A two-dimensional Cd^II coordination polymer based on naphthalenedi­imide: synthesis, crystal structure and photochromic properties

Naphthalenedi­imides, a class of organic dyes with an expanded π-electron-deficient plane, have attracted considerable inter­est because of their photo­induced electron transfer from neutral organic moieties to stable anionic radicals. This makes them excellent candidates for organic linkers in the construction of photochromic coordination polymers. Such a photochromic two-dimensional coordination polymer has been prepared using N,N′-bis­(pyridin-4-ylmeth­yl)naphthalene-1,8:4,5-bis(dicarboximide) (DPMNI). In crystallization tubes, upon slow diffusion of an MeOH solution of cadmium perchlorate into a CHCl₃ solution of DPMNI, the complex poly[[bis­[μ₂-2,7-bis­(pyridin-4-ylmeth­yl)benzo[imn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetrone-κ²N:N′]bis­(perchlorato-κO)cadmium(II)] chloro­form tetra­solvate], {[Cd(C₂₆H₁₆N₄O₄)₂(ClO₄)₂]·4CHCl₃}_n, (I), was obtained. The asymmetric unit contains one Cd²⁺ cation, two DPMNI ligands, two coordinated ClO₄⁻ anions and four CHCl₃ solvent mol­ecules. Each Cd²⁺ cation is inter­connected by four DPMNI linkers to generate a neutral two-dimensional naphthalenedi­imide coordination network with all the ClO₄⁻ anions above or below this plane. Strong inter­laminar anion–π inter­actions between the coordinated ClO₄⁻ anions and the imide rings of an adjacent layer lead to a three-dimensional supra­molecular structure. Compound (I) exhibits reversible photochromic behaviour and photocontrolled tunable luminescence properties, which may originate from the photoinduced electron-transfer generation of radicals in the DPMNI ligand.

Computing details

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[[bis[µ₂-2,7-bis(pyridine-4-ylmethyl)benzo[imn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetrone]bis(perchlorato)cadmium(II)] chloroform tetrasolvate]

Crystal data

[Cd(C26H16N4O4)2(ClO4)2]·4CHCl3	F(000) = 1684
Mr = 1685.63	Dx = 1.707 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 13.8485 (7) Å	Cell parameters from 9390 reflections
b = 15.0536 (6) Å	θ = 2.6–29.4°
c = 16.6819 (9) Å	µ = 0.98 mm^−1
β = 109.395 (6)°	T = 153 K
V = 3280.3 (3) Å^3	Block, yellow
Z = 2	0.28 × 0.16 × 0.06 mm

Data collection

Rigaku Saturn 724 CCD area-detector diffractometer	9441 reflections with I > 2σ(I)
ω scans	Rint = 0.041
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 1998)	θmax = 26.4°, θmin = 2.7°
Tmin = 0.983, Tmax = 1.000	h = −16→17
26057 measured reflections	k = −18→13
11605 independent reflections	l = −20→20

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.0495P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.100	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.78 e Å^−3
11605 reflections	Δρmin = −0.43 e Å^−3
867 parameters	Absolute structure: Refined as an inversion twin
1 restraint	Absolute structure parameter: 0.48 (3)

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. Refined as a 2-component inversion twin

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd1	0.50334 (3)	0.33181 (5)	0.25408 (3)	0.02399 (12)
Cl1	0.73523 (11)	0.31696 (12)	0.43672 (10)	0.0290 (4)
Cl2	0.25955 (13)	0.37010 (11)	0.08334 (11)	0.0302 (4)
Cl3	1.03183 (19)	0.89307 (15)	0.00229 (17)	0.0704 (7)
Cl4	0.9881 (2)	0.97417 (17)	−0.16328 (18)	0.0739 (8)
Cl5	1.14047 (19)	0.8347 (2)	−0.10730 (18)	0.0873 (8)
Cl6A	0.3679 (16)	0.293 (2)	0.6445 (10)	0.067 (4)	0.62 (8)
Cl6B	0.3826 (13)	0.323 (3)	0.622 (4)	0.068 (9)	0.38 (8)
Cl7	0.4754 (2)	0.27303 (19)	0.51361 (16)	0.0831 (9)
Cl8	0.57474 (17)	0.23161 (18)	0.68969 (15)	0.0649 (7)
Cl9	0.6200 (2)	0.3596 (2)	0.9033 (2)	0.1015 (12)
Cl10	0.4874 (2)	0.41857 (16)	0.99309 (15)	0.0634 (6)
Cl11	0.43782 (18)	0.45736 (17)	0.81532 (14)	0.0599 (6)
Cl12	−0.01239 (17)	0.71582 (15)	0.69113 (16)	0.0641 (6)
Cl13	−0.15871 (19)	0.8099 (2)	0.55370 (19)	0.0899 (9)
Cl14	0.0308 (2)	0.89337 (17)	0.64720 (18)	0.0756 (7)
O1	0.8728 (4)	0.7580 (4)	0.2271 (3)	0.0391 (13)
O2	0.6610 (3)	0.6230 (3)	−0.0091 (3)	0.0338 (12)
O3	1.2941 (3)	0.6663 (3)	0.0900 (3)	0.0363 (12)
O4	1.0755 (4)	0.5556 (3)	−0.1577 (3)	0.0421 (13)
O5	0.3167 (3)	0.5172 (4)	0.6021 (3)	0.0386 (13)
O6	0.1129 (4)	0.6493 (4)	0.3616 (3)	0.0418 (13)
O7	−0.1171 (4)	0.4196 (4)	0.7184 (3)	0.0386 (12)
O8	−0.3172 (3)	0.5755 (3)	0.4907 (3)	0.0337 (12)
O9	0.6329 (3)	0.2856 (3)	0.3860 (3)	0.0348 (12)
O10	0.7486 (4)	0.4036 (3)	0.4066 (3)	0.0473 (14)
O11	0.8096 (4)	0.2567 (3)	0.4274 (3)	0.0461 (14)
O12	0.7401 (4)	0.3202 (4)	0.5238 (3)	0.0459 (12)
O13	0.3669 (4)	0.3483 (4)	0.1218 (3)	0.0554 (17)
O14	0.2028 (4)	0.3146 (3)	0.1222 (3)	0.0456 (13)
O15	0.2457 (4)	0.4611 (3)	0.1012 (4)	0.0475 (14)
O16	0.2304 (4)	0.3536 (3)	−0.0051 (3)	0.0456 (15)
N1	0.5705 (4)	0.4626 (4)	0.2200 (4)	0.0279 (13)
N2	0.7675 (4)	0.6898 (4)	0.1092 (3)	0.0250 (13)
N3	1.1844 (4)	0.6049 (4)	−0.0317 (4)	0.0279 (13)
N4	1.4075 (4)	0.7478 (4)	−0.1858 (3)	0.0267 (13)
N5	0.4237 (4)	0.4215 (4)	0.3272 (4)	0.0255 (13)
N6	0.2143 (4)	0.5847 (4)	0.4829 (4)	0.0273 (14)
N7	−0.2166 (4)	0.4968 (3)	0.6034 (4)	0.0262 (13)
N8	−0.4272 (4)	0.7030 (4)	0.7195 (4)	0.0259 (13)
C1	0.5112 (5)	0.5348 (5)	0.1956 (4)	0.0300 (17)
H1	0.4429	0.5327	0.1962	0.036*
C2	0.5454 (5)	0.6118 (5)	0.1697 (4)	0.0275 (16)
H2	0.5009	0.6615	0.1535	0.033*
C3	0.6433 (5)	0.6177 (4)	0.1670 (4)	0.0235 (15)
C4	0.7050 (5)	0.5436 (5)	0.1926 (5)	0.0309 (17)
H4	0.7737	0.5450	0.1929	0.037*
C5	0.6667 (5)	0.4673 (5)	0.2177 (5)	0.0288 (18)
H5	0.7097	0.4166	0.2338	0.035*
C6	0.6805 (5)	0.7025 (5)	0.1382 (5)	0.0334 (18)
H6A	0.6235	0.7289	0.0915	0.040*
H6B	0.6998	0.7453	0.1860	0.040*
C7	0.7474 (5)	0.6491 (5)	0.0300 (4)	0.0277 (16)
C8	0.8345 (5)	0.6377 (4)	−0.0021 (4)	0.0253 (15)
C9	0.9324 (5)	0.6671 (4)	0.0489 (4)	0.0233 (15)
C10	0.9506 (5)	0.7083 (4)	0.1283 (4)	0.0250 (15)
C11	0.8636 (5)	0.7225 (5)	0.1604 (4)	0.0286 (16)
C12	1.0484 (5)	0.7322 (5)	0.1778 (5)	0.0348 (18)
H12	1.0598	0.7617	0.2304	0.042*
C13	1.1309 (5)	0.7127 (5)	0.1498 (5)	0.0346 (18)
H13	1.1982	0.7282	0.1847	0.041*
C14	1.1170 (5)	0.6712 (5)	0.0723 (4)	0.0278 (16)
C15	1.0170 (5)	0.6497 (4)	0.0201 (4)	0.0247 (15)
C16	0.9992 (5)	0.6096 (4)	−0.0594 (4)	0.0261 (15)
C17	0.9001 (5)	0.5854 (4)	−0.1093 (4)	0.0302 (16)
H17	0.8882	0.5599	−0.1638	0.036*
C18	0.8194 (5)	0.5987 (5)	−0.0794 (4)	0.0304 (16)
H18	0.7525	0.5806	−0.1130	0.036*
C19	1.2064 (5)	0.6496 (5)	0.0465 (5)	0.0308 (17)
C20	1.0874 (5)	0.5877 (4)	−0.0886 (5)	0.0313 (17)
C21	1.2726 (5)	0.5690 (5)	−0.0514 (5)	0.0328 (17)
H21A	1.2511	0.5147	−0.0862	0.039*
H21B	1.3263	0.5518	0.0024	0.039*
C22	1.3177 (5)	0.6342 (5)	−0.0986 (5)	0.0306 (17)
C23	1.4180 (5)	0.6610 (5)	−0.0633 (4)	0.0323 (17)
H23	1.4580	0.6414	−0.0082	0.039*
C24	1.4606 (6)	0.7174 (5)	−0.1095 (5)	0.0352 (18)
H24	1.5303	0.7345	−0.0851	0.042*
C25	1.3101 (6)	0.7199 (5)	−0.2205 (5)	0.039 (2)
H25	1.2722	0.7386	−0.2765	0.047*
C26	1.2629 (5)	0.6653 (6)	−0.1785 (5)	0.042 (2)
H26	1.1931	0.6493	−0.2044	0.051*
C27	0.4844 (5)	0.4685 (4)	0.3919 (4)	0.0238 (15)
H27	0.5563	0.4604	0.4068	0.029*
C28	0.4497 (5)	0.5279 (4)	0.4384 (4)	0.0266 (15)
H28	0.4968	0.5590	0.4845	0.032*
C29	0.3454 (5)	0.5421 (4)	0.4176 (4)	0.0246 (15)
C30	0.2815 (5)	0.4939 (5)	0.3507 (5)	0.0344 (18)
H30	0.2094	0.5015	0.3343	0.041*
C31	0.3226 (5)	0.4342 (5)	0.3075 (5)	0.0302 (18)
H31	0.2773	0.4010	0.2620	0.036*
C32	0.3070 (5)	0.6123 (5)	0.4637 (5)	0.0296 (16)
H32A	0.3618	0.6270	0.5176	0.035*
H32B	0.2912	0.6668	0.4285	0.035*
C33	0.2305 (5)	0.5381 (4)	0.5581 (4)	0.0277 (16)
C34	0.1187 (5)	0.6149 (5)	0.4277 (5)	0.0330 (17)
C35	0.0299 (5)	0.5984 (4)	0.4569 (4)	0.0233 (15)
C36	0.0412 (5)	0.5492 (4)	0.5294 (4)	0.0234 (15)
C37	0.1386 (5)	0.5160 (5)	0.5810 (4)	0.0263 (16)
C38	0.1481 (5)	0.4675 (5)	0.6522 (5)	0.0326 (17)
H38	0.2135	0.4464	0.6863	0.039*
C39	0.0605 (5)	0.4483 (5)	0.6757 (5)	0.0318 (17)
H39	0.0671	0.4135	0.7248	0.038*
C40	−0.0332 (5)	0.4800 (4)	0.6275 (4)	0.0232 (15)
C41	−0.0453 (5)	0.5303 (4)	0.5540 (4)	0.0201 (14)
C42	−0.1405 (5)	0.5640 (4)	0.5043 (4)	0.0247 (15)
C43	−0.1506 (5)	0.6135 (5)	0.4332 (4)	0.0291 (16)
H43	−0.2157	0.6365	0.4005	0.035*
C44	−0.0645 (5)	0.6303 (5)	0.4083 (4)	0.0316 (16)
H44	−0.0716	0.6634	0.3582	0.038*
C45	−0.1220 (5)	0.4610 (4)	0.6551 (5)	0.0256 (16)
C46	−0.2314 (5)	0.5473 (4)	0.5296 (5)	0.0265 (17)
C47	−0.3080 (5)	0.4757 (5)	0.6265 (5)	0.0301 (16)
H47A	−0.2912	0.4277	0.6695	0.036*
H47B	−0.3630	0.4538	0.5755	0.036*
C48	−0.2889 (5)	0.6327 (5)	0.6871 (5)	0.0306 (17)
H48	−0.2217	0.6369	0.6843	0.037*
C49	−0.3322 (5)	0.7024 (5)	0.7165 (5)	0.0332 (19)
H49	−0.2914	0.7538	0.7360	0.040*
C50	−0.4810 (5)	0.6287 (5)	0.6956 (4)	0.0284 (16)
H50	−0.5484	0.6269	0.6983	0.034*
C51	−0.4447 (5)	0.5541 (5)	0.6671 (5)	0.0316 (17)
H51	−0.4858	0.5023	0.6514	0.038*
C52	−0.3466 (5)	0.5563 (4)	0.6618 (4)	0.0253 (15)
C53	1.0223 (7)	0.8768 (6)	−0.1039 (6)	0.057 (2)
H53	0.9681	0.8312	−0.1290	0.068*
C54	0.4576 (5)	0.2365 (6)	0.6078 (5)	0.0422 (19)
H54	0.4329	0.1738	0.5970	0.051*
C55	0.5375 (6)	0.4452 (6)	0.9124 (5)	0.047 (2)
H55	0.5767	0.5021	0.9269	0.056*
C56	−0.0290 (6)	0.7952 (6)	0.6085 (6)	0.054 (2)
H56	0.0032	0.7707	0.5677	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0236 (2)	0.0257 (2)	0.0290 (2)	−0.00186 (19)	0.01731 (17)	−0.0044 (2)
Cl1	0.0289 (8)	0.0238 (10)	0.0336 (9)	0.0005 (7)	0.0098 (7)	0.0019 (8)
Cl2	0.0312 (9)	0.0246 (9)	0.0322 (10)	−0.0007 (7)	0.0073 (7)	0.0016 (7)
Cl3	0.0817 (18)	0.0569 (15)	0.0694 (16)	0.0053 (12)	0.0210 (13)	−0.0109 (12)
Cl4	0.0826 (18)	0.0541 (15)	0.0798 (18)	0.0179 (13)	0.0199 (14)	−0.0005 (13)
Cl5	0.0682 (16)	0.099 (2)	0.0953 (19)	0.0359 (17)	0.0283 (14)	0.005 (2)
Cl6A	0.065 (4)	0.063 (7)	0.073 (5)	0.015 (5)	0.022 (3)	−0.015 (4)
Cl6B	0.046 (5)	0.058 (12)	0.097 (15)	0.013 (6)	0.021 (5)	−0.031 (12)
Cl7	0.113 (2)	0.0781 (18)	0.0525 (15)	−0.0222 (16)	0.0203 (14)	0.0166 (13)
Cl8	0.0493 (13)	0.0854 (18)	0.0520 (14)	−0.0036 (12)	0.0062 (11)	−0.0085 (13)
Cl9	0.0739 (17)	0.129 (3)	0.099 (2)	0.0483 (18)	0.0253 (16)	−0.0238 (19)
Cl10	0.0974 (18)	0.0519 (13)	0.0501 (13)	0.0142 (12)	0.0368 (13)	0.0099 (10)
Cl11	0.0703 (15)	0.0655 (15)	0.0407 (13)	0.0020 (12)	0.0140 (11)	−0.0017 (11)
Cl12	0.0591 (14)	0.0521 (14)	0.0696 (16)	−0.0045 (11)	0.0061 (12)	0.0040 (12)
Cl13	0.0652 (15)	0.084 (2)	0.094 (2)	0.0235 (14)	−0.0089 (14)	−0.0117 (16)
Cl14	0.0806 (18)	0.0626 (17)	0.0848 (19)	−0.0098 (13)	0.0290 (15)	0.0086 (14)
O1	0.046 (3)	0.043 (3)	0.033 (3)	−0.001 (2)	0.019 (2)	−0.009 (2)
O2	0.021 (3)	0.043 (3)	0.036 (3)	−0.009 (2)	0.008 (2)	−0.003 (2)
O3	0.021 (3)	0.043 (3)	0.047 (3)	−0.003 (2)	0.013 (2)	0.006 (2)
O4	0.039 (3)	0.052 (3)	0.042 (3)	−0.008 (2)	0.023 (3)	−0.013 (3)
O5	0.021 (3)	0.044 (3)	0.052 (3)	0.004 (2)	0.014 (2)	0.003 (3)
O6	0.036 (3)	0.056 (4)	0.040 (3)	0.004 (2)	0.022 (2)	0.011 (3)
O7	0.038 (3)	0.046 (3)	0.037 (3)	0.004 (2)	0.019 (2)	0.013 (3)
O8	0.022 (3)	0.039 (3)	0.041 (3)	0.000 (2)	0.011 (2)	−0.006 (2)
O9	0.029 (3)	0.045 (3)	0.028 (3)	−0.003 (2)	0.005 (2)	−0.003 (2)
O10	0.056 (4)	0.031 (3)	0.056 (4)	−0.008 (3)	0.019 (3)	0.011 (3)
O11	0.040 (3)	0.044 (3)	0.056 (4)	0.016 (2)	0.018 (3)	0.003 (3)
O12	0.059 (3)	0.050 (3)	0.026 (2)	−0.010 (3)	0.011 (2)	0.002 (3)
O13	0.034 (3)	0.089 (5)	0.039 (3)	0.019 (3)	0.006 (2)	0.001 (3)
O14	0.059 (3)	0.031 (3)	0.050 (3)	−0.016 (2)	0.022 (3)	0.008 (2)
O15	0.072 (4)	0.022 (3)	0.063 (4)	0.011 (3)	0.043 (3)	0.008 (2)
O16	0.055 (3)	0.047 (4)	0.030 (3)	−0.010 (2)	0.008 (2)	−0.002 (2)
N1	0.024 (3)	0.037 (4)	0.027 (3)	−0.003 (3)	0.014 (3)	0.000 (3)
N2	0.028 (3)	0.025 (3)	0.027 (3)	−0.002 (2)	0.016 (3)	0.002 (2)
N3	0.023 (3)	0.033 (3)	0.033 (3)	0.001 (3)	0.015 (3)	0.007 (3)
N4	0.023 (3)	0.032 (3)	0.029 (3)	0.002 (3)	0.014 (3)	0.008 (3)
N5	0.025 (3)	0.028 (3)	0.030 (3)	−0.004 (2)	0.018 (3)	−0.005 (3)
N6	0.019 (3)	0.032 (3)	0.035 (3)	−0.002 (2)	0.014 (3)	−0.010 (3)
N7	0.026 (3)	0.021 (3)	0.038 (3)	0.001 (2)	0.018 (3)	−0.001 (3)
N8	0.018 (3)	0.036 (4)	0.026 (3)	−0.001 (3)	0.010 (2)	−0.003 (3)
C1	0.022 (4)	0.034 (4)	0.041 (4)	−0.001 (3)	0.019 (3)	0.002 (4)
C2	0.029 (4)	0.030 (4)	0.027 (4)	0.001 (3)	0.013 (3)	−0.005 (3)
C3	0.024 (4)	0.027 (4)	0.020 (3)	−0.003 (3)	0.008 (3)	0.002 (3)
C4	0.016 (4)	0.043 (5)	0.037 (4)	−0.004 (3)	0.013 (3)	0.005 (4)
C5	0.025 (4)	0.031 (4)	0.032 (4)	0.007 (3)	0.012 (3)	0.010 (3)
C6	0.025 (4)	0.035 (4)	0.047 (5)	0.004 (3)	0.020 (3)	0.002 (3)
C7	0.023 (4)	0.030 (4)	0.032 (4)	−0.003 (3)	0.011 (3)	0.008 (3)
C8	0.020 (3)	0.029 (4)	0.026 (4)	0.002 (3)	0.006 (3)	0.007 (3)
C9	0.025 (4)	0.022 (4)	0.025 (4)	0.000 (3)	0.011 (3)	0.009 (3)
C10	0.027 (4)	0.023 (4)	0.028 (4)	0.004 (3)	0.013 (3)	0.001 (3)
C11	0.030 (4)	0.027 (4)	0.032 (4)	−0.002 (3)	0.015 (3)	0.002 (3)
C12	0.032 (4)	0.042 (5)	0.030 (4)	−0.016 (3)	0.011 (3)	−0.009 (3)
C13	0.029 (4)	0.043 (5)	0.031 (4)	−0.009 (3)	0.008 (3)	0.001 (3)
C14	0.022 (4)	0.029 (4)	0.034 (4)	−0.004 (3)	0.011 (3)	0.004 (3)
C15	0.023 (4)	0.020 (4)	0.031 (4)	−0.002 (3)	0.008 (3)	0.004 (3)
C16	0.032 (4)	0.024 (4)	0.028 (4)	0.003 (3)	0.019 (3)	0.008 (3)
C17	0.030 (4)	0.035 (4)	0.025 (4)	−0.008 (3)	0.010 (3)	−0.005 (3)
C18	0.021 (4)	0.035 (4)	0.036 (4)	−0.007 (3)	0.011 (3)	0.000 (3)
C19	0.024 (4)	0.028 (4)	0.044 (4)	−0.001 (3)	0.017 (3)	0.010 (3)
C20	0.039 (4)	0.026 (4)	0.037 (4)	−0.002 (3)	0.024 (4)	0.007 (3)
C21	0.032 (4)	0.031 (4)	0.043 (5)	0.007 (3)	0.021 (4)	0.012 (3)
C22	0.029 (4)	0.032 (4)	0.040 (4)	0.006 (3)	0.024 (3)	0.001 (3)
C23	0.037 (4)	0.035 (4)	0.025 (4)	0.002 (3)	0.010 (3)	0.007 (3)
C24	0.036 (4)	0.035 (4)	0.039 (4)	−0.004 (3)	0.018 (3)	0.000 (3)
C25	0.026 (4)	0.054 (5)	0.039 (5)	0.000 (4)	0.014 (3)	0.018 (4)
C26	0.017 (4)	0.057 (5)	0.049 (5)	0.003 (3)	0.007 (3)	0.025 (4)
C27	0.018 (3)	0.028 (4)	0.027 (4)	−0.001 (3)	0.011 (3)	−0.003 (3)
C28	0.024 (4)	0.025 (4)	0.034 (4)	0.000 (3)	0.014 (3)	−0.002 (3)
C29	0.026 (4)	0.024 (4)	0.028 (4)	−0.005 (3)	0.014 (3)	−0.007 (3)
C30	0.021 (4)	0.045 (5)	0.037 (4)	0.000 (3)	0.010 (3)	−0.008 (3)
C31	0.028 (4)	0.031 (4)	0.031 (4)	−0.004 (3)	0.009 (3)	−0.009 (3)
C32	0.024 (4)	0.031 (4)	0.039 (4)	−0.003 (3)	0.018 (3)	−0.007 (3)
C33	0.026 (4)	0.024 (4)	0.034 (4)	0.005 (3)	0.011 (3)	−0.004 (3)
C34	0.036 (4)	0.029 (4)	0.038 (4)	−0.001 (3)	0.019 (4)	−0.003 (3)
C35	0.019 (4)	0.024 (4)	0.029 (4)	0.001 (3)	0.012 (3)	−0.005 (3)
C36	0.022 (4)	0.026 (4)	0.024 (4)	0.001 (3)	0.009 (3)	−0.006 (3)
C37	0.025 (4)	0.029 (4)	0.024 (4)	0.009 (3)	0.006 (3)	−0.001 (3)
C38	0.023 (4)	0.037 (4)	0.035 (4)	0.006 (3)	0.006 (3)	−0.005 (3)
C39	0.033 (4)	0.034 (4)	0.033 (4)	−0.001 (3)	0.018 (3)	0.005 (3)
C40	0.022 (4)	0.017 (3)	0.034 (4)	0.000 (3)	0.015 (3)	−0.007 (3)
C41	0.015 (3)	0.025 (4)	0.022 (3)	−0.002 (3)	0.008 (3)	−0.004 (3)
C42	0.022 (4)	0.026 (4)	0.029 (4)	−0.002 (3)	0.012 (3)	−0.006 (3)
C43	0.025 (4)	0.035 (4)	0.028 (4)	0.005 (3)	0.009 (3)	0.003 (3)
C44	0.033 (4)	0.038 (4)	0.027 (4)	0.009 (3)	0.015 (3)	0.002 (3)
C45	0.030 (4)	0.014 (3)	0.036 (4)	−0.001 (3)	0.015 (3)	−0.006 (3)
C46	0.022 (4)	0.027 (4)	0.032 (4)	0.000 (3)	0.011 (3)	−0.008 (3)
C47	0.027 (4)	0.029 (4)	0.042 (4)	0.002 (3)	0.021 (3)	0.000 (3)
C48	0.017 (4)	0.036 (4)	0.040 (4)	−0.001 (3)	0.011 (3)	−0.006 (4)
C49	0.028 (4)	0.034 (5)	0.039 (5)	−0.002 (3)	0.013 (4)	−0.009 (4)
C50	0.021 (4)	0.036 (4)	0.030 (4)	0.001 (3)	0.012 (3)	0.004 (3)
C51	0.028 (4)	0.029 (4)	0.042 (5)	0.000 (3)	0.018 (3)	−0.004 (3)
C52	0.021 (4)	0.031 (4)	0.028 (4)	0.001 (3)	0.013 (3)	0.003 (3)
C53	0.059 (6)	0.042 (5)	0.068 (6)	−0.001 (4)	0.020 (5)	−0.021 (5)
C54	0.036 (4)	0.043 (5)	0.046 (5)	0.001 (4)	0.013 (4)	−0.005 (4)
C55	0.046 (5)	0.045 (5)	0.052 (5)	0.002 (4)	0.020 (4)	−0.013 (4)
C56	0.053 (5)	0.052 (6)	0.053 (5)	0.020 (4)	0.011 (4)	0.002 (4)

Geometric parameters (Å, º)

Cd1—N4^i	2.314 (5)	C9—C15	1.430 (9)
Cd1—N8^ii	2.318 (6)	C10—C12	1.380 (9)
Cd1—N1	2.326 (6)	C10—C11	1.487 (9)
Cd1—N5	2.328 (5)	C12—C13	1.401 (10)
Cd1—O13	2.395 (5)	C12—H12	0.9500
Cd1—O9	2.434 (4)	C13—C14	1.390 (10)
Cl1—O11	1.420 (5)	C13—H13	0.9500
Cl1—O12	1.432 (5)	C14—C15	1.406 (9)
Cl1—O10	1.432 (5)	C14—C19	1.475 (9)
Cl1—O9	1.467 (5)	C15—C16	1.404 (9)
Cl2—O16	1.415 (5)	C16—C17	1.396 (9)
Cl2—O15	1.428 (5)	C16—C20	1.494 (9)
Cl2—O14	1.440 (5)	C17—C18	1.382 (9)
Cl2—O13	1.447 (5)	C17—H17	0.9500
Cl3—C53	1.750 (9)	C18—H18	0.9500
Cl4—C53	1.744 (10)	C21—C22	1.517 (9)
Cl5—C53	1.773 (9)	C21—H21A	0.9900
Cl6A—C54	1.772 (15)	C21—H21B	0.9900
Cl6B—C54	1.734 (19)	C22—C23	1.376 (9)
Cl7—C54	1.757 (8)	C22—C26	1.379 (10)
Cl8—C54	1.741 (7)	C23—C24	1.402 (10)
Cl9—C55	1.762 (8)	C23—H23	0.9500
Cl10—C55	1.754 (9)	C24—H24	0.9500
Cl11—C55	1.754 (8)	C25—C26	1.378 (10)
Cl12—C56	1.781 (9)	C25—H25	0.9500
Cl13—C56	1.738 (8)	C26—H26	0.9500
Cl14—C56	1.712 (9)	C27—C28	1.371 (9)
O1—C11	1.202 (8)	C27—H27	0.9500
O2—C7	1.222 (7)	C28—C29	1.386 (8)
O3—C19	1.216 (8)	C28—H28	0.9500
O4—C20	1.209 (8)	C29—C30	1.378 (9)
O5—C33	1.218 (7)	C29—C32	1.504 (9)
O6—C34	1.196 (8)	C30—C31	1.387 (10)
O7—C45	1.208 (8)	C30—H30	0.9500
O8—C46	1.226 (8)	C31—H31	0.9500
N1—C1	1.342 (9)	C32—H32A	0.9900
N1—C5	1.348 (8)	C32—H32B	0.9900
N2—C7	1.398 (8)	C33—C37	1.483 (9)
N2—C11	1.410 (8)	C34—C35	1.487 (9)
N2—C6	1.453 (8)	C35—C44	1.376 (9)
N3—C20	1.388 (9)	C35—C36	1.383 (9)
N3—C19	1.409 (9)	C36—C41	1.418 (8)
N3—C21	1.469 (8)	C36—C37	1.428 (9)
N4—C24	1.321 (8)	C37—C38	1.362 (10)
N4—C25	1.347 (9)	C38—C39	1.424 (9)
N4—Cd1^iii	2.314 (5)	C38—H38	0.9500
N5—C27	1.330 (8)	C39—C40	1.365 (9)
N5—C31	1.341 (8)	C39—H39	0.9500
N6—C33	1.389 (9)	C40—C41	1.404 (9)
N6—C34	1.413 (9)	C40—C45	1.477 (9)
N6—C32	1.481 (8)	C41—C42	1.398 (9)
N7—C46	1.402 (9)	C42—C43	1.369 (9)
N7—C45	1.414 (8)	C42—C46	1.475 (9)
N7—C47	1.476 (8)	C43—C44	1.410 (9)
N8—C50	1.330 (9)	C43—H43	0.9500
N8—C49	1.333 (8)	C44—H44	0.9500
N8—Cd1^iv	2.318 (6)	C47—C52	1.521 (9)
C1—C2	1.374 (10)	C47—H47A	0.9900
C1—H1	0.9500	C47—H47B	0.9900
C2—C3	1.374 (9)	C48—C49	1.377 (10)
C2—H2	0.9500	C48—C52	1.385 (9)
C3—C4	1.383 (9)	C48—H48	0.9500
C3—C6	1.513 (9)	C49—H49	0.9500
C4—C5	1.387 (10)	C50—C51	1.377 (10)
C4—H4	0.9500	C50—H50	0.9500
C5—H5	0.9500	C51—C52	1.390 (9)
C6—H6A	0.9900	C51—H51	0.9500
C6—H6B	0.9900	C53—H53	1.0000
C7—C8	1.483 (9)	C54—H54	1.0000
C8—C18	1.368 (9)	C55—H55	1.0000
C8—C9	1.412 (9)	C56—H56	1.0000
C9—C10	1.407 (9)
N4^i—Cd1—N8^ii	89.26 (19)	C26—C22—C21	122.2 (7)
N4^i—Cd1—N1	91.2 (2)	C22—C23—C24	119.4 (7)
N8^ii—Cd1—N1	176.3 (2)	C22—C23—H23	120.3
N4^i—Cd1—N5	176.2 (2)	C24—C23—H23	120.3
N8^ii—Cd1—N5	93.5 (2)	N4—C24—C23	122.6 (7)
N1—Cd1—N5	86.24 (19)	N4—C24—H24	118.7
N4^i—Cd1—O13	89.40 (19)	C23—C24—H24	118.7
N8^ii—Cd1—O13	89.5 (2)	N4—C25—C26	123.0 (7)
N1—Cd1—O13	86.8 (2)	N4—C25—H25	118.5
N5—Cd1—O13	93.26 (19)	C26—C25—H25	118.5
N4^i—Cd1—O9	86.30 (18)	C25—C26—C22	119.5 (7)
N8^ii—Cd1—O9	80.46 (18)	C25—C26—H26	120.2
N1—Cd1—O9	103.20 (18)	C22—C26—H26	120.2
N5—Cd1—O9	91.55 (18)	N5—C27—C28	124.1 (6)
O13—Cd1—O9	169.16 (18)	N5—C27—H27	118.0
O11—Cl1—O12	109.9 (3)	C28—C27—H27	118.0
O11—Cl1—O10	111.1 (3)	C27—C28—C29	119.4 (6)
O12—Cl1—O10	111.0 (3)	C27—C28—H28	120.3
O11—Cl1—O9	109.2 (3)	C29—C28—H28	120.3
O12—Cl1—O9	107.9 (3)	C30—C29—C28	117.2 (6)
O10—Cl1—O9	107.7 (3)	C30—C29—C32	122.9 (6)
O16—Cl2—O15	112.0 (3)	C28—C29—C32	119.8 (6)
O16—Cl2—O14	111.0 (3)	C29—C30—C31	119.9 (6)
O15—Cl2—O14	109.4 (3)	C29—C30—H30	120.1
O16—Cl2—O13	108.5 (3)	C31—C30—H30	120.1
O15—Cl2—O13	108.3 (4)	N5—C31—C30	122.7 (7)
O14—Cl2—O13	107.6 (3)	N5—C31—H31	118.7
Cl1—O9—Cd1	135.2 (3)	C30—C31—H31	118.7
Cl2—O13—Cd1	144.3 (3)	N6—C32—C29	113.0 (5)
C1—N1—C5	117.3 (6)	N6—C32—H32A	109.0
C1—N1—Cd1	120.4 (4)	C29—C32—H32A	109.0
C5—N1—Cd1	122.1 (5)	N6—C32—H32B	109.0
C7—N2—C11	125.3 (5)	C29—C32—H32B	109.0
C7—N2—C6	116.5 (5)	H32A—C32—H32B	107.8
C11—N2—C6	118.2 (6)	O5—C33—N6	120.5 (6)
C20—N3—C19	125.8 (6)	O5—C33—C37	122.7 (6)
C20—N3—C21	117.8 (6)	N6—C33—C37	116.8 (6)
C19—N3—C21	116.3 (5)	O6—C34—N6	120.1 (6)
C24—N4—C25	117.6 (6)	O6—C34—C35	124.4 (7)
C24—N4—Cd1^iii	116.5 (4)	N6—C34—C35	115.5 (6)
C25—N4—Cd1^iii	125.5 (5)	C44—C35—C36	120.8 (6)
C27—N5—C31	116.8 (6)	C44—C35—C34	118.4 (6)
C27—N5—Cd1	116.9 (4)	C36—C35—C34	120.7 (6)
C31—N5—Cd1	126.3 (5)	C35—C36—C41	119.9 (6)
C33—N6—C34	125.9 (6)	C35—C36—C37	121.6 (6)
C33—N6—C32	116.4 (5)	C41—C36—C37	118.4 (6)
C34—N6—C32	117.4 (6)	C38—C37—C36	120.8 (6)
C46—N7—C45	125.3 (6)	C38—C37—C33	120.1 (6)
C46—N7—C47	117.3 (5)	C36—C37—C33	119.1 (6)
C45—N7—C47	117.4 (6)	C37—C38—C39	120.3 (7)
C50—N8—C49	116.3 (6)	C37—C38—H38	119.9
C50—N8—Cd1^iv	121.1 (4)	C39—C38—H38	119.9
C49—N8—Cd1^iv	122.0 (5)	C40—C39—C38	119.8 (7)
N1—C1—C2	122.6 (6)	C40—C39—H39	120.1
N1—C1—H1	118.7	C38—C39—H39	120.1
C2—C1—H1	118.7	C39—C40—C41	121.2 (6)
C1—C2—C3	120.8 (6)	C39—C40—C45	118.4 (6)
C1—C2—H2	119.6	C41—C40—C45	120.4 (6)
C3—C2—H2	119.6	C42—C41—C40	121.9 (5)
C2—C3—C4	116.9 (6)	C42—C41—C36	118.5 (6)
C2—C3—C6	120.6 (6)	C40—C41—C36	119.6 (6)
C4—C3—C6	122.5 (6)	C43—C42—C41	121.0 (6)
C3—C4—C5	120.1 (6)	C43—C42—C46	119.3 (6)
C3—C4—H4	119.9	C41—C42—C46	119.6 (6)
C5—C4—H4	119.9	C42—C43—C44	120.0 (6)
N1—C5—C4	122.3 (7)	C42—C43—H43	120.0
N1—C5—H5	118.9	C44—C43—H43	120.0
C4—C5—H5	118.9	C35—C44—C43	119.6 (6)
N2—C6—C3	113.7 (6)	C35—C44—H44	120.2
N2—C6—H6A	108.8	C43—C44—H44	120.2
C3—C6—H6A	108.8	O7—C45—N7	120.1 (6)
N2—C6—H6B	108.8	O7—C45—C40	124.1 (6)
C3—C6—H6B	108.8	N7—C45—C40	115.8 (6)
H6A—C6—H6B	107.7	O8—C46—N7	119.0 (6)
O2—C7—N2	119.8 (6)	O8—C46—C42	124.0 (7)
O2—C7—C8	122.7 (6)	N7—C46—C42	117.0 (6)
N2—C7—C8	117.5 (5)	N7—C47—C52	111.8 (5)
C18—C8—C9	121.2 (6)	N7—C47—H47A	109.3
C18—C8—C7	120.1 (6)	C52—C47—H47A	109.3
C9—C8—C7	118.6 (6)	N7—C47—H47B	109.3
C10—C9—C8	122.8 (6)	C52—C47—H47B	109.3
C10—C9—C15	119.1 (6)	H47A—C47—H47B	107.9
C8—C9—C15	118.0 (6)	C49—C48—C52	117.8 (6)
C12—C10—C9	120.7 (6)	C49—C48—H48	121.1
C12—C10—C11	120.0 (6)	C52—C48—H48	121.1
C9—C10—C11	119.3 (6)	N8—C49—C48	124.8 (7)
O1—C11—N2	120.3 (6)	N8—C49—H49	117.6
O1—C11—C10	123.2 (6)	C48—C49—H49	117.6
N2—C11—C10	116.5 (6)	N8—C50—C51	123.9 (6)
C10—C12—C13	119.5 (7)	N8—C50—H50	118.1
C10—C12—H12	120.2	C51—C50—H50	118.1
C13—C12—H12	120.2	C50—C51—C52	118.6 (6)
C14—C13—C12	121.9 (6)	C50—C51—H51	120.7
C14—C13—H13	119.1	C52—C51—H51	120.7
C12—C13—H13	119.1	C48—C52—C51	118.5 (6)
C13—C14—C15	118.8 (6)	C48—C52—C47	122.6 (6)
C13—C14—C19	119.9 (6)	C51—C52—C47	118.8 (6)
C15—C14—C19	121.2 (6)	Cl4—C53—Cl3	111.8 (5)
C16—C15—C14	120.8 (6)	Cl4—C53—Cl5	111.2 (5)
C16—C15—C9	119.3 (6)	Cl3—C53—Cl5	108.8 (5)
C14—C15—C9	119.9 (6)	Cl4—C53—H53	108.3
C17—C16—C15	120.4 (6)	Cl3—C53—H53	108.3
C17—C16—C20	119.8 (6)	Cl5—C53—H53	108.3
C15—C16—C20	119.8 (6)	Cl6B—C54—Cl8	111.6 (9)
C18—C17—C16	120.0 (6)	Cl6B—C54—Cl7	99 (3)
C18—C17—H17	120.0	Cl8—C54—Cl7	110.1 (4)
C16—C17—H17	120.0	Cl8—C54—Cl6A	109.0 (6)
C8—C18—C17	120.9 (6)	Cl7—C54—Cl6A	118.9 (11)
C8—C18—H18	119.5	Cl8—C54—H54	106.0
C17—C18—H18	119.5	Cl7—C54—H54	106.0
O3—C19—N3	121.1 (6)	Cl6A—C54—H54	106.0
O3—C19—C14	123.3 (7)	Cl10—C55—Cl11	110.0 (4)
N3—C19—C14	115.5 (6)	Cl10—C55—Cl9	109.4 (5)
O4—C20—N3	121.4 (6)	Cl11—C55—Cl9	109.3 (4)
O4—C20—C16	122.0 (6)	Cl10—C55—H55	109.4
N3—C20—C16	116.6 (6)	Cl11—C55—H55	109.4
N3—C21—C22	113.2 (5)	Cl9—C55—H55	109.4
N3—C21—H21A	108.9	Cl14—C56—Cl13	112.0 (5)
C22—C21—H21A	108.9	Cl14—C56—Cl12	111.4 (5)
N3—C21—H21B	108.9	Cl13—C56—Cl12	109.8 (5)
C22—C21—H21B	108.9	Cl14—C56—H56	107.8
H21A—C21—H21B	107.8	Cl13—C56—H56	107.8
C23—C22—C26	117.8 (6)	Cl12—C56—H56	107.8
C23—C22—C21	119.9 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21B···O15^v	0.99	2.65	3.144 (8)	111
C24—H24···O2^v	0.95	2.48	3.073 (9)	120
C24—H24···O13^iii	0.95	2.43	3.155 (9)	133
C25—H25···O11^iii	0.95	2.41	3.341 (9)	168
C26—H26···O4	0.95	2.47	3.191 (9)	133
C27—H27···O8^v	0.95	2.53	3.139 (8)	122
C28—H28···O8^v	0.95	2.56	3.134 (8)	120
C31—H31···O14	0.95	2.57	3.484 (9)	162
C32—H32B···O12^vi	0.99	2.53	3.217 (9)	127
C49—H49···O14^iv	0.95	2.45	3.179 (9)	133
C50—H50···O5^vii	0.95	2.61	3.193 (9)	120
C51—H51···O5^vii	0.95	2.59	3.165 (8)	119
C53—H53···O14^viii	1.00	2.42	3.171 (10)	131
C54—H54···O8^ii	1.00	2.31	3.199 (9)	147
C55—H55···O2^ix	1.00	2.23	3.211 (10)	166
C56—H56···O11^vi	1.00	2.57	3.336 (10)	133

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