Crystal structure of trans-di-fluoridotetra-kis(pyridine-κN)chromium(III) tri-chlorido-(pyridine-κN)zincate monohydrate from synchrotron data.

In the asymmetric unit of the title compound, [CrF2(C5H5N)4][ZnCl3(C5H5N)]·H2O, there are two independent complex cations, one tri-chlorido-(pyridine-κN)zincate anion and one solvent water mol-ecule. The cations lie on inversion centers. The Cr(III) ions are coordinated by four pyridine (py) N atoms in the equatorial plane and two F atoms in a trans axial arrangement, displaying a slightly distorted octa-hedral geometry. The Cr-N(py) bond lengths are in the range 2.0873 (14) to 2.0926 (17) Å while the Cr-F bond lengths are 1.8609 (10) and 1.8645 (10) Å. The [ZnCl3(C5H5N)](-) anion has a distorted tetra-hedral geometry. The Cl atoms of the anion were refined as disordered over two sets of sites in a 0.631 (9):0.369 (9) ratio. In the crystal, two anions and two water mol-ecules are linked via O-H⋯Cl hydrogen bonds, forming centrosymmetric aggregates. In addition, weak C-H⋯Cl, C-H⋯π and π-π stacking inter-actions [centroid-centroid distances = 3.712 (2) and 3.780 (2)Å] link the components of the structure into a three-dimensional network.

Chemical context

Anionic species play very important roles in chemistry, medicine, catalysis, mol­ecular assembly, biology and environmental processes, yet their binding characteristics have not received much recognition (Martínez-Máñez & Sancenón, 2003 ▶; Fabbrizzi & Poggi, 2013 ▶). The study of the effect of anions and geometric isomers in octa­hedral metal complexes may be expected to yield a great variety of new structures and properties of both chemical and biological significance. Octa­hedral CrIII complexes and their 3d–4f clusters containing lanthanides revealing paramagnetic features are of great importance for the development of new mol­ecule-based magnets and solid-state laser materials (Powell, 1998 ▶; Dreiser et al., 2012 ▶; Singh et al., 2013 ▶). We are therefore inter­ested in the preparation, crystal structures and spectroscopic properties of chromium(III) complexes containing mixed various ligands (Choi, 2000a ▶,b ▶; Choi et al., 2004 ▶, 2006 ▶; Choi & Moon, 2014 ▶).

Here we report the structure of [CrF2(py)4][ZnCl3(py)]·H2O, where py is the pyridine (C5H5N), in order to establish the exact arrangement of four py mol­ecules, two F atoms, counter-anion and water mol­ecule. This is another example of a trans-[CrF2(py)4]+ structure but with a different counter-anion system (Fochi et al., 1991 ▶; Moon & Choi, 2013 ▶; Moon et al., 2014 ▶; Singh et al., 2013 ▶).

Structural commentary

In the mol­ecular structure, there are two independent CrIII complex cations in which the four nitro­gen atoms of four py ligands occupy the equatorial sites and the two F atoms coordinate to the Cr atom in a trans configuration. An ellipsoid plot of one independent complex cation, the unique ZnCl3(py)− anion and one water mol­ecule in the title compound is shown in Fig. 1 ▶.

Figure 1

The mol­ecular structure of the title compound showing 50% probability displacement ellipsoids. Only one of the independent cations is shown. The minor disorder component of the anion is not shown. The primed atoms are related by the symmetry code (−x, −y + 1, −z).

The Cr—N(py) bond lengths range from 2.0873 (14) to 2.0926 (17) Å and the Cr—F bond lengths are 1.8609 (10) and 1.8645 (10) Å (Table 1 ▶). These Cr—N(py) and Cr—F bond lengths are in good agreement with those observed in trans-[CrF2(py)4]PF6, trans-[CrF2(py)4]ClO4, trans-[CrF2(py)4]2NaClO4 and trans-[CrF2(py)4][Cr(py)4F(μ-F)Li(H2O)3][Cr(py)4F(μ-F)Li(H2O)4]Cl5·6H2O (Fochi et al., 1991 ▶; Moon & Choi, 2013 ▶; Moon et al., 2014 ▶; Birk et al., 2010 ▶). The Cr—F bond lengths are also similar to the values found in trans-[Cr(15aneN4)F2]ClO4 (15aneN4 = 1,4,8,12-tetraaza­cyclo­penta­decane) and trans-[Cr(2,2,3-tet)F2]ClO4 (2,2,3-tet = 1,4,7,11-tetraazaundecane) (Choi et al., 2006 ▶; Choi & Moon, 2014 ▶). However, the Cr—F bond lengths are somewhat shorter than those found for bridging fluorides [1.9045 (14)–1.9145 (14) Å; Dreiser et al., 2012 ▶).

Table 1

Selected bond lengths ()

Cr1AF1A	1.8645(10)	Cr2BN1B	2.0916(15)
Cr1AN2A	2.0873(14)	Zn1CN1C	2.0752(16)
Cr1AN1A	2.0926(17)	Zn1CCl2C	2.188(2)
Cr2BF1B	1.8609(10)	Zn1CCl3C	2.302(2)
Cr2BN2B	2.0886(17)	Zn1CCl1C	2.303(8)

The [ZnCl3(py)]− anion and uncoordinating water mol­ecule remain outside the coordination sphere. In the counter-anion, the ZnII ion is in a distorted tetra­hedral environment, coordinated by one N atom of the py ligand and by three Cl atoms. The Cl atoms of the anion were refined as disordered over two sets of sites in a 0.631 (9):0.369 (9) ratio (Fig. 2 ▶). The Zn—Cl distances, ranging from 2.126 (14) to 2.360 (2) Å, and the Zn—N(py) distance of 2.075 (2) Å are in agreement with those found in the anion of [Cr(acacen)(py)2][ZnCl3(py)] [acacen = N,N′-ethylenebis(acetylacetoneiminato)] (Toscano et al., 1994 ▶). The mean Cl—Zn—Cl angle of 115.22° is larger than the corresponding tetra­hedral angle and the mean Cl—Zn—N angle of 105.45 (10)°. The charge of the tri­chlorido­(pyridine)­zincate anion is counter-balanced by two half trans-[CrF2(py)4]+ cations. The complex cations lie on inversion centers and therefore the cations have exact mol­ecular C symmetry.

Figure 2

The mol­ecular structure of the anion. The minor disorder component is shown with dashed lines.

Supra­molecular features

In the crystal, two anions and two water mol­ecules are linked via O—H⋯Cl hydrogen bonds, forming centrosymmetric aggregates with (12) rings (Fig. 3 ▶). In addition, weak C—H⋯Cl (Table 2 ▶), C—H⋯π (Table 3 ▶) and π–π stacking inter­actions link the components of the structure into a three-dimensional network. The centroid–centroid distances of the π–π stacking inter­actions are Cg1⋯Cg2(−1 + x, y, z) = 3.712 (2) and Cg3⋯Cg4 3.780 (2) Å, Where Cg1, Cg2, Cg3 and Cg4 are the centroids defined by ring atoms N1A/C1A–C5A, N1C/C1C–C5C, N2B/C6B–C10B and N2A/C6A–C10A, respectively.

Figure 3

Part of the crystal structure with hydrogen bonds shown as dashed lines.

Table 2

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1WH1O1Cl2C i	0.86(1)	2.41(2)	3.263(6)	173(8)
O1WH2O1Cl3C ii	0.86(1)	2.48(4)	3.281(5)	157(8)
O1WH2O1Cl4C ii	0.86(1)	2.22(2)	3.053(6)	165(8)
C2BH2BCl3C	0.95	2.81	3.749(4)	170
C3BH3BCl3C ii	0.95	2.82	3.511(3)	130
C3CH3CCl2C iii	0.95	2.71	3.627(4)	162
C4AH4ACl1C iv	0.95	2.82	3.717(8)	158
C10AH10ACl3C v	0.95	2.86	3.617(4)	137
C10BH10BCl1C vi	0.95	2.73	3.534(9)	142

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Table 4

Experimental details

Crystal data
Chemical formula	[CrF2(C5H5N)4][ZnCl3(C5H5N)]H2O
M r	675.23
Crystal system, space group	Triclinic, P
Temperature (K)	100
a, b, c ()	9.1350(18), 12.852(3), 13.607(3)
, , ()	103.69(3), 105.07(3), 101.25(3)
V (3)	1441.6(6)
Z	2
Radiation type	Synchrotron, = 0.62998
(mm1)	1.09
Crystal size (mm)	0.10 0.02 0.02
Data collection
Diffractometer	ADSC Q210 CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski Minor, 1997 ▶)
T min, T max	0.899, 0.978
No. of measured, independent and observed [I > 2(I)] reflections	15474, 7929, 7758
R int	0.023
(sin /)max (1)	0.696
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.037, 0.100, 1.03
No. of reflections	7929
No. of parameters	380
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
max, min (e 3)	0.74, 0.85

Computer programs: PAL ADSC Quantum-210 ADX Software (Arvai Nielsen, 1983 ▶), HKL3000sm (Otwinowski Minor, 1997 ▶), SHELXS2014 and SHELXL2014 (Sheldrick, 2008 ▶), DIAMOND (Brandenburg, 2007 ▶), Mercury (Macrae et al., 2006 ▶). PLATON (Spek, 2009 ▶), WinGX (Farrugia, 2012 ▶) and publCIF (Westrip, 2010 ▶).

Synthesis and crystallization

All chemicals were reagent grade materials and used without further purification. The starting material, trans-[CrF2(py)4]ClO4 was prepared according to the literature (Glerup et al., 1970 ▶). The crude trans-[CrF2(py)4]ClO4 (0.2 g) was dissolved in 10 mL water. The 10 mL solution of 1M HCl and 0.5 g of ZnCl2 were added to this solution. The mixture was refluxed at 328 K for 30 min and then cooled to room temperature. The crystalline product which formed was filtered, washed with cold 2-propanol and diethyl ether. Recrystallization from a hot aqueous solution of the title compound yielded purple crystals suitable for X-ray structure analysis.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▶. C–bound H–atoms were placed in calculated positions (C—H = 0.95 Å) and were included in the refinement in the riding-model approximation with U iso(H) set to 1.2U eq(C). The hydrogen atoms of the solvent water mol­ecule were refined with U iso(H) set to 1.5 U eq(O) and geometrically restrained to O—H = 0.86 (1) and H⋯H 1.34 (2) Å. The Cl atoms of the anion were refined as disordered over two sets of sites with refined occupancies of 0.631 (9) and 0.369 (9), respectively.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681402145X/lh5726sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402145X/lh5726Isup2.hkl

CCDC reference: 1026562

Additional supporting information: crystallographic information; 3D view; checkCIF report

[CrF2(C5H5N)4][ZnCl3(C5H5N)]·H2O	Z = 2
Mr = 675.23	F(000) = 686
Triclinic, P1	Dx = 1.556 Mg m−3
a = 9.1350 (18) Å	Synchrotron radiation, λ = 0.62998 Å
b = 12.852 (3) Å	Cell parameters from 70974 reflections
c = 13.607 (3) Å	θ = 0.4–33.6°
α = 103.69 (3)°	µ = 1.09 mm−1
β = 105.07 (3)°	T = 100 K
γ = 101.25 (3)°	Rod, purple
V = 1441.6 (6) Å3	0.10 × 0.02 × 0.02 mm

ADSC Q210 CCD area-detector diffractometer	7758 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.023
ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements) (HKL3000smSCALEPACK; Otwinowski & Minor, 1997)	h = −12→12
Tmin = 0.899, Tmax = 0.978	k = −17→17
15474 measured reflections	l = −18→18
7929 independent reflections

Refinement on F2	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0457P)2 + 1.3104P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
7929 reflections	Δρmax = 0.74 e Å−3
380 parameters	Δρmin = −0.85 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cr1A	0.0000	0.5000	0.0000	0.01952 (8)
F1A	0.20948 (11)	0.50546 (9)	0.01167 (8)	0.02511 (19)
N1A	0.07291 (16)	0.61748 (11)	0.15115 (11)	0.0222 (2)
N2A	−0.01489 (17)	0.36975 (11)	0.06719 (11)	0.0225 (3)
C1A	0.2264 (2)	0.67086 (14)	0.20341 (14)	0.0270 (3)
H1A	0.3020	0.6555	0.1696	0.032*
C2A	0.2784 (2)	0.74746 (16)	0.30481 (15)	0.0319 (4)
H2A	0.3875	0.7835	0.3395	0.038*
C3A	0.1682 (2)	0.77060 (15)	0.35485 (15)	0.0317 (4)
H3A	0.2009	0.8216	0.4246	0.038*
C4A	0.0096 (2)	0.71743 (15)	0.30051 (15)	0.0308 (4)
H4A	−0.0683	0.7325	0.3322	0.037*
C5A	−0.0336 (2)	0.64231 (15)	0.19958 (15)	0.0267 (3)
H5A	−0.1423	0.6067	0.1627	0.032*
C6A	0.1138 (2)	0.34067 (16)	0.11190 (17)	0.0340 (4)
H6A	0.2137	0.3811	0.1135	0.041*
C7A	0.1058 (3)	0.25331 (17)	0.15599 (19)	0.0419 (5)
H7A	0.1989	0.2343	0.1867	0.050*
C8A	−0.0382 (3)	0.19486 (16)	0.15455 (16)	0.0369 (4)
H8A	−0.0458	0.1355	0.1850	0.044*
C9A	−0.1710 (3)	0.22358 (17)	0.10840 (19)	0.0382 (4)
H9A	−0.2719	0.1841	0.1060	0.046*
C10A	−0.1550 (2)	0.31122 (15)	0.06538 (17)	0.0308 (4)
H10A	−0.2471	0.3306	0.0333	0.037*
Cr2B	0.5000	0.5000	0.5000	0.02188 (8)
F1B	0.47526 (13)	0.63979 (8)	0.49752 (9)	0.0287 (2)
N1B	0.51583 (17)	0.46810 (12)	0.34563 (11)	0.0250 (3)
N2B	0.25547 (17)	0.43358 (11)	0.44125 (11)	0.0233 (3)
C1B	0.5327 (2)	0.55046 (16)	0.30013 (15)	0.0305 (3)
H1B	0.5344	0.6229	0.3389	0.037*
C2B	0.5478 (2)	0.5336 (2)	0.19893 (16)	0.0366 (4)
H2B	0.5610	0.5936	0.1696	0.044*
C3B	0.5431 (3)	0.4285 (2)	0.14199 (17)	0.0436 (5)
H3B	0.5516	0.4147	0.0722	0.052*
C4B	0.5259 (3)	0.3428 (2)	0.18750 (17)	0.0409 (5)
H4B	0.5223	0.2697	0.1493	0.049*
C5B	0.5140 (2)	0.36571 (16)	0.29025 (15)	0.0296 (3)
H5B	0.5044	0.3074	0.3220	0.035*
C6B	0.1601 (2)	0.49004 (14)	0.39770 (14)	0.0268 (3)
H6B	0.2060	0.5583	0.3880	0.032*
C7B	−0.0021 (2)	0.45198 (16)	0.36673 (15)	0.0311 (4)
H7B	−0.0664	0.4930	0.3353	0.037*
C8B	−0.0704 (2)	0.35292 (16)	0.38210 (15)	0.0314 (3)
H8B	−0.1816	0.3259	0.3625	0.038*
C9B	0.0272 (2)	0.29453 (15)	0.42650 (14)	0.0286 (3)
H9B	−0.0163	0.2266	0.4377	0.034*
C10B	0.1885 (2)	0.33643 (14)	0.45424 (13)	0.0261 (3)
H10B	0.2549	0.2954	0.4835	0.031*
Zn1C	0.70830 (2)	0.92169 (2)	0.25840 (2)	0.02919 (7)	0.631 (9)
Cl1C	0.7295 (8)	0.8517 (6)	0.4009 (5)	0.0297 (5)	0.631 (9)
Cl2C	0.6522 (2)	1.0811 (2)	0.2693 (4)	0.0462 (7)	0.631 (9)
Cl3C	0.5638 (4)	0.7835 (3)	0.10101 (11)	0.0511 (8)	0.631 (9)
Zn2C	0.70830 (2)	0.92169 (2)	0.25840 (2)	0.02919 (7)	0.369 (9)
Cl4C	0.5292 (3)	0.8210 (4)	0.10518 (17)	0.0433 (6)	0.369 (9)
Cl5C	0.6694 (3)	1.09905 (17)	0.3178 (5)	0.0361 (6)	0.369 (9)
Cl6C	0.7250 (16)	0.8618 (11)	0.3926 (10)	0.0352 (17)	0.369 (9)
N1C	0.93153 (18)	0.94763 (12)	0.24287 (12)	0.0262 (3)
C1C	1.0575 (2)	1.00830 (14)	0.32876 (14)	0.0276 (3)
H1C	1.0421	1.0336	0.3958	0.033*
C2C	1.2089 (2)	1.03503 (17)	0.32268 (18)	0.0360 (4)
H2C	1.2954	1.0788	0.3843	0.043*
C3C	1.2318 (3)	0.9969 (2)	0.2255 (2)	0.0457 (5)
H3C	1.3343	1.0140	0.2193	0.055*
C4C	1.1034 (3)	0.9336 (2)	0.1378 (2)	0.0464 (5)
H4C	1.1165	0.9061	0.0703	0.056*
C5C	0.9552 (3)	0.91061 (17)	0.14915 (16)	0.0361 (4)
H5C	0.8673	0.8671	0.0884	0.043*
O1W	0.3884 (7)	0.0474 (5)	0.0419 (4)	0.162 (2)
H1O1	0.462 (7)	0.063 (8)	0.102 (4)	0.243*
H2O1	0.429 (10)	0.090 (7)	0.010 (6)	0.243*

	U11	U22	U33	U12	U13	U23
Cr1A	0.01680 (15)	0.02073 (16)	0.02493 (17)	0.00694 (12)	0.00807 (12)	0.01100 (13)
F1A	0.0185 (4)	0.0295 (5)	0.0311 (5)	0.0090 (4)	0.0093 (4)	0.0126 (4)
N1A	0.0219 (6)	0.0222 (6)	0.0271 (6)	0.0082 (5)	0.0095 (5)	0.0120 (5)
N2A	0.0243 (6)	0.0208 (6)	0.0243 (6)	0.0069 (5)	0.0080 (5)	0.0097 (5)
C1A	0.0248 (7)	0.0265 (7)	0.0303 (8)	0.0063 (6)	0.0093 (6)	0.0097 (6)
C2A	0.0319 (9)	0.0298 (8)	0.0311 (8)	0.0055 (7)	0.0078 (7)	0.0092 (7)
C3A	0.0411 (10)	0.0266 (8)	0.0298 (8)	0.0119 (7)	0.0122 (7)	0.0097 (6)
C4A	0.0378 (9)	0.0295 (8)	0.0341 (9)	0.0154 (7)	0.0181 (7)	0.0133 (7)
C5A	0.0266 (8)	0.0279 (8)	0.0322 (8)	0.0109 (6)	0.0136 (6)	0.0134 (6)
C6A	0.0260 (8)	0.0279 (8)	0.0444 (10)	0.0051 (6)	−0.0001 (7)	0.0185 (8)
C7A	0.0402 (11)	0.0300 (9)	0.0489 (12)	0.0064 (8)	−0.0034 (9)	0.0221 (9)
C8A	0.0562 (12)	0.0236 (8)	0.0344 (9)	0.0103 (8)	0.0147 (9)	0.0154 (7)
C9A	0.0481 (11)	0.0292 (9)	0.0552 (12)	0.0151 (8)	0.0344 (10)	0.0218 (9)
C10A	0.0311 (9)	0.0274 (8)	0.0450 (10)	0.0122 (7)	0.0214 (8)	0.0178 (7)
Cr2B	0.02634 (18)	0.01837 (16)	0.02080 (16)	0.00761 (13)	0.00498 (13)	0.00737 (12)
F1B	0.0342 (5)	0.0205 (4)	0.0322 (5)	0.0106 (4)	0.0076 (4)	0.0103 (4)
N1B	0.0231 (6)	0.0271 (7)	0.0233 (6)	0.0069 (5)	0.0048 (5)	0.0078 (5)
N2B	0.0278 (7)	0.0215 (6)	0.0202 (6)	0.0080 (5)	0.0055 (5)	0.0069 (5)
C1B	0.0281 (8)	0.0344 (9)	0.0282 (8)	0.0065 (7)	0.0053 (6)	0.0139 (7)
C2B	0.0253 (8)	0.0593 (13)	0.0329 (9)	0.0142 (8)	0.0112 (7)	0.0242 (9)
C3B	0.0354 (10)	0.0760 (16)	0.0312 (9)	0.0296 (11)	0.0167 (8)	0.0193 (10)
C4B	0.0379 (10)	0.0554 (13)	0.0323 (9)	0.0260 (10)	0.0134 (8)	0.0056 (9)
C5B	0.0251 (8)	0.0331 (8)	0.0292 (8)	0.0125 (7)	0.0068 (6)	0.0054 (7)
C6B	0.0323 (8)	0.0248 (7)	0.0255 (7)	0.0105 (6)	0.0080 (6)	0.0107 (6)
C7B	0.0324 (9)	0.0301 (8)	0.0333 (9)	0.0142 (7)	0.0078 (7)	0.0127 (7)
C8B	0.0285 (8)	0.0322 (9)	0.0331 (9)	0.0098 (7)	0.0082 (7)	0.0100 (7)
C9B	0.0320 (8)	0.0257 (7)	0.0274 (8)	0.0068 (6)	0.0076 (6)	0.0098 (6)
C10B	0.0311 (8)	0.0230 (7)	0.0231 (7)	0.0077 (6)	0.0053 (6)	0.0085 (6)
Zn1C	0.02382 (11)	0.02802 (11)	0.02942 (11)	−0.00267 (8)	−0.00014 (8)	0.01480 (8)
Cl1C	0.0301 (9)	0.0387 (8)	0.0288 (11)	0.0119 (8)	0.0107 (8)	0.0223 (11)
Cl2C	0.0305 (5)	0.0382 (8)	0.0857 (19)	0.0136 (5)	0.0246 (8)	0.0373 (11)
Cl3C	0.0450 (9)	0.0514 (12)	0.0299 (4)	−0.0202 (8)	−0.0006 (5)	0.0047 (5)
Zn2C	0.02382 (11)	0.02802 (11)	0.02942 (11)	−0.00267 (8)	−0.00014 (8)	0.01480 (8)
Cl4C	0.0341 (8)	0.0450 (13)	0.0311 (7)	0.0061 (9)	−0.0027 (6)	−0.0056 (7)
Cl5C	0.0309 (7)	0.0232 (6)	0.0530 (17)	0.0075 (5)	0.0144 (9)	0.0085 (8)
Cl6C	0.0364 (14)	0.052 (3)	0.0316 (16)	0.0196 (15)	0.0127 (10)	0.0318 (12)
N1C	0.0300 (7)	0.0211 (6)	0.0262 (7)	0.0052 (5)	0.0065 (5)	0.0089 (5)
C1C	0.0289 (8)	0.0231 (7)	0.0294 (8)	0.0080 (6)	0.0065 (6)	0.0079 (6)
C2C	0.0280 (9)	0.0355 (9)	0.0433 (10)	0.0103 (7)	0.0076 (8)	0.0130 (8)
C3C	0.0380 (11)	0.0567 (14)	0.0553 (13)	0.0235 (10)	0.0237 (10)	0.0222 (11)
C4C	0.0554 (14)	0.0520 (13)	0.0419 (11)	0.0256 (11)	0.0259 (10)	0.0124 (10)
C5C	0.0448 (11)	0.0312 (9)	0.0296 (9)	0.0108 (8)	0.0101 (8)	0.0061 (7)
O1W	0.193 (5)	0.152 (4)	0.114 (3)	−0.015 (3)	0.014 (3)	0.079 (3)

Cr1A—F1Ai	1.8645 (10)	C1B—H1B	0.9500
Cr1A—F1A	1.8645 (10)	C2B—C3B	1.375 (4)
Cr1A—N2Ai	2.0873 (14)	C2B—H2B	0.9500
Cr1A—N2A	2.0873 (14)	C3B—C4B	1.388 (4)
Cr1A—N1Ai	2.0926 (17)	C3B—H3B	0.9500
Cr1A—N1A	2.0926 (17)	C4B—C5B	1.396 (3)
N1A—C1A	1.348 (2)	C4B—H4B	0.9500
N1A—C5A	1.355 (2)	C5B—H5B	0.9500
N2A—C6A	1.341 (2)	C6B—C7B	1.381 (3)
N2A—C10A	1.343 (2)	C6B—H6B	0.9500
C1A—C2A	1.390 (3)	C7B—C8B	1.392 (3)
C1A—H1A	0.9500	C7B—H7B	0.9500
C2A—C3A	1.394 (3)	C8B—C9B	1.385 (3)
C2A—H2A	0.9500	C8B—H8B	0.9500
C3A—C4A	1.390 (3)	C9B—C10B	1.382 (3)
C3A—H3A	0.9500	C9B—H9B	0.9500
C4A—C5A	1.384 (3)	C10B—H10B	0.9500
C4A—H4A	0.9500	Zn1C—N1C	2.0752 (16)
C5A—H5A	0.9500	Zn1C—Cl2C	2.188 (2)
C6A—C7A	1.391 (3)	Zn1C—Cl3C	2.302 (2)
C6A—H6A	0.9500	Zn1C—Cl1C	2.303 (8)
C7A—C8A	1.374 (3)	Zn2C—N1C	2.0752 (16)
C7A—H7A	0.9500	Zn2C—Cl6C	2.126 (14)
C8A—C9A	1.375 (3)	Zn2C—Cl4C	2.196 (2)
C8A—H8A	0.9500	Zn2C—Cl5C	2.360 (2)
C9A—C10A	1.387 (3)	N1C—C5C	1.340 (2)
C9A—H9A	0.9500	N1C—C1C	1.348 (2)
C10A—H10A	0.9500	C1C—C2C	1.387 (3)
Cr2B—F1B	1.8609 (10)	C1C—H1C	0.9500
Cr2B—F1Bii	1.8609 (10)	C2C—C3C	1.381 (3)
Cr2B—N2Bii	2.0885 (17)	C2C—H2C	0.9500
Cr2B—N2B	2.0886 (17)	C3C—C4C	1.379 (4)
Cr2B—N1B	2.0916 (15)	C3C—H3C	0.9500
Cr2B—N1Bii	2.0916 (15)	C4C—C5C	1.385 (3)
N1B—C5B	1.347 (2)	C4C—H4C	0.9500
N1B—C1B	1.350 (2)	C5C—H5C	0.9500
N2B—C6B	1.349 (2)	O1W—H1O1	0.862 (10)
N2B—C10B	1.352 (2)	O1W—H2O1	0.855 (10)
C1B—C2B	1.389 (3)
F1Ai—Cr1A—F1A	180.0	C1B—N1B—Cr2B	120.77 (13)
F1Ai—Cr1A—N2Ai	90.11 (6)	C6B—N2B—C10B	118.27 (16)
F1A—Cr1A—N2Ai	89.89 (6)	C6B—N2B—Cr2B	121.31 (12)
F1Ai—Cr1A—N2A	89.89 (6)	C10B—N2B—Cr2B	120.20 (12)
F1A—Cr1A—N2A	90.11 (6)	N1B—C1B—C2B	122.68 (19)
N2Ai—Cr1A—N2A	180.0	N1B—C1B—H1B	118.7
F1Ai—Cr1A—N1Ai	90.10 (6)	C2B—C1B—H1B	118.7
F1A—Cr1A—N1Ai	89.90 (6)	C3B—C2B—C1B	118.8 (2)
N2Ai—Cr1A—N1Ai	91.02 (6)	C3B—C2B—H2B	120.6
N2A—Cr1A—N1Ai	88.98 (6)	C1B—C2B—H2B	120.6
F1Ai—Cr1A—N1A	89.90 (6)	C2B—C3B—C4B	119.32 (19)
F1A—Cr1A—N1A	90.10 (6)	C2B—C3B—H3B	120.3
N2Ai—Cr1A—N1A	88.98 (6)	C4B—C3B—H3B	120.3
N2A—Cr1A—N1A	91.02 (6)	C3B—C4B—C5B	119.0 (2)
N1Ai—Cr1A—N1A	180.0	C3B—C4B—H4B	120.5
C1A—N1A—C5A	117.88 (15)	C5B—C4B—H4B	120.5
C1A—N1A—Cr1A	121.38 (12)	N1B—C5B—C4B	121.85 (19)
C5A—N1A—Cr1A	120.73 (12)	N1B—C5B—H5B	119.1
C6A—N2A—C10A	117.91 (15)	C4B—C5B—H5B	119.1
C6A—N2A—Cr1A	121.44 (12)	N2B—C6B—C7B	122.20 (16)
C10A—N2A—Cr1A	120.64 (12)	N2B—C6B—H6B	118.9
N1A—C1A—C2A	122.59 (17)	C7B—C6B—H6B	118.9
N1A—C1A—H1A	118.7	C6B—C7B—C8B	119.28 (17)
C2A—C1A—H1A	118.7	C6B—C7B—H7B	120.4
C1A—C2A—C3A	119.05 (18)	C8B—C7B—H7B	120.4
C1A—C2A—H2A	120.5	C9B—C8B—C7B	118.69 (18)
C3A—C2A—H2A	120.5	C9B—C8B—H8B	120.7
C4A—C3A—C2A	118.61 (18)	C7B—C8B—H8B	120.7
C4A—C3A—H3A	120.7	C10B—C9B—C8B	119.09 (17)
C2A—C3A—H3A	120.7	C10B—C9B—H9B	120.5
C5A—C4A—C3A	119.13 (17)	C8B—C9B—H9B	120.5
C5A—C4A—H4A	120.4	N2B—C10B—C9B	122.45 (16)
C3A—C4A—H4A	120.4	N2B—C10B—H10B	118.8
N1A—C5A—C4A	122.72 (17)	C9B—C10B—H10B	118.8
N1A—C5A—H5A	118.6	N1C—Zn1C—Cl2C	105.20 (6)
C4A—C5A—H5A	118.6	N1C—Zn1C—Cl3C	100.81 (11)
N2A—C6A—C7A	122.21 (19)	Cl2C—Zn1C—Cl3C	114.17 (7)
N2A—C6A—H6A	118.9	N1C—Zn1C—Cl1C	104.3 (2)
C7A—C6A—H6A	118.9	Cl2C—Zn1C—Cl1C	119.5 (2)
C8A—C7A—C6A	119.26 (19)	Cl3C—Zn1C—Cl1C	110.34 (17)
C8A—C7A—H7A	120.4	N1C—Zn2C—Cl6C	105.5 (4)
C6A—C7A—H7A	120.4	N1C—Zn2C—Cl4C	110.44 (9)
C7A—C8A—C9A	119.03 (17)	Cl6C—Zn2C—Cl4C	118.5 (3)
C7A—C8A—H8A	120.5	N1C—Zn2C—Cl5C	106.82 (8)
C9A—C8A—H8A	120.5	Cl6C—Zn2C—Cl5C	103.3 (4)
C8A—C9A—C10A	118.84 (19)	Cl4C—Zn2C—Cl5C	111.42 (9)
C8A—C9A—H9A	120.6	C5C—N1C—C1C	118.27 (17)
C10A—C9A—H9A	120.6	C5C—N1C—Zn1C	122.44 (14)
N2A—C10A—C9A	122.74 (18)	C1C—N1C—Zn1C	119.22 (13)
N2A—C10A—H10A	118.6	C5C—N1C—Zn2C	122.44 (14)
C9A—C10A—H10A	118.6	C1C—N1C—Zn2C	119.22 (13)
F1B—Cr2B—F1Bii	180.0	N1C—C1C—C2C	122.33 (18)
F1B—Cr2B—N2Bii	90.15 (6)	N1C—C1C—H1C	118.8
F1Bii—Cr2B—N2Bii	89.85 (6)	C2C—C1C—H1C	118.8
F1B—Cr2B—N2B	89.85 (6)	C3C—C2C—C1C	118.9 (2)
F1Bii—Cr2B—N2B	90.15 (6)	C3C—C2C—H2C	120.6
N2Bii—Cr2B—N2B	180.00 (4)	C1C—C2C—H2C	120.6
F1B—Cr2B—N1B	90.00 (6)	C4C—C3C—C2C	118.9 (2)
F1Bii—Cr2B—N1B	90.01 (6)	C4C—C3C—H3C	120.5
N2Bii—Cr2B—N1B	88.16 (6)	C2C—C3C—H3C	120.5
N2B—Cr2B—N1B	91.84 (6)	C3C—C4C—C5C	119.3 (2)
F1B—Cr2B—N1Bii	90.00 (6)	C3C—C4C—H4C	120.4
F1Bii—Cr2B—N1Bii	90.00 (6)	C5C—C4C—H4C	120.4
N2Bii—Cr2B—N1Bii	91.84 (6)	N1C—C5C—C4C	122.3 (2)
N2B—Cr2B—N1Bii	88.16 (7)	N1C—C5C—H5C	118.9
N1B—Cr2B—N1Bii	180.0	C4C—C5C—H5C	118.9
C5B—N1B—C1B	118.29 (16)	H1O1—O1W—H2O1	104 (2)
C5B—N1B—Cr2B	120.92 (13)
C5A—N1A—C1A—C2A	1.5 (2)	C1B—N1B—C5B—C4B	−1.3 (3)
Cr1A—N1A—C1A—C2A	−178.56 (13)	Cr2B—N1B—C5B—C4B	−179.40 (15)
N1A—C1A—C2A—C3A	−0.1 (3)	C3B—C4B—C5B—N1B	1.3 (3)
C1A—C2A—C3A—C4A	−1.1 (3)	C10B—N2B—C6B—C7B	0.2 (3)
C2A—C3A—C4A—C5A	1.0 (3)	Cr2B—N2B—C6B—C7B	−174.36 (13)
C1A—N1A—C5A—C4A	−1.6 (2)	N2B—C6B—C7B—C8B	0.9 (3)
Cr1A—N1A—C5A—C4A	178.42 (13)	C6B—C7B—C8B—C9B	−1.1 (3)
C3A—C4A—C5A—N1A	0.4 (3)	C7B—C8B—C9B—C10B	0.1 (3)
C10A—N2A—C6A—C7A	−0.3 (3)	C6B—N2B—C10B—C9B	−1.3 (2)
Cr1A—N2A—C6A—C7A	−179.28 (17)	Cr2B—N2B—C10B—C9B	173.40 (13)
N2A—C6A—C7A—C8A	−0.4 (4)	C8B—C9B—C10B—N2B	1.1 (3)
C6A—C7A—C8A—C9A	0.7 (3)	C5C—N1C—C1C—C2C	1.2 (3)
C7A—C8A—C9A—C10A	−0.4 (3)	Zn1C—N1C—C1C—C2C	−175.74 (14)
C6A—N2A—C10A—C9A	0.6 (3)	Zn2C—N1C—C1C—C2C	−175.74 (14)
Cr1A—N2A—C10A—C9A	179.61 (16)	N1C—C1C—C2C—C3C	−0.9 (3)
C8A—C9A—C10A—N2A	−0.2 (3)	C1C—C2C—C3C—C4C	0.0 (3)
C5B—N1B—C1B—C2B	0.2 (3)	C2C—C3C—C4C—C5C	0.4 (4)
Cr2B—N1B—C1B—C2B	178.31 (14)	C1C—N1C—C5C—C4C	−0.7 (3)
N1B—C1B—C2B—C3B	0.9 (3)	Zn1C—N1C—C5C—C4C	176.14 (17)
C1B—C2B—C3B—C4B	−0.9 (3)	Zn2C—N1C—C5C—C4C	176.14 (17)
C2B—C3B—C4B—C5B	−0.1 (3)	C3C—C4C—C5C—N1C	−0.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1O1···Cl2Ciii	0.86 (1)	2.41 (2)	3.263 (6)	173 (8)
O1W—H2O1···Cl3Civ	0.86 (1)	2.48 (4)	3.281 (5)	157 (8)
O1W—H2O1···Cl4Civ	0.86 (1)	2.22 (2)	3.053 (6)	165 (8)
C2B—H2B···Cl3C	0.95	2.81	3.749 (4)	170
C3B—H3B···Cl3Civ	0.95	2.82	3.511 (3)	130
C3C—H3C···Cl2Cv	0.95	2.71	3.627 (4)	162
C4A—H4A···Cl1Cvi	0.95	2.82	3.717 (8)	158
C10A—H10A···Cl3Ci	0.95	2.86	3.617 (4)	137
C10B—H10B···Cl1Cii	0.95	2.73	3.534 (9)	142

Table 3

CH interaction geometry (,)

Cg1Cg4 are the centroids defined by the ring atoms N2A/C6AC10A, N1B/C1BC5B, N1A/C1AC5A and N1C/C1CC5C, respectively.

DHCg	DH	HCg	DCg	DHCg
C4CH4C Cg1i	0.95	2.82	3.630(3)	144
C6AH6A Cg2	0.95	2.81	3.579(2)	139
C6BH6B Cg3	0.95	2.90	3.660(2)	138
C8AH8A Cg4ii	0.95	2.73	3.558(3)	147

Symmetry codes: (i) x+1, y+1, z; (ii) x1, y1, z.