A two­fold inter­penetrating two-dimensional zinc(II) coordination polymer: synthesis, crystal structure and physical properties

A novel two­fold inter­penetrating two-dimensional (2D) Zn^II coordination framework, poly[[(μ-1,3-bis­(2-methyl-1H-imidazol-1-yl)benzene-κ²N³:N³)(μ-naphthalene-2,6-di­carboxyl­ato-κ²O²:O⁶)zinc(II)] di­methyl­formamide monosolvate], {[Zn(C₁₂H₆O₄)(C₁₄H₁₄N₄)]·C₃H₇NO}_n or {[Zn(1,3-BMIB)(NDC)]·DMF}_n (I), where H₂NDC is naphthalene-2,6-di­carb­oxy­lic acid, 1,3-BMIB is 1,3-bis­(2-methyl-1H-imidazol-1-yl)benzene and DMF is dimethylformamide, was pre­pared and characterized through IR spectroscopy, elemental analysis, thermal analysis and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that (I) exhibits an unusual two­fold inter­penetrating 2D network. In addition, it displays strong fluorescence emissions and a high photocatalytic activity for the degradation of Rhodamine B (RhB) under UV-light irradiation.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Poly[[(µ-1,3-bis(2-methyl-1H-imidazol-1-yl)benzene-κ²N³:N³)(µ-naphthalene-2,6-dicarboxylato-κ²O²:O⁶)zinc(II)] dimethylformamide monosolvate]

Crystal data

[Zn(C12H6O4)(C14H14N4)]·C3H7NO	Z = 4
Mr = 590.95	F(000) = 1224
Triclinic, P1	Dx = 1.401 Mg m^−3
a = 11.588 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.995 (8) Å	Cell parameters from 9132 reflections
c = 20.431 (12) Å	θ = 2.7–27.4°
α = 80.65 (3)°	µ = 0.92 mm^−1
β = 89.97 (2)°	T = 293 K
γ = 89.99 (4)°	Block, colorless
V = 2802 (3) Å^3	0.21 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer	7872 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.043
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 25.0°, θmin = 2.4°
Tmin = 0.721, Tmax = 0.851	h = −13→13
138582 measured reflections	k = −14→14
9807 independent reflections	l = −24→24

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 1.856P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.002
9807 reflections	Δρmax = 0.54 e Å^−3
729 parameters	Δρmin = −0.35 e Å^−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.

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

	x	y	z	Uiso*/Ueq
C4	0.0025 (2)	0.5486 (2)	0.97860 (14)	0.0403 (7)
C1	0.0056 (3)	0.3984 (3)	0.81317 (15)	0.0452 (7)
C2	0.0025 (2)	0.4193 (3)	0.88545 (14)	0.0422 (7)
C3	0.0057 (2)	0.5282 (3)	0.91125 (14)	0.0429 (7)
H3	0.0105	0.5925	0.8791	0.051*
C5	−0.0038 (3)	0.3231 (3)	0.92770 (15)	0.0479 (8)
H5	−0.0071	0.2523	0.9148	0.057*
C6	−0.0050 (3)	0.3401 (3)	0.99380 (15)	0.0488 (8)
H6	−0.0076	0.2748	1.0253	0.059*
C7	−0.1834 (2)	0.4394 (2)	0.59205 (15)	0.0417 (7)
C8	−0.3071 (2)	0.4621 (2)	0.56779 (15)	0.0416 (7)
C9	−0.3836 (3)	0.4826 (3)	0.61342 (16)	0.0512 (8)
H9	−0.3628	0.4817	0.6575	0.061*
C10	−0.4952 (3)	0.5049 (3)	0.59143 (16)	0.0536 (8)
H10	−0.5491	0.5182	0.6230	0.064*
C11	−0.3465 (3)	0.4649 (3)	0.50182 (15)	0.0457 (7)
H11	−0.2921	0.4489	0.4712	0.055*
C12	−0.4625 (3)	0.4901 (2)	0.47671 (15)	0.0417 (7)
C13	−0.0175 (3)	0.6870 (3)	0.56219 (16)	0.0543 (8)
H13A	0.0001	0.6331	0.5336	0.081*
H13B	−0.0204	0.7614	0.5365	0.081*
H13C	−0.0908	0.6690	0.5831	0.081*
C14	0.0794 (2)	0.6826 (2)	0.61717 (13)	0.0350 (6)
C15	0.1925 (3)	0.6350 (3)	0.70699 (17)	0.0550 (9)
H15	0.2184	0.5888	0.7452	0.066*
C16	0.2360 (3)	0.7319 (3)	0.68480 (18)	0.0583 (9)
H16	0.2965	0.7708	0.7007	0.070*
C17	0.1754 (2)	0.8638 (2)	0.58915 (14)	0.0386 (6)
C18	0.1678 (2)	0.9704 (2)	0.61815 (14)	0.0386 (6)
H18	0.1527	0.9666	0.6632	0.046*
C19	0.1821 (2)	1.0683 (2)	0.58119 (14)	0.0382 (6)
C20	0.2044 (3)	1.0590 (3)	0.51725 (15)	0.0447 (7)
H20	0.2155	1.1259	0.4878	0.054*
C21	0.2129 (3)	0.9512 (3)	0.48966 (15)	0.0483 (8)
H21	0.2299	0.9552	0.4449	0.058*
C22	0.1976 (3)	0.8521 (2)	0.52521 (15)	0.0453 (7)
H22	0.2013	0.7837	0.5094	0.054*
C23	−0.0125 (3)	1.1665 (3)	0.64953 (19)	0.0556 (9)
H23A	−0.0221	1.1199	0.6159	0.083*
H23B	−0.0761	1.2183	0.6478	0.083*
H23C	−0.0102	1.1198	0.6924	0.083*
C24	0.0922 (2)	1.2281 (2)	0.63842 (13)	0.0349 (6)
C25	0.2564 (3)	1.2651 (3)	0.60729 (19)	0.0588 (10)
H25	0.3295	1.2603	0.5892	0.071*
C26	0.2192 (3)	1.3606 (2)	0.63505 (18)	0.0534 (9)
H26	0.2608	1.4257	0.6384	0.064*
C27	0.3165 (3)	0.0612 (2)	0.09216 (16)	0.0428 (7)
C28	0.1928 (2)	0.0382 (2)	0.06781 (15)	0.0410 (7)
C29	0.1170 (3)	0.0180 (3)	0.11336 (16)	0.0509 (8)
H29	0.1340	0.0183	0.1578	0.061*
C30	0.0050 (3)	−0.0050 (3)	0.09136 (16)	0.0519 (8)
H30	−0.0504	−0.0192	0.1246	0.062*
C31	0.1534 (3)	0.0350 (2)	0.00156 (15)	0.0447 (7)
H31	0.2096	0.0513	−0.0311	0.054*
C32	0.0377 (3)	0.0099 (2)	−0.02347 (15)	0.0412 (7)
C33	0.5058 (3)	0.1005 (3)	0.31307 (15)	0.0462 (8)
C34	0.5025 (2)	0.0810 (3)	0.38554 (14)	0.0426 (7)
C35	0.5057 (2)	−0.0286 (3)	0.41101 (14)	0.0415 (7)
H35	0.5097	−0.0858	0.3853	0.050*
C36	0.5024 (2)	−0.0481 (2)	0.47891 (14)	0.0396 (7)
C37	0.5050 (3)	−0.1607 (3)	0.50613 (15)	0.0473 (8)
H37	0.5073	−0.2191	0.4813	0.057*
C38	0.5039 (3)	−0.1764 (3)	0.57227 (15)	0.0489 (8)
H38	0.5072	−0.2504	0.5946	0.059*
C39	0.4876 (3)	0.3332 (3)	0.14922 (19)	0.0584 (10)
H39A	0.4965	0.3673	0.1883	0.088*
H39B	0.4235	0.2820	0.1549	0.088*
H39C	0.4740	0.3910	0.1117	0.088*
C40	0.5915 (2)	0.2722 (2)	0.13839 (13)	0.0350 (6)
C41	0.7565 (3)	0.2350 (3)	0.10708 (19)	0.0598 (10)
H41	0.8290	0.2466	0.0876	0.072*
C42	0.7185 (3)	0.1393 (2)	0.13484 (18)	0.0541 (9)
H42	0.7552	0.0695	0.1400	0.065*
C43	0.6821 (2)	0.4321 (2)	0.08140 (14)	0.0372 (6)
C44	0.7046 (2)	0.4409 (3)	0.01722 (15)	0.0426 (7)
H44	0.7134	0.3801	−0.0054	0.051*
C45	0.7129 (3)	0.5493 (3)	−0.01022 (15)	0.0493 (8)
H45	0.7294	0.5648	−0.0553	0.059*
C46	0.6980 (3)	0.6481 (3)	0.02517 (15)	0.0468 (7)
H46	0.7052	0.7206	0.0012	0.056*
C47	0.6752 (2)	0.6364 (2)	0.08893 (14)	0.0380 (6)
C48	0.6680 (2)	0.5293 (2)	0.11831 (14)	0.0388 (7)
H48	0.6536	0.5142	0.1637	0.047*
C49	0.4823 (3)	0.8133 (3)	0.06205 (16)	0.0510 (8)
H49A	0.5003	0.8675	0.0234	0.077*
H49B	0.4085	0.8308	0.0791	0.077*
H49C	0.4802	0.7390	0.0504	0.077*
C50	0.5793 (2)	0.8178 (2)	0.11755 (13)	0.0348 (6)
C51	0.6928 (3)	0.8646 (3)	0.20656 (16)	0.0516 (8)
H51	0.7213	0.9003	0.2403	0.062*
C52	0.7353 (3)	0.7681 (3)	0.18478 (17)	0.0554 (8)
H52	0.7994	0.7276	0.2027	0.067*
C53	0.4740 (4)	0.6780 (4)	0.2517 (2)	0.0879 (14)
H53	0.5105	0.7288	0.2747	0.105*
C54	0.3062 (6)	0.7911 (5)	0.2548 (4)	0.135 (3)
H54A	0.3630	0.8427	0.2665	0.202*
H54B	0.2595	0.7638	0.2929	0.202*
H54C	0.2582	0.8292	0.2199	0.202*
C55	0.3052 (6)	0.6098 (7)	0.1910 (4)	0.144 (3)
H55A	0.3630	0.5762	0.1666	0.217*
H55B	0.2504	0.6497	0.1606	0.217*
H55C	0.2663	0.5517	0.2207	0.217*
C56	0.0256 (4)	0.1779 (4)	0.2482 (2)	0.0898 (14)
H56	−0.0112	0.2387	0.2225	0.108*
C57	0.1954 (6)	0.1102 (7)	0.3102 (4)	0.166 (3)
H57A	0.1423	0.0674	0.3405	0.249*
H57B	0.2523	0.1445	0.3346	0.249*
H57C	0.2327	0.0609	0.2842	0.249*
C58	0.1937 (5)	0.2913 (4)	0.2449 (4)	0.133 (2)
H58A	0.2493	0.2765	0.2125	0.199*
H58B	0.2327	0.3171	0.2810	0.199*
H58C	0.1407	0.3482	0.2248	0.199*
N1	0.0954 (2)	0.60380 (18)	0.66495 (11)	0.0387 (5)
N2	0.1633 (2)	0.76236 (19)	0.62811 (12)	0.0391 (6)
N3	0.1766 (2)	1.18142 (18)	0.60934 (12)	0.0400 (6)
N4	0.11546 (19)	1.33639 (18)	0.65443 (11)	0.0361 (5)
N5	0.61524 (19)	0.16344 (18)	0.15429 (11)	0.0366 (5)
N6	0.6769 (2)	0.31867 (18)	0.10957 (12)	0.0407 (6)
N7	0.6636 (2)	0.73750 (18)	0.12813 (12)	0.0395 (6)
N8	0.5953 (2)	0.89566 (18)	0.16487 (11)	0.0378 (5)
N9	0.3646 (3)	0.6949 (3)	0.23199 (17)	0.0762 (10)
N10	0.1349 (3)	0.1949 (3)	0.26789 (18)	0.0774 (10)
O1	0.0298 (2)	0.4865 (2)	0.78021 (10)	0.0572 (6)
O2	−0.0140 (2)	0.3031 (2)	0.78917 (12)	0.0668 (7)
O3	−0.14938 (17)	0.46125 (19)	0.65338 (11)	0.0525 (6)
O4	−0.1221 (2)	0.4033 (2)	0.55397 (12)	0.0638 (6)
O5	0.35065 (17)	0.0388 (2)	0.15350 (11)	0.0535 (6)
O6	0.3782 (2)	0.0967 (2)	0.05397 (12)	0.0675 (7)
O7	0.5299 (2)	0.0135 (2)	0.28031 (10)	0.0566 (6)
O8	0.4856 (2)	0.1971 (2)	0.28909 (12)	0.0703 (7)
O9	0.5297 (4)	0.5890 (4)	0.2384 (2)	0.1329 (15)
O10	−0.0298 (3)	0.0884 (4)	0.2613 (2)	0.1455 (19)
Zn1	0.01244 (3)	0.45688 (2)	0.68441 (2)	0.03313 (10)
Zn2	0.51241 (3)	0.04311 (2)	0.18440 (2)	0.03336 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C4	0.0340 (15)	0.0465 (16)	0.0356 (15)	−0.0028 (12)	0.0106 (12)	0.0081 (12)
C1	0.0347 (16)	0.065 (2)	0.0325 (16)	0.0025 (14)	0.0054 (12)	0.0015 (15)
C2	0.0359 (15)	0.0548 (18)	0.0324 (15)	−0.0017 (13)	0.0088 (12)	0.0038 (13)
C3	0.0412 (16)	0.0485 (17)	0.0335 (15)	−0.0025 (13)	0.0092 (12)	0.0097 (13)
C5	0.0565 (19)	0.0444 (17)	0.0409 (17)	−0.0025 (14)	0.0154 (14)	−0.0011 (13)
C6	0.053 (2)	0.0456 (17)	0.0420 (18)	−0.0028 (14)	0.0134 (15)	0.0094 (13)
C7	0.0349 (15)	0.0401 (16)	0.0465 (18)	−0.0005 (12)	−0.0009 (14)	0.0041 (13)
C8	0.0357 (15)	0.0378 (15)	0.0466 (17)	−0.0020 (12)	0.0013 (13)	0.0075 (13)
C9	0.0426 (18)	0.065 (2)	0.0406 (17)	−0.0005 (15)	0.0030 (14)	0.0071 (15)
C10	0.0393 (18)	0.073 (2)	0.0429 (18)	0.0018 (15)	0.0090 (14)	0.0081 (15)
C11	0.0385 (16)	0.0480 (17)	0.0459 (18)	0.0008 (13)	0.0065 (13)	0.0066 (13)
C12	0.0394 (16)	0.0402 (16)	0.0410 (16)	−0.0036 (12)	0.0061 (12)	0.0072 (12)
C13	0.0451 (18)	0.060 (2)	0.0502 (19)	−0.0069 (15)	0.0011 (15)	0.0157 (15)
C14	0.0396 (15)	0.0308 (14)	0.0325 (14)	0.0059 (11)	0.0073 (12)	0.0009 (11)
C15	0.059 (2)	0.0445 (18)	0.053 (2)	−0.0110 (15)	−0.0156 (16)	0.0157 (15)
C16	0.060 (2)	0.051 (2)	0.058 (2)	−0.0156 (16)	−0.0171 (17)	0.0083 (16)
C17	0.0399 (16)	0.0306 (14)	0.0418 (16)	−0.0023 (11)	0.0055 (13)	0.0045 (12)
C18	0.0437 (16)	0.0347 (15)	0.0344 (15)	−0.0027 (12)	0.0092 (12)	0.0027 (12)
C19	0.0341 (15)	0.0329 (15)	0.0449 (17)	−0.0005 (11)	0.0085 (12)	0.0019 (12)
C20	0.0415 (16)	0.0434 (17)	0.0433 (17)	−0.0012 (13)	0.0110 (13)	0.0107 (13)
C21	0.0525 (19)	0.0528 (19)	0.0364 (16)	−0.0012 (14)	0.0136 (14)	0.0022 (14)
C22	0.0551 (19)	0.0377 (16)	0.0427 (17)	−0.0029 (13)	0.0083 (14)	−0.0058 (13)
C23	0.0417 (18)	0.0460 (18)	0.079 (2)	−0.0121 (14)	0.0260 (17)	−0.0096 (16)
C24	0.0327 (14)	0.0327 (14)	0.0357 (15)	0.0007 (11)	0.0075 (12)	0.0052 (11)
C25	0.0392 (18)	0.0487 (19)	0.083 (3)	−0.0055 (14)	0.0314 (17)	0.0054 (17)
C26	0.0435 (18)	0.0343 (16)	0.079 (2)	−0.0098 (13)	0.0254 (17)	−0.0006 (15)
C27	0.0379 (16)	0.0400 (16)	0.0481 (19)	0.0006 (13)	−0.0023 (15)	−0.0003 (13)
C28	0.0359 (15)	0.0387 (16)	0.0462 (17)	0.0026 (12)	0.0011 (13)	−0.0001 (13)
C29	0.0432 (18)	0.066 (2)	0.0408 (17)	0.0013 (15)	0.0022 (14)	−0.0002 (15)
C30	0.0400 (18)	0.072 (2)	0.0409 (17)	−0.0025 (15)	0.0071 (14)	−0.0014 (15)
C31	0.0374 (16)	0.0472 (17)	0.0472 (18)	0.0005 (13)	0.0063 (13)	−0.0006 (13)
C32	0.0398 (16)	0.0394 (16)	0.0423 (16)	0.0040 (12)	0.0061 (12)	−0.0001 (12)
C33	0.0360 (16)	0.067 (2)	0.0316 (15)	−0.0028 (14)	0.0060 (12)	0.0047 (15)
C34	0.0341 (15)	0.0541 (18)	0.0354 (16)	0.0028 (13)	0.0091 (12)	0.0055 (13)
C35	0.0407 (16)	0.0495 (18)	0.0338 (15)	0.0025 (13)	0.0086 (12)	−0.0058 (13)
C36	0.0356 (15)	0.0481 (17)	0.0335 (15)	0.0040 (12)	0.0112 (12)	−0.0019 (12)
C37	0.058 (2)	0.0435 (17)	0.0390 (17)	0.0033 (14)	0.0140 (15)	−0.0031 (13)
C38	0.0543 (19)	0.0468 (17)	0.0412 (17)	0.0026 (14)	0.0148 (14)	0.0062 (13)
C39	0.0412 (18)	0.0448 (18)	0.080 (2)	0.0122 (14)	0.0236 (17)	0.0166 (16)
C40	0.0326 (14)	0.0333 (14)	0.0364 (15)	0.0000 (11)	0.0086 (12)	0.0025 (11)
C41	0.0382 (17)	0.0495 (19)	0.087 (3)	0.0067 (14)	0.0315 (17)	0.0026 (17)
C42	0.0435 (18)	0.0332 (16)	0.080 (2)	0.0095 (13)	0.0271 (17)	0.0074 (15)
C43	0.0352 (15)	0.0301 (14)	0.0429 (16)	−0.0005 (11)	0.0086 (12)	0.0042 (12)
C44	0.0411 (16)	0.0435 (17)	0.0423 (17)	0.0029 (13)	0.0106 (13)	−0.0044 (13)
C45	0.0529 (19)	0.0546 (19)	0.0356 (16)	0.0020 (15)	0.0136 (14)	0.0067 (14)
C46	0.0521 (18)	0.0409 (16)	0.0418 (17)	0.0019 (13)	0.0085 (14)	0.0102 (13)
C47	0.0405 (16)	0.0315 (14)	0.0390 (16)	0.0033 (11)	0.0055 (12)	0.0032 (12)
C48	0.0416 (16)	0.0366 (15)	0.0344 (15)	0.0024 (12)	0.0096 (12)	0.0056 (12)
C49	0.0449 (18)	0.060 (2)	0.0481 (19)	0.0068 (15)	−0.0020 (14)	−0.0071 (15)
C50	0.0382 (15)	0.0284 (13)	0.0338 (14)	−0.0041 (11)	0.0083 (12)	0.0066 (11)
C51	0.062 (2)	0.0464 (18)	0.0471 (18)	0.0086 (15)	−0.0157 (16)	−0.0091 (14)
C52	0.058 (2)	0.053 (2)	0.053 (2)	0.0179 (16)	−0.0134 (16)	−0.0003 (15)
C53	0.074 (3)	0.098 (3)	0.087 (3)	−0.010 (3)	0.035 (3)	0.001 (3)
C54	0.105 (4)	0.086 (4)	0.203 (8)	0.003 (3)	0.022 (4)	0.005 (4)
C55	0.095 (4)	0.210 (8)	0.137 (6)	−0.012 (5)	−0.013 (4)	−0.052 (5)
C56	0.070 (3)	0.100 (4)	0.091 (3)	0.011 (3)	0.034 (3)	0.009 (3)
C57	0.100 (5)	0.216 (8)	0.144 (6)	0.018 (5)	−0.012 (4)	0.083 (6)
C58	0.106 (4)	0.085 (4)	0.194 (7)	−0.002 (3)	0.018 (4)	0.015 (4)
N1	0.0418 (13)	0.0328 (12)	0.0379 (13)	−0.0016 (10)	0.0029 (10)	0.0053 (10)
N2	0.0454 (14)	0.0310 (12)	0.0375 (13)	−0.0041 (10)	0.0038 (11)	0.0043 (10)
N3	0.0388 (13)	0.0291 (12)	0.0484 (14)	0.0002 (10)	0.0136 (11)	0.0042 (10)
N4	0.0329 (12)	0.0305 (12)	0.0415 (13)	−0.0027 (9)	0.0117 (10)	0.0042 (10)
N5	0.0326 (12)	0.0334 (12)	0.0403 (13)	0.0036 (9)	0.0118 (10)	0.0047 (10)
N6	0.0383 (13)	0.0291 (12)	0.0507 (15)	0.0006 (10)	0.0152 (11)	0.0059 (10)
N7	0.0447 (14)	0.0311 (12)	0.0389 (13)	0.0040 (10)	0.0054 (11)	0.0060 (10)
N8	0.0419 (13)	0.0325 (12)	0.0355 (13)	0.0024 (10)	0.0038 (10)	0.0047 (10)
N9	0.061 (2)	0.087 (2)	0.073 (2)	−0.0154 (18)	0.0185 (17)	0.0087 (18)
N10	0.063 (2)	0.087 (2)	0.076 (2)	0.0159 (18)	0.0192 (18)	0.0052 (18)
O1	0.0650 (15)	0.0720 (16)	0.0298 (11)	−0.0063 (12)	0.0134 (10)	0.0060 (11)
O2	0.0859 (19)	0.0686 (16)	0.0451 (14)	−0.0076 (13)	0.0215 (13)	−0.0070 (12)
O3	0.0332 (11)	0.0713 (15)	0.0489 (13)	0.0043 (10)	0.0024 (9)	0.0027 (11)
O4	0.0424 (13)	0.0879 (18)	0.0594 (15)	0.0127 (12)	0.0052 (11)	−0.0068 (13)
O5	0.0332 (11)	0.0731 (15)	0.0478 (13)	−0.0040 (10)	0.0022 (9)	0.0094 (11)
O6	0.0426 (13)	0.0884 (18)	0.0602 (15)	−0.0114 (12)	0.0056 (12)	0.0212 (13)
O7	0.0650 (15)	0.0703 (15)	0.0300 (11)	0.0074 (12)	0.0146 (10)	0.0057 (10)
O8	0.0866 (19)	0.0687 (17)	0.0458 (14)	0.0086 (14)	0.0219 (13)	0.0196 (12)
O9	0.095 (3)	0.158 (4)	0.153 (4)	−0.014 (3)	0.055 (3)	−0.046 (3)
O10	0.091 (3)	0.160 (4)	0.157 (4)	0.014 (3)	0.053 (3)	0.060 (3)
Zn1	0.03329 (18)	0.03396 (18)	0.02965 (17)	0.00069 (12)	0.00534 (13)	0.00226 (12)
Zn2	0.03320 (18)	0.03401 (18)	0.02967 (17)	−0.00034 (13)	0.00529 (13)	0.00446 (12)

Geometric parameters (Å, º)

C4—C4^i	1.340 (5)	C34—C35	1.333 (4)
C4—C3	1.437 (4)	C34—C38^iv	1.543 (5)
C4—C6^i	1.532 (5)	C35—C36	1.369 (4)
C1—O1	1.190 (4)	C35—H35	0.9300
C1—O2	1.335 (4)	C36—C37	1.375 (4)
C1—C2	1.538 (4)	C36—C36^iv	1.550 (6)
C2—C5	1.326 (4)	C37—C38	1.334 (4)
C2—C3	1.486 (4)	C37—H37	0.9300
C3—H3	0.9300	C38—C34^iv	1.542 (5)
C5—C6	1.398 (4)	C38—H38	0.9300
C5—H5	0.9300	C39—C40	1.445 (4)
C6—C4^i	1.532 (5)	C39—H39A	0.9600
C6—H6	0.9300	C39—H39B	0.9600
C7—O4	1.186 (4)	C39—H39C	0.9600
C7—O3	1.379 (4)	C40—N6	1.237 (3)
C7—C8	1.527 (4)	C40—N5	1.321 (3)
C8—C9	1.338 (4)	C41—C42	1.273 (4)
C8—C11	1.419 (4)	C41—N6	1.370 (4)
C9—C10	1.381 (5)	C41—H41	0.9300
C9—H9	0.9300	C42—N5	1.308 (4)
C10—C12^ii	1.468 (5)	C42—H42	0.9300
C10—H10	0.9300	C43—C44	1.324 (4)
C11—C12	1.453 (4)	C43—N6	1.390 (3)
C11—H11	0.9300	C43—C48	1.497 (4)
C12—C12^ii	1.338 (6)	C44—C45	1.333 (4)
C12—C10^ii	1.468 (5)	C44—H44	0.9300
C13—C14	1.584 (4)	C45—C46	1.496 (5)
C13—H13A	0.9600	C45—H45	0.9300
C13—H13B	0.9600	C46—C47	1.314 (4)
C13—H13C	0.9600	C46—H46	0.9300
C14—N1	1.257 (3)	C47—C48	1.329 (4)
C14—N2	1.407 (4)	C47—N7	1.564 (4)
C15—C16	1.280 (4)	C48—H48	0.9300
C15—N1	1.500 (4)	C49—C50	1.604 (4)
C15—H15	0.9300	C49—H49A	0.9600
C16—N2	1.431 (4)	C49—H49B	0.9600
C16—H16	0.9300	C49—H49C	0.9600
C17—N2	1.349 (3)	C50—N7	1.365 (4)
C17—C22	1.361 (4)	C50—N8	1.461 (4)
C17—C18	1.497 (4)	C51—C52	1.396 (5)
C18—C19	1.299 (4)	C51—N8	1.428 (4)
C18—H18	0.9300	C51—H51	0.9300
C19—C20	1.354 (4)	C52—N7	1.517 (4)
C19—N3	1.559 (4)	C52—H52	0.9300
C20—C21	1.496 (5)	C53—O9	1.313 (6)
C20—H20	0.9300	C53—N9	1.336 (6)
C21—C22	1.300 (4)	C53—H53	0.9300
C21—H21	0.9300	C54—N9	1.476 (7)
C22—H22	0.9300	C54—H54A	0.9600
C23—C24	1.419 (4)	C54—H54B	0.9600
C23—H23A	0.9600	C54—H54C	0.9600
C23—H23B	0.9600	C55—N9	1.580 (7)
C23—H23C	0.9600	C55—H55A	0.9600
C24—N3	1.316 (4)	C55—H55B	0.9600
C24—N4	1.416 (4)	C55—H55C	0.9600
C25—N3	1.360 (4)	C56—O10	1.243 (6)
C25—C26	1.425 (5)	C56—N10	1.354 (6)
C25—H25	0.9300	C56—H56	0.9300
C26—N4	1.284 (4)	C57—N10	1.409 (6)
C26—H26	0.9300	C57—H57A	0.9600
C27—O6	1.092 (4)	C57—H57B	0.9600
C27—O5	1.300 (4)	C57—H57C	0.9600
C27—C28	1.557 (4)	C58—N10	1.358 (6)
C28—C29	1.274 (4)	C58—H58A	0.9600
C28—C31	1.435 (4)	C58—H58B	0.9600
C29—C30	1.415 (5)	C58—H58C	0.9600
C29—H29	0.9300	N1—Zn1	1.990 (3)
C30—C32^iii	1.482 (5)	N4—Zn1^v	2.043 (2)
C30—H30	0.9300	N5—Zn2	1.895 (2)
C31—C32	1.484 (4)	N8—Zn2^v	2.107 (3)
C31—H31	0.9300	O1—Zn1	2.055 (3)
C32—C32^iii	1.290 (6)	O3—Zn1	1.978 (2)
C32—C30^iii	1.482 (5)	O5—Zn2	1.982 (2)
C33—O8	1.205 (4)	O7—Zn2	1.944 (2)
C33—O7	1.357 (4)	Zn1—N4^vi	2.043 (2)
C33—C34	1.462 (4)	Zn2—N8^vi	2.107 (3)
C4^i—C4—C3	111.2 (4)	H39A—C39—H39B	109.5
C4^i—C4—C6^i	118.6 (4)	C40—C39—H39C	109.5
C3—C4—C6^i	130.3 (2)	H39A—C39—H39C	109.5
O1—C1—O2	124.5 (3)	H39B—C39—H39C	109.5
O1—C1—C2	106.3 (3)	N6—C40—N5	107.5 (2)
O2—C1—C2	129.2 (3)	N6—C40—C39	122.6 (3)
C5—C2—C3	119.5 (3)	N5—C40—C39	129.8 (2)
C5—C2—C1	111.5 (3)	C42—C41—N6	111.3 (3)
C3—C2—C1	129.0 (3)	C42—C41—H41	124.3
C4—C3—C2	129.4 (3)	N6—C41—H41	124.3
C4—C3—H3	115.3	C41—C42—N5	102.9 (3)
C2—C3—H3	115.3	C41—C42—H42	128.5
C2—C5—C6	112.4 (3)	N5—C42—H42	128.5
C2—C5—H5	123.8	C44—C43—N6	109.5 (3)
C6—C5—H5	123.8	C44—C43—C48	125.3 (2)
C5—C6—C4^i	128.9 (3)	N6—C43—C48	125.2 (3)
C5—C6—H6	115.6	C43—C44—C45	110.2 (3)
C4^i—C6—H6	115.6	C43—C44—H44	124.9
O4—C7—O3	124.7 (3)	C45—C44—H44	124.9
O4—C7—C8	114.4 (3)	C44—C45—C46	125.7 (3)
O3—C7—C8	120.9 (3)	C44—C45—H45	117.1
C9—C8—C11	118.0 (3)	C46—C45—H45	117.1
C9—C8—C7	116.0 (3)	C47—C46—C45	122.5 (3)
C11—C8—C7	125.9 (3)	C47—C46—H46	118.8
C8—C9—C10	116.2 (3)	C45—C46—H46	118.8
C8—C9—H9	121.9	C46—C47—C48	113.6 (3)
C10—C9—H9	121.9	C46—C47—N7	123.9 (2)
C9—C10—C12^ii	126.7 (3)	C48—C47—N7	122.4 (3)
C9—C10—H10	116.7	C47—C48—C43	122.7 (3)
C12^ii—C10—H10	116.7	C47—C48—H48	118.7
C8—C11—C12	127.3 (3)	C43—C48—H48	118.7
C8—C11—H11	116.4	C50—C49—H49A	109.5
C12—C11—H11	116.4	C50—C49—H49B	109.5
C12^ii—C12—C11	113.6 (4)	H49A—C49—H49B	109.5
C12^ii—C12—C10^ii	118.2 (4)	C50—C49—H49C	109.5
C11—C12—C10^ii	128.2 (3)	H49A—C49—H49C	109.5
C14—C13—H13A	109.5	H49B—C49—H49C	109.5
C14—C13—H13B	109.5	N7—C50—N8	108.3 (2)
H13A—C13—H13B	109.5	N7—C50—C49	120.7 (3)
C14—C13—H13C	109.5	N8—C50—C49	131.0 (2)
H13A—C13—H13C	109.5	C52—C51—N8	103.8 (3)
H13B—C13—H13C	109.5	C52—C51—H51	128.1
N1—C14—N2	102.7 (2)	N8—C51—H51	128.1
N1—C14—C13	126.1 (3)	C51—C52—N7	111.5 (3)
N2—C14—C13	131.2 (2)	C51—C52—H52	124.3
C16—C15—N1	112.9 (3)	N7—C52—H52	124.3
C16—C15—H15	123.5	O9—C53—N9	119.5 (5)
N1—C15—H15	123.5	O9—C53—H53	120.2
C15—C16—N2	98.8 (3)	N9—C53—H53	120.2
C15—C16—H16	130.6	N9—C54—H54A	109.5
N2—C16—H16	130.6	N9—C54—H54B	109.5
N2—C17—C22	111.2 (3)	H54A—C54—H54B	109.5
N2—C17—C18	120.5 (3)	N9—C54—H54C	109.5
C22—C17—C18	128.3 (2)	H54A—C54—H54C	109.5
C19—C18—C17	120.8 (3)	H54B—C54—H54C	109.5
C19—C18—H18	119.6	N9—C55—H55A	109.5
C17—C18—H18	119.6	N9—C55—H55B	109.5
C18—C19—C20	112.2 (3)	H55A—C55—H55B	109.5
C18—C19—N3	122.6 (3)	N9—C55—H55C	109.5
C20—C19—N3	125.2 (2)	H55A—C55—H55C	109.5
C19—C20—C21	126.0 (3)	H55B—C55—H55C	109.5
C19—C20—H20	117.0	O10—C56—N10	125.8 (5)
C21—C20—H20	117.0	O10—C56—H56	117.1
C22—C21—C20	123.3 (3)	N10—C56—H56	117.1
C22—C21—H21	118.4	N10—C57—H57A	109.5
C20—C21—H21	118.4	N10—C57—H57B	109.5
C21—C22—C17	109.5 (3)	H57A—C57—H57B	109.5
C21—C22—H22	125.2	N10—C57—H57C	109.5
C17—C22—H22	125.2	H57A—C57—H57C	109.5
C24—C23—H23A	109.5	H57B—C57—H57C	109.5
C24—C23—H23B	109.5	N10—C58—H58A	109.5
H23A—C23—H23B	109.5	N10—C58—H58B	109.5
C24—C23—H23C	109.5	H58A—C58—H58B	109.5
H23A—C23—H23C	109.5	N10—C58—H58C	109.5
H23B—C23—H23C	109.5	H58A—C58—H58C	109.5
N3—C24—N4	115.8 (2)	H58B—C58—H58C	109.5
N3—C24—C23	117.4 (3)	C14—N1—C15	109.2 (2)
N4—C24—C23	126.8 (2)	C14—N1—Zn1	127.9 (2)
N3—C25—C26	114.8 (3)	C15—N1—Zn1	122.92 (17)
N3—C25—H25	122.6	C17—N2—C14	123.3 (2)
C26—C25—H25	122.6	C17—N2—C16	120.2 (3)
N4—C26—C25	104.5 (3)	C14—N2—C16	116.4 (2)
N4—C26—H26	127.8	C24—N3—C25	98.8 (2)
C25—C26—H26	127.8	C24—N3—C19	131.0 (2)
O6—C27—O5	119.0 (3)	C25—N3—C19	130.1 (2)
O6—C27—C28	116.3 (3)	C26—N4—C24	106.1 (2)
O5—C27—C28	124.7 (3)	C26—N4—Zn1^v	120.3 (2)
C29—C28—C31	115.9 (3)	C24—N4—Zn1^v	132.67 (18)
C29—C28—C27	115.1 (3)	C42—N5—C40	112.0 (2)
C31—C28—C27	128.9 (3)	C42—N5—Zn2	118.6 (2)
C28—C29—C30	115.1 (3)	C40—N5—Zn2	128.21 (19)
C28—C29—H29	122.4	C40—N6—C41	106.2 (2)
C30—C29—H29	122.4	C40—N6—C43	124.5 (2)
C29—C30—C32^iii	130.0 (3)	C41—N6—C43	129.0 (2)
C29—C30—H30	115.0	C50—N7—C52	105.1 (2)
C32^iii—C30—H30	115.0	C50—N7—C47	124.5 (2)
C28—C31—C32	130.7 (3)	C52—N7—C47	130.4 (2)
C28—C31—H31	114.7	C51—N8—C50	111.3 (2)
C32—C31—H31	114.7	C51—N8—Zn2^v	113.18 (19)
C32^iii—C32—C30^iii	116.1 (4)	C50—N8—Zn2^v	135.53 (18)
C32^iii—C32—C31	112.2 (4)	C53—N9—C54	115.3 (5)
C30^iii—C32—C31	131.7 (3)	C53—N9—C55	119.6 (5)
O8—C33—O7	127.2 (3)	C54—N9—C55	125.0 (5)
O8—C33—C34	113.1 (3)	C56—N10—C58	121.8 (4)
O7—C33—C34	119.7 (3)	C56—N10—C57	121.3 (5)
C35—C34—C33	112.3 (3)	C58—N10—C57	116.8 (5)
C35—C34—C38^iv	123.9 (3)	C1—O1—Zn1	103.9 (2)
C33—C34—C38^iv	123.8 (3)	C7—O3—Zn1	124.30 (18)
C34—C35—C36	113.0 (3)	C27—O5—Zn2	125.67 (19)
C34—C35—H35	123.5	C33—O7—Zn2	116.54 (19)
C36—C35—H35	123.5	O3—Zn1—N1	114.68 (10)
C35—C36—C37	113.9 (3)	O3—Zn1—N4^vi	116.16 (10)
C35—C36—C36^iv	123.0 (3)	N1—Zn1—N4^vi	107.73 (10)
C37—C36—C36^iv	123.2 (3)	O3—Zn1—O1	113.51 (10)
C38—C37—C36	112.2 (3)	N1—Zn1—O1	81.85 (10)
C38—C37—H37	123.9	N4^vi—Zn1—O1	117.90 (10)
C36—C37—H37	123.9	N5—Zn2—O7	105.42 (11)
C37—C38—C34^iv	124.8 (3)	N5—Zn2—O5	123.31 (10)
C37—C38—H38	117.6	O7—Zn2—O5	114.20 (10)
C34^iv—C38—H38	117.6	N5—Zn2—N8^vi	105.69 (10)
C40—C39—H39A	109.5	O7—Zn2—N8^vi	97.01 (10)
C40—C39—H39B	109.5	O5—Zn2—N8^vi	107.74 (10)
O1—C1—C2—C5	−169.1 (3)	C18—C17—N2—C14	122.9 (3)
O2—C1—C2—C5	10.9 (5)	C22—C17—N2—C16	122.4 (3)
O1—C1—C2—C3	10.9 (4)	C18—C17—N2—C16	−55.7 (4)
O2—C1—C2—C3	−169.1 (3)	N1—C14—N2—C17	−177.9 (3)
C4^i—C4—C3—C2	1.0 (5)	C13—C14—N2—C17	−0.8 (5)
C6^i—C4—C3—C2	−179.6 (3)	N1—C14—N2—C16	0.7 (3)
C5—C2—C3—C4	−0.2 (5)	C13—C14—N2—C16	177.9 (3)
C1—C2—C3—C4	179.8 (3)	C15—C16—N2—C17	177.8 (3)
C3—C2—C5—C6	−0.9 (4)	C15—C16—N2—C14	−0.9 (4)
C1—C2—C5—C6	179.1 (3)	N4—C24—N3—C25	0.1 (3)
C2—C5—C6—C4^i	1.4 (5)	C23—C24—N3—C25	179.1 (3)
O4—C7—C8—C9	168.0 (3)	N4—C24—N3—C19	−176.3 (2)
O3—C7—C8—C9	−12.5 (4)	C23—C24—N3—C19	2.7 (5)
O4—C7—C8—C11	−13.0 (4)	C26—C25—N3—C24	0.0 (4)
O3—C7—C8—C11	166.5 (3)	C26—C25—N3—C19	176.5 (3)
C11—C8—C9—C10	−0.1 (4)	C18—C19—N3—C24	−61.8 (4)
C7—C8—C9—C10	179.0 (3)	C20—C19—N3—C24	119.8 (3)
C8—C9—C10—C12^ii	−0.8 (5)	C18—C19—N3—C25	122.9 (4)
C9—C8—C11—C12	1.3 (5)	C20—C19—N3—C25	−55.5 (5)
C7—C8—C11—C12	−177.7 (3)	C25—C26—N4—C24	0.2 (3)
C8—C11—C12—C12^ii	−1.5 (5)	C25—C26—N4—Zn1^v	−169.9 (2)
C8—C11—C12—C10^ii	179.0 (3)	N3—C24—N4—C26	−0.1 (4)
N1—C15—C16—N2	0.7 (4)	C23—C24—N4—C26	−179.1 (3)
N2—C17—C18—C19	178.4 (3)	N3—C24—N4—Zn1^v	168.1 (2)
C22—C17—C18—C19	0.7 (5)	C23—C24—N4—Zn1^v	−10.8 (4)
C17—C18—C19—C20	−0.6 (4)	C41—C42—N5—C40	0.0 (4)
C17—C18—C19—N3	−179.1 (2)	C41—C42—N5—Zn2	168.6 (3)
C18—C19—C20—C21	−0.1 (4)	N6—C40—N5—C42	−0.3 (4)
N3—C19—C20—C21	178.4 (3)	C39—C40—N5—C42	178.6 (4)
C19—C20—C21—C22	1.0 (5)	N6—C40—N5—Zn2	−167.5 (2)
C20—C21—C22—C17	−0.9 (5)	C39—C40—N5—Zn2	11.4 (5)
N2—C17—C22—C21	−177.7 (3)	N5—C40—N6—C41	0.5 (4)
C18—C17—C22—C21	0.2 (5)	C39—C40—N6—C41	−178.5 (3)
N3—C25—C26—N4	−0.1 (4)	N5—C40—N6—C43	175.6 (3)
O6—C27—C28—C29	−166.9 (3)	C39—C40—N6—C43	−3.4 (5)
O5—C27—C28—C29	14.7 (4)	C42—C41—N6—C40	−0.5 (5)
O6—C27—C28—C31	14.1 (5)	C42—C41—N6—C43	−175.3 (3)
O5—C27—C28—C31	−164.3 (3)	C44—C43—N6—C40	−120.7 (3)
C31—C28—C29—C30	0.2 (4)	C48—C43—N6—C40	61.0 (4)
C27—C28—C29—C30	−178.9 (3)	C44—C43—N6—C41	53.2 (5)
C28—C29—C30—C32^iii	0.4 (5)	C48—C43—N6—C41	−125.0 (4)
C29—C28—C31—C32	−1.2 (5)	N8—C50—N7—C52	−0.2 (3)
C27—C28—C31—C32	177.8 (3)	C49—C50—N7—C52	−178.4 (2)
C28—C31—C32—C32^iii	1.4 (5)	N8—C50—N7—C47	178.4 (2)
C28—C31—C32—C30^iii	−179.4 (3)	C49—C50—N7—C47	0.2 (4)
O8—C33—C34—C35	169.5 (3)	C51—C52—N7—C50	0.0 (3)
O7—C33—C34—C35	−10.5 (4)	C51—C52—N7—C47	−178.4 (3)
O8—C33—C34—C38^iv	−10.5 (4)	C46—C47—N7—C50	65.1 (4)
O7—C33—C34—C38^iv	169.5 (3)	C48—C47—N7—C50	−118.2 (3)
C33—C34—C35—C36	−179.9 (3)	C46—C47—N7—C52	−116.8 (4)
C38^iv—C34—C35—C36	0.1 (4)	C48—C47—N7—C52	60.0 (4)
C34—C35—C36—C37	179.7 (3)	C52—C51—N8—C50	−0.2 (3)
C34—C35—C36—C36^iv	−0.9 (5)	C52—C51—N8—Zn2^v	−178.9 (2)
C35—C36—C37—C38	178.8 (3)	N7—C50—N8—C51	0.3 (3)
C36^iv—C36—C37—C38	−0.6 (5)	C49—C50—N8—C51	178.2 (3)
C36—C37—C38—C34^iv	1.4 (5)	N7—C50—N8—Zn2^v	178.46 (18)
N6—C41—C42—N5	0.3 (5)	C49—C50—N8—Zn2^v	−3.6 (4)
N6—C43—C44—C45	−178.4 (3)	O9—C53—N9—C54	174.5 (4)
C48—C43—C44—C45	−0.1 (4)	O9—C53—N9—C55	−1.9 (6)
C43—C44—C45—C46	−0.6 (5)	O10—C56—N10—C58	172.1 (6)
C44—C45—C46—C47	0.4 (5)	O10—C56—N10—C57	−3.8 (8)
C45—C46—C47—C48	0.6 (4)	O2—C1—O1—Zn1	6.8 (4)
C45—C46—C47—N7	177.6 (3)	C2—C1—O1—Zn1	−173.20 (18)
C46—C47—C48—C43	−1.3 (4)	O4—C7—O3—Zn1	9.0 (4)
N7—C47—C48—C43	−178.3 (2)	C8—C7—O3—Zn1	−170.48 (18)
C44—C43—C48—C47	1.1 (5)	O6—C27—O5—Zn2	−9.1 (4)
N6—C43—C48—C47	179.1 (3)	C28—C27—O5—Zn2	169.3 (2)
N8—C51—C52—N7	0.1 (4)	O8—C33—O7—Zn2	−7.8 (4)
N2—C14—N1—C15	−0.2 (3)	C34—C33—O7—Zn2	172.2 (2)
C13—C14—N1—C15	−177.6 (3)	C42—N5—Zn2—O7	94.7 (3)
N2—C14—N1—Zn1	−178.69 (18)	C40—N5—Zn2—O7	−98.8 (3)
C13—C14—N1—Zn1	3.9 (4)	C42—N5—Zn2—O5	−131.6 (3)
C16—C15—N1—C14	−0.4 (4)	C40—N5—Zn2—O5	34.8 (3)
C16—C15—N1—Zn1	178.2 (3)	C42—N5—Zn2—N8^vi	−7.3 (3)
C22—C17—N2—C14	−59.1 (4)	C40—N5—Zn2—N8^vi	159.1 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O4^vii	0.96	2.38	3.202 (5)	144
C16—H16···O8^viii	0.93	2.57	3.401 (5)	149
C18—H18···O10^vii	0.93	2.12	2.924 (5)	144
C23—H23C···O10^vii	0.96	2.56	3.331 (6)	137
C46—H46···O6^ix	0.93	2.49	3.340 (4)	152
C48—H48···O9	0.93	2.37	3.108 (5)	136
C49—H49A···O6^ix	0.96	2.11	2.926 (4)	142
C52—H52···O2^viii	0.93	2.52	3.361 (5)	151

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