 (18)
C8—C9—C10—C5	1.6 (14)	O2'—Cd1—O1—C21	24.3 (19)
C7—C8—C11—N3	−137.9 (8)	N1—Cd1—O1—C21	160.5 (19)
C9—C8—C11—N3	44.7 (13)	O2—Cd1—O1—C21	0.1 (19)
N4—C13—C14—N3	−0.8 (10)	O4'^ii—Cd1—O1—C21	−101.6 (19)
N2—C3—N1—C1	1.5 (7)	O3'^ii—Cd1—O1—C21	−63 (2)
N2—C3—N1—Cd1	−170.7 (4)	O4^ii—Cd1—O1—C21	−117.0 (19)
C2—C1—N1—C3	−1.8 (7)	O4'^ii—Cd1—O2—C21	85.6 (19)
C2—C1—N1—Cd1	172.4 (4)	O3'^ii—Cd1—O2—C21	142.5 (19)
N4^i—Cd1—N1—C3	−2.1 (7)	O4^ii—Cd1—O2—C21	86.2 (19)
O2'—Cd1—N1—C3	−102.9 (7)	O3^ii—Cd1—O2—C21	130.5 (19)
O2—Cd1—N1—C3	−114.4 (8)	O1—Cd1—O2—C21	−0.1 (19)
O4'^ii—Cd1—N1—C3	132.6 (7)	O1'—Cd1—O2—C21	25.4 (19)
O3'^ii—Cd1—N1—C3	79.8 (8)	C28'^ii—Cd1—O2—C21	114.0 (19)
O4^ii—Cd1—N1—C3	119.2 (7)	C19—C20—C22—C23	−127.5 (9)
O3^ii—Cd1—N1—C3	101.9 (8)	C15—C20—C22—C23	42.2 (13)
O1—Cd1—N1—C3	−135.9 (8)	C19—C20—C22—C27	47.1 (13)
O1'—Cd1—N1—C3	−153.8 (7)	C15—C20—C22—C27	−143.1 (9)
C21—Cd1—N1—C3	−126.6 (10)	C27—C22—C23—C24	0.0
C28'^ii—Cd1—N1—C3	110.5 (11)	C20—C22—C23—C24	174.6 (10)
N4^i—Cd1—N1—C1	−173.6 (5)	C22—C23—C24—C25	0.0
O2'—Cd1—N1—C1	85.5 (6)	C23—C24—C25—C26	0.0
O2—Cd1—N1—C1	74.1 (7)	C23—C24—C25—C28	−174.1 (19)
O4'^ii—Cd1—N1—C1	−38.9 (6)	C24—C25—C26—C27	0.0
O3'^ii—Cd1—N1—C1	−91.7 (6)	C28—C25—C26—C27	174.1 (18)
O4^ii—Cd1—N1—C1	−52.4 (5)	C25—C26—C27—C22	0.0
O3^ii—Cd1—N1—C1	−69.7 (7)	C23—C22—C27—C26	0.0
O1—Cd1—N1—C1	52.5 (6)	C20—C22—C27—C26	−174.6 (10)
O1'—Cd1—N1—C1	34.6 (5)	C24—C25—C28—O4	−159 (2)
C21—Cd1—N1—C1	61.8 (9)	C26—C25—C28—O4	27 (4)
C28'^ii—Cd1—N1—C1	−61.1 (10)	C24—C25—C28—O3	13 (4)
N1—C3—N2—C2	−0.6 (7)	C26—C25—C28—O3	−161 (3)
N1—C3—N2—C4	178.3 (5)	O4—C28—O3—Cd1^ii	−4 (4)
C1—C2—N2—C3	−0.5 (7)	C25—C28—O3—Cd1^ii	−176 (3)
C1—C2—N2—C4	−179.5 (5)	O3—C28—O4—Cd1^ii	4 (4)
C5—C4—N2—C3	−81.5 (8)	C25—C28—O4—Cd1^ii	176 (3)
C5—C4—N2—C2	97.3 (7)	C20'—C15'—C16'—C17'	0.0
N4—C12—N3—C14	−1.2 (8)	C21'—C15'—C16'—C17'	−179 (2)
N4—C12—N3—C11	179.5 (6)	C15'—C16'—C17'—C18'	0.0
C13—C14—N3—C12	1.2 (9)	C16'—C17'—C18'—C19'	0.0
C13—C14—N3—C11	−179.5 (7)	C17'—C18'—C19'—C20'	0.0
C8—C11—N3—C12	−94.9 (10)	C18'—C19'—C20'—C15'	0.0
C8—C11—N3—C14	85.8 (11)	C18'—C19'—C20'—C22'	−173.4 (17)
N3—C12—N4—C13	0.7 (8)	C16'—C15'—C20'—C19'	0.0
N3—C12—N4—Cd1^iii	−176.4 (4)	C21'—C15'—C20'—C19'	179 (2)
C14—C13—N4—C12	0.1 (8)	C16'—C15'—C20'—C22'	173.0 (19)
C14—C13—N4—Cd1^iii	176.9 (5)	N1—Cd1—C21'—O2'	112.9 (19)
C20—C15—C16—C17	0.0	O2—Cd1—C21'—O2'	−43.5 (11)
C21—C15—C16—C17	176.4 (17)	N4^i—Cd1—C21'—O1'	−170.7 (14)
C15—C16—C17—C18	0.0	O3'^ii—Cd1—C21'—O1'	91.1 (19)
C16—C17—C18—C19	0.0	O4^ii—Cd1—C21'—O1'	29 (2)
C17—C18—C19—C20	0.0	O3^ii—Cd1—C21'—O1'	85.7 (19)
C18—C19—C20—C15	0.0	O1—Cd1—C21'—O1'	−47.9 (11)
C18—C19—C20—C22	169.8 (15)	C19'—C20'—C22'—C23'	134.9 (12)
C16—C15—C20—C19	0.0	C15'—C20'—C22'—C23'	−38.3 (18)
C21—C15—C20—C19	−176.1 (19)	C19'—C20'—C22'—C27'	−45.3 (16)
C16—C15—C20—C22	−169.6 (15)	C15'—C20'—C22'—C27'	141.5 (12)
C21—C15—C20—C22	14.2 (19)	C27'—C22'—C23'—C24'	0.0
N4^i—Cd1—C21—O2	51 (2)	C20'—C22'—C23'—C24'	179.8 (12)
O2'—Cd1—C21—O2	48.2 (11)	C22'—C23'—C24'—C25'	0.0
N1—Cd1—C21—O2	159.9 (16)	C23'—C24'—C25'—C26'	0.0
O4'^ii—Cd1—C21—O2	−99.1 (17)	C25'—C26'—C27'—C22'	0.0
O3'^ii—Cd1—C21—O2	−44 (2)	C23'—C22'—C27'—C26'	0.0
O4^ii—Cd1—C21—O2	−108.1 (16)	C20'—C22'—C27'—C26'	−179.8 (12)

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