A two-dimensional cadmium(II) coordination polymer constructed from 4-carboxy-1-(4-car­box­yl­atobenz­yl)-2-propyl-1H-imidazole-5-carboxyl­ate and 1-(4-carboxyl­atobenz­yl)-2-propyl-1H-imid­azole-4-carboxyl­ate ligands

Crystals of poly[[aqua­[μ₃-4-carb­oxy-1-(4-carboxyl­atobenz­yl)-2-propyl-1H-imidazole-5-carboxyl­ato-κ⁵O¹O^1′:N³,O⁴:O⁵][μ₄-1-(4-carboxyl­atobenz­yl)-2-propyl-1H-imidazole-4-carboxyl­ato-κ⁷N³,O⁴:O⁴,O^4′:O¹,O^1′:O¹]cadmium(II)] monohydrate], {[Cd₂(C₁₅H₁₄N₂O₄)(C₁₆H₁₄N₂O₆)(H₂O)]·H₂O}_n or {[Cd₂(Hcpimda)(cpima)(H₂O)]·H₂O}_n, (I), were obtained from 1-(4-carb­oxy­benz­yl)-2-propyl-1H-imidazole-4,5-di­carb­oxy­lic acid (H₃cpimda) and cadmium(II) chloride under hydro­thermal conditions. The structure indicates that in-situ deca­rboxylation of H₃cpimda occurred during the synthesis process. The asymmetric unit consists of two Cd²⁺ centres, one 4-carb­oxy-1-(4-carboxyl­atobenz­yl)-2-propyl-1H-imidazole-5-carboxyl­ate (Hcpimda²⁻) anion, one 1-(4-carboxyl­atobenz­yl)-2-propyl-1H-imidazole-4-carboxyl­ate (cpima²⁻) anion, one coordinated water mol­ecule and one lattice water mol­ecule. One Cd²⁺ centre, i.e. Cd1, is hexa­coordinated and displays a slightly distorted octa­hedral CdN₂O₄ geometry. The other Cd centre, i.e. Cd2, is coordinated by seven O atoms originating from one Hcpimda²⁻ ligand and three cpima²⁻ ligands. This Cd²⁺ centre can be described as having a distorted capped octa­hedral coordination geometry. Two carboxyl­ate groups of the benzoate moieties of two cpima²⁻ ligands bridge between Cd2 centres to generate [Cd₂O₂] units, which are further linked by two cpima²⁻ ligands to produce one-dimensional (1D) infinite chains based around large 26-membered rings. Meanwhile, adjacent Cd1 centres are linked by Hcpimda²⁻ ligands to generate 1D zigzag chains. The two types of chains are linked through a μ₂-η² bidentate bridging mode from an O atom of an imidazole carboxyl­ate unit of cpima²⁻ to give a two-dimensional (2D) coordination polymer. The simplified 2D net structure can be described as a 3,6-coordinated net which has a (4³)₂(4⁶.6⁶.8³) topology. Furthermore, the FT–IR spectroscopic properties, photoluminescence properties, powder X-ray diffraction (PXRD) pattern and thermogravimetric behaviour of the polymer have been investigated.

Computing details

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: BAINT (Bruker, 2000); program(s) used to solve structure: SHELXT2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: pubCIF (Westrip, 2010).

Poly[[aqua[µ₃-4-carboxy-1-(4-carboxylatobenzyl)-2-propyl-1H-imidazole-5-carboxylato-κ⁵O¹O^1':N³,O⁴:O⁵][µ₄-1-(4-carboxylatobenzyl)-2-propyl-1H-imidazole-4-carboxylato-κ⁷N³,O⁴:O⁴,O^4':O¹,O^1':O¹]cadmium(II)] monohydrate]

Crystal data

[Cd2(C15H14N2O4)(C16H14N2O6)(H2O)]·H2O	F(000) = 1752
Mr = 877.40	Dx = 1.793 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.2716 (5) Å	Cell parameters from 9846 reflections
b = 26.9672 (11) Å	θ = 3.0–28.2°
c = 11.3809 (5) Å	µ = 1.38 mm^−1
β = 109.986 (1)°	T = 298 K
V = 3251.0 (2) Å^3	Block, colorless
Z = 4	0.15 × 0.1 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer	6956 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.031
φ and ω scans	θmax = 28.3°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −15→15
Tmin = 0.640, Tmax = 0.746	k = −35→34
30736 measured reflections	l = −15→13
8004 independent reflections

Refinement

Refinement on F^2	14 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.0227P)^2 + 12.2789P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.106	(Δ/σ)max = 0.001
S = 1.17	Δρmax = 1.79 e Å^−3
8004 reflections	Δρmin = −0.91 e Å^−3
447 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	−0.07148 (3)	0.14182 (2)	−0.03212 (3)	0.03578 (9)
Cd2	0.57375 (3)	0.06124 (2)	0.97164 (3)	0.02978 (9)
N1	−0.0046 (4)	0.19672 (14)	0.1350 (3)	0.0345 (8)
N2	0.0650 (4)	0.23923 (14)	0.3097 (3)	0.0364 (9)
N3	0.0442 (3)	0.07866 (14)	0.0794 (3)	0.0301 (8)
N4	0.1733 (3)	0.02251 (15)	0.1936 (3)	0.0309 (8)
O1	0.0616 (4)	0.20142 (15)	−0.0751 (4)	0.0573 (10)
O2	0.1766 (5)	0.26818 (18)	−0.0133 (4)	0.0681 (13)
H2	0.193 (8)	0.286 (3)	0.063 (8)	0.102*
O3	0.2561 (4)	0.31613 (15)	0.1811 (4)	0.0628 (11)
O4	0.2620 (4)	0.31090 (14)	0.3779 (4)	0.0553 (10)
O5	0.5288 (3)	0.11135 (15)	0.7916 (3)	0.0497 (9)
O6	0.4056 (4)	0.11631 (16)	0.9033 (3)	0.0520 (10)
O7	−0.2132 (3)	0.08439 (12)	0.0015 (3)	0.0350 (7)
O8	−0.2315 (3)	0.00929 (12)	0.0642 (3)	0.0401 (8)
O9	0.4695 (3)	−0.00770 (16)	0.8655 (3)	0.0487 (9)
O10	0.3803 (3)	−0.08025 (14)	0.8220 (3)	0.0444 (8)
O11	−0.0705 (4)	0.10708 (19)	−0.2151 (4)	0.0730 (14)
H11A	−0.108890	0.129852	−0.259823	0.110*
H11B	−0.008245	0.100232	−0.233587	0.110*
C1	−0.0118 (5)	0.20180 (18)	0.2471 (4)	0.0391 (11)
C2	0.0785 (4)	0.23190 (17)	0.1227 (4)	0.0361 (10)
C3	0.1233 (4)	0.25888 (16)	0.2307 (4)	0.0367 (10)
C4	0.0807 (5)	0.25454 (19)	0.4377 (4)	0.0451 (12)
H4A	0.000259	0.251476	0.450592	0.054*
H4B	0.105125	0.289196	0.448085	0.054*
C5	0.1794 (4)	0.22400 (17)	0.5370 (4)	0.0351 (10)
C6	0.2787 (5)	0.20132 (17)	0.5129 (4)	0.0386 (10)
H6	0.289401	0.206287	0.436310	0.046*
C7	0.3623 (4)	0.17119 (17)	0.6020 (4)	0.0346 (10)
H7	0.428092	0.155702	0.584463	0.042*
C8	0.3483 (4)	0.16415 (17)	0.7166 (4)	0.0348 (10)
C9	0.2524 (5)	0.1884 (2)	0.7428 (5)	0.0496 (13)
H9	0.244708	0.185016	0.821138	0.060*
C10	0.1670 (5)	0.2181 (2)	0.6524 (5)	0.0482 (13)
H10	0.101656	0.233853	0.670056	0.058*
C11	0.4344 (4)	0.12860 (19)	0.8103 (4)	0.0371 (10)
C12	0.1048 (5)	0.2332 (2)	0.0038 (5)	0.0463 (12)
C13	0.2211 (5)	0.29881 (18)	0.2659 (5)	0.0442 (12)
C14	−0.0854 (7)	0.1685 (3)	0.3010 (6)	0.070 (2)
H14A	−0.157693	0.155353	0.234468	0.084*
H14B	−0.116151	0.187141	0.357594	0.084*
C15	0.0008 (8)	0.1245 (3)	0.3737 (7)	0.092 (3)
H15A	0.032692	0.107001	0.316196	0.110*
H15B	0.072821	0.138413	0.439136	0.110*
C16	−0.0607 (12)	0.0889 (5)	0.4299 (12)	0.170 (6)
H16A	−0.116348	0.068304	0.365737	0.255*
H16B	−0.108278	0.106231	0.472590	0.255*
H16C	0.002088	0.068581	0.488424	0.255*
C17	0.1649 (4)	0.06624 (17)	0.1321 (4)	0.0305 (9)
C18	−0.0255 (4)	0.04161 (16)	0.1067 (4)	0.0263 (8)
C19	0.0533 (4)	0.00655 (18)	0.1776 (4)	0.0312 (9)
H19	0.030465	−0.022403	0.208848	0.037*
C20	0.2892 (4)	−0.0061 (2)	0.2571 (4)	0.0357 (10)
H20A	0.360529	0.011159	0.246737	0.043*
H20B	0.282549	−0.038167	0.216856	0.043*
C21	0.3145 (4)	−0.01387 (17)	0.3947 (4)	0.0295 (9)
C22	0.3169 (5)	0.02490 (19)	0.4746 (4)	0.0415 (11)
H22	0.295669	0.056702	0.442770	0.050*
C23	0.3507 (5)	0.01668 (19)	0.6020 (4)	0.0421 (11)
H23	0.355316	0.043256	0.655509	0.051*
C24	0.3774 (4)	−0.03032 (17)	0.6500 (4)	0.0301 (9)
C25	0.3715 (5)	−0.06960 (19)	0.5703 (4)	0.0386 (10)
H25	0.387338	−0.101682	0.601773	0.046*
C26	0.3417 (4)	−0.06109 (18)	0.4431 (4)	0.0375 (10)
H26	0.340179	−0.087496	0.390037	0.045*
C27	0.4111 (4)	−0.03978 (19)	0.7878 (4)	0.0334 (10)
C28	−0.1652 (4)	0.04459 (17)	0.0563 (4)	0.0281 (9)
C29	0.2710 (4)	0.09756 (19)	0.1242 (5)	0.0402 (11)
H29A	0.242470	0.115901	0.046168	0.048*
H29B	0.339397	0.076073	0.122472	0.048*
C30	0.3213 (5)	0.1340 (2)	0.2316 (5)	0.0514 (13)
H30A	0.250883	0.151083	0.244228	0.062*
H30B	0.365705	0.115878	0.307470	0.062*
C31	0.4098 (6)	0.1720 (2)	0.2085 (7)	0.0659 (17)
H31A	0.484431	0.155703	0.205656	0.099*
H31B	0.432507	0.195950	0.274935	0.099*
H31C	0.368419	0.188439	0.130361	0.099*
O12	0.1523 (5)	0.07501 (19)	0.7973 (5)	0.0934 (18)
H12A	0.215293	0.091191	0.835614	0.140*
H12B	0.153742	0.049765	0.837890	0.140*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.03797 (18)	0.02936 (16)	0.03433 (17)	−0.00002 (14)	0.00501 (14)	0.00264 (13)
Cd2	0.02322 (14)	0.04444 (19)	0.01941 (13)	0.00058 (13)	0.00435 (10)	0.00541 (12)
N1	0.0347 (19)	0.0330 (19)	0.0295 (18)	−0.0042 (16)	0.0030 (15)	0.0013 (15)
N2	0.039 (2)	0.0319 (19)	0.0287 (18)	0.0039 (16)	−0.0016 (16)	0.0010 (15)
N3	0.0219 (16)	0.0367 (19)	0.0284 (17)	0.0009 (14)	0.0043 (14)	0.0000 (15)
N4	0.0198 (16)	0.053 (2)	0.0197 (15)	0.0065 (15)	0.0064 (13)	0.0075 (15)
O1	0.075 (3)	0.056 (2)	0.046 (2)	−0.020 (2)	0.027 (2)	−0.0096 (18)
O2	0.085 (3)	0.069 (3)	0.054 (3)	−0.031 (3)	0.027 (2)	−0.002 (2)
O3	0.073 (3)	0.051 (2)	0.057 (3)	−0.028 (2)	0.013 (2)	−0.0030 (19)
O4	0.054 (2)	0.041 (2)	0.051 (2)	−0.0080 (17)	−0.0081 (18)	−0.0062 (17)
O5	0.0373 (19)	0.066 (2)	0.0408 (19)	0.0110 (18)	0.0071 (15)	0.0169 (17)
O6	0.048 (2)	0.073 (3)	0.0364 (19)	0.0153 (19)	0.0157 (16)	0.0207 (18)
O7	0.0216 (14)	0.0460 (18)	0.0335 (16)	0.0084 (13)	0.0044 (12)	0.0112 (14)
O8	0.0228 (14)	0.0393 (18)	0.052 (2)	0.0002 (13)	0.0047 (14)	−0.0037 (15)
O9	0.0384 (18)	0.085 (3)	0.0205 (15)	−0.0206 (18)	0.0072 (13)	−0.0119 (16)
O10	0.055 (2)	0.053 (2)	0.0250 (16)	0.0093 (17)	0.0128 (15)	0.0086 (14)
O11	0.068 (3)	0.105 (4)	0.040 (2)	0.042 (3)	0.009 (2)	−0.003 (2)
C1	0.040 (3)	0.036 (2)	0.033 (2)	−0.003 (2)	0.002 (2)	0.0008 (19)
C2	0.032 (2)	0.031 (2)	0.036 (2)	−0.0002 (18)	−0.0017 (18)	0.0024 (18)
C3	0.036 (2)	0.027 (2)	0.035 (2)	0.0031 (18)	−0.0035 (19)	0.0039 (18)
C4	0.053 (3)	0.040 (3)	0.032 (2)	0.014 (2)	0.001 (2)	−0.003 (2)
C5	0.038 (2)	0.031 (2)	0.027 (2)	0.0050 (19)	−0.0002 (18)	−0.0039 (17)
C6	0.048 (3)	0.037 (2)	0.029 (2)	0.006 (2)	0.010 (2)	0.0048 (18)
C7	0.033 (2)	0.036 (2)	0.033 (2)	0.0012 (19)	0.0079 (18)	0.0034 (18)
C8	0.030 (2)	0.036 (2)	0.032 (2)	−0.0013 (18)	0.0014 (18)	0.0011 (18)
C9	0.055 (3)	0.062 (3)	0.030 (2)	0.014 (3)	0.012 (2)	0.006 (2)
C10	0.049 (3)	0.058 (3)	0.039 (3)	0.019 (3)	0.016 (2)	0.001 (2)
C11	0.030 (2)	0.045 (3)	0.029 (2)	−0.001 (2)	0.0010 (18)	0.0006 (19)
C12	0.048 (3)	0.046 (3)	0.042 (3)	−0.006 (2)	0.012 (2)	0.004 (2)
C13	0.042 (3)	0.034 (2)	0.040 (3)	0.005 (2)	−0.007 (2)	−0.002 (2)
C14	0.086 (5)	0.083 (5)	0.045 (3)	−0.036 (4)	0.026 (3)	−0.011 (3)
C15	0.102 (5)	0.095 (5)	0.066 (4)	−0.040 (5)	0.013 (4)	0.004 (4)
C16	0.161 (11)	0.179 (12)	0.160 (11)	−0.034 (9)	0.041 (9)	0.039 (9)
C17	0.0223 (18)	0.043 (2)	0.0232 (18)	0.0030 (18)	0.0044 (15)	−0.0024 (17)
C18	0.0239 (19)	0.034 (2)	0.0204 (17)	0.0013 (16)	0.0070 (15)	0.0006 (15)
C19	0.0238 (19)	0.047 (3)	0.0233 (19)	0.0056 (18)	0.0083 (16)	0.0088 (17)
C20	0.024 (2)	0.061 (3)	0.0205 (19)	0.013 (2)	0.0056 (16)	0.0081 (19)
C21	0.0187 (17)	0.047 (3)	0.0197 (18)	0.0025 (17)	0.0027 (14)	0.0018 (17)
C22	0.056 (3)	0.038 (3)	0.027 (2)	0.001 (2)	0.009 (2)	0.0036 (18)
C23	0.058 (3)	0.042 (3)	0.024 (2)	−0.004 (2)	0.010 (2)	−0.0071 (19)
C24	0.0241 (19)	0.048 (3)	0.0157 (17)	−0.0015 (18)	0.0034 (15)	−0.0014 (16)
C25	0.044 (3)	0.044 (3)	0.023 (2)	0.008 (2)	0.0043 (19)	0.0039 (18)
C26	0.041 (2)	0.044 (3)	0.0219 (19)	0.012 (2)	0.0029 (18)	−0.0046 (18)
C27	0.0223 (19)	0.059 (3)	0.0198 (19)	0.0069 (19)	0.0080 (16)	0.0002 (19)
C28	0.0230 (19)	0.041 (2)	0.0183 (17)	0.0039 (17)	0.0047 (15)	−0.0027 (16)
C29	0.027 (2)	0.049 (3)	0.045 (3)	−0.004 (2)	0.012 (2)	−0.002 (2)
C30	0.042 (3)	0.058 (3)	0.050 (3)	−0.010 (2)	0.010 (2)	−0.008 (3)
C31	0.052 (3)	0.053 (4)	0.085 (5)	−0.012 (3)	0.012 (3)	−0.006 (3)
O12	0.097 (4)	0.067 (3)	0.096 (4)	0.026 (3)	0.007 (3)	0.013 (3)

Geometric parameters (Å, º)

Cd1—O4^i	2.210 (4)	C6—C7	1.387 (6)
Cd1—N3	2.254 (4)	C6—H6	0.9300
Cd1—O11	2.287 (4)	C7—C8	1.379 (6)
Cd1—N1	2.323 (4)	C7—H7	0.9300
Cd1—O7	2.348 (3)	C8—C9	1.381 (7)
Cd1—O1	2.360 (4)	C8—C11	1.513 (6)
Cd2—O10^ii	2.284 (3)	C9—C10	1.396 (7)
Cd2—O9	2.308 (4)	C9—H9	0.9300
Cd2—O6	2.323 (4)	C10—H10	0.9300
Cd2—O5	2.361 (3)	C14—C15	1.577 (8)
Cd2—O7^iii	2.390 (3)	C14—H14A	0.9700
Cd2—O8^iii	2.512 (3)	C14—H14B	0.9700
Cd2—O9^ii	2.525 (4)	C15—C16	1.455 (8)
Cd2—C11	2.677 (5)	C15—H15A	0.9700
Cd2—C27^ii	2.746 (4)	C15—H15B	0.9700
N1—C1	1.313 (6)	C16—H16A	0.9600
N1—C2	1.374 (6)	C16—H16B	0.9600
N2—C1	1.362 (6)	C16—H16C	0.9600
N2—C3	1.387 (6)	C17—C29	1.492 (6)
N2—C4	1.466 (6)	C18—C19	1.358 (6)
N3—C17	1.328 (5)	C18—C28	1.482 (5)
N3—C18	1.371 (5)	C19—H19	0.9300
N4—C17	1.358 (6)	C20—C21	1.507 (5)
N4—C19	1.371 (5)	C20—H20A	0.9700
N4—C20	1.476 (5)	C20—H20B	0.9700
O1—C12	1.216 (6)	C21—C26	1.380 (6)
O2—C12	1.301 (6)	C21—C22	1.380 (6)
O2—H2	0.96 (8)	C22—C23	1.386 (6)
O3—C13	1.251 (7)	C22—H22	0.9300
O4—C13	1.242 (6)	C23—C24	1.372 (7)
O5—C11	1.245 (6)	C23—H23	0.9300
O6—C11	1.253 (6)	C24—C25	1.381 (6)
O7—C28	1.266 (5)	C24—C27	1.503 (5)
O8—C28	1.233 (5)	C25—C26	1.389 (6)
O9—C27	1.252 (6)	C25—H25	0.9300
O10—C27	1.247 (6)	C26—H26	0.9300
O11—H11A	0.8201	C29—C30	1.520 (7)
O11—H11B	0.8200	C29—H29A	0.9700
C1—C14	1.489 (8)	C29—H29B	0.9700
C2—C3	1.368 (6)	C30—C31	1.513 (8)
C2—C12	1.480 (7)	C30—H30A	0.9700
C3—C13	1.494 (7)	C30—H30B	0.9700
C4—C5	1.528 (6)	C31—H31A	0.9600
C4—H4A	0.9700	C31—H31B	0.9600
C4—H4B	0.9700	C31—H31C	0.9600
C5—C10	1.376 (7)	O12—H12A	0.8200
C5—C6	1.382 (7)	O12—H12B	0.8201
O4^i—Cd1—N3	158.94 (14)	C6—C7—H7	119.9
O4^i—Cd1—O11	94.71 (15)	C7—C8—C9	119.3 (4)
N3—Cd1—O11	91.22 (14)	C7—C8—C11	120.0 (4)
O4^i—Cd1—N1	89.88 (14)	C9—C8—C11	120.6 (4)
N3—Cd1—N1	93.29 (13)	C8—C9—C10	120.4 (5)
O11—Cd1—N1	154.88 (17)	C8—C9—H9	119.8
O4^i—Cd1—O7	86.48 (13)	C10—C9—H9	119.8
N3—Cd1—O7	72.84 (11)	C5—C10—C9	120.0 (5)
O11—Cd1—O7	95.36 (16)	C5—C10—H10	120.0
N1—Cd1—O7	109.59 (13)	C9—C10—H10	120.0
O4^i—Cd1—O1	90.59 (16)	O5—C11—O6	121.9 (4)
N3—Cd1—O1	110.17 (14)	O5—C11—C8	119.7 (4)
O11—Cd1—O1	83.65 (17)	O6—C11—C8	118.3 (4)
N1—Cd1—O1	71.60 (13)	O5—C11—Cd2	61.8 (3)
O7—Cd1—O1	176.83 (13)	O6—C11—Cd2	60.1 (3)
O10^ii—Cd2—O9	127.94 (13)	C8—C11—Cd2	176.1 (3)
O10^ii—Cd2—O6	94.18 (13)	O1—C12—O2	120.9 (5)
O9—Cd2—O6	97.40 (15)	O1—C12—C2	120.3 (5)
O10^ii—Cd2—O5	132.08 (14)	O2—C12—C2	118.9 (5)
O9—Cd2—O5	95.00 (13)	O4—C13—O3	126.1 (5)
O6—Cd2—O5	55.60 (12)	O4—C13—C3	116.5 (5)
O10^ii—Cd2—O7^iii	86.08 (12)	O3—C13—C3	117.4 (4)
O9—Cd2—O7^iii	126.29 (12)	C1—C14—C15	109.8 (6)
O6—Cd2—O7^iii	123.07 (13)	C1—C14—H14A	109.7
O5—Cd2—O7^iii	83.15 (11)	C15—C14—H14A	109.7
O10^ii—Cd2—O8^iii	80.53 (12)	C1—C14—H14B	109.7
O9—Cd2—O8^iii	89.19 (12)	C15—C14—H14B	109.7
O6—Cd2—O8^iii	173.25 (13)	H14A—C14—H14B	108.2
O5—Cd2—O8^iii	125.50 (12)	C16—C15—C14	115.3 (8)
O7^iii—Cd2—O8^iii	52.74 (11)	C16—C15—H15A	108.5
O10^ii—Cd2—O9^ii	53.57 (12)	C14—C15—H15A	108.5
O9—Cd2—O9^ii	74.45 (12)	C16—C15—H15B	108.5
O6—Cd2—O9^ii	105.73 (13)	C14—C15—H15B	108.5
O5—Cd2—O9^ii	157.92 (12)	H15A—C15—H15B	107.5
O7^iii—Cd2—O9^ii	118.80 (10)	C15—C16—H16A	109.5
O8^iii—Cd2—O9^ii	74.55 (12)	C15—C16—H16B	109.5
O10^ii—Cd2—C11	115.25 (14)	H16A—C16—H16B	109.5
O9—Cd2—C11	96.50 (14)	C15—C16—H16C	109.5
O6—Cd2—C11	27.89 (13)	H16A—C16—H16C	109.5
O5—Cd2—C11	27.71 (13)	H16B—C16—H16C	109.5
O7^iii—Cd2—C11	104.22 (13)	N3—C17—N4	109.4 (4)
O8^iii—Cd2—C11	152.85 (14)	N3—C17—C29	123.3 (4)
O9^ii—Cd2—C11	132.55 (14)	N4—C17—C29	127.4 (4)
O10^ii—Cd2—C27^ii	26.73 (14)	C19—C18—N3	109.5 (4)
O9—Cd2—C27^ii	101.49 (14)	C19—C18—C28	131.3 (4)
O6—Cd2—C27^ii	103.54 (13)	N3—C18—C28	119.2 (4)
O5—Cd2—C27^ii	155.23 (14)	C18—C19—N4	106.0 (4)
O7^iii—Cd2—C27^ii	101.30 (11)	C18—C19—H19	127.0
O8^iii—Cd2—C27^ii	73.54 (12)	N4—C19—H19	127.0
O9^ii—Cd2—C27^ii	27.06 (13)	N4—C20—C21	113.8 (3)
C11—Cd2—C27^ii	130.46 (14)	N4—C20—H20A	108.8
C1—N1—C2	107.3 (4)	C21—C20—H20A	108.8
C1—N1—Cd1	138.7 (3)	N4—C20—H20B	108.8
C2—N1—Cd1	113.5 (3)	C21—C20—H20B	108.8
C1—N2—C3	107.6 (4)	H20A—C20—H20B	107.7
C1—N2—C4	124.6 (4)	C26—C21—C22	119.0 (4)
C3—N2—C4	127.9 (4)	C26—C21—C20	118.8 (4)
C17—N3—C18	107.0 (4)	C22—C21—C20	122.2 (4)
C17—N3—Cd1	138.7 (3)	C21—C22—C23	120.4 (5)
C18—N3—Cd1	114.3 (3)	C21—C22—H22	119.8
C17—N4—C19	108.2 (3)	C23—C22—H22	119.8
C17—N4—C20	126.9 (4)	C24—C23—C22	120.6 (4)
C19—N4—C20	124.7 (4)	C24—C23—H23	119.7
C12—O1—Cd1	116.7 (4)	C22—C23—H23	119.7
C12—O2—H2	100 (5)	C23—C24—C25	119.5 (4)
C13—O4—Cd1^iv	125.8 (4)	C23—C24—C27	121.0 (4)
C11—O5—Cd2	90.4 (3)	C25—C24—C27	119.5 (4)
C11—O6—Cd2	92.0 (3)	C24—C25—C26	119.9 (4)
C28—O7—Cd1	116.0 (3)	C24—C25—H25	120.1
C28—O7—Cd2^v	95.1 (3)	C26—C25—H25	120.1
Cd1—O7—Cd2^v	148.80 (14)	C21—C26—C25	120.7 (4)
C28—O8—Cd2^v	90.2 (3)	C21—C26—H26	119.7
C27—O9—Cd2	167.8 (3)	C25—C26—H26	119.7
C27—O9—Cd2^ii	86.4 (3)	O10—C27—O9	121.3 (4)
Cd2—O9—Cd2^ii	105.55 (11)	O10—C27—C24	118.4 (4)
C27—O10—Cd2^ii	97.8 (3)	O9—C27—C24	120.3 (4)
Cd1—O11—H11A	95.3	O10—C27—Cd2^ii	55.5 (2)
Cd1—O11—H11B	126.6	O9—C27—Cd2^ii	66.6 (2)
H11A—O11—H11B	109.0	C24—C27—Cd2^ii	169.4 (3)
N1—C1—N2	110.3 (4)	O8—C28—O7	121.5 (4)
N1—C1—C14	124.4 (5)	O8—C28—C18	121.3 (4)
N2—C1—C14	125.1 (5)	O7—C28—C18	117.1 (4)
C3—C2—N1	109.3 (4)	C17—C29—C30	113.9 (4)
C3—C2—C12	133.0 (5)	C17—C29—H29A	108.8
N1—C2—C12	117.7 (4)	C30—C29—H29A	108.8
C2—C3—N2	105.6 (4)	C17—C29—H29B	108.8
C2—C3—C13	129.5 (5)	C30—C29—H29B	108.8
N2—C3—C13	124.8 (4)	H29A—C29—H29B	107.7
N2—C4—C5	113.2 (4)	C31—C30—C29	112.7 (5)
N2—C4—H4A	108.9	C31—C30—H30A	109.1
C5—C4—H4A	108.9	C29—C30—H30A	109.1
N2—C4—H4B	108.9	C31—C30—H30B	109.1
C5—C4—H4B	108.9	C29—C30—H30B	109.1
H4A—C4—H4B	107.8	H30A—C30—H30B	107.8
C10—C5—C6	119.4 (4)	C30—C31—H31A	109.5
C10—C5—C4	118.8 (4)	C30—C31—H31B	109.5
C6—C5—C4	121.7 (4)	H31A—C31—H31B	109.5
C5—C6—C7	120.5 (4)	C30—C31—H31C	109.5
C5—C6—H6	119.7	H31A—C31—H31C	109.5
C7—C6—H6	119.7	H31B—C31—H31C	109.5
C8—C7—C6	120.2 (4)	H12A—O12—H12B	107.2
C8—C7—H7	119.9
C2—N1—C1—N2	−0.4 (5)	C18—N3—C17—N4	−0.8 (5)
Cd1—N1—C1—N2	170.7 (3)	Cd1—N3—C17—N4	176.9 (3)
C2—N1—C1—C14	−175.7 (5)	C18—N3—C17—C29	−179.5 (4)
Cd1—N1—C1—C14	−4.7 (8)	Cd1—N3—C17—C29	−1.9 (7)
C3—N2—C1—N1	0.3 (5)	C19—N4—C17—N3	0.8 (5)
C4—N2—C1—N1	−179.4 (4)	C20—N4—C17—N3	175.4 (4)
C3—N2—C1—C14	175.6 (5)	C19—N4—C17—C29	179.5 (4)
C4—N2—C1—C14	−4.1 (8)	C20—N4—C17—C29	−6.0 (7)
C1—N1—C2—C3	0.3 (5)	C17—N3—C18—C19	0.5 (5)
Cd1—N1—C2—C3	−173.3 (3)	Cd1—N3—C18—C19	−177.8 (3)
C1—N1—C2—C12	178.9 (4)	C17—N3—C18—C28	−178.1 (4)
Cd1—N1—C2—C12	5.3 (5)	Cd1—N3—C18—C28	3.6 (5)
N1—C2—C3—N2	−0.1 (5)	N3—C18—C19—N4	0.0 (5)
C12—C2—C3—N2	−178.4 (5)	C28—C18—C19—N4	178.4 (4)
N1—C2—C3—C13	175.7 (4)	C17—N4—C19—C18	−0.5 (5)
C12—C2—C3—C13	−2.6 (9)	C20—N4—C19—C18	−175.2 (4)
C1—N2—C3—C2	−0.2 (5)	C17—N4—C20—C21	120.4 (5)
C4—N2—C3—C2	179.6 (4)	C19—N4—C20—C21	−65.9 (6)
C1—N2—C3—C13	−176.2 (4)	N4—C20—C21—C26	130.6 (5)
C4—N2—C3—C13	3.5 (7)	N4—C20—C21—C22	−52.3 (6)
C1—N2—C4—C5	85.2 (6)	C26—C21—C22—C23	2.4 (7)
C3—N2—C4—C5	−94.5 (6)	C20—C21—C22—C23	−174.7 (4)
N2—C4—C5—C10	−151.7 (5)	C21—C22—C23—C24	−2.6 (8)
N2—C4—C5—C6	26.8 (7)	C22—C23—C24—C25	0.6 (8)
C10—C5—C6—C7	2.6 (7)	C22—C23—C24—C27	−178.5 (4)
C4—C5—C6—C7	−175.8 (5)	C23—C24—C25—C26	1.6 (7)
C5—C6—C7—C8	−0.9 (7)	C27—C24—C25—C26	−179.3 (4)
C6—C7—C8—C9	−1.8 (7)	C22—C21—C26—C25	−0.2 (7)
C6—C7—C8—C11	175.9 (4)	C20—C21—C26—C25	177.0 (4)
C7—C8—C9—C10	2.8 (8)	C24—C25—C26—C21	−1.8 (7)
C11—C8—C9—C10	−174.8 (5)	Cd2^ii—O10—C27—O9	10.8 (5)
C6—C5—C10—C9	−1.5 (8)	Cd2^ii—O10—C27—C24	−169.8 (3)
C4—C5—C10—C9	176.9 (5)	Cd2—O9—C27—O10	−178.1 (13)
C8—C9—C10—C5	−1.2 (9)	Cd2^ii—O9—C27—O10	−9.7 (4)
Cd2—O5—C11—O6	2.0 (5)	Cd2—O9—C27—C24	2.5 (18)
Cd2—O5—C11—C8	−175.9 (4)	Cd2^ii—O9—C27—C24	171.0 (4)
Cd2—O6—C11—O5	−2.0 (5)	Cd2—O9—C27—Cd2^ii	−168.4 (16)
Cd2—O6—C11—C8	175.9 (4)	C23—C24—C27—O10	148.3 (5)
C7—C8—C11—O5	10.4 (7)	C25—C24—C27—O10	−30.8 (6)
C9—C8—C11—O5	−171.9 (5)	C23—C24—C27—O9	−32.3 (6)
C7—C8—C11—O6	−167.5 (5)	C25—C24—C27—O9	148.6 (5)
C9—C8—C11—O6	10.2 (7)	C23—C24—C27—Cd2^ii	95.8 (19)
Cd1—O1—C12—O2	−178.4 (4)	C25—C24—C27—Cd2^ii	−83.2 (19)
Cd1—O1—C12—C2	3.0 (7)	Cd2^v—O8—C28—O7	−6.9 (4)
C3—C2—C12—O1	172.4 (5)	Cd2^v—O8—C28—C18	175.3 (3)
N1—C2—C12—O1	−5.9 (7)	Cd1—O7—C28—O8	−170.3 (3)
C3—C2—C12—O2	−6.2 (9)	Cd2^v—O7—C28—O8	7.2 (4)
N1—C2—C12—O2	175.5 (5)	Cd1—O7—C28—C18	7.6 (5)
Cd1^iv—O4—C13—O3	−9.9 (8)	Cd2^v—O7—C28—C18	−174.8 (3)
Cd1^iv—O4—C13—C3	168.4 (3)	C19—C18—C28—O8	−8.1 (7)
C2—C3—C13—O4	−166.7 (5)	N3—C18—C28—O8	170.2 (4)
N2—C3—C13—O4	8.4 (7)	C19—C18—C28—O7	174.0 (4)
C2—C3—C13—O3	11.7 (8)	N3—C18—C28—O7	−7.7 (6)
N2—C3—C13—O3	−173.2 (5)	N3—C17—C29—C30	91.6 (6)
N1—C1—C14—C15	90.6 (7)	N4—C17—C29—C30	−86.9 (6)
N2—C1—C14—C15	−84.0 (7)	C17—C29—C30—C31	−168.5 (5)
C1—C14—C15—C16	−179.4 (8)

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

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the N1/N2/C1/C2/C3 ring, Cg2 that of the N3/N4/C17/C18/C19 ring, Cg3 that of the C21/C22/C23/C24/C25/C26 ring and Cg4 that of the C5/C6/C7/C8/C9/C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.95 (9)	1.52 (8)	2.453 (6)	164 (9)
O11—H11A···O3^i	0.82	2.05	2.815 (6)	156
O11—H11B···O12^vi	0.82	1.85	2.615 (7)	154
C4—H4B···O4	0.97	2.25	2.811 (7)	116
C19—H19···O11^vii	0.93	2.32	3.091 (7)	140
C19—H19···O12^viii	0.93	2.48	3.278 (8)	144
O12—H12A···O6	0.82	2.13	2.914 (7)	161
O12—H12B···O8^viii	0.82	1.97	2.736 (6)	155
C15—H15A···Cg2	0.97	2.86	3.813 (8)	168
C15—H15B···Cg4	0.97	2.90	3.857 (8)	171
C30—H30A···Cg1	0.97	2.95	3.872 (6)	159
Cg1···Cg4^i			3.714 (3)
Cg2···Cg2^vii			3.835 (3)
Cg3···Cg3^ix			3.879 (3)

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