A new twofold inter­penetrated two-dimensional cadmium(II) coordination polymer constructed from 2,2′-(benzene-1,4-dicarboxamido)­dipropionate

In recent years, much initial inter­est and enthusiasm has focused on the self-assembly of coordination polymers due to the aesthetics of their crystalline architectures and their potential applications as new functional materials. As part of an exploration of chiral coordination polymers, a new twofold inter­­penetrated two-dimensional (2D) coordination polymer, namely, poly[[tetra­aqua­bis­[μ₃-(2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)­dipropionato-κ⁵O,O′:O′′,O′′′:O′′]dicadmium(II)] trihydrate], {[Cd₂(C₁₄H₁₄N₂O₆)₂(H₂O)₄]·3H₂O}_n, has been synthesized by the reaction of Cd(CH₃COO)₂·2H₂O with the designed ligand (2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)­dipropionic acid (H₂L). The compound has been structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analysis. In the crystal structure, each Cd^II cation binds to three carboxyl­ate groups from two crystallographically independent L²⁻ dianions. Four carboxyl­ate groups link two crystallographically independent cadmium cations into a 4,4-connected secondary building unit (SBU). The resulting SBUs are extended into a two-dimensional folding sheet via the terephthalamide moiety of the ligand as a spacer, which can be simplified as a (4,4)-connected 4,4L15 net with the point symbol (3.5³.6²)(3².5².6²). In the lattice, two independent folding sheets inter­penetrate each other to yield a double-sheet layer. The resulting 2D layers pack in parallel arrays through inter­molecular hydrogen bonds and interlayer π–π inter­actions. The thermal stability and photoluminescence properties of the title compound have been investigated and it exhibits an enhanced fluorescence emission and a longer lifetime compared with free H₂L.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Poly[[tetraaquabis[µ₃-(2R,2'R)-2,2'-(benzene-1,4-dicarboxamido)dipropionato-κ⁵O,O':O'',O''':O'']dicadmium(II)] trihydrate]

Crystal data

[Cd2(C14H14N2O6)2(H2O)4]·3H2O	F(000) = 972
Mr = 963.45	Dx = 1.769 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 9.2072 (8) Å	Cell parameters from 8708 reflections
b = 15.0256 (13) Å	θ = 2.7–27.4°
c = 13.6139 (12) Å	µ = 1.26 mm^−1
β = 106.177 (5)°	T = 298 K
V = 1808.8 (3) Å^3	Sheet, colourless
Z = 2	0.35 × 0.18 × 0.02 mm

Data collection

CCD area detector diffractometer	6414 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
Bruker APEXII phi and ω scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→11
Tmin = 0.667, Tmax = 0.978	k = −15→19
23758 measured reflections	l = −17→17
7584 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.063	w = 1/[σ^2(Fo^2) + (0.0238P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
7584 reflections	Δρmax = 0.39 e Å^−3
482 parameters	Δρmin = −0.41 e Å^−3
1 restraint	Absolute structure: Flack x determined using 2353 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.005 (16)

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. Single-crystal X-ray diffraction measurements for the complex (I) was carried out on a Bruker APEXII CCD diffractometer with graphite monochromatized Mo Kα radiation (λ = 0.71073 Å) using both φ- and ω-scan modes at 298K. Data reduction was made with the SAINT package (Bruker, 2004). Absorption correction was performed using the SADABS program (Bruker, 2004). The structure was solved by direct method using SHELXS97 (Sheldrick, 2008) (and were refined on F² by full-matrix least-squares using SHELXL2014/7 (Sheldrick, 2015) with anisotropic displacement parameters for all non-hydrogen atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	1.3890 (6)	0.6046 (4)	0.2117 (5)	0.0261 (13)
C2	1.4564 (6)	0.5330 (4)	0.2909 (4)	0.0265 (13)
H1	1.4558	0.5555	0.4363	0.032*
C3	1.6286 (6)	0.5370 (4)	0.3241 (5)	0.0366 (15)
H3A	1.6607	0.5933	0.3562	0.055*
H3B	1.6660	0.5305	0.2653	0.055*
H3C	1.6676	0.4898	0.3717	0.055*
H2	1.4270	0.4752	0.2585	0.044*
C4	1.2535 (6)	0.5158 (4)	0.3696 (5)	0.0330 (14)
C5	0.9188 (6)	0.3946 (4)	0.8735 (5)	0.0284 (14)
C6	1.0138 (5)	0.4781 (4)	0.8769 (4)	0.0252 (11)
H6	0.9531	0.5298	0.8845	0.030*
C7	1.1518 (6)	0.4713 (5)	0.9711 (4)	0.0353 (14)
H7A	1.2114	0.4205	0.9642	0.053*
H7B	1.1183	0.4648	1.0315	0.053*
H7C	1.2118	0.5242	0.9765	0.053*
C8	0.9874 (6)	0.5326 (4)	0.7025 (5)	0.0280 (13)
C9	1.0615 (6)	0.5393 (4)	0.6194 (5)	0.0271 (13)
C10	1.2186 (6)	0.5453 (4)	0.6376 (5)	0.0345 (15)
H10	1.2805	0.5528	0.7039	0.041*
C11	1.2803 (6)	0.5407 (4)	0.5572 (5)	0.0357 (15)
H11	1.3847	0.5445	0.5697	0.043*
C12	1.1919 (6)	0.5301 (4)	0.4574 (5)	0.0290 (13)
C13	1.0349 (7)	0.5292 (5)	0.4395 (5)	0.0421 (17)
H13	0.9728	0.5257	0.3728	0.051*
C14	0.9725 (6)	0.5344 (5)	0.5192 (5)	0.0379 (16)
H14	0.8678	0.5346	0.5058	0.046*
H16	−0.6090	0.2931	0.1280	0.046*
C15	−0.6171 (7)	0.1575 (4)	0.1357 (5)	0.0283 (13)
C16	−0.6231 (6)	0.2510 (4)	0.1792 (4)	0.0311 (13)
C17	−0.7734 (7)	0.2727 (4)	0.1994 (6)	0.0487 (19)
H17A	−0.7941	0.2297	0.2460	0.073*
H17B	−0.8525	0.2709	0.1362	0.073*
H17C	−0.7687	0.3310	0.2288	0.073*
C18	0.4073 (6)	0.3396 (4)	0.8277 (4)	0.0242 (12)
C19	0.3087 (5)	0.2587 (4)	0.7889 (4)	0.0261 (13)
H19	0.3682	0.2165	0.7611	0.031*
C20	0.2706 (7)	0.2144 (4)	0.8778 (5)	0.0419 (17)
H20A	0.2083	0.2533	0.9045	0.063*
H20B	0.3622	0.2016	0.9302	0.063*
H20C	0.2172	0.1599	0.8552	0.063*
C21	0.1702 (6)	0.2773 (4)	0.6099 (5)	0.0301 (14)
C22	0.0245 (6)	0.2885 (4)	0.5272 (5)	0.0283 (13)
C23	0.0360 (7)	0.3028 (5)	0.4298 (5)	0.0400 (16)
H23	0.1308	0.3094	0.4191	0.048*
C24	−0.0923 (7)	0.3074 (5)	0.3474 (5)	0.0383 (16)
H24	−0.0831	0.3167	0.2819	0.046*
C25	−0.2346 (6)	0.2983 (4)	0.3615 (5)	0.0288 (13)
C26	−0.2464 (6)	0.2852 (4)	0.4596 (5)	0.0370 (15)
H26	−0.3413	0.2795	0.4706	0.044*
C27	−0.1170 (6)	0.2805 (5)	0.5424 (5)	0.0394 (16)
H27	−0.1263	0.2719	0.6080	0.047*
C28	−0.3671 (6)	0.3012 (4)	0.2682 (5)	0.0285 (13)
Cd1	0.76277 (4)	0.24331 (3)	0.90938 (3)	0.02744 (11)
Cd2	0.60257 (4)	0.47990 (2)	0.89586 (3)	0.02782 (11)
N1	1.3982 (5)	0.5383 (3)	0.3784 (4)	0.0309 (12)
N2	1.0652 (5)	0.4901 (3)	0.7865 (3)	0.0282 (11)
H2A	1.1520	0.4684	0.7871	0.034*
N3	0.1709 (5)	0.2796 (3)	0.7071 (4)	0.0292 (11)
H3D	0.0896	0.2937	0.7228	0.035*
N4	−0.4960 (5)	0.2630 (3)	0.2707 (4)	0.0316 (13)
H4	−0.5056	0.2449	0.3284	0.038*
O1	1.3177 (5)	0.6683 (3)	0.2377 (4)	0.0372 (11)
O2	1.4095 (5)	0.5994 (3)	0.1252 (3)	0.0364 (11)
O3	0.9219 (4)	0.3315 (3)	0.8160 (4)	0.0399 (11)
O4	0.8414 (5)	0.3919 (3)	0.9386 (4)	0.0383 (11)
O5	0.5416 (4)	0.3262 (3)	0.8796 (3)	0.0359 (11)
O6	0.3558 (4)	0.4169 (3)	0.8126 (3)	0.0336 (10)
O7	−0.4904 (5)	0.1242 (3)	0.1396 (4)	0.0378 (12)
O8	−0.7386 (5)	0.1166 (3)	0.0978 (3)	0.0334 (11)
O9	0.5739 (6)	0.4792 (4)	1.0541 (3)	0.0564 (13)
H9A	0.5676	0.4258	1.0730	0.085*
H9B	0.6499	0.5042	1.0948	0.085*
O10	0.6232 (4)	0.4802 (3)	0.7334 (3)	0.0392 (10)
H10A	0.6227	0.4268	0.7127	0.059*
H10B	0.7058	0.5051	0.7326	0.059*
O11	0.7439 (5)	0.2162 (3)	1.0698 (3)	0.0436 (14)
H11A	0.7936	0.2556	1.1103	0.065*
H11B	0.6516	0.2182	1.0696	0.065*
O12	0.9751 (5)	0.1574 (3)	0.9594 (4)	0.0446 (12)
H12A	1.0524	0.1910	0.9759	0.067*
H12B	0.9803	0.1238	0.9103	0.067*
O13	1.1767 (5)	0.4815 (4)	0.2894 (3)	0.0514 (12)
O14	0.2887 (4)	0.2626 (3)	0.5849 (3)	0.0420 (12)
O15	−0.3518 (5)	0.3372 (3)	0.1891 (3)	0.0369 (10)
O16	0.8588 (4)	0.5628 (3)	0.6929 (4)	0.0402 (11)
O17	0.5818 (5)	0.3219 (3)	0.6348 (4)	0.0530 (13)
H17D	0.6471	0.2850	0.6680	0.079*
H17E	0.4936	0.3027	0.6309	0.079*
O18	0.3934 (5)	0.1585 (3)	0.4420 (4)	0.0499 (13)
H18A	0.3224	0.1282	0.4032	0.060*
H18B	0.3592	0.2011	0.4702	0.060*
O19	0.0696 (6)	0.0226 (5)	0.8597 (5)	0.087 (2)
H19A	0.0496	0.0053	0.7979	0.105*
H19B	0.1072	−0.0214	0.8975	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.023 (3)	0.030 (3)	0.024 (3)	−0.007 (2)	0.004 (2)	−0.001 (3)
C2	0.031 (3)	0.024 (3)	0.027 (3)	−0.003 (2)	0.011 (2)	0.003 (3)
C3	0.032 (3)	0.038 (4)	0.037 (4)	0.004 (3)	0.007 (3)	0.000 (3)
C4	0.035 (3)	0.030 (3)	0.034 (4)	0.000 (3)	0.011 (3)	0.000 (3)
C5	0.015 (3)	0.036 (4)	0.032 (4)	0.002 (2)	0.004 (2)	0.009 (3)
C6	0.024 (3)	0.025 (3)	0.029 (3)	−0.001 (3)	0.010 (2)	−0.003 (3)
C7	0.030 (3)	0.045 (4)	0.029 (3)	−0.006 (3)	0.004 (2)	−0.002 (3)
C8	0.025 (3)	0.027 (3)	0.031 (4)	−0.003 (2)	0.006 (2)	0.003 (3)
C9	0.026 (3)	0.027 (3)	0.030 (3)	0.002 (2)	0.012 (2)	0.004 (3)
C10	0.029 (3)	0.046 (4)	0.028 (4)	−0.006 (3)	0.008 (3)	0.007 (3)
C11	0.021 (3)	0.051 (4)	0.035 (4)	−0.009 (3)	0.008 (3)	0.006 (3)
C12	0.033 (3)	0.023 (3)	0.034 (4)	−0.001 (2)	0.012 (3)	0.003 (3)
C13	0.035 (3)	0.058 (5)	0.031 (4)	−0.001 (3)	0.005 (3)	0.001 (3)
C14	0.022 (3)	0.057 (4)	0.035 (4)	0.005 (3)	0.007 (3)	0.000 (3)
C15	0.038 (3)	0.024 (3)	0.021 (3)	−0.003 (2)	0.005 (3)	0.001 (2)
C16	0.034 (3)	0.026 (3)	0.027 (3)	0.002 (3)	−0.001 (2)	0.001 (3)
C17	0.036 (3)	0.041 (4)	0.065 (5)	0.008 (3)	0.007 (3)	−0.013 (4)
C18	0.019 (3)	0.029 (3)	0.027 (3)	0.003 (2)	0.011 (2)	−0.002 (3)
C19	0.019 (2)	0.030 (3)	0.028 (3)	0.002 (2)	0.003 (2)	−0.002 (3)
C20	0.040 (4)	0.043 (4)	0.041 (4)	−0.002 (3)	0.008 (3)	0.013 (3)
C21	0.025 (3)	0.030 (3)	0.035 (4)	0.001 (2)	0.008 (3)	−0.001 (3)
C22	0.025 (3)	0.031 (3)	0.027 (3)	0.000 (2)	0.005 (2)	−0.003 (3)
C23	0.027 (3)	0.056 (4)	0.038 (4)	0.000 (3)	0.011 (3)	0.004 (3)
C24	0.038 (3)	0.053 (4)	0.025 (4)	−0.004 (3)	0.012 (3)	0.007 (3)
C25	0.028 (3)	0.028 (3)	0.028 (3)	−0.001 (2)	0.005 (2)	−0.002 (3)
C26	0.025 (3)	0.059 (4)	0.029 (4)	−0.002 (3)	0.010 (3)	0.001 (3)
C27	0.028 (3)	0.068 (5)	0.022 (3)	−0.004 (3)	0.007 (2)	−0.004 (3)
C28	0.035 (3)	0.024 (3)	0.026 (3)	0.004 (2)	0.007 (3)	0.000 (3)
Cd1	0.02478 (19)	0.0263 (2)	0.0301 (2)	0.00085 (18)	0.00565 (16)	−0.0015 (2)
Cd2	0.0275 (2)	0.0265 (2)	0.0304 (2)	−0.00243 (18)	0.00971 (17)	0.0005 (2)
N1	0.029 (3)	0.038 (3)	0.026 (3)	−0.002 (2)	0.008 (2)	0.003 (2)
N2	0.025 (2)	0.032 (3)	0.032 (3)	0.003 (2)	0.0145 (19)	0.004 (3)
N3	0.021 (2)	0.036 (3)	0.030 (3)	0.0000 (19)	0.006 (2)	−0.006 (2)
N4	0.034 (3)	0.036 (3)	0.022 (3)	−0.006 (2)	0.004 (2)	0.001 (2)
O1	0.041 (2)	0.030 (3)	0.043 (3)	0.0112 (19)	0.016 (2)	0.008 (2)
O2	0.039 (3)	0.043 (3)	0.025 (3)	−0.001 (2)	0.007 (2)	0.006 (2)
O3	0.035 (2)	0.033 (3)	0.052 (3)	−0.0039 (18)	0.012 (2)	−0.007 (2)
O4	0.029 (2)	0.043 (3)	0.046 (3)	−0.0003 (19)	0.014 (2)	0.011 (2)
O5	0.019 (2)	0.031 (3)	0.050 (3)	0.0013 (17)	−0.0029 (19)	−0.005 (2)
O6	0.023 (2)	0.031 (2)	0.047 (3)	0.0025 (17)	0.0087 (18)	0.004 (2)
O7	0.027 (2)	0.035 (3)	0.051 (3)	0.0040 (19)	0.010 (2)	−0.002 (2)
O8	0.030 (2)	0.031 (3)	0.038 (3)	−0.0029 (18)	0.008 (2)	−0.001 (2)
O9	0.095 (4)	0.043 (3)	0.038 (3)	0.015 (3)	0.031 (3)	0.009 (3)
O10	0.038 (2)	0.044 (3)	0.040 (3)	−0.009 (2)	0.0167 (19)	0.001 (3)
O11	0.043 (3)	0.052 (4)	0.037 (3)	0.001 (2)	0.012 (2)	−0.002 (2)
O12	0.032 (2)	0.049 (3)	0.053 (3)	0.007 (2)	0.011 (2)	0.005 (2)
O13	0.041 (2)	0.069 (3)	0.045 (3)	−0.013 (3)	0.013 (2)	−0.020 (3)
O14	0.0234 (19)	0.068 (4)	0.036 (3)	0.003 (2)	0.0106 (18)	−0.005 (2)
O15	0.042 (2)	0.041 (3)	0.028 (2)	0.0016 (19)	0.010 (2)	0.004 (2)
O16	0.024 (2)	0.052 (3)	0.047 (3)	0.0112 (19)	0.013 (2)	0.014 (2)
O17	0.039 (3)	0.075 (4)	0.047 (3)	−0.009 (2)	0.016 (2)	−0.007 (3)
O18	0.042 (3)	0.056 (3)	0.051 (3)	−0.003 (2)	0.012 (2)	−0.017 (3)
O19	0.067 (4)	0.104 (6)	0.081 (5)	−0.006 (4)	0.006 (3)	−0.022 (4)

Geometric parameters (Å, º)

C1—O2	1.246 (7)	C21—O14	1.249 (6)
C1—O1	1.265 (7)	C21—N3	1.322 (7)
C1—C2	1.527 (8)	C21—C22	1.502 (8)
C2—N1	1.440 (7)	C22—C23	1.375 (9)
C2—C3	1.524 (8)	C22—C27	1.380 (8)
C2—H2	0.9774	C23—C24	1.386 (8)
C3—H3A	0.9600	C23—H23	0.9300
C3—H3B	0.9600	C24—C25	1.383 (8)
C3—H3C	0.9600	C24—H24	0.9300
C4—O13	1.236 (7)	C25—C26	1.384 (8)
C4—N1	1.346 (7)	C25—C28	1.497 (7)
C4—C12	1.475 (8)	C26—C27	1.395 (8)
C5—O3	1.235 (7)	C26—H26	0.9299
C5—O4	1.283 (7)	C27—H27	0.9301
C5—C6	1.523 (8)	C28—O15	1.248 (7)
C6—N2	1.447 (7)	C28—N4	1.327 (7)
C6—C7	1.537 (7)	Cd1—O1^ii	2.237 (4)
C6—H6	0.9801	Cd1—O11	2.276 (4)
C7—H7A	0.9600	Cd1—O12	2.282 (4)
C7—H7B	0.9600	Cd1—O5	2.324 (4)
C7—H7C	0.9600	Cd1—O4	2.347 (4)
C8—O16	1.240 (6)	Cd1—O3	2.561 (4)
C8—N2	1.331 (7)	Cd1—O2^ii	2.645 (5)
C8—C9	1.479 (8)	Cd2—O9	2.242 (4)
C9—C14	1.383 (8)	Cd2—O10	2.271 (4)
C9—C10	1.401 (7)	Cd2—O5	2.372 (4)
C10—C11	1.369 (8)	Cd2—O7^iii	2.393 (4)
C10—H10	0.9300	Cd2—O8^iii	2.396 (4)
C11—C12	1.384 (8)	Cd2—O6	2.431 (4)
C11—H11	0.9300	Cd2—O4	2.492 (4)
C12—C13	1.397 (8)	Cd2—C15^iii	2.712 (6)
C13—C14	1.365 (8)	N1—H1	0.8583
C13—H13	0.9300	N2—H2A	0.8601
C14—H14	0.9300	N3—H3D	0.8600
C15—O8	1.254 (7)	N4—H4	0.8600
C15—O7	1.257 (7)	O1—Cd1^iv	2.237 (4)
C15—C16	1.532 (8)	O2—Cd1^iv	2.645 (5)
C15—Cd2^i	2.712 (6)	O7—Cd2^i	2.393 (4)
C16—N4	1.463 (6)	O8—Cd2^i	2.396 (4)
C16—C17	1.520 (8)	O9—H9A	0.8501
C16—H16	0.9775	O9—H9B	0.8500
C17—H17A	0.9600	O10—H10A	0.8499
C17—H17B	0.9600	O10—H10B	0.8500
C17—H17C	0.9600	O11—H11A	0.8500
C18—O6	1.250 (6)	O11—H11B	0.8499
C18—O5	1.258 (6)	O12—H12A	0.8500
C18—C19	1.521 (7)	O12—H12B	0.8500
C18—Cd2	2.759 (5)	O17—H17D	0.8501
C19—N3	1.470 (6)	O17—H17E	0.8499
C19—C20	1.505 (8)	O18—H18A	0.8500
C19—H19	0.9799	O18—H18B	0.8499
C20—H20A	0.9600	O19—H19A	0.8500
C20—H20B	0.9600	O19—H19B	0.8500
C20—H20C	0.9600
O2—C1—O1	122.6 (6)	C25—C26—C27	120.5 (5)
O2—C1—C2	118.9 (5)	C25—C26—H26	119.8
O1—C1—C2	118.4 (5)	C27—C26—H26	119.7
N1—C2—C3	110.4 (5)	C22—C27—C26	120.3 (6)
N1—C2—C1	111.9 (5)	C22—C27—H27	120.0
C3—C2—C1	111.5 (5)	C26—C27—H27	119.7
N1—C2—H2	107.6	O15—C28—N4	121.7 (5)
C3—C2—H2	107.7	O15—C28—C25	118.9 (5)
C1—C2—H2	107.5	N4—C28—C25	119.3 (5)
C2—C3—H3A	109.5	O1^ii—Cd1—O11	132.41 (16)
C2—C3—H3B	109.5	O1^ii—Cd1—O12	91.42 (17)
H3A—C3—H3B	109.5	O11—Cd1—O12	84.26 (16)
C2—C3—H3C	109.5	O1^ii—Cd1—O5	93.34 (15)
H3A—C3—H3C	109.5	O11—Cd1—O5	88.07 (16)
H3B—C3—H3C	109.5	O12—Cd1—O5	172.31 (17)
O13—C4—N1	119.5 (6)	O1^ii—Cd1—O4	129.84 (16)
O13—C4—C12	121.4 (5)	O11—Cd1—O4	96.33 (17)
N1—C4—C12	119.1 (5)	O12—Cd1—O4	106.83 (16)
O3—C5—O4	122.0 (6)	O5—Cd1—O4	74.54 (14)
O3—C5—C6	122.5 (5)	O1^ii—Cd1—O3	84.76 (15)
O4—C5—C6	115.4 (5)	O11—Cd1—O3	140.94 (16)
N2—C6—C5	113.5 (5)	O12—Cd1—O3	83.11 (15)
N2—C6—C7	109.1 (4)	O5—Cd1—O3	103.33 (15)
C5—C6—C7	107.7 (5)	O4—Cd1—O3	53.10 (15)
N2—C6—H6	108.8	O1^ii—Cd1—O2^ii	52.86 (15)
C5—C6—H6	108.5	O11—Cd1—O2^ii	79.75 (16)
C7—C6—H6	109.1	O12—Cd1—O2^ii	90.69 (15)
C6—C7—H7A	109.5	O5—Cd1—O2^ii	87.38 (14)
C6—C7—H7B	109.5	O4—Cd1—O2^ii	161.67 (14)
H7A—C7—H7B	109.5	O3—Cd1—O2^ii	137.08 (14)
C6—C7—H7C	109.5	O9—Cd2—O10	178.12 (16)
H7A—C7—H7C	109.5	O9—Cd2—O5	89.84 (18)
H7B—C7—H7C	109.5	O10—Cd2—O5	89.58 (17)
O16—C8—N2	122.4 (6)	O9—Cd2—O7^iii	92.20 (18)
O16—C8—C9	121.6 (5)	O10—Cd2—O7^iii	87.15 (17)
N2—C8—C9	115.9 (5)	O5—Cd2—O7^iii	141.80 (14)
C14—C9—C10	118.5 (6)	O9—Cd2—O8^iii	99.79 (18)
C14—C9—C8	118.5 (5)	O10—Cd2—O8^iii	81.28 (16)
C10—C9—C8	122.9 (5)	O5—Cd2—O8^iii	161.09 (14)
C11—C10—C9	119.5 (6)	O7^iii—Cd2—O8^iii	54.68 (14)
C11—C10—H10	120.3	O9—Cd2—O6	95.81 (17)
C9—C10—H10	120.2	O10—Cd2—O6	82.41 (14)
C10—C11—C12	122.0 (5)	O5—Cd2—O6	53.92 (13)
C10—C11—H11	119.2	O7^iii—Cd2—O6	87.94 (14)
C12—C11—H11	118.9	O8^iii—Cd2—O6	139.68 (14)
C11—C12—C13	118.0 (6)	O9—Cd2—O4	96.07 (16)
C11—C12—C4	123.9 (5)	O10—Cd2—O4	85.43 (15)
C13—C12—C4	118.1 (5)	O5—Cd2—O4	71.08 (14)
C14—C13—C12	120.3 (6)	O7^iii—Cd2—O4	146.22 (14)
C14—C13—H13	120.0	O8^iii—Cd2—O4	91.60 (14)
C12—C13—H13	119.7	O6—Cd2—O4	123.48 (14)
C13—C14—C9	121.5 (5)	O9—Cd2—C15^iii	100.44 (19)
C13—C14—H14	119.1	O10—Cd2—C15^iii	79.77 (18)
C9—C14—H14	119.4	O5—Cd2—C15^iii	164.54 (16)
O8—C15—O7	122.3 (6)	O7^iii—Cd2—C15^iii	27.61 (15)
O8—C15—C16	118.9 (5)	O8^iii—Cd2—C15^iii	27.54 (15)
O7—C15—C16	118.8 (5)	O6—Cd2—C15^iii	112.98 (16)
O8—C15—Cd2^i	62.1 (3)	O4—Cd2—C15^iii	118.65 (16)
O7—C15—Cd2^i	61.9 (3)	O9—Cd2—C18	94.56 (19)
C16—C15—Cd2^i	166.6 (4)	O10—Cd2—C18	84.12 (17)
N4—C16—C17	111.9 (5)	O5—Cd2—C18	27.07 (14)
N4—C16—C15	109.7 (5)	O7^iii—Cd2—C18	114.87 (16)
C17—C16—C15	113.5 (5)	O8^iii—Cd2—C18	162.35 (15)
N4—C16—H16	107.1	O6—Cd2—C18	26.92 (14)
C17—C16—H16	107.4	O4—Cd2—C18	97.08 (15)
C15—C16—H16	107.0	C15^iii—Cd2—C18	139.03 (17)
C16—C17—H17A	109.5	C4—N1—C2	120.0 (5)
C16—C17—H17B	109.5	C4—N1—H1	120.0
H17A—C17—H17B	109.5	C2—N1—H1	120.0
C16—C17—H17C	109.5	C8—N2—C6	124.4 (5)
H17A—C17—H17C	109.5	C8—N2—H2A	117.8
H17B—C17—H17C	109.5	C6—N2—H2A	117.9
O6—C18—O5	120.6 (5)	C21—N3—C19	121.0 (5)
O6—C18—C19	121.6 (5)	C21—N3—H3D	119.6
O5—C18—C19	117.8 (5)	C19—N3—H3D	119.5
O6—C18—Cd2	61.8 (3)	C28—N4—C16	122.8 (5)
O5—C18—Cd2	59.1 (3)	C28—N4—H4	118.7
C19—C18—Cd2	176.1 (4)	C16—N4—H4	118.5
N3—C19—C20	111.0 (4)	C1—O1—Cd1^iv	101.4 (4)
N3—C19—C18	113.4 (5)	C1—O2—Cd1^iv	82.9 (4)
C20—C19—C18	108.9 (5)	C5—O3—Cd1	88.0 (4)
N3—C19—H19	107.7	C5—O4—Cd1	96.7 (4)
C20—C19—H19	107.7	C5—O4—Cd2	116.5 (3)
C18—C19—H19	107.9	Cd1—O4—Cd2	104.75 (15)
C19—C20—H20A	109.5	C18—O5—Cd1	149.3 (4)
C19—C20—H20B	109.5	C18—O5—Cd2	93.9 (3)
H20A—C20—H20B	109.5	Cd1—O5—Cd2	109.42 (16)
C19—C20—H20C	109.5	C18—O6—Cd2	91.3 (3)
H20A—C20—H20C	109.5	C15—O7—Cd2^i	90.5 (3)
H20B—C20—H20C	109.5	C15—O8—Cd2^i	90.4 (4)
O14—C21—N3	121.1 (5)	Cd2—O9—H9A	109.4
O14—C21—C22	118.7 (6)	Cd2—O9—H9B	109.2
N3—C21—C22	120.1 (5)	H9A—O9—H9B	109.5
C23—C22—C27	119.2 (5)	Cd2—O10—H10A	109.1
C23—C22—C21	116.6 (5)	Cd2—O10—H10B	109.4
C27—C22—C21	124.1 (6)	H10A—O10—H10B	109.5
C22—C23—C24	120.7 (6)	Cd1—O11—H11A	109.1
C22—C23—H23	119.7	Cd1—O11—H11B	109.5
C24—C23—H23	119.6	H11A—O11—H11B	109.5
C25—C24—C23	120.6 (6)	Cd1—O12—H12A	109.1
C25—C24—H24	119.5	Cd1—O12—H12B	109.4
C23—C24—H24	119.9	H12A—O12—H12B	109.5
C24—C25—C26	118.7 (5)	H17D—O17—H17E	109.5
C24—C25—C28	117.3 (6)	H18A—O18—H18B	111.6
C26—C25—C28	124.0 (5)	H19A—O19—H19B	107.5
O2—C1—C2—N1	−168.4 (5)	C28—C25—C26—C27	177.9 (6)
O1—C1—C2—N1	13.4 (7)	C23—C22—C27—C26	1.2 (10)
O2—C1—C2—C3	67.4 (6)	C21—C22—C27—C26	−175.1 (6)
O1—C1—C2—C3	−110.8 (6)	C25—C26—C27—C22	−0.3 (10)
O3—C5—C6—N2	19.8 (7)	C24—C25—C28—O15	−21.4 (8)
O4—C5—C6—N2	−163.9 (5)	C26—C25—C28—O15	160.0 (6)
O3—C5—C6—C7	−101.1 (6)	C24—C25—C28—N4	156.5 (6)
O4—C5—C6—C7	75.2 (6)	C26—C25—C28—N4	−22.1 (9)
O16—C8—C9—C14	−33.8 (9)	O13—C4—N1—C2	8.0 (9)
N2—C8—C9—C14	144.3 (6)	C12—C4—N1—C2	−174.0 (5)
O16—C8—C9—C10	149.8 (6)	C3—C2—N1—C4	−164.9 (5)
N2—C8—C9—C10	−32.0 (8)	C1—C2—N1—C4	70.3 (7)
C14—C9—C10—C11	−4.1 (9)	O16—C8—N2—C6	−3.2 (9)
C8—C9—C10—C11	172.2 (6)	C9—C8—N2—C6	178.7 (5)
C9—C10—C11—C12	0.1 (10)	C5—C6—N2—C8	88.3 (7)
C10—C11—C12—C13	3.4 (9)	C7—C6—N2—C8	−151.6 (5)
C10—C11—C12—C4	−173.7 (6)	O14—C21—N3—C19	−4.4 (8)
O13—C4—C12—C11	158.4 (7)	C22—C21—N3—C19	173.0 (5)
N1—C4—C12—C11	−19.5 (9)	C20—C19—N3—C21	−147.0 (5)
O13—C4—C12—C13	−18.7 (9)	C18—C19—N3—C21	89.9 (6)
N1—C4—C12—C13	163.3 (6)	O15—C28—N4—C16	7.3 (9)
C11—C12—C13—C14	−3.0 (10)	C25—C28—N4—C16	−170.5 (5)
C4—C12—C13—C14	174.3 (6)	C17—C16—N4—C28	−137.6 (6)
C12—C13—C14—C9	−1.1 (10)	C15—C16—N4—C28	95.5 (6)
C10—C9—C14—C13	4.6 (10)	O2—C1—O1—Cd1^iv	5.3 (6)
C8—C9—C14—C13	−171.9 (6)	C2—C1—O1—Cd1^iv	−176.7 (4)
O8—C15—C16—N4	143.0 (5)	O1—C1—O2—Cd1^iv	−4.4 (5)
O7—C15—C16—N4	−36.8 (7)	C2—C1—O2—Cd1^iv	177.5 (4)
Cd2^i—C15—C16—N4	52.5 (19)	O4—C5—O3—Cd1	−4.7 (5)
O8—C15—C16—C17	17.1 (8)	C6—C5—O3—Cd1	171.4 (5)
O7—C15—C16—C17	−162.7 (6)	O3—C5—O4—Cd1	5.1 (6)
Cd2^i—C15—C16—C17	−73.4 (18)	C6—C5—O4—Cd1	−171.2 (4)
O6—C18—C19—N3	19.0 (8)	O3—C5—O4—Cd2	−105.1 (5)
O5—C18—C19—N3	−164.0 (5)	C6—C5—O4—Cd2	78.6 (5)
O6—C18—C19—C20	−105.1 (6)	O6—C18—O5—Cd1	−145.7 (6)
O5—C18—C19—C20	71.9 (7)	C19—C18—O5—Cd1	37.2 (11)
O14—C21—C22—C23	−14.9 (8)	Cd2—C18—O5—Cd1	−140.1 (8)
N3—C21—C22—C23	167.7 (6)	O6—C18—O5—Cd2	−5.6 (6)
O14—C21—C22—C27	161.5 (6)	C19—C18—O5—Cd2	177.3 (4)
N3—C21—C22—C27	−16.0 (9)	O5—C18—O6—Cd2	5.5 (6)
C27—C22—C23—C24	−1.3 (10)	C19—C18—O6—Cd2	−177.6 (5)
C21—C22—C23—C24	175.3 (6)	O8—C15—O7—Cd2^i	−15.1 (6)
C22—C23—C24—C25	0.4 (10)	C16—C15—O7—Cd2^i	164.7 (5)
C23—C24—C25—C26	0.6 (10)	O7—C15—O8—Cd2^i	15.0 (6)
C23—C24—C25—C28	−178.1 (6)	C16—C15—O8—Cd2^i	−164.7 (5)
C24—C25—C26—C27	−0.6 (10)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O18^iv	0.86	2.40	3.210 (7)	156
N2—H2A···O6^v	0.86	1.97	2.822 (6)	171
N3—H3D···O3^vi	0.86	2.33	3.155 (6)	162
N4—H4···O18^vi	0.86	2.40	3.205 (7)	157
O9—H9A···O15^vii	0.85	2.04	2.775 (6)	144
O9—H9B···O19^viii	0.85	2.50	3.229 (8)	145
O10—H10A···O17	0.85	1.88	2.706 (7)	164
O10—H10B···O16	0.85	1.86	2.687 (6)	164
O11—H11A···O15^vii	0.85	2.29	2.742 (6)	113
O11—H11B···O7^vii	0.85	2.30	2.934 (6)	131
O11—H11A···O15^vii	0.85	2.29	2.742 (6)	113
O12—H12A···O8^ix	0.85	2.43	2.847 (6)	111
O12—H12B···O19^v	0.85	1.94	2.713 (8)	150
O17—H17D···O1^ii	0.85	2.14	2.881 (7)	145
O17—H17E···O14	0.85	1.91	2.742 (6)	165
O18—H18A···O16^x	0.85	2.06	2.908 (6)	176
O18—H18B···O14	0.85	2.07	2.865 (6)	156
O19—H19A···O13^x	0.85	2.12	2.661 (8)	121
O19—H19B···O4^xi	0.85	2.51	3.289 (9)	152
C6—H6···O8^iii	0.98	2.43	3.370 (7)	160
C7—H7C···O2^xii	0.96	2.58	3.311 (8)	134
C10—H10···O6^v	0.93	2.50	3.053 (7)	118
C16—H16···O15	0.98	2.38	2.784 (7)	104
C17—H17C···O13^xiii	0.96	2.50	3.445 (8)	166
C20—H20C···O19	0.96	2.48	3.396 (9)	160

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