Bis{2,6-bis[3-(2,4,6-trimethylphenyl)pyrazol-1-yl-κN²]pyridine-κN}zinc(II) diperchlorate bis(nitromethane) solvate

The title compound, [Zn(C₂₉H₂₉N₅)₂](ClO₄)₂·2CH₃NO₂, contains a Zn^II ion showing only small deviations from local D_2d symmetry. The lower rhombicity exhibited by this complex compared with that of its Cu^II congener suggests that the highly rhombic stereochemistry exhibited by the latter is largely imposed by the stereoelectronic preferences of the Cu^II ion.

S1. Comment

We have recently described the complex [CuL₂](ClO₄)₂·2CH₃NO₂, (I) {L is 2,6-bis[3-(2,4,6-trimethylphenyl)pyrazol-1-yl]pyridine}, which exhibits a rhombic six-coordinate stereochemistry in the crystal (Solanki et al., 1998). This complex exhibits an unusual {d_z2}¹ electronic ground state, which is imposed by intramolecular steric repulsions at the metal ion between the mesityl substituents of one ligand and the pyridine ring of the other (Solanki et al., 1998; Bridgeman et al., 1999). We were interested in comparing the molecular structure of (I) with an analogue containing a metal ion with a spherical d shell, to determine the extent to which the {d_z2}¹ unpaired electron dictates the stereochemistry of the Cu^II ion. We have therefore determined the crystal structure of the title compound, [ZnL₂](ClO₄)₂·2CH₃NO₂, (II). \sch

Compound (II) is isomorphous with its Cu^II congener (Solanki et al., 1998), also crystallizing in space group P2₁2₁2₁. The asymmetric unit contains one formula unit, with the cation and all anions and solvent molecules in general positions. The Zn^II ion adopts a rhombic coordination geometry, with the Zn—N_pyrazole bonds to one ligand (Zn1—N9 and Zn1—N23) being shorter than the corresponding bonds to the other ligand (Zn1—N43 and Zn1—N57) by 0.027 (3)–0.037 (3) Å. This is a lower rhombicity than is exhibited by the Cu^II complex, however, where the Cu—N_pyrazole bonds to one ligand are 0.091 (8)–0.114 (8) Å shorter than to the other. Interestingly, although one ligand (N2—C35) is bound symmetrically to the Zn^II ion, the other (N36—C69) is slightly asymmetrically coordinated, with Zn1—N43 being 0.018 (3) Å shorter than Zn—N57. Since space-filling models show no steric contacts that could impose these small distortions from ideal D_{2 d} symmetry, both the rhombicity of the coordination sphere and the asymmetric binding of ligand N36—C69 are probably imposed by the local lattice environment. Overall, the coordination geometry in this complex closely resembles those of stereochemically similar Zn^II complexes containing two terpyridyl derivatives as ligands (Whittle et al., 1998; Alcock et al., 2000). The small rhombicity exhibited by (II) suggests that the more rhombic stereochemistry adopted by (I) is largely driven by the electronic preferences of the Cu^II ion.

The mesityl rings of each ligand in (II) sandwich the pyridine ring of the coligand, forming two perpendicular triple π-π stacks. The metric parameters for these π-π interactions are given in Table 2. For comparison, the Cu—N_pyrazole bonds in (I) range from 2.136 (6)–2.256 (6) Å, while the π-π interplanar distances are in the range 3.5–3.7 Å and the dihedral angles in the range 2.0 (2)–13.2 (2)° (Solanki et al., 1998). The small horizontal offsets of these interacting rings are consistent with these being electrostatically repulsive π-π interactions (Hunter & Sanders, 1990). There are no close intermolecular contacts within the crystal lattice.

S2. Experimental

Complexation of Zn(ClO₄)₂·6H₂O by 2 molar equivalents of L (Solanki et al., 1998) in CH₃NO₂ yielded a pale yellow solution, which was filtered and concentrated in vacuo. Vapour diffusion of Et₂O into this solution afforded colourless blocks of (II) of diffraction quality. Elemental analysis: found: C 65.1, H 6.6, N 7.5%; calculated for C₅₈H₅₈Cl₂N₁₀O₄Zn·2CH₃NO₂: C 65.3, H 6.6, N 7.6%.

S3. Refinement

Methyl H atoms were located in difference Fourier syntheses, while sp² H atoms were placed geometrically. All sp² H atoms were refined with C—H 0.925 Å and U_iso = 1.2U_eq(C), while for methyl groups the corresponding values were 0.98 Å and 1.5 U_eq(C). The slightly high R_int value for the structure reflects a very large dataset containing a great deal of redundancy, collected from a sample of only moderate quality.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1996); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97 and local software.

Figures

Fig. 1. The molecular structure of the cation of (II) with 35% probability displacement ellipsoids, showing the atom-numbering scheme employed. For clarity, H atoms have been removed.

Bis{2,6-bis[3-(2,4,6-trimethylphenyl)pyrazol-1-yl-N²]pyridine-N}zinc(II) diperchlorate bis(nitromethane) solvate

Crystal data

[Zn(C29H29N5)2](ClO4)2·2CH3NO2	F(000) = 2672
Mr = 1281.50	Dx = 1.441 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9913 (2) Å	Cell parameters from 86756 reflections
b = 19.8605 (3) Å	θ = 1.6–27.5°
c = 25.1833 (3) Å	µ = 0.58 mm^−1
β = 100.0240 (9)°	T = 150 K
V = 5905.93 (15) Å^3	Block, colourless
Z = 4	0.54 × 0.42 × 0.28 mm

Data collection

Nonius KappaCCD area-detector diffractometer	13519 independent reflections
Radiation source: fine-focus sealed tube	9275 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.100
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 1.6°
ϕ and ω scans	h = −15→15
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −25→25
Tmin = 0.745, Tmax = 0.854	l = −32→32
86756 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0718P)^2 + 1.2064P] where P = (Fo^2 + 2Fc^2)/3
13519 reflections	(Δ/σ)max = 0.001
784 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.96 e Å^−3

Special details

Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Structure solution was achieved by direct methods using SHELXS97 (Sheldrick, 1990), while least squares refinement used SHELXL97 (Sheldrick, 1997). No disorder was detected during refinement, and no restraints were applied. All non-H atoms were refined anisotropically, while H atoms were placed in calculated positions and refined using a riding model.

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

	x	y	z	Uiso*/Ueq
Zn1	0.25188 (2)	0.135096 (14)	0.221358 (10)	0.02305 (9)
N2	0.23192 (16)	0.10188 (10)	0.29666 (8)	0.0241 (4)
C3	0.2317 (2)	0.14607 (12)	0.33649 (9)	0.0248 (5)
C4	0.2117 (2)	0.12758 (14)	0.38686 (10)	0.0324 (6)
H4	0.2107	0.1592	0.4139	0.039*
C5	0.1919 (2)	0.05971 (14)	0.39458 (10)	0.0356 (6)
H5	0.1803	0.0452	0.4281	0.043*
C6	0.1930 (2)	0.01284 (13)	0.35415 (10)	0.0312 (6)
H6	0.1804	−0.0327	0.3597	0.037*
C7	0.2130 (2)	0.03688 (13)	0.30523 (9)	0.0265 (5)
N8	0.25111 (17)	0.21324 (10)	0.32173 (8)	0.0265 (4)
N9	0.25170 (16)	0.22712 (10)	0.26826 (7)	0.0237 (4)
C10	0.2573 (2)	0.29429 (12)	0.26476 (10)	0.0267 (5)
C11	0.2618 (3)	0.32293 (14)	0.31634 (11)	0.0385 (7)
H11	0.2678	0.3688	0.3242	0.046*
C12	0.2560 (2)	0.27083 (13)	0.35087 (10)	0.0355 (6)
H12	0.2542	0.2752	0.3872	0.043*
C13	0.2521 (2)	0.32558 (12)	0.21062 (10)	0.0281 (5)
C14	0.3500 (2)	0.32899 (12)	0.18694 (10)	0.0300 (6)
C15	0.3408 (2)	0.35056 (13)	0.13390 (11)	0.0346 (6)
H15	0.4064	0.3538	0.1194	0.041*
C16	0.2367 (2)	0.36844 (14)	0.10340 (11)	0.0369 (6)
C17	0.1428 (2)	0.36878 (14)	0.12845 (11)	0.0360 (6)
H17	0.0743	0.3814	0.1080	0.043*
C18	0.1483 (2)	0.34901 (13)	0.18202 (11)	0.0313 (6)
C19	0.4644 (2)	0.31224 (14)	0.21895 (11)	0.0376 (6)
H19A	0.4617	0.2677	0.2354	0.056*
H19B	0.4853	0.3461	0.2473	0.056*
H19C	0.5207	0.3120	0.1950	0.056*
C20	0.2273 (3)	0.39009 (18)	0.04545 (12)	0.0511 (8)
H20A	0.2088	0.3510	0.0218	0.077*
H20B	0.2996	0.4094	0.0398	0.077*
H20C	0.1675	0.4240	0.0371	0.077*
C21	0.0427 (2)	0.35688 (15)	0.20654 (12)	0.0398 (7)
H21A	0.0614	0.3496	0.2456	0.060*
H21B	−0.0139	0.3237	0.1906	0.060*
H21C	0.0121	0.4024	0.1994	0.060*
N22	0.21654 (17)	−0.00361 (10)	0.25928 (8)	0.0261 (4)
N23	0.23673 (16)	0.02669 (10)	0.21282 (8)	0.0251 (4)
C24	0.2401 (2)	−0.02316 (13)	0.17746 (10)	0.0279 (5)
C25	0.2221 (2)	−0.08545 (14)	0.20130 (11)	0.0365 (6)
H25	0.2177	−0.1273	0.1845	0.044*
C26	0.2082 (2)	−0.07178 (13)	0.25287 (11)	0.0331 (6)
H26	0.1949	−0.1031	0.2784	0.040*
C27	0.2586 (2)	−0.00694 (12)	0.12194 (10)	0.0278 (5)
C28	0.1660 (2)	0.01270 (13)	0.08261 (10)	0.0311 (6)
C29	0.1844 (2)	0.03229 (14)	0.03216 (10)	0.0345 (6)
H29	0.1232	0.0448	0.0064	0.041*
C30	0.2921 (2)	0.03306 (14)	0.01853 (10)	0.0337 (6)
C31	0.3820 (2)	0.01139 (14)	0.05731 (10)	0.0346 (6)
H31	0.4542	0.0105	0.0490	0.042*
C32	0.3680 (2)	−0.00917 (13)	0.10885 (10)	0.0319 (6)
C33	0.0474 (2)	0.01174 (15)	0.09475 (11)	0.0380 (6)
H33A	0.0471	0.0319	0.1302	0.057*
H33B	0.0206	−0.0349	0.0947	0.057*
H33C	−0.0027	0.0376	0.0672	0.057*
C34	0.3091 (3)	0.05579 (16)	−0.03660 (11)	0.0449 (7)
H34A	0.3202	0.0164	−0.0585	0.067*
H34B	0.3759	0.0849	−0.0331	0.067*
H34C	0.2422	0.0808	−0.0540	0.067*
C35	0.4696 (2)	−0.03141 (16)	0.14910 (11)	0.0430 (7)
H35A	0.5277	0.0037	0.1528	0.065*
H35B	0.5001	−0.0731	0.1365	0.065*
H35C	0.4469	−0.0393	0.1841	0.065*
N36	0.27249 (16)	0.16691 (10)	0.14625 (8)	0.0241 (4)
C37	0.3748 (2)	0.17057 (12)	0.13305 (9)	0.0258 (5)
C38	0.3939 (2)	0.19174 (13)	0.08331 (10)	0.0305 (6)
H38	0.4657	0.1922	0.0745	0.037*
C39	0.2992 (2)	0.21033 (14)	0.04640 (10)	0.0322 (6)
H39	0.3074	0.2239	0.0122	0.039*
C40	0.1916 (2)	0.20829 (13)	0.05927 (10)	0.0298 (6)
H40	0.1284	0.2213	0.0350	0.036*
C41	0.1825 (2)	0.18510 (12)	0.10997 (9)	0.0243 (5)
N42	0.46307 (16)	0.15183 (11)	0.17565 (8)	0.0272 (5)
N43	0.43613 (16)	0.13750 (10)	0.22510 (8)	0.0262 (4)
C44	0.5351 (2)	0.13201 (12)	0.25860 (10)	0.0276 (5)
C45	0.6248 (2)	0.14277 (15)	0.23018 (11)	0.0370 (6)
H45	0.7018	0.1413	0.2431	0.044*
C46	0.5766 (2)	0.15579 (15)	0.17853 (11)	0.0355 (6)
H46	0.6122	0.1652	0.1496	0.043*
C47	0.5358 (2)	0.12010 (13)	0.31711 (10)	0.0300 (6)
C48	0.5084 (2)	0.05632 (14)	0.33536 (10)	0.0321 (6)
C49	0.4966 (2)	0.04885 (16)	0.38919 (11)	0.0391 (7)
H49	0.4760	0.0070	0.4011	0.047*
C50	0.5124 (2)	0.10200 (18)	0.42526 (11)	0.0455 (8)
C51	0.5473 (3)	0.16296 (18)	0.40722 (12)	0.0476 (8)
H51	0.5649	0.1985	0.4312	0.057*
C52	0.5615 (2)	0.17350 (14)	0.35396 (11)	0.0383 (7)
C53	0.4957 (2)	−0.00390 (14)	0.29854 (11)	0.0381 (6)
H53A	0.5666	−0.0114	0.2851	0.057*
H53B	0.4343	0.0042	0.2681	0.057*
H53C	0.4779	−0.0437	0.3185	0.057*
C54	0.4938 (3)	0.0939 (2)	0.48266 (13)	0.0717 (12)
H54A	0.4126	0.0895	0.4831	0.108*
H54B	0.5235	0.1335	0.5037	0.108*
H54C	0.5333	0.0535	0.4984	0.108*
C55	0.6033 (3)	0.24092 (16)	0.33919 (13)	0.0570 (9)
H55A	0.6170	0.2396	0.3020	0.086*
H55B	0.6739	0.2519	0.3635	0.086*
H55C	0.5462	0.2753	0.3424	0.086*
N56	0.07836 (16)	0.17746 (10)	0.12830 (7)	0.0253 (4)
N57	0.07650 (16)	0.15035 (10)	0.17828 (7)	0.0230 (4)
C58	−0.0332 (2)	0.14385 (12)	0.18158 (10)	0.0258 (5)
C59	−0.1009 (2)	0.16743 (14)	0.13377 (10)	0.0315 (6)
H59	−0.1792	0.1693	0.1262	0.038*
C60	−0.0284 (2)	0.18787 (14)	0.10107 (10)	0.0321 (6)
H60	−0.0477	0.2060	0.0669	0.039*
C61	−0.0707 (2)	0.11603 (13)	0.23065 (10)	0.0267 (5)
C62	−0.0634 (2)	0.15634 (13)	0.27712 (10)	0.0281 (5)
C63	−0.0994 (2)	0.13056 (14)	0.32232 (10)	0.0319 (6)
H63	−0.0927	0.1577	0.3538	0.038*
C64	−0.1448 (2)	0.06649 (14)	0.32325 (10)	0.0320 (6)
C65	−0.1555 (2)	0.02854 (14)	0.27646 (11)	0.0359 (6)
H65	−0.1839	−0.0152	0.2761	0.043*
C66	−0.1197 (2)	0.05181 (14)	0.22986 (11)	0.0329 (6)
C67	−0.0279 (2)	0.22861 (14)	0.27643 (11)	0.0385 (6)
H67A	−0.0929	0.2562	0.2603	0.058*
H67B	0.0326	0.2331	0.2551	0.058*
H67C	−0.0004	0.2438	0.3134	0.058*
C68	−0.1852 (3)	0.04075 (16)	0.37298 (11)	0.0438 (7)
H68A	−0.2351	0.0743	0.3852	0.066*
H68B	−0.1199	0.0327	0.4015	0.066*
H68C	−0.2269	−0.0014	0.3645	0.066*
C69	−0.1427 (3)	0.00802 (17)	0.18013 (13)	0.0569 (9)
H69A	−0.0875	−0.0288	0.1836	0.085*
H69B	−0.1362	0.0351	0.1483	0.085*
H69C	−0.2194	−0.0107	0.1763	0.085*
Cl70	−0.00754 (5)	0.19456 (3)	−0.07600 (2)	0.03230 (15)
O71	−0.01943 (17)	0.15782 (11)	−0.02791 (7)	0.0448 (5)
O72	−0.11652 (17)	0.21764 (13)	−0.10213 (9)	0.0556 (6)
O73	0.06568 (18)	0.25182 (11)	−0.06190 (8)	0.0483 (5)
O74	0.0402 (2)	0.15169 (11)	−0.11171 (9)	0.0561 (6)
Cl75	−0.29084 (6)	0.31741 (3)	0.11716 (3)	0.03563 (16)
O76	−0.2692 (2)	0.28740 (12)	0.17002 (9)	0.0567 (6)
O77	−0.37365 (19)	0.36966 (12)	0.11554 (9)	0.0563 (6)
O78	−0.3295 (2)	0.26673 (12)	0.07827 (10)	0.0671 (7)
O79	−0.18724 (17)	0.34644 (12)	0.10737 (9)	0.0548 (6)
C80	−0.1349 (4)	0.34720 (19)	−0.00958 (16)	0.0790 (13)
H80A	−0.2005	0.3358	−0.0352	0.119*
H80B	−0.1253	0.3149	0.0191	0.119*
H80C	−0.0697	0.3466	−0.0267	0.119*
N81	−0.1442 (2)	0.41736 (13)	0.00974 (10)	0.0457 (6)
O82	−0.2376 (2)	0.44344 (13)	0.00165 (9)	0.0588 (6)
O83	−0.0606 (2)	0.44538 (14)	0.03337 (11)	0.0685 (7)
C84	−0.2679 (3)	0.15195 (18)	−0.01551 (13)	0.0499 (8)
H84A	−0.2163	0.1171	−0.0009	0.075*
H84B	−0.2368	0.1953	−0.0042	0.075*
H84C	−0.2806	0.1495	−0.0539	0.075*
N85	−0.3764 (2)	0.14521 (13)	0.00379 (11)	0.0422 (6)
O87	−0.4603 (2)	0.17022 (14)	−0.02297 (10)	0.0656 (7)
O86	−0.3762 (2)	0.11557 (12)	0.04645 (10)	0.0575 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02420 (15)	0.02458 (15)	0.02087 (15)	−0.00018 (11)	0.00532 (11)	0.00108 (11)
N2	0.0237 (10)	0.0259 (11)	0.0227 (10)	0.0006 (8)	0.0042 (8)	0.0006 (8)
C3	0.0235 (12)	0.0271 (13)	0.0236 (12)	0.0020 (10)	0.0037 (9)	0.0016 (10)
C4	0.0405 (15)	0.0349 (15)	0.0229 (13)	0.0034 (12)	0.0087 (11)	−0.0005 (11)
C5	0.0425 (16)	0.0407 (16)	0.0261 (13)	0.0038 (13)	0.0124 (11)	0.0079 (12)
C6	0.0356 (14)	0.0277 (13)	0.0317 (14)	0.0001 (11)	0.0102 (11)	0.0076 (11)
C7	0.0245 (12)	0.0281 (13)	0.0274 (13)	0.0012 (10)	0.0055 (10)	0.0022 (10)
N8	0.0321 (11)	0.0255 (11)	0.0218 (10)	0.0033 (9)	0.0047 (8)	−0.0004 (8)
N9	0.0267 (10)	0.0244 (10)	0.0206 (10)	0.0002 (8)	0.0061 (8)	0.0014 (8)
C10	0.0257 (13)	0.0259 (13)	0.0284 (13)	0.0010 (10)	0.0044 (10)	−0.0005 (10)
C11	0.0570 (18)	0.0239 (13)	0.0343 (15)	0.0014 (13)	0.0072 (13)	−0.0042 (11)
C12	0.0501 (17)	0.0316 (14)	0.0248 (13)	0.0039 (13)	0.0067 (12)	−0.0053 (11)
C13	0.0334 (14)	0.0210 (12)	0.0294 (13)	−0.0018 (10)	0.0044 (11)	0.0010 (10)
C14	0.0341 (14)	0.0222 (13)	0.0346 (14)	0.0006 (11)	0.0089 (11)	−0.0006 (11)
C15	0.0398 (15)	0.0264 (14)	0.0407 (15)	−0.0022 (12)	0.0159 (12)	0.0022 (11)
C16	0.0470 (17)	0.0298 (14)	0.0350 (15)	0.0023 (12)	0.0103 (12)	0.0046 (12)
C17	0.0378 (15)	0.0342 (15)	0.0340 (14)	−0.0007 (12)	0.0010 (12)	0.0059 (12)
C18	0.0323 (14)	0.0257 (13)	0.0359 (14)	−0.0010 (11)	0.0061 (11)	0.0032 (11)
C19	0.0330 (15)	0.0344 (15)	0.0466 (16)	0.0029 (12)	0.0100 (12)	0.0037 (13)
C20	0.062 (2)	0.057 (2)	0.0358 (16)	0.0020 (17)	0.0139 (15)	0.0118 (15)
C21	0.0314 (15)	0.0437 (17)	0.0454 (17)	0.0011 (12)	0.0095 (12)	0.0122 (13)
N22	0.0290 (11)	0.0246 (11)	0.0263 (10)	−0.0004 (9)	0.0088 (8)	0.0016 (9)
N23	0.0243 (10)	0.0253 (11)	0.0259 (10)	0.0003 (8)	0.0049 (8)	0.0014 (8)
C24	0.0253 (12)	0.0264 (13)	0.0325 (13)	−0.0003 (10)	0.0065 (10)	−0.0028 (11)
C25	0.0459 (16)	0.0244 (13)	0.0402 (15)	−0.0003 (12)	0.0102 (12)	−0.0042 (12)
C26	0.0387 (15)	0.0210 (13)	0.0414 (15)	−0.0029 (11)	0.0121 (12)	0.0005 (11)
C27	0.0312 (13)	0.0246 (13)	0.0282 (13)	−0.0015 (10)	0.0064 (10)	−0.0053 (10)
C28	0.0307 (14)	0.0278 (13)	0.0348 (14)	0.0000 (11)	0.0061 (11)	−0.0090 (11)
C29	0.0379 (15)	0.0327 (15)	0.0301 (14)	0.0046 (12)	−0.0015 (11)	−0.0046 (11)
C30	0.0418 (15)	0.0298 (14)	0.0303 (13)	−0.0002 (12)	0.0083 (11)	−0.0041 (11)
C31	0.0327 (14)	0.0368 (15)	0.0361 (15)	−0.0006 (12)	0.0110 (11)	−0.0044 (12)
C32	0.0321 (14)	0.0312 (14)	0.0317 (14)	0.0013 (11)	0.0036 (11)	−0.0061 (11)
C33	0.0290 (14)	0.0428 (16)	0.0418 (16)	0.0005 (12)	0.0049 (12)	−0.0113 (13)
C34	0.0520 (18)	0.0511 (19)	0.0326 (15)	0.0027 (15)	0.0103 (13)	0.0044 (14)
C35	0.0335 (15)	0.0566 (19)	0.0393 (16)	0.0083 (14)	0.0073 (12)	−0.0011 (14)
N36	0.0232 (10)	0.0270 (11)	0.0224 (10)	0.0002 (8)	0.0044 (8)	−0.0003 (8)
C37	0.0254 (13)	0.0263 (13)	0.0265 (12)	0.0003 (10)	0.0064 (10)	0.0013 (10)
C38	0.0304 (14)	0.0341 (14)	0.0305 (13)	−0.0004 (11)	0.0153 (11)	0.0012 (11)
C39	0.0403 (15)	0.0345 (15)	0.0233 (13)	−0.0009 (12)	0.0094 (11)	0.0032 (11)
C40	0.0334 (14)	0.0317 (14)	0.0237 (12)	0.0000 (11)	0.0033 (10)	0.0017 (10)
C41	0.0249 (12)	0.0240 (12)	0.0241 (12)	−0.0002 (10)	0.0043 (10)	−0.0011 (10)
N42	0.0227 (10)	0.0324 (12)	0.0279 (11)	0.0015 (9)	0.0086 (8)	0.0037 (9)
N43	0.0259 (11)	0.0270 (11)	0.0259 (11)	−0.0002 (9)	0.0054 (8)	0.0038 (9)
C44	0.0226 (12)	0.0259 (13)	0.0334 (13)	0.0020 (10)	0.0028 (10)	0.0038 (11)
C45	0.0204 (13)	0.0464 (17)	0.0432 (16)	0.0033 (12)	0.0032 (11)	0.0075 (13)
C46	0.0244 (13)	0.0433 (16)	0.0412 (16)	0.0018 (12)	0.0124 (11)	0.0073 (13)
C47	0.0222 (12)	0.0355 (15)	0.0313 (14)	0.0036 (11)	0.0018 (10)	0.0025 (11)
C48	0.0241 (13)	0.0384 (15)	0.0334 (14)	0.0018 (11)	0.0041 (10)	0.0037 (12)
C49	0.0306 (14)	0.0516 (18)	0.0348 (15)	−0.0012 (13)	0.0046 (11)	0.0086 (13)
C50	0.0337 (15)	0.069 (2)	0.0328 (15)	0.0054 (15)	0.0025 (12)	−0.0009 (15)
C51	0.0454 (18)	0.057 (2)	0.0364 (16)	0.0086 (15)	−0.0052 (13)	−0.0132 (15)
C52	0.0348 (15)	0.0373 (16)	0.0382 (16)	0.0053 (12)	−0.0067 (12)	−0.0020 (12)
C53	0.0381 (15)	0.0323 (15)	0.0427 (16)	0.0011 (12)	0.0035 (12)	0.0064 (12)
C54	0.062 (2)	0.117 (4)	0.0371 (18)	0.002 (2)	0.0115 (16)	−0.001 (2)
C55	0.069 (2)	0.0400 (18)	0.053 (2)	−0.0062 (17)	−0.0136 (17)	−0.0024 (15)
N56	0.0229 (10)	0.0316 (11)	0.0212 (10)	−0.0004 (9)	0.0032 (8)	0.0034 (8)
N57	0.0228 (10)	0.0259 (11)	0.0210 (10)	0.0003 (8)	0.0055 (8)	0.0015 (8)
C58	0.0231 (12)	0.0253 (13)	0.0293 (13)	−0.0022 (10)	0.0052 (10)	−0.0025 (10)
C59	0.0204 (12)	0.0391 (15)	0.0339 (14)	0.0023 (11)	0.0020 (10)	0.0053 (12)
C60	0.0253 (13)	0.0397 (15)	0.0292 (13)	0.0023 (11)	−0.0011 (10)	0.0059 (11)
C61	0.0220 (12)	0.0280 (13)	0.0300 (13)	0.0022 (10)	0.0046 (10)	0.0016 (10)
C62	0.0253 (13)	0.0303 (13)	0.0287 (13)	−0.0020 (11)	0.0046 (10)	−0.0012 (11)
C63	0.0306 (14)	0.0381 (15)	0.0265 (13)	−0.0020 (12)	0.0035 (10)	0.0001 (11)
C64	0.0291 (13)	0.0345 (14)	0.0333 (14)	0.0027 (11)	0.0078 (11)	0.0083 (12)
C65	0.0400 (15)	0.0250 (13)	0.0462 (16)	−0.0008 (12)	0.0174 (13)	0.0039 (12)
C66	0.0314 (14)	0.0320 (14)	0.0378 (14)	−0.0015 (11)	0.0135 (11)	−0.0037 (12)
C67	0.0452 (16)	0.0350 (15)	0.0379 (15)	−0.0110 (13)	0.0144 (13)	−0.0059 (12)
C68	0.0490 (18)	0.0470 (18)	0.0377 (16)	0.0004 (14)	0.0137 (13)	0.0117 (14)
C69	0.081 (2)	0.0422 (18)	0.056 (2)	−0.0224 (17)	0.0356 (18)	−0.0164 (16)
Cl70	0.0337 (3)	0.0351 (3)	0.0283 (3)	−0.0018 (3)	0.0058 (3)	0.0025 (3)
O71	0.0442 (12)	0.0576 (13)	0.0324 (10)	−0.0101 (10)	0.0060 (9)	0.0132 (9)
O72	0.0395 (12)	0.0737 (17)	0.0511 (13)	0.0063 (11)	0.0007 (10)	0.0195 (12)
O73	0.0589 (13)	0.0428 (12)	0.0431 (12)	−0.0191 (10)	0.0086 (10)	0.0002 (10)
O74	0.0751 (16)	0.0441 (13)	0.0583 (14)	0.0007 (11)	0.0369 (12)	−0.0070 (11)
Cl75	0.0357 (4)	0.0320 (3)	0.0397 (4)	−0.0015 (3)	0.0082 (3)	−0.0017 (3)
O76	0.0733 (16)	0.0534 (14)	0.0461 (13)	0.0096 (12)	0.0183 (11)	0.0138 (11)
O77	0.0541 (14)	0.0526 (14)	0.0633 (15)	0.0208 (11)	0.0135 (11)	0.0021 (11)
O78	0.0718 (16)	0.0554 (15)	0.0673 (16)	−0.0050 (13)	−0.0070 (13)	−0.0288 (13)
O79	0.0378 (12)	0.0576 (14)	0.0703 (15)	−0.0079 (10)	0.0136 (10)	0.0145 (12)
C80	0.132 (4)	0.050 (2)	0.059 (2)	0.022 (2)	0.025 (2)	−0.0066 (18)
N81	0.0570 (17)	0.0443 (15)	0.0369 (14)	0.0088 (14)	0.0108 (12)	0.0047 (12)
O82	0.0584 (15)	0.0613 (15)	0.0555 (14)	0.0128 (12)	0.0062 (11)	−0.0002 (12)
O83	0.0543 (15)	0.0724 (18)	0.0759 (17)	−0.0039 (13)	0.0032 (13)	0.0069 (14)
C84	0.0414 (17)	0.057 (2)	0.0556 (19)	−0.0111 (15)	0.0210 (15)	−0.0082 (16)
N85	0.0408 (15)	0.0376 (14)	0.0516 (16)	−0.0062 (11)	0.0176 (12)	−0.0101 (12)
O87	0.0430 (14)	0.0776 (19)	0.0764 (17)	−0.0005 (13)	0.0107 (12)	0.0010 (14)
O86	0.0739 (16)	0.0465 (13)	0.0614 (15)	−0.0039 (12)	0.0375 (12)	0.0003 (12)

Geometric parameters (Å, º)

Zn1—N2	2.0607 (19)	C38—C39	1.386 (4)
Zn1—N9	2.176 (2)	C39—C40	1.385 (4)
Zn1—N23	2.168 (2)	C40—C41	1.379 (3)
Zn1—N36	2.0497 (19)	C41—N56	1.413 (3)
Zn1—N43	2.195 (2)	N42—C46	1.353 (3)
Zn1—N57	2.2130 (19)	N42—N43	1.370 (3)
N2—C3	1.333 (3)	N43—C44	1.335 (3)
N2—C7	1.335 (3)	C44—C45	1.408 (4)
C3—C4	1.381 (3)	C44—C47	1.491 (4)
C3—N8	1.415 (3)	C45—C46	1.353 (4)
C4—C5	1.388 (4)	C47—C48	1.406 (4)
C5—C6	1.381 (4)	C47—C52	1.408 (4)
C6—C7	1.381 (3)	C48—C49	1.395 (4)
C7—N22	1.416 (3)	C48—C53	1.505 (4)
N8—C12	1.355 (3)	C49—C50	1.384 (4)
N8—N9	1.376 (3)	C50—C51	1.383 (5)
N9—C10	1.339 (3)	C50—C54	1.509 (4)
C10—C11	1.410 (3)	C51—C52	1.397 (4)
C10—C13	1.490 (3)	C52—C55	1.499 (4)
C11—C12	1.361 (4)	N56—C60	1.359 (3)
C13—C18	1.404 (4)	N56—N57	1.373 (3)
C13—C14	1.408 (4)	N57—C58	1.339 (3)
C14—C15	1.389 (4)	C58—C59	1.410 (3)
C14—C19	1.502 (4)	C58—C61	1.492 (3)
C15—C16	1.392 (4)	C59—C60	1.360 (4)
C16—C17	1.384 (4)	C61—C66	1.403 (4)
C16—C20	1.507 (4)	C61—C62	1.408 (3)
C17—C18	1.396 (4)	C62—C63	1.384 (4)
C18—C21	1.510 (4)	C62—C67	1.498 (4)
N22—C26	1.365 (3)	C63—C64	1.386 (4)
N22—N23	1.374 (3)	C64—C65	1.386 (4)
N23—C24	1.337 (3)	C64—C68	1.509 (4)
C24—C25	1.408 (4)	C65—C66	1.397 (4)
C24—C27	1.489 (3)	C66—C69	1.510 (4)
C25—C26	1.365 (4)	Cl70—O74	1.428 (2)
C27—C28	1.408 (4)	Cl70—O72	1.432 (2)
C27—C32	1.408 (4)	Cl70—O71	1.4420 (19)
C28—C29	1.383 (4)	Cl70—O73	1.443 (2)
C28—C33	1.506 (4)	Cl75—O78	1.424 (2)
C29—C30	1.393 (4)	Cl75—O79	1.429 (2)
C30—C31	1.391 (4)	Cl75—O77	1.432 (2)
C30—C34	1.507 (4)	Cl75—O76	1.440 (2)
C31—C32	1.399 (4)	C80—N81	1.486 (4)
C32—C35	1.509 (4)	N81—O83	1.209 (3)
N36—C37	1.327 (3)	N81—O82	1.218 (3)
N36—C41	1.337 (3)	C84—N85	1.472 (4)
C37—C38	1.378 (3)	N85—O87	1.215 (3)
C37—N42	1.420 (3)	N85—O86	1.225 (3)
N2—Zn1—N9	76.01 (8)	C41—N36—Zn1	120.08 (16)
N2—Zn1—N23	75.65 (8)	N36—C37—C38	123.5 (2)
N2—Zn1—N36	179.25 (8)	N36—C37—N42	113.4 (2)
N2—Zn1—N43	104.16 (7)	C38—C37—N42	123.2 (2)
N2—Zn1—N57	104.02 (7)	C37—C38—C39	116.4 (2)
N9—Zn1—N23	151.62 (7)	C40—C39—C38	121.5 (2)
N9—Zn1—N36	104.69 (8)	C41—C40—C39	117.0 (2)
N9—Zn1—N43	93.12 (7)	N36—C41—C40	122.6 (2)
N9—Zn1—N57	93.47 (7)	N36—C41—N56	113.7 (2)
N23—Zn1—N36	103.65 (8)	C40—C41—N56	123.7 (2)
N23—Zn1—N43	95.29 (7)	C46—N42—N43	111.0 (2)
N23—Zn1—N57	91.79 (7)	C46—N42—C37	129.5 (2)
N36—Zn1—N43	75.57 (7)	N43—N42—C37	118.60 (19)
N36—Zn1—N57	76.25 (7)	C44—N43—N42	105.49 (19)
N43—Zn1—N57	151.82 (7)	C44—N43—Zn1	143.36 (17)
C3—N2—C7	119.5 (2)	N42—N43—Zn1	111.12 (14)
C3—N2—Zn1	119.82 (16)	N43—C44—C45	109.9 (2)
C7—N2—Zn1	120.59 (16)	N43—C44—C47	119.3 (2)
N2—C3—C4	122.6 (2)	C45—C44—C47	130.7 (2)
N2—C3—N8	113.6 (2)	C46—C45—C44	106.4 (2)
C4—C3—N8	123.7 (2)	C45—C46—N42	107.3 (2)
C3—C4—C5	116.6 (2)	C48—C47—C52	120.0 (2)
C6—C5—C4	121.8 (2)	C48—C47—C44	120.3 (2)
C7—C6—C5	116.7 (2)	C52—C47—C44	119.7 (2)
N2—C7—C6	122.7 (2)	C49—C48—C47	118.8 (3)
N2—C7—N22	112.8 (2)	C49—C48—C53	119.9 (3)
C6—C7—N22	124.6 (2)	C47—C48—C53	121.3 (2)
C12—N8—N9	110.7 (2)	C50—C49—C48	122.1 (3)
C12—N8—C3	130.3 (2)	C51—C50—C49	117.8 (3)
N9—N8—C3	118.37 (19)	C51—C50—C54	120.8 (3)
C10—N9—N8	105.83 (19)	C49—C50—C54	121.4 (3)
C10—N9—Zn1	142.75 (16)	C50—C51—C52	122.8 (3)
N8—N9—Zn1	111.32 (14)	C51—C52—C47	118.1 (3)
N9—C10—C11	109.6 (2)	C51—C52—C55	118.3 (3)
N9—C10—C13	118.7 (2)	C47—C52—C55	123.6 (3)
C11—C10—C13	131.6 (2)	C60—N56—N57	110.99 (19)
C12—C11—C10	106.5 (2)	C60—N56—C41	128.9 (2)
N8—C12—C11	107.3 (2)	N57—N56—C41	119.87 (18)
C18—C13—C14	119.8 (2)	C58—N57—N56	105.53 (18)
C18—C13—C10	120.0 (2)	C58—N57—Zn1	144.75 (16)
C14—C13—C10	120.2 (2)	N56—N57—Zn1	109.73 (13)
C15—C14—C13	119.3 (2)	N57—C58—C59	109.9 (2)
C15—C14—C19	119.8 (2)	N57—C58—C61	121.8 (2)
C13—C14—C19	120.8 (2)	C59—C58—C61	128.2 (2)
C14—C15—C16	121.5 (3)	C60—C59—C58	106.4 (2)
C17—C16—C15	118.2 (3)	N56—C60—C59	107.1 (2)
C17—C16—C20	120.7 (3)	C66—C61—C62	119.6 (2)
C15—C16—C20	121.1 (3)	C66—C61—C58	120.7 (2)
C16—C17—C18	122.3 (3)	C62—C61—C58	119.6 (2)
C17—C18—C13	118.6 (2)	C63—C62—C61	119.3 (2)
C17—C18—C21	117.6 (2)	C63—C62—C67	119.6 (2)
C13—C18—C21	123.8 (2)	C61—C62—C67	120.8 (2)
C26—N22—N23	110.7 (2)	C62—C63—C64	122.2 (2)
C26—N22—C7	130.4 (2)	C65—C64—C63	117.6 (2)
N23—N22—C7	118.82 (19)	C65—C64—C68	121.7 (2)
C24—N23—N22	105.85 (19)	C63—C64—C68	120.6 (2)
C24—N23—Zn1	142.16 (17)	C64—C65—C66	122.5 (2)
N22—N23—Zn1	111.99 (14)	C65—C66—C61	118.6 (2)
N23—C24—C25	110.0 (2)	C65—C66—C69	117.9 (2)
N23—C24—C27	119.5 (2)	C61—C66—C69	123.4 (2)
C25—C24—C27	130.5 (2)	O74—Cl70—O72	109.57 (15)
C26—C25—C24	106.5 (2)	O74—Cl70—O71	109.65 (14)
C25—C26—N22	106.9 (2)	O72—Cl70—O71	109.40 (13)
C28—C27—C32	119.8 (2)	O74—Cl70—O73	109.36 (14)
C28—C27—C24	119.5 (2)	O72—Cl70—O73	109.16 (14)
C32—C27—C24	120.7 (2)	O71—Cl70—O73	109.69 (12)
C29—C28—C27	119.5 (2)	O78—Cl75—O79	110.77 (16)
C29—C28—C33	119.8 (2)	O78—Cl75—O77	110.59 (15)
C27—C28—C33	120.7 (2)	O79—Cl75—O77	108.79 (14)
C28—C29—C30	122.2 (2)	O78—Cl75—O76	109.14 (15)
C31—C30—C29	117.5 (2)	O79—Cl75—O76	107.71 (14)
C31—C30—C34	121.8 (2)	O77—Cl75—O76	109.79 (14)
C29—C30—C34	120.7 (2)	O83—N81—O82	123.1 (3)
C30—C31—C32	122.6 (2)	O83—N81—C80	119.3 (3)
C31—C32—C27	118.4 (2)	O82—N81—C80	117.6 (3)
C31—C32—C35	119.7 (2)	O87—N85—O86	123.9 (3)
C27—C32—C35	121.9 (2)	O87—N85—C84	118.3 (3)
C37—N36—C41	119.0 (2)	O86—N85—C84	117.8 (3)
C37—N36—Zn1	120.87 (16)