([mu]-C-meso-5,5,7,12,12,14-Hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-N-acetato-1[kappa]⁵N,N',N'',N''',O:2[kappa]O')­tetra­chloro-1[kappa]Cl,2[kappa]³Cl-cobalt(III)­zinc(II)

The crystal structure of the title compound, [CoCl(C₁₈H₃₇N₄O₂){ZnCl₃}], has been determined by X-ray diffraction.C-meso-5,5,7,12,12,14-Hexa­methyl-1,4,8,11-tetra­aza­cyclotetradecane-N-acetate acts as a bridging ligand to coodinate with Co^III and Zn^II ions. The Co^III ion is six-coordinate in a nearly octahedral environment provided by one Cl atom, four N atoms of the bridging ligand, and one O atom. The Zn^II ion is four-coordinate in a distorted tetrahedral environment completed by three Cl atoms and an O atom of the bridging ligand.

S1. Comment

Metal complexes of polyaza macrocycles with additional pendant functional groups have attracted interest owing to their diverse applications in fundamental and applied science (Bernhardt & Lawrance, 1990; Kaden, 1993). The coordination behaviour of Ni^II and Cu^II ions with C-meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane- N-acetate has been studied chemically and crystallographically (Panneerselvam et al., 1998; Xu et al., 1988). In this study, we present the crystal structure of the title compound, (I), to expand the knowledge of this area.

The X-ray structure shows that an asymmetric unit contains two independent molecules (denoted as molecules A and B). The two molecules have almost identical bond lengths and angles. In both molecules, the C-meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-N-acetate acts as a bridging ligand between the Co^III and Zn^II ions. The Co^III ion is six-coordinate in a nearly octahedral environment provided by one Cl atom, four N atoms of the bridging ligand, and one O atom. The macrocyclic moiety adopts a conformation in which the two six-membered rings are in a chair form and the two five-membered rings are in a gauche form. This combination of these four chelate rings has been found in several similar crystal stuctures (Clay et al., 1979; Panneerselvam et al., 1998; Tasker & Sklar, 1975). The Co—N distances [1.981 (4)–2.020 (5) Å] are longer than those in the trans-dichloro(1,4,8,11-tetraazacyclotetradecane)cobalt(III) cation [1.978 (4) Å; Sosa-Torres & Toscano, 1997] and the [1,4-N,N'-bis(carboxymethyl)-1,4,8,11-tetraazacyclotetradecane]cobalt(III) cation [1.969 (4) Å; Ware et al., 1996]. The Co—O distances [1.885 (4) and 1.909 (4) Å] agree with the corresponding values found in the [1,4-N,N'-bis(carboxymethyl)-1,4,8,11-tetraazacyclotetradecane]cobalt(III) cation [1.969 (4) Å; Ware et al., 1996]. The Co—Cl distances [2.219 (2) Å for molecule A and 2.237 (2) Å for molecule B] are shorter than those found in Co^III complexes such as chloro(1,5,8,11,14-pentaazacyclohexadecane)cobalt(III) diperchlorate [2.242 (9) Å; Bombieri et al., 1982], chloro(1,4,7,11,14-pentaazacycloheptadecane)cobalt(III) diperchlorate [2.249 (1) Å; Tahirov et al., 1993] and the trans-dichloro(1,4,8,11-tetraazacyclotetradecane)cobalt(III) cation [2.252 (1) Å; Sosa-Torres & Toscano, 1997].

The Zn^II ion is four-coordinate in a distorted tetrahedral environment completed by three Cl atoms and an O atom of the bridging ligand. The Zn—O bond lengths are 2.066 (4) and 2.080 (4) Å, which are shorter than that found in (1,4,8,11-tetraazacyclotetradecane-N,N',N'',N'''-dihydrogentetraactato)zinc(II) tetrahydrate [Zn—O 2.127 (1) Å; Riesen et al. 1991], but longer than that found in dichlorobis(pyridine betaine)zinc(II) [Zn—O 1.988 (3) and 1.964 (2) Å; Chen & Mak, 1991]. The average Zn—Cl bond length [2.236 (3) Å] is shorter than that in the [ZnCl₄]^2- ion found in bis(2-amino-4,5-dihydro-3H⁺-1,3-thiazolium) tetrachlorozincate(II) [2.243 (1)–2.301 (1) Å; Kubiak & Glowiak, 1984].

This crystal structure is stabilized by coordination bonds as well as hydrogen bonds. The hydrogen bonds between the complex cations and chloride anions are detailed in Table 2.

S2. Experimental

Na₃[Co(CO₃)₃]·3H₂O and the ligand C-meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-N-acetic acid were prepared according to a literature method (Bauer & Drinkard, 1960; Xu et al., 1988). Na₃[Co(CO₃)₃]·3H₂O (1.0 g) and the ligand (1.0 g) were suspended in water (50 ml). The mixture was heated on a water bath for 2 h. An aliqot of aqueous 12 M HCl (4 ml) was added dropwise to the solution. The solution was heated for a further 30 min, NaClO₄ (4.0 g) was added, and the solution was cooled. The green powder obtained upon cooling was filtered off, washed with ethanol and diethyl ether, and dried in vacuo. The crystals for X-ray analysis were recrystallized from a 1 M ZnCl₂/2M HCl mixture by slow evaporation.

S3. Refinement

The maximum 2θ for data collection is 50.0°. The data collection would not go beyond this limit, because the crystal quality was not good. The hydrogen atoms were fixed geometrically and refined with constraint.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe, et al., 1989); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: NRCVAX (Gabe et al., 1989); software used to prepare material for publication: SHELXL93.

[Chlorocobalt(III)(µ-C-meso-5,5,7,12,12,14-hexamethyl-1,4,8,11- tetraazacyclotetradecane-N-acetato-N,N',N'',N''',O:O')trichlorozinc(II)]

Crystal data

[CoZnCl4(C18H37N4O2)]	Z = 4
Mr = 607.62	F(000) = 1256
Triclinic, P1	Dx = 1.608 Mg m^−3
a = 10.242 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.874 (2) Å	Cell parameters from 25 reflections
c = 23.168 (5) Å	θ = 6.1–15.3°
α = 92.50 (2)°	µ = 2.07 mm^−1
β = 100.39 (2)°	T = 293 K
γ = 97.60 (2)°	Pillar, green
V = 2509.6 (8) Å^3	0.28 × 0.18 × 0.11 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	5321 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.061
Graphite monochromator	θmax = 25.0°, θmin = 1.8°
ω/2θ scans	h = −12→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.656, Tmax = 0.798	l = −27→27
9300 measured reflections	3 standard reflections every 60 min
8792 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: geometrically
wR(F^2) = 0.131	H-atom parameters constrained
S = 0.93	Calculated w = 1/[s^2(Fo^2) + (0.0689P)^2] where P = (Fo^2 + 2Fc^2)/3
8792 reflections	(Δ/σ)max = 0.002
541 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Co1A	0.36747 (8)	0.24346 (7)	0.13674 (3)	0.0245 (2)
Cl1A	0.3612 (2)	0.43108 (14)	0.17694 (7)	0.0395 (4)
N1A	0.5378 (4)	0.2924 (4)	0.1065 (2)	0.0264 (11)
N2A	0.4575 (5)	0.1863 (4)	0.2130 (2)	0.0269 (11)
H1A	0.4653	0.1060	0.2033	0.080*
N3A	0.1970 (5)	0.1866 (5)	0.1630 (2)	0.0294 (11)
H2A	0.1702	0.2561	0.1776	0.080*
N4A	0.2742 (5)	0.3045 (5)	0.0620 (2)	0.0328 (12)
H3A	0.2567	0.3799	0.0746	0.080*
O1A	0.3712 (4)	0.0800 (4)	0.1041 (2)	0.0312 (9)
C1A	0.6533 (6)	0.3494 (6)	0.1540 (3)	0.0366 (15)
H4A	0.6250	0.4204	0.1735	0.080*
C2A	0.6887 (6)	0.2585 (6)	0.2001 (3)	0.040 (2)
H5A	0.7791	0.2871	0.2213	0.080*
H6A	0.6900	0.1787	0.1800	0.080*
C3A	0.5965 (6)	0.2376 (6)	0.2456 (2)	0.0345 (14)
C4A	0.3559 (6)	0.1732 (6)	0.2514 (3)	0.037 (2)
H7A	0.3432	0.2542	0.2668	0.080*
H8A	0.3844	0.1244	0.2842	0.080*
C5A	0.2288 (6)	0.1092 (6)	0.2143 (3)	0.038 (2)
H9A	0.1569	0.1025	0.2366	0.080*
H10A	0.2400	0.0262	0.2008	0.080*
C6A	0.0825 (6)	0.1266 (6)	0.1171 (3)	0.038 (2)
H11A	0.1104	0.0553	0.0976	0.080*
C7A	0.0478 (6)	0.2189 (7)	0.0720 (3)	0.044 (2)
H12A	0.0433	0.2969	0.0930	0.080*
H13A	−0.0416	0.1894	0.0500	0.080*
C8A	0.1393 (6)	0.2466 (7)	0.0278 (3)	0.046 (2)
C9A	0.3734 (7)	0.3398 (6)	0.0249 (3)	0.044 (2)
H14A	0.3821	0.2682	0.0001	0.080*
H15A	0.3444	0.4038	−0.0003	0.080*
C10A	0.5032 (6)	0.3863 (5)	0.0628 (2)	0.0335 (14)
H16A	0.4981	0.4647	0.0833	0.080*
H17A	0.5721	0.4001	0.0391	0.080*
C11A	0.5694 (7)	0.1785 (5)	0.0764 (3)	0.040 (2)
H18A	0.6618	0.1681	0.0913	0.080*
H19A	0.5602	0.1890	0.0345	0.080*
C12A	0.4785 (7)	0.0636 (6)	0.0858 (2)	0.0341 (15)
C13A	0.7765 (6)	0.3981 (7)	0.1288 (3)	0.052 (2)
H20A	0.7526	0.4554	0.0996	0.080*
H21A	0.8092	0.3298	0.1111	0.080*
H22A	0.8452	0.4398	0.1598	0.080*
C14A	0.6519 (7)	0.1381 (7)	0.2841 (3)	0.050 (2)
H23A	0.6483	0.0630	0.2602	0.080*
H24A	0.5988	0.1218	0.3139	0.080*
H25A	0.7431	0.1672	0.3025	0.080*
C15A	0.6018 (7)	0.3570 (6)	0.2835 (3)	0.048 (2)
H26A	0.5671	0.4190	0.2593	0.080*
H27A	0.6930	0.3863	0.3019	0.080*
H28A	0.5486	0.3407	0.3132	0.080*
C16A	−0.0397 (7)	0.0801 (7)	0.1439 (3)	0.052 (2)
H29A	−0.0158	0.0214	0.1723	0.080*
H30A	−0.1109	0.0406	0.1133	0.080*
H31A	−0.0688	0.1492	0.1627	0.080*
C17A	0.1490 (8)	0.1288 (8)	−0.0085 (3)	0.065 (2)
H32A	0.2071	0.1488	−0.0359	0.080*
H33A	0.0614	0.0941	−0.0295	0.080*
H34A	0.1846	0.0694	0.0172	0.080*
C18A	0.0822 (8)	0.3412 (9)	−0.0135 (3)	0.080 (3)
H35A	0.1392	0.3594	−0.0416	0.080*
H36A	0.0780	0.4162	0.0091	0.080*
H37A	−0.0062	0.3070	−0.0338	0.080*
Zn1A	0.47081 (8)	−0.20003 (7)	0.11607 (3)	0.0362 (2)
Cl2A	0.6652 (2)	−0.2770 (2)	0.12971 (8)	0.0586 (5)
Cl3A	0.4359 (2)	−0.1294 (2)	0.20381 (7)	0.0470 (4)
Cl4A	0.3048 (2)	−0.3162 (2)	0.05356 (8)	0.0612 (5)
O2A	0.5110 (5)	−0.0392 (4)	0.0743 (2)	0.0493 (13)
Co1B	0.21427 (8)	0.75133 (7)	0.36890 (3)	0.0250 (2)
Cl1B	0.3095 (2)	0.94735 (14)	0.36482 (7)	0.0376 (4)
N1B	0.2059 (5)	0.7626 (4)	0.4553 (2)	0.0316 (12)
N2B	0.3899 (5)	0.6827 (4)	0.3828 (2)	0.0295 (11)
H1B	0.3643	0.6012	0.3880	0.080*
N3B	0.2164 (5)	0.7222 (4)	0.2841 (2)	0.0280 (11)
H2B	0.2528	0.7954	0.2721	0.080*
N4B	0.0377 (5)	0.8190 (5)	0.3556 (2)	0.0323 (12)
H3B	0.0629	0.9013	0.3519	0.080*
O1B	0.1278 (4)	0.5870 (3)	0.3683 (2)	0.0299 (9)
C1B	0.3388 (7)	0.8045 (6)	0.4957 (3)	0.042 (2)
H4B	0.3734	0.8866	0.4843	0.080*
C2B	0.4425 (7)	0.7210 (7)	0.4905 (3)	0.045 (2)
H5B	0.4022	0.6365	0.4940	0.080*
H6B	0.5150	0.7423	0.5240	0.080*
C3B	0.5050 (7)	0.7212 (6)	0.4347 (3)	0.042 (2)
C4B	0.4341 (6)	0.6773 (6)	0.3255 (2)	0.038 (2)
H7B	0.4990	0.6198	0.3257	0.080*
H8B	0.4754	0.7588	0.3177	0.080*
C5B	0.3115 (6)	0.6338 (5)	0.2796 (2)	0.0335 (14)
H9B	0.3343	0.6321	0.2408	0.080*
H10B	0.2725	0.5507	0.2865	0.080*
C6B	0.0845 (6)	0.6837 (6)	0.2433 (2)	0.0359 (15)
H11B	0.0426	0.6048	0.2551	0.080*
C7B	−0.0063 (7)	0.7796 (6)	0.2479 (3)	0.041 (2)
H12B	−0.0773	0.7671	0.2134	0.080*
H13B	0.0448	0.8608	0.2465	0.080*
C8B	−0.0712 (6)	0.7825 (6)	0.3020 (3)	0.039 (2)
C9B	−0.0103 (7)	0.8192 (6)	0.4123 (3)	0.043 (2)
H14B	−0.0572	0.7379	0.4171	0.080*
H15B	−0.0715	0.8798	0.4133	0.080*
C10B	0.1102 (7)	0.8519 (6)	0.4606 (3)	0.041 (2)
H16B	0.1527	0.9359	0.4575	0.080*
H17B	0.0832	0.8479	0.4986	0.080*
C11B	0.1449 (7)	0.6368 (5)	0.4701 (3)	0.038 (2)
H18B	0.0674	0.6461	0.4877	0.080*
H19B	0.2097	0.6033	0.4988	0.080*
C12B	0.1028 (6)	0.5474 (5)	0.4167 (3)	0.0291 (13)
C13B	0.3242 (8)	0.8202 (8)	0.5605 (3)	0.061 (2)
H20B	0.2581	0.8737	0.5639	0.080*
H21B	0.4087	0.8564	0.5839	0.080*
H22B	0.2966	0.7404	0.5740 (3)	0.080*
C14B	0.5981 (7)	0.6236 (7)	0.4398 (3)	0.053 (2)
H23B	0.5481	0.5439	0.4431	0.080*
H24B	0.6672	0.6443	0.4740	0.080*
H25B	0.6379	0.6205	0.4054	0.080*
C15B	0.5842 (7)	0.8473 (7)	0.4295 (3)	0.056 (2)
H26B	0.5251	0.9093	0.4262	0.080*
H27B	0.6243	0.8443	0.3952	0.080*
H28B	0.6531	0.8680	0.4639	0.080*
C16B	0.1028 (7)	0.6651 (7)	0.1796 (2)	0.053 (2)
H29B	0.1610	0.6036	0.1769	0.080*
H30B	0.1417	0.7423	0.1671	0.080*
H31B	0.0172	0.6377	0.1548	0.080*
C17B	−0.1552 (7)	0.6578 (7)	0.3062 (3)	0.058 (2)
H32B	−0.1954	0.6613	0.3405	0.080*
H33B	−0.0989	0.5936	0.3090	0.080*
H34B	−0.2243	0.6400	0.2718	0.080*
C18B	−0.1641 (7)	0.8832 (7)	0.2949 (4)	0.062 (2)
H35B	−0.2067	0.8875	0.3285	0.080*
H36B	−0.2313	0.8626	0.2600	0.080*
H37B	−0.1124	0.9622	0.2919	0.080*
Zn1B	0.10743 (8)	0.30893 (7)	0.36618 (3)	0.0372 (2)
Cl2B	0.0358 (2)	0.3264 (2)	0.27019 (8)	0.0568 (5)
Cl3B	0.3314 (2)	0.3666 (2)	0.38745 (7)	0.0475 (4)
Cl4B	0.0281 (3)	0.1367 (2)	0.40312 (11)	0.0800 (7)
O2B	0.0516 (5)	0.4401 (4)	0.4215 (2)	0.0476 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1A	0.0289 (4)	0.0271 (4)	0.0196 (4)	0.0053 (3)	0.0085 (3)	0.0043 (3)
Cl1A	0.0507 (10)	0.0314 (8)	0.0405 (9)	0.0111 (7)	0.0160 (8)	0.0002 (7)
N1A	0.023 (3)	0.033 (3)	0.024 (2)	−0.002 (2)	0.010 (2)	0.005 (2)
N2A	0.030 (3)	0.030 (3)	0.022 (2)	0.008 (2)	0.007 (2)	0.004 (2)
N3A	0.029 (3)	0.036 (3)	0.027 (3)	0.006 (2)	0.012 (2)	0.005 (2)
N4A	0.033 (3)	0.037 (3)	0.026 (3)	0.002 (2)	0.002 (2)	0.008 (2)
O1A	0.038 (2)	0.032 (2)	0.026 (2)	0.005 (2)	0.011 (2)	0.002 (2)
C1A	0.029 (3)	0.044 (4)	0.036 (3)	−0.002 (3)	0.010 (3)	0.007 (3)
C2A	0.026 (3)	0.057 (4)	0.038 (4)	0.007 (3)	0.005 (3)	0.012 (3)
C3A	0.034 (4)	0.042 (4)	0.025 (3)	0.002 (3)	0.002 (3)	0.004 (3)
C4A	0.044 (4)	0.046 (4)	0.026 (3)	0.012 (3)	0.014 (3)	0.009 (3)
C5A	0.039 (4)	0.045 (4)	0.034 (3)	0.005 (3)	0.015 (3)	0.011 (3)
C6A	0.032 (4)	0.046 (4)	0.037 (4)	0.000 (3)	0.011 (3)	0.001 (3)
C7A	0.025 (4)	0.064 (5)	0.040 (4)	0.002 (3)	−0.001 (3)	0.009 (3)
C8A	0.034 (4)	0.065 (5)	0.035 (4)	0.001 (4)	0.001 (3)	0.016 (3)
C9A	0.055 (5)	0.047 (4)	0.030 (3)	0.000 (4)	0.010 (3)	0.016 (3)
C10A	0.041 (4)	0.032 (3)	0.027 (3)	−0.005 (3)	0.010 (3)	0.010 (3)
C11A	0.055 (4)	0.032 (3)	0.042 (4)	0.016 (3)	0.024 (3)	0.008 (3)
C12A	0.054 (4)	0.037 (4)	0.013 (3)	0.009 (3)	0.010 (3)	0.004 (2)
C13A	0.023 (4)	0.065 (5)	0.064 (5)	−0.010 (3)	0.011 (3)	0.017 (4)
C14A	0.046 (4)	0.064 (5)	0.038 (4)	0.010 (4)	0.001 (3)	0.017 (3)
C15A	0.044 (4)	0.054 (4)	0.040 (4)	−0.006 (4)	0.003 (3)	−0.003 (3)
C16A	0.034 (4)	0.071 (5)	0.049 (4)	−0.002 (4)	0.014 (3)	−0.003 (4)
C17A	0.077 (6)	0.079 (6)	0.032 (4)	−0.028 (5)	0.018 (4)	−0.002 (4)
C18A	0.051 (5)	0.129 (8)	0.053 (5)	0.010 (5)	−0.012 (4)	0.044 (5)
Zn1A	0.0464 (5)	0.0364 (4)	0.0287 (4)	0.0065 (4)	0.0141 (3)	0.0045 (3)
Cl2A	0.0549 (12)	0.0732 (13)	0.0503 (11)	0.0249 (10)	0.0069 (9)	0.0002 (10)
Cl3A	0.0752 (13)	0.0415 (9)	0.0319 (8)	0.0116 (9)	0.0261 (8)	0.0092 (7)
Cl4A	0.0536 (12)	0.0865 (15)	0.0382 (10)	−0.0090 (11)	0.0096 (9)	−0.0031 (10)
O2A	0.092 (4)	0.028 (2)	0.043 (3)	0.021 (3)	0.041 (3)	0.013 (2)
Co1B	0.0324 (5)	0.0250 (4)	0.0196 (4)	0.0039 (4)	0.0097 (3)	0.0054 (3)
Cl1B	0.0483 (10)	0.0289 (8)	0.0364 (8)	−0.0014 (7)	0.0140 (7)	0.0063 (6)
N1B	0.046 (3)	0.026 (3)	0.026 (3)	−0.001 (2)	0.017 (2)	0.001 (2)
N2B	0.036 (3)	0.033 (3)	0.020 (2)	0.003 (2)	0.008 (2)	0.007 (2)
N3B	0.034 (3)	0.030 (3)	0.020 (2)	−0.002 (2)	0.006 (2)	0.008 (2)
N4B	0.039 (3)	0.031 (3)	0.031 (3)	0.011 (2)	0.013 (2)	0.005 (2)
O1B	0.038 (2)	0.027 (2)	0.027 (2)	0.001 (2)	0.014 (2)	0.006 (2)
C1B	0.057 (5)	0.040 (4)	0.026 (3)	0.001 (3)	0.006 (3)	−0.002 (3)
C2B	0.050 (4)	0.064 (5)	0.021 (3)	0.013 (4)	0.003 (3)	0.015 (3)
C3B	0.042 (4)	0.053 (4)	0.030 (3)	0.007 (3)	0.003 (3)	0.011 (3)
C4B	0.041 (4)	0.049 (4)	0.030 (3)	0.013 (3)	0.014 (3)	0.010 (3)
C5B	0.048 (4)	0.032 (3)	0.025 (3)	0.010 (3)	0.015 (3)	0.008 (3)
C6B	0.039 (4)	0.045 (4)	0.020 (3)	−0.005 (3)	0.006 (3)	−0.001 (3)
C7B	0.045 (4)	0.048 (4)	0.030 (3)	0.006 (3)	0.006 (3)	0.014 (3)
C8B	0.026 (3)	0.047 (4)	0.045 (4)	0.007 (3)	0.005 (3)	0.004 (3)
C9B	0.048 (4)	0.048 (4)	0.043 (4)	0.018 (3)	0.027 (3)	0.009 (3)
C10B	0.064 (5)	0.037 (4)	0.031 (3)	0.016 (3)	0.021 (3)	−0.002 (3)
C11B	0.062 (5)	0.029 (3)	0.027 (3)	0.010 (3)	0.015 (3)	0.006 (3)
C12B	0.036 (4)	0.022 (3)	0.033 (3)	0.008 (3)	0.012 (3)	0.005 (3)
C13B	0.077 (6)	0.072 (5)	0.029 (4)	−0.002 (5)	0.007 (4)	−0.001 (4)
C14B	0.041 (4)	0.077 (5)	0.046 (4)	0.019 (4)	0.008 (3)	0.019 (4)
C15B	0.048 (5)	0.063 (5)	0.050 (4)	−0.007 (4)	0.006 (4)	0.000 (4)
C16B	0.059 (5)	0.082 (6)	0.016 (3)	0.006 (4)	0.004 (3)	0.003 (3)
C17B	0.046 (5)	0.070 (5)	0.056 (5)	0.003 (4)	0.013 (4)	0.003 (4)
C18B	0.048 (5)	0.074 (6)	0.069 (5)	0.027 (4)	0.007 (4)	0.009 (4)
Zn1B	0.0461 (5)	0.0331 (4)	0.0349 (4)	0.0047 (4)	0.0151 (3)	0.0031 (3)
Cl2B	0.0502 (11)	0.0730 (13)	0.0405 (10)	0.0086 (10)	−0.0067 (8)	−0.0067 (9)
Cl3B	0.0425 (10)	0.0542 (11)	0.0427 (10)	0.0107 (8)	−0.0036 (8)	0.0059 (8)
Cl4B	0.117 (2)	0.0380 (11)	0.107 (2)	0.0138 (12)	0.073 (2)	0.0201 (11)
O2B	0.072 (3)	0.027 (2)	0.054 (3)	0.001 (2)	0.041 (3)	0.006 (2)

Geometric parameters (Å, º)

Co1A—O1A	1.909 (4)	Co1B—O1B	1.885 (4)
Co1A—N3A	1.983 (4)	Co1B—N3B	1.981 (4)
Co1A—N2A	2.004 (4)	Co1B—N2B	2.016 (5)
Co1A—N4A	2.006 (5)	Co1B—N1B	2.018 (4)
Co1A—N1A	2.012 (4)	Co1B—N4B	2.020 (5)
Co1A—Cl1A	2.219 (2)	Co1B—Cl1B	2.237 (2)
N1A—C11A	1.496 (7)	N1B—C10B	1.484 (7)
N1A—C10A	1.499 (7)	N1B—C11B	1.507 (7)
N1A—C1A	1.508 (7)	N1B—C1B	1.509 (8)
N2A—C4A	1.485 (7)	N2B—C4B	1.478 (7)
N2A—C3A	1.508 (7)	N2B—C3B	1.526 (8)
N2A—H1A	0.91	N2B—H1B	0.91
N3A—C6A	1.491 (8)	N3B—C5B	1.469 (7)
N3A—C5A	1.498 (7)	N3B—C6B	1.500 (7)
N3A—H2A	0.91	N3B—H2B	0.91
N4A—C9A	1.470 (7)	N4B—C9B	1.484 (7)
N4A—C8A	1.504 (8)	N4B—C8B	1.510 (8)
N4A—H3A	0.91	N4B—H3B	0.91
O1A—C12A	1.278 (7)	O1B—C12B	1.275 (6)
C1A—C2A	1.515 (8)	C1B—C2B	1.503 (9)
C1A—C13A	1.527 (8)	C1B—C13B	1.540 (8)
C1A—H4A	0.98	C1B—H4B	0.98
C2A—C3A	1.542 (8)	C2B—C3B	1.541 (8)
C2A—H5A	0.97	C2B—H5B	0.97
C2A—H6A	0.97	C2B—H6B	0.97
C3A—C15A	1.524 (9)	C3B—C14B	1.513 (9)
C3A—C14A	1.534 (8)	C3B—C15B	1.519 (9)
C4A—C5A	1.491 (9)	C4B—C5B	1.500 (8)
C4A—H7A	0.97	C4B—H7B	0.97
C4A—H8A	0.97	C4B—H8B	0.97
C5A—H9A	0.97	C5B—H9B	0.97
C5A—H10A	0.97	C5B—H10B	0.97
C6A—C7A	1.510 (9)	C6B—C7B	1.499 (9)
C6A—C16A	1.531 (8)	C6B—C16B	1.528 (7)
C6A—H11A	0.98	C6B—H11B	0.98
C7A—C8A	1.521 (9)	C7B—C8B	1.522 (8)
C7A—H12A	0.97	C7B—H12B	0.97
C7A—H13A	0.97	C7B—H13B	0.97
C8A—C17A	1.526 (10)	C8B—C17B	1.524 (9)
C8A—C18A	1.535 (10)	C8B—C18B	1.538 (9)
C9A—C10A	1.468 (8)	C9B—C10B	1.501 (9)
C9A—H14A	0.97	C9B—H14B	0.97
C9A—H15A	0.97	C9B—H15B	0.97
C10A—H16A	0.97	C10B—H16B	0.97
C10A—H17A	0.97	C10B—H17B	0.97
C11A—C12A	1.505 (8)	C11B—C12B	1.501 (8)
C11A—H18A	0.97	C11B—H18B	0.97
C11A—H19A	0.97	C11B—H19B	0.97
C12A—O2A	1.240 (7)	C12B—O2B	1.232 (7)
C13A—H20A	0.96	C13B—H20B	0.96
C13A—H21A	0.96	C13B—H21B	0.96
C13A—H22A	0.96	C13B—H22B	0.96
C14A—H23A	0.96	C14B—H23B	0.96
C14A—H24A	0.96	C14B—H24B	0.96
C14A—H25A	0.96	C14B—H25B	0.96
C15A—H26A	0.96	C15B—H26B	0.96
C15A—H27A	0.96	C15B—H27B	0.96
C15A—H28A	0.96	C15B—H28B	0.96
C16A—H29A	0.96	C16B—H29B	0.96
C16A—H30A	0.96	C16B—H30B	0.96
C16A—H31A	0.96	C16B—H31B	0.96
C17A—H32A	0.96	C17B—H32B	0.96
C17A—H33A	0.96	C17B—H33B	0.96
C17A—H34A	0.96	C17B—H34B	0.96
C18A—H35A	0.96	C18B—H35B	0.96
C18A—H36A	0.96	C18B—H36B	0.96
C18A—H37A	0.96	C18B—H37B	0.96
Zn1A—O2A	2.066 (4)	Zn1B—O2B	2.080 (4)
Zn1A—Cl4A	2.229 (2)	Zn1B—Cl4B	2.211 (2)
Zn1A—Cl2A	2.237 (2)	Zn1B—Cl2B	2.237 (2)
Zn1A—Cl3A	2.247 (2)	Zn1B—Cl3B	2.254 (2)
O1A—Co1A—N3A	90.8 (2)	O1B—Co1B—N3B	88.9 (2)
O1A—Co1A—N2A	86.2 (2)	O1B—Co1B—N2B	87.7 (2)
N3A—Co1A—N2A	85.7 (2)	N3B—Co1B—N2B	85.7 (2)
O1A—Co1A—N4A	95.5 (2)	O1B—Co1B—N1B	85.5 (2)
N3A—Co1A—N4A	93.3 (2)	N3B—Co1B—N1B	174.2 (2)
N2A—Co1A—N4A	178.0 (2)	N2B—Co1B—N1B	93.1 (2)
O1A—Co1A—N1A	86.0 (2)	O1B—Co1B—N4B	91.9 (2)
N3A—Co1A—N1A	176.6 (2)	N3B—Co1B—N4B	94.6 (2)
N2A—Co1A—N1A	95.4 (2)	N2B—Co1B—N4B	179.4 (2)
N4A—Co1A—N1A	85.8 (2)	N1B—Co1B—N4B	86.5 (2)
O1A—Co1A—Cl1A	178.3 (1)	O1B—Co1B—Cl1B	176.8 (1)
N3A—Co1A—Cl1A	88.0 (1)	N3B—Co1B—Cl1B	88.8 (1)
N2A—Co1A—Cl1A	92.6 (1)	N2B—Co1B—Cl1B	94.3 (1)
N4A—Co1A—Cl1A	85.7 (2)	N1B—Co1B—Cl1B	96.9 (1)
N1A—Co1A—Cl1A	95.2 (1)	N4B—Co1B—Cl1B	86.1 (2)
C11A—N1A—C10A	110.5 (4)	C10B—N1B—C11B	108.4 (5)
C11A—N1A—C1A	111.4 (5)	C10B—N1B—C1B	110.9 (5)
C10A—N1A—C1A	109.8 (4)	C11B—N1B—C1B	110.6 (5)
C11A—N1A—Co1A	107.3 (3)	C10B—N1B—Co1B	104.4 (4)
C10A—N1A—Co1A	104.4 (3)	C11B—N1B—Co1B	107.5 (3)
C1A—N1A—Co1A	113.1 (3)	C1B—N1B—Co1B	114.7 (4)
C4A—N2A—C3A	113.4 (4)	C4B—N2B—C3B	113.3 (5)
C4A—N2A—Co1A	106.6 (3)	C4B—N2B—Co1B	106.6 (3)
C3A—N2A—Co1A	125.4 (3)	C3B—N2B—Co1B	125.5 (4)
C4A—N2A—H1A	102.8	C4B—N2B—H1B	102.8
C3A—N2A—H1A	102.8	C3B—N2B—H1B	102.8
Co1A—N2A—H1A	102.8	Co1B—N2B—H1B	102.8
C6A—N3A—C5A	113.5 (5)	C5B—N3B—C6B	112.2 (5)
C6A—N3A—Co1A	116.9 (3)	C5B—N3B—Co1B	106.7 (3)
C5A—N3A—Co1A	107.7 (3)	C6B—N3B—Co1B	117.7 (3)
C6A—N3A—H2A	106.0	C5B—N3B—H2B	106.5
C5A—N3A—H2A	106.0	C6B—N3B—H2B	106.5
Co1A—N3A—H2A	106.0	Co1B—N3B—H2B	106.5
C9A—N4A—C8A	113.7 (5)	C9B—N4B—C8B	114.5 (5)
C9A—N4A—Co1A	108.9 (4)	C9B—N4B—Co1B	107.3 (4)
C8A—N4A—Co1A	124.8 (4)	C8B—N4B—Co1B	123.6 (4)
C9A—N4A—H3A	101.9	C9B—N4B—H3B	102.8
C8A—N4A—H3A	101.9	C8B—N4B—H3B	102.8
Co1A—N4A—H3A	101.8	Co1B—N4B—H3B	102.8
C12A—O1A—Co1A	115.5 (4)	C12B—O1B—Co1B	118.2 (4)
N1A—C1A—C2A	111.5 (5)	C2B—C1B—N1B	113.6 (5)
N1A—C1A—C13A	111.8 (5)	C2B—C1B—C13B	109.4 (6)
C2A—C1A—C13A	110.4 (5)	N1B—C1B—C13B	112.1 (6)
N1A—C1A—H4A	107.7	C2B—C1B—H4B	107.1
C2A—C1A—H4A	107.7	N1B—C1B—H4B	107.1
C13A—C1A—H4A	107.7	C13B—C1B—H4B	107.1
C1A—C2A—C3A	117.1 (5)	C1B—C2B—C3B	118.9 (5)
C1A—C2A—H5A	108.0	C1B—C2B—H5B	107.6
C3A—C2A—H5A	108.0	C3B—C2B—H5B	107.6
C1A—C2A—H6A	108.0	C1B—C2B—H6B	107.6
C3A—C2A—H6A	108.0	C3B—C2B—H6B	107.6
H5A—C2A—H6A	107.3	H5B—C2B—H6B	107.0
N2A—C3A—C15A	113.6 (5)	C14B—C3B—C15B	109.4 (6)
N2A—C3A—C14A	108.8 (5)	C14B—C3B—N2B	109.0 (5)
C15A—C3A—C14A	109.7 (5)	C15B—C3B—N2B	113.0 (5)
N2A—C3A—C2A	108.1 (5)	C14B—C3B—C2B	107.4 (5)
C15A—C3A—C2A	110.7 (5)	C15B—C3B—C2B	111.1 (6)
C14A—C3A—C2A	105.6 (5)	N2B—C3B—C2B	106.7 (5)
N2A—C4A—C5A	106.7 (5)	N2B—C4B—C5B	106.9 (5)
N2A—C4A—H7A	110.4	N2B—C4B—H7B	110.3
C5A—C4A—H7A	110.4	C5B—C4B—H7B	110.3
N2A—C4A—H8A	110.4	N2B—C4B—H8B	110.3
C5A—C4A—H8A	110.4	C5B—C4B—H8B	110.3
H7A—C4A—H8A	108.6	H7B—C4B—H8B	108.6
C4A—C5A—N3A	106.7 (5)	N3B—C5B—C4B	106.9 (5)
C4A—C5A—H9A	110.4	N3B—C5B—H9B	110.3
N3A—C5A—H9A	110.4	C4B—C5B—H9B	110.3
C4A—C5A—H10A	110.4	N3B—C5B—H10B	110.3
N3A—C5A—H10A	110.4	C4B—C5B—H10B	110.3
H9A—C5A—H10A	108.6	H9B—C5B—H10B	108.6
N3A—C6A—C7A	108.8 (5)	C7B—C6B—N3B	109.9 (5)
N3A—C6A—C16A	111.5 (5)	C7B—C6B—C16B	109.8 (5)
C7A—C6A—C16A	110.6 (6)	N3B—C6B—C16B	111.5 (5)
N3A—C6A—H11A	108.6	C7B—C6B—H11B	108.5
C7A—C6A—H11A	108.6	N3B—C6B—H11B	108.5
C16A—C6A—H11A	108.6	C16B—C6B—H11B	108.5
C6A—C7A—C8A	118.5 (6)	C6B—C7B—C8B	117.3 (5)
C6A—C7A—H12A	107.7	C6B—C7B—H12B	108.0
C8A—C7A—H12A	107.7	C8B—C7B—H12B	108.0
C6A—C7A—H13A	107.7	C6B—C7B—H13B	108.0
C8A—C7A—H13A	107.7	C8B—C7B—H13B	108.0
H12A—C7A—H13A	107.1	H12B—C7B—H13B	107.2
N4A—C8A—C7A	107.3 (5)	N4B—C8B—C7B	108.5 (5)
N4A—C8A—C17A	111.6 (6)	N4B—C8B—C17B	112.7 (5)
C7A—C8A—C17A	111.1 (6)	C7B—C8B—C17B	110.6 (6)
N4A—C8A—C18A	108.8 (6)	N4B—C8B—C18B	108.9 (5)
C7A—C8A—C18A	108.7 (6)	C7B—C8B—C18B	107.3 (6)
C17A—C8A—C18A	109.2 (6)	C17B—C8B—C18B	108.7 (6)
C10A—C9A—N4A	109.0 (5)	N4B—C9B—C10B	107.6 (5)
C10A—C9A—H14A	109.9	N4B—C9B—H14B	110.2
N4A—C9A—H14A	109.9	C10B—C9B—H14B	110.2
C10A—C9A—H15A	109.9	N4B—C9B—H15B	110.2
N4A—C9A—H15A	109.9	C10B—C9B—H15B	110.2
H14A—C9A—H15A	108.3	H14B—C9B—H15B	108.5
C9A—C10A—N1A	109.0 (5)	N1B—C10B—C9B	108.8 (5)
C9A—C10A—H16A	109.9	N1B—C10B—H16B	109.9
N1A—C10A—H16A	109.9	C9B—C10B—H16B	109.9
C9A—C10A—H17A	109.9	N1B—C10B—H17B	109.9
N1A—C10A—H17A	109.9	C9B—C10B—H17B	109.9
H16A—C10A—H17A	108.3	H16B—C10B—H17B	108.3
N1A—C11A—C12A	111.8 (5)	N1B—C11B—C12B	111.9 (5)
N1A—C11A—H18A	109.2	N1B—C11B—H18B	109.2
C12A—C11A—H18A	109.2	C12B—C11B—H18B	109.2
N1A—C11A—H19A	109.2	N1B—C11B—H19B	109.2
C12A—C11A—H19A	109.2	C12B—C11B—H19B	109.2
H18A—C11A—H19A	107.9	H18B—C11B—H19B	107.9
O2A—C12A—O1A	124.8 (6)	O2B—C12B—O1B	123.2 (5)
O2A—C12A—C11A	118.2 (6)	O2B—C12B—C11B	120.0 (5)
O1A—C12A—C11A	116.9 (5)	O1B—C12B—C11B	116.7 (5)
C1A—C13A—H20A	109.5	C1B—C13B—H20B	109.5
C1A—C13A—H21A	109.5	C1B—C13B—H21B	109.5
H20A—C13A—H21A	109.5	H20B—C13B—H21B	109.5
C1A—C13A—H22A	109.5	C1B—C13B—H22B	109.5
H20A—C13A—H22A	109.5	H20B—C13B—H22B	109.5
H21A—C13A—H22A	109.5	H21B—C13B—H22B	109.5
C3A—C14A—H23A	109.5	C3B—C14B—H23B	109.5
C3A—C14A—H24A	109.5	C3B—C14B—H24B	109.5
H23A—C14A—H24A	109.5	H23B—C14B—H24B	109.5
C3A—C14A—H25A	109.5	C3B—C14B—H25B	109.5
H23A—C14A—H25A	109.5	H23B—C14B—H25B	109.5
H24A—C14A—H25A	109.5	H24B—C14B—H25B	109.5
C3A—C15A—H26A	109.5	C3B—C15B—H26B	109.5
C3A—C15A—H27A	109.5	C3B—C15B—H27B	109.5
H26A—C15A—H27A	109.5	H26B—C15B—H27B	109.5
C3A—C15A—H28A	109.5	C3B—C15B—H28B	109.5
H26A—C15A—H28A	109.5	H26B—C15B—H28B	109.5
H27A—C15A—H28A	109.5	H27B—C15B—H28B	109.5
C6A—C16A—H29A	109.5	C6B—C16B—H29B	109.5
C6A—C16A—H30A	109.5	C6B—C16B—H30B	109.5
H29A—C16A—H30A	109.5	H29B—C16B—H30B	109.5
C6A—C16A—H31A	109.5	C6B—C16B—H31B	109.5
H29A—C16A—H31A	109.5	H29B—C16B—H31B	109.5
H30A—C16A—H31A	109.5	H30B—C16B—H31B	109.5
C8A—C17A—H32A	109.5	C8B—C17B—H32B	109.5
C8A—C17A—H33A	109.5	C8B—C17B—H33B	109.5
H32A—C17A—H33A	109.5	H32B—C17B—H33B	109.5
C8A—C17A—H34A	109.5	C8B—C17B—H34B	109.5
H32A—C17A—H34A	109.5	H32B—C17B—H34B	109.5
H33A—C17A—H34A	109.5	H33B—C17B—H34B	109.5
C8A—C18A—H35A	109.5	C8B—C18B—H35B	109.5
C8A—C18A—H36A	109.5	C8B—C18B—H36B	109.5
H35A—C18A—H36A	109.5	H35B—C18B—H36B	109.5
C8A—C18A—H37A	109.5	C8B—C18B—H37B	109.5
H35A—C18A—H37A	109.5	H35B—C18B—H37B	109.5
H36A—C18A—H37A	109.5	H36B—C18B—H37B	109.5
O2A—Zn1A—Cl4A	104.8 (2)	O2B—Zn1B—Cl4B	99.7 (1)
O2A—Zn1A—Cl2A	103.8 (1)	O2B—Zn1B—Cl2B	114.6 (1)
Cl4A—Zn1A—Cl2A	114.4 (1)	Cl4B—Zn1B—Cl2B	116.7 (1)
O2A—Zn1A—Cl3A	103.3 (1)	O2B—Zn1B—Cl3B	98.8 (1)
Cl4A—Zn1A—Cl3A	120.0 (1)	Cl4B—Zn1B—Cl3B	116.8 (1)
Cl2A—Zn1A—Cl3A	108.6 (1)	Cl2B—Zn1B—Cl3B	108.7 (1)
C12A—O2A—Zn1A	126.5 (4)	C12B—O2B—Zn1B	113.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H1A···CL3A	0.91	2.53	3.406 (5)	160
N3A—H2A···CL2B	0.91	2.88	3.608 (5)	138
N3A—H2A···CL1A	0.91	2.54	2.923 (5)	106
N4A—H3A···CL1A	0.91	2.43	2.878 (5)	111
N2B—H1B···CL3B	0.91	2.53	3.420 (5)	167
N3B—H2B···CL1B	0.91	2.58	2.957 (5)	105
N3B—H2B···CL3A^i	0.91	2.73	3.454 (5)	137
N4B—H3B···CL4B^i	0.91	2.87	3.599 (5)	139
N4B—H3B···CL1B	0.91	2.47	2.911 (5)	110

Symmetry code: (i) x, y+1, z.