Crystal structure of trans-di­fluoridotetra­kis(pyridine-κN)chromium(III) tri­chlorido­(pyridine-κN)zincate monohydrate from synchrotron data

Moon, D.; Choi, J.-H.

doi:10.1107/S160053681402145X

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ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 290-293

doi:10.1107/S160053681402145X

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Crystal structure of trans-difluoridotetrakis(pyridine-κN)chromium(III) trichlorido(pyridine-κN)zincate monohydrate from synchrotron data

Dohyun Moon ^a and Jong-Ha Choi ^b ^*

^aPohang Accelerator Laboratory, POSTECH, Pohang 790-784, Republic of Korea, and ^bDepartment of Chemistry, Andong National University, Andong 760-749, Republic of Korea
^*Correspondence e-mail: jhchoi@anu.ac.kr

Edited by A. J. Lough, University of Toronto, Canada (Received 24 August 2014; accepted 27 September 2014; online 4 October 2014)

In the asymmetric unit of the title compound, [CrF₂(C₅H₅N)₄][ZnCl₃(C₅H₅N)]·H₂O, there are two independent complex cations, one trichlorido(pyridine-κN)zincate anion and one solvent water molecule. 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 octahedral 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 tetrahedral 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 molecules are linked via O—H⋯Cl hydrogen bonds, forming centrosymmetric aggregates. In addition, weak C—H⋯Cl, C—H⋯π and π–π stacking interactions [centroid–centroid distances = 3.712 (2) and 3.780 (2)Å] link the components of the structure into a three-dimensional network.

Keywords: crystal structure; fluoride ligand; pyridine ligand; trans-isomer; chromium(III) complex.

CCDC reference: 1026562

1. 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 Cr^III 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).

2. Structural commentary

In the molecular structure, there are two independent Cr^III 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 (Å)

Cr1A—F1A	1.8645 (10)	Cr2B—N1B	2.0916 (15)
Cr1A—N2A	2.0873 (14)	Zn1C—N1C	2.0752 (16)
Cr1A—N1A	2.0926 (17)	Zn1C—Cl2C	2.188 (2)
Cr2B—F1B	1.8609 (10)	Zn1C—Cl3C	2.302 (2)
Cr2B—N2B	2.0886 (17)	Zn1C—Cl1C	2.303 (8)

The [ZnCl₃(py)]⁻ anion and uncoordinating water molecule remain outside the coordination sphere. In the counter-anion, the Zn^II 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_i symmetry.

Figure 2
The molecular structure of the anion. The minor disorder component is shown with dashed lines.

3. Supramolecular features

In the crystal, two anions and two water molecules are linked via O—H⋯Cl hydrogen bonds, forming centrosymmetric aggregates with R₄⁴(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.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1O1⋯Cl2Cⁱ	0.86 (1)	2.41 (2)	3.263 (6)	173 (8)
O1W—H2O1⋯Cl3Cⁱⁱ	0.86 (1)	2.48 (4)	3.281 (5)	157 (8)
O1W—H2O1⋯Cl4Cⁱⁱ	0.86 (1)	2.22 (2)	3.053 (6)	165 (8)
C2B—H2B⋯Cl3C	0.95	2.81	3.749 (4)	170
C3B—H3B⋯Cl3Cⁱⁱ	0.95	2.82	3.511 (3)	130
C3C—H3C⋯Cl2Cⁱⁱⁱ	0.95	2.71	3.627 (4)	162
C4A—H4A⋯Cl1C^iv	0.95	2.82	3.717 (8)	158
C10A—H10A⋯Cl3C^v	0.95	2.86	3.617 (4)	137
C10B—H10B⋯Cl1C^vi	0.95	2.73	3.534 (9)	142
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+1, -z; (iii) x+1, y, z; (iv) x-1, y, z; (v) -x, -y+1, -z; (vi) -x+1, -y+1, -z+1.

Table 3
C—H⋯π interaction geometry (Å,°)

Cg1–Cg4 are the centroids defined by the ring atoms N2A/C6A–C10A, N1B/C1B–C5B, N1A/C1A–C5A and N1C/C1C–C5C, respectively.

D—H⋯Cg	D—H	H⋯Cg	D⋯Cg	D—H⋯Cg
C4C—H4C⋯Cg1ⁱ	0.95	2.82	3.630 (3)	144
C6A—H6A⋯Cg2	0.95	2.81	3.579 (2)	139
C6B—H6B⋯Cg3	0.95	2.90	3.660 (2)	138
C8A—H8A⋯Cg4ⁱⁱ	0.95	2.73	3.558 (3)	147
Symmetry codes: (i) −x + 1, −y + 1, −z; (ii) x − 1, y − 1, z.

Figure 3
Part of the crystal structure with hydrogen bonds shown as dashed lines.

4. 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.

5. 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.

Table 4
Experimental details

Crystal data
Chemical formula	[CrF₂(C₅H₅N)₄][ZnCl₃(C₅H₅N)]·H₂O
M_r	675.23
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.1350 (18), 12.852 (3), 13.607 (3)
α, β, γ (°)	103.69 (3), 105.07 (3), 101.25 (3)
V (Å³)	1441.6 (6)
Z	2
Radiation type	Synchrotron, λ = 0.62998 Å
μ (mm⁻¹)	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 > 2σ(I)] reflections	15474, 7929, 7758
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (e Å⁻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 ).

Supporting information

CCDC reference: 1026562

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

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

checkCIF report

Chemical context top

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 Cr^III 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 top

In the molecular structure, there are two independent Cr^III 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.

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]₂ZnCl₄·NaClO₄ 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 and trans-[Cr(2,2,3-tet)F₂]ClO₄ (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).

The [ZnCl₃(py)]^- anion and uncoordinating water molecule remain outside the coordination sphere. In the counter-anion, the Zn^II 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)] (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(II) 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_i symmetry.

Supramolecular features top

In the crystal, two anions and two water molecules are linked via O—H···O hydrogen bonds, forming centrosymmetric aggregates with R⁴₄(12) rings (Fig. 3). In addition, weak C—H···Cl, C—H···π 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.

Synthesis and crystallization top

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 (0.2g) 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 55°C 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 top

Crystal data, data collection and structure refinement details are summarized in Table 4. Non-hydrogen atoms were refined anisotropically; 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 0.631 (9) and 0.369 (9), respectively.

Related literature top

For related literature, see: Birk et al. (2010); Choi (2000a, 2000b); Choi & Moon (2014); Choi et al. (2004, 2006); Dreiser et al. (2012); Fabbrizzi & Poggi (2013); Fochi et al. (1991); Glerup et al. (1970); Martínez-Máñez & Sancenón (2003); Moon & Choi (2013); Moon et al. (2014).

Computing details top

Data collection: PAL ADSC Quantum-210 ADX Software (Arvai & Nielsen, 1983); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2007), Mercury (Macrae et al., 2006) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Figures top

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

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

trans-Difluoridotetrakis-(pyridine-κN)chromium(III) trichlorido(pyridine-κN)zincate monohydrate top

Crystal data top

[CrF₂(C₅H₅N)₄][ZnCl₃(C₅H₅N)]·H₂O	Z = 2
M_r = 675.23	F(000) = 686
Triclinic, P1	D_x = 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

Data collection top

ADSC Q210 CCD area-detector diffractometer	7758 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.023
ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −12→12
T_min = 0.899, T_max = 0.978	k = −17→17
15474 measured reflections	l = −18→18
7929 independent reflections

Refinement top

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(F_o²) + (0.0457P)² + 1.3104P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
7929 reflections	Δρ_max = 0.74 e Å⁻³
380 parameters	Δρ_min = −0.85 e Å⁻³

Crystal data top

[CrF₂(C₅H₅N)₄][ZnCl₃(C₅H₅N)]·H₂O	γ = 101.25 (3)°
M_r = 675.23	V = 1441.6 (6) Å³
Triclinic, P1	Z = 2
a = 9.1350 (18) Å	Synchrotron radiation, λ = 0.62998 Å
b = 12.852 (3) Å	µ = 1.09 mm⁻¹
c = 13.607 (3) Å	T = 100 K
α = 103.69 (3)°	0.10 × 0.02 × 0.02 mm
β = 105.07 (3)°

Data collection top

ADSC Q210 CCD area-detector diffractometer	7929 independent reflections
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	7758 reflections with I > 2σ(I)
T_min = 0.899, T_max = 0.978	R_int = 0.023
15474 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	3 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.74 e Å⁻³
7929 reflections	Δρ_min = −0.85 e Å⁻³
380 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

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

Hydrogen-bond geometry (Å, º) top

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···Cl3C^iv	0.86 (1)	2.48 (4)	3.281 (5)	157 (8)
O1W—H2O1···Cl4C^iv	0.86 (1)	2.22 (2)	3.053 (6)	165 (8)
C2B—H2B···Cl3C	0.95	2.81	3.749 (4)	170
C3B—H3B···Cl3C^iv	0.95	2.82	3.511 (3)	130
C3C—H3C···Cl2C^v	0.95	2.71	3.627 (4)	162
C4A—H4A···Cl1C^vi	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

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

Selected bond lengths (Å) top

Cr1A—F1A	1.8645 (10)	Cr2B—N1B	2.0916 (15)
Cr1A—N2A	2.0873 (14)	Zn1C—N1C	2.0752 (16)
Cr1A—N1A	2.0926 (17)	Zn1C—Cl2C	2.188 (2)
Cr2B—F1B	1.8609 (10)	Zn1C—Cl3C	2.302 (2)
Cr2B—N2B	2.0886 (17)	Zn1C—Cl1C	2.303 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1O1···Cl2Cⁱ	0.86 (1)	2.41 (2)	3.263 (6)	173 (8)
O1W—H2O1···Cl3Cⁱⁱ	0.86 (1)	2.48 (4)	3.281 (5)	157 (8)
O1W—H2O1···Cl4Cⁱⁱ	0.86 (1)	2.22 (2)	3.053 (6)	165 (8)
C2B—H2B···Cl3C	0.95	2.81	3.749 (4)	170
C3B—H3B···Cl3Cⁱⁱ	0.95	2.82	3.511 (3)	130
C3C—H3C···Cl2Cⁱⁱⁱ	0.95	2.71	3.627 (4)	162
C4A—H4A···Cl1C^iv	0.95	2.82	3.717 (8)	158
C10A—H10A···Cl3C^v	0.95	2.86	3.617 (4)	137
C10B—H10B···Cl1C^vi	0.95	2.73	3.534 (9)	142

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

C—H···π interaction geometry (Å,°) top

Cg1–Cg4 are the centroids defined by the ring atoms N2A/C6A–C10A, N1B/C1B–C5B, N1A/C1A–C5A and N1C/C1C–C5C, respectively.

D—H···Cg	D—H	H···Cg	D···Cg	D—H···Cg
C4C—H4C···Cg1ⁱ	0.95	2.82	3.630 (3)	144
C6A—H6A···Cg2	0.95	2.81	3.579 (2)	139
C6B—H6B···Cg3	0.95	2.90	3.660 (2)	138
C8A—H8A···Cg4ⁱⁱ	0.95	2.73	3.558 (3)	147

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

Experimental details

Crystal data
Chemical formula	[CrF₂(C₅H₅N)₄][ZnCl₃(C₅H₅N)]·H₂O
M_r	675.23
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.1350 (18), 12.852 (3), 13.607 (3)
α, β, γ (°)	103.69 (3), 105.07 (3), 101.25 (3)
V (Å³)	1441.6 (6)
Z	2
Radiation type	Synchrotron, λ = 0.62998 Å
µ (mm⁻¹)	1.09
Crystal size (mm)	0.10 × 0.02 × 0.02

Data collection
Diffractometer	ADSC Q210 CCD area-detector diffractometer
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 > 2σ(I)] reflections	15474, 7929, 7758
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.85

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

Acknowledgements

This work was supported by a grant from the 2012 Academic Research Fund of Andong National University. The experiment at the PLS-II 2D-SMC beamline was supported in part by MEST and POSTECH.

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Volume 70| Part 11| November 2014| Pages 290-293

doi:10.1107/S160053681402145X

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of trans-di­fluorido­tetra­kis(pyridine-κN)chromium(III) tri­chlorido­(pyridine-κN)zincate monohydrate from synchrotron data

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Synthesis and crystallization

5. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of trans-difluoridotetrakis(pyridine-κN)chromium(III) trichlorido(pyridine-κN)zincate monohydrate from synchrotron data

3. Supramolecular features