cis-Aqua­bis(2,2′-bipyridine-κ2N,N′)fluoridochromium(III) bis­(perchlorate) dihydrate

Birk, T.; Bendix, J.

doi:10.1107/S1600536810000127

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m121-m122

https://doi.org/10.1107/S1600536810000127

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cis-Aquabis(2,2′-bipyridine-κ²N,N′)fluoridochromium(III) bis(perchlorate) dihydrate

Torben Birk ^a ^* and Jesper Bendix ^a

^aDepartment of Chemistry, University of Copenhagen, Universitetsparken 5, DK.2100 Copenhagen Ø, Denmark
^*Correspondence e-mail: birk@kiku.dk

(Received 21 December 2009; accepted 3 January 2010; online 9 January 2010)

The title mixed aqua–fluoride complex, [CrF(C₁₀H₈N₂)₂(H₂O)](ClO₄)₂·2H₂O, has been synthesized by aquation of the corresponding difluoride complex using lanthanide(III) ions as F⁻ acceptors. The complex crystallizes with a Cr^III ion at the center of a distorted octahedral coordination polyhedron with a cis arrangement of ligands. The crystal packing shows a hydrogen-bonding pattern involving water molecules, the coordinated F atom and the perchlorate anions

Related literature

For related difluoride complexes, see: Birk et al. (2008 ); Brenčič et al. (1987 ); Brenčič & Leban (1981 ); DeJovine et al. (1974 ); Delavar & Staples (1981 ); Kavitha et al. (2005 ); Vaughn et al. (1968 ); Vaughn & Seiler (1979 ); Yamaguchi-Terasaki et al. (2007 ). For related structures, see: Casellato et al. (1986 ); Liu (2009 ). For details of the synthesis, see: Glerup et al. (1970 ).

Experimental

Crystal data

[CrF(C₁₀H₈N₂)₂(H₂O)](ClO₄)₂·2H₂O
M_r = 636.32
Triclinic, $[P \overline 1]$
a = 9.577 (1) Å
b = 11.4050 (6) Å
c = 11.8150 (11) Å
α = 77.273 (6)°
β = 79.427 (9)°
γ = 83.590 (5)°
V = 1234.01 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 122 K
0.41 × 0.24 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: Gaussian (Coppens, 1970 ) T_min = 0.805, T_max = 0.925
27824 measured reflections
5691 independent reflections
5244 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.070
S = 1.03
5691 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Selected bond lengths (Å)

Cr1—F1	1.8614 (8)
Cr1—O1	1.9579 (10)
Cr1—N1	2.0501 (12)
Cr1—N2	2.0456 (12)
Cr1—N3	2.0545 (12)
Cr1—N4	2.0571 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯F1ⁱ	0.83	1.73	2.5482 (13)	174
O1—H1B⋯O2ⁱⁱ	0.83	1.73	2.5548 (15)	176
O2—H2A⋯O3	0.90	1.89	2.7887 (18)	179
O2—H2B⋯O5	0.84	2.14	2.9380 (17)	158
O3—H3A⋯O10ⁱⁱⁱ	0.91	2.00	2.890 (2)	167
O3—H3B⋯O8	0.87	2.19	3.050 (2)	168
O3—H3B⋯O9	0.87	2.48	3.123 (2)	132
Symmetry codes: (i) -x+1, -y, -z+2; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z+1.

Table 3
M—F bond distances (Å) for related cis/trans-[M(L)₂F₂]⁺ complexes

(I)	(II)	(III)	(IV)	(V)
1.8621 (10)	1.8541 (10)	1.887 (6)	1.887 (5)	1.7389 (15)
1.8444 (10)	1.8409 (10)	1.878 (6)	1.868 (4)	1.7232 (15)
Notes: (I) cis-[Cr(phen)₂F₂]ClO₄·H₂O (Birk et al., 2008); (II) cis-[Cr(bipy)₂F₂]ClO₄·H₂O (Yamaguchi-Terasaki et al., 2007); (III) trans-[Cr(en)₂F₂]ClO₄ (Brenčič & Leban, 1981); (IV) cis-[Cr(en)₂F₂]ClO₄·NaClO₄·H₂O (Brenčič et al., 1987); (V) cis-[V(bipy)₂F₂]BF₄ (Kavitha et al., 2005). en = ethane-1,2-diamine; bipy = 2,2′-bipyridine; phen = 1,10-phenanthroline.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: COLLECT; data reduction: EVALCCD (Duisenberg et al., 2003 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810000127/hy2268sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000127/hy2268Isup2.hkl

checkCIF report

Comment top

Water and fluoride are both hard donor ligands favoring the same central ions. Nevertheless, no transition metal complexes of the general type cis-[M(L)₂(H₂O)F]²⁺ with L being a bidentate ligand such as 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen) or ethane-1,2-diamine (en) have previously been characterized by X-ray diffraction. This report presents the synthesis and crystal structure of such a system exemplified by the title complex cis-[Cr(bipy)₂(H₂O)F](ClO₄)₂.2H₂O.

All trivalent lanthanid ions, Ln³⁺ are known to be hard Lewis acids. This Lewis acidity gives rise to favorable bond formation with ligands containing oxygen and fluorine ligator atoms. The interactions between lanthanid ions and coordinated fluoride have not received much attention compared to the plethora of oxygen bridged systems reported. We have initiated a study on the reactivity of lanthanid ions towards coordinated fluoride ligands to assess if new fluoride contaning complexes can be synthesized this way. In the context of these studies, we found that the title complex, as well as the corresponding phen complex, can be synthesized by a lanthanid ion assisted aquation of the difluoride complex cis-[Cr(bipy)₂F₂]ClO₄. The normal aquation reaction is performed in strong acid and has been studied preparatively and kinetic for difluoride complexes as trans-[Cr(en)₂F₂]⁺ and cis-[Cr(bipy)₂F₂]⁺ (DeJovine et al., 1974; Delavar & Staples, 1981; Vaughn et al., 1968; Vaughn & Seiler, 1979). However, the present synthetic approach is more general, as it can be applied also to systems with an acid-labile auxillary ligand sphere.

The most important structural element in the title compound is the cis arrangement of ligators in a distorted octahedral coordination polyhedron around the central Cr^III ion (Fig. 1). Distortion from ideal geometry is dictated by the nearly fixed bite angles of the two bipy ligands [79.51 (5) and 79.24 (5)°]. This pattern is also seen in the structurally related difluoride complexes cis-[V(bipy)₂F₂]BF₄ (Kavitha et al., 2005) and cis-[Cr(bipy)F₂]ClO₄.H₂O (Yamaguchi-Terasaki et al., 2007). The Cr1—F1 bond distance of 1.8614 (8) Å (Table 1) is in accordance with the structurally characterized difluoride complexes, as shown in Table 3. The Cr1—O1 bond distance of 1.9579 (10)Å is shorter than what is seen in both the tricationic, diaqua complex cis-[Cr(bipy)₂(H₂O)₂](NO₃)₃ [2.00 (1) and 1.98 (1) Å] (Casellato et al., 1986), as well as in the uncharged [Cr(bipy)(H₂O)F₃].2H₂O [1.979 (2) Å] (Liu, 2009). In the structure of cis-[Cr(bipy)₂F₂]⁺, a trans influence leading to the Cr—N bond distances trans to the fluorido ligand being longer that the corresponding cis distances was identified by Yamaguchi-Terasaki et al. (2007). This situation was also found in cis-[Cr(phen)₂F₂]⁺ (Birk et al., 2008), but is not discernible in the structure reported here.

The crystal packing in the title complex (Fig. 2) shows a hydrogen bonding pattern involving water molecules, coordinated F atom and perchlorate anions (Table 2).

Related literature top

For related difluoride complexes, see: Birk et al. (2008); Brenčič et al. (1987); Brenčič & Leban (1981); DeJovine et al. (1974); Delavar & Staples (1981); Kavitha et al. (2005); Vaughn et al. (1968); Vaughn & Seiler (1979); Yamaguchi-Terasaki et al. (2007). For related structures, see: Casellato et al. (1986); Liu (2009). For details of the synthesis, see: Glerup et al. (1970).

Experimental top

Safety remark: Perchlorate complexes of metal ions are potentially explosive. The title complex burns with high intensity when ignited in a gas flame. According to Delavar & Staples (1981), the corresponding phen complex is explosive.

All chemicals were used as received. cis-[Cr(bipy)₂F₂]ClO₄ was synthesized by reflux of trans-difluorotetrakis(pyridine)chromium(III) perchlorate and bipy in 2-methoxyethanol according to the published method (Glerup et al., 1970).

Nd₂O₃ (0.251 g, 0.746 mmol) was dissolved in 0.5 ml HClO₄ (60%) by gentle heating giving a pink solution to which was added a mixture of cis-[Cr(bipy)₂F₂]ClO₄ (1.011 g, 2.015 mmol) in acteonitrile (60 ml) and water (20 ml). Mixing gave rise to a slight color change from purple to red. The solution was placed in a water bath (~70°C) and was stirred for 30–35 min. The resulting muddy red suspension was solidified by cooling to room temperature. Extraction with a mixture of acetonitrile and water (2:1, 30 ml) gave an orange turbid solution which was separated into a clear solution and white precipitate by centrifugation. Slow evaporation gave an orange crystalline product which contained crystals of suitable quality for X-ray diffraction. The product was isolated by filtering, washed with ice water and dried in air (yield 1.073 g, 83.7%). Analysis, calculated for C₂₀H₂₂Cl₂CrFN₄O₁₁: C 37.75, H 3.48, N 8.80%; found: C 37.97, H 3.41, N 8.70%.

The corresponding phen complex, cis-[Cr(phen)₂(H₂O)F](ClO₄)₂.H₂O can be synthesized from cis-[Cr(phen)₂F₂]ClO₄ (1.034 g, 1.88 mmol) by a similar procedure (yield 0.781 g, 60.7%). Analysis, calculated for C₂₄H₂₂Cl₂CrFN₄O₁₁: C 42.12, H 3.24, N 8.19%; found: C 42.07, H 2.73, N 8.02%.

Structure description top

The crystal packing in the title complex (Fig. 2) shows a hydrogen bonding pattern involving water molecules, coordinated F atom and perchlorate anions (Table 2).

For related difluoride complexes, see: Birk et al. (2008); Brenčič et al. (1987); Brenčič & Leban (1981); DeJovine et al. (1974); Delavar & Staples (1981); Kavitha et al. (2005); Vaughn et al. (1968); Vaughn & Seiler (1979); Yamaguchi-Terasaki et al. (2007). For related structures, see: Casellato et al. (1986); Liu (2009). For details of the synthesis, see: Glerup et al. (1970).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT (Nonius, 1998); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability.
	Fig. 2. The crystal packing in the title compound. Displacement ellipsoids are drawn at the 50% probability. H atoms except those of water molecules have been omitted for clarity.

cis-Aquabis(2,2'-bipyridine-κ²N,N')fluoridochromium(III) bis(perchlorate) dihydrate top

Crystal data top

[CrF(C₁₀H₈N₂)₂(H₂O)](ClO₄)₂·2H₂O	Z = 2
M_r = 636.32	F(000) = 650
Triclinic, P1	D_x = 1.712 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.577 (1) Å	Cell parameters from 19362 reflections
b = 11.4050 (6) Å	θ = 1.8–27.6°
c = 11.8150 (11) Å	µ = 0.76 mm⁻¹
α = 77.273 (6)°	T = 122 K
β = 79.427 (9)°	Block, orange
γ = 83.590 (5)°	0.41 × 0.24 × 0.14 mm
V = 1234.01 (19) Å³

Data collection top

Nonius KappaCCD diffractometer	5691 independent reflections
Radiation source: fine-focus sealed tube	5244 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω and φ scans	θ_max = 27.6°, θ_min = 1.8°
Absorption correction: gaussian (Coppens, 1970)	h = −12→12
T_min = 0.805, T_max = 0.925	k = −14→11
27824 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0294P)² + 1.0724P] where P = (F_o² + 2F_c²)/3
5691 reflections	(Δ/σ)_max = 0.001
352 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[CrF(C₁₀H₈N₂)₂(H₂O)](ClO₄)₂·2H₂O	γ = 83.590 (5)°
M_r = 636.32	V = 1234.01 (19) Å³
Triclinic, P1	Z = 2
a = 9.577 (1) Å	Mo Kα radiation
b = 11.4050 (6) Å	µ = 0.76 mm⁻¹
c = 11.8150 (11) Å	T = 122 K
α = 77.273 (6)°	0.41 × 0.24 × 0.14 mm
β = 79.427 (9)°

Data collection top

Nonius KappaCCD diffractometer	5691 independent reflections
Absorption correction: gaussian (Coppens, 1970)	5244 reflections with I > 2σ(I)
T_min = 0.805, T_max = 0.925	R_int = 0.021
27824 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.03	Δρ_max = 0.55 e Å⁻³
5691 reflections	Δρ_min = −0.42 e Å⁻³
352 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cr1	0.35121 (2)	0.123062 (19)	0.848099 (18)	0.00991 (6)
Cl2	0.01627 (4)	0.74580 (3)	0.50375 (3)	0.02144 (9)
N3	0.35227 (12)	0.26595 (10)	0.70747 (10)	0.0118 (2)
N1	0.22015 (12)	0.21617 (10)	0.96126 (10)	0.0126 (2)
N2	0.15621 (12)	0.08156 (10)	0.82758 (10)	0.0126 (2)
N4	0.47511 (12)	0.04749 (10)	0.71710 (10)	0.0127 (2)
O9	0.15767 (16)	0.70270 (13)	0.45676 (13)	0.0404 (3)
C11	0.27881 (15)	0.37340 (13)	0.70730 (13)	0.0157 (3)
H11	0.2249	0.3889	0.7791	0.019*
C10	0.13318 (16)	0.00256 (13)	0.76532 (12)	0.0166 (3)
H10	0.2127	−0.0408	0.7285	0.020*
C5	0.07893 (15)	0.21767 (12)	0.95836 (12)	0.0138 (3)
C6	0.04290 (15)	0.14086 (12)	0.88386 (12)	0.0136 (3)
C16	0.51342 (15)	0.12642 (12)	0.61489 (12)	0.0134 (3)
O8	−0.07727 (16)	0.74614 (14)	0.42147 (13)	0.0422 (4)
C12	0.27874 (16)	0.46239 (13)	0.60644 (14)	0.0191 (3)
H12	0.2266	0.5379	0.6092	0.023*
C1	0.26327 (16)	0.27937 (13)	1.03060 (12)	0.0164 (3)
H1	0.3622	0.2785	1.0322	0.020*
C13	0.35579 (17)	0.43951 (14)	0.50168 (13)	0.0201 (3)
H13	0.3546	0.4981	0.4308	0.024*
C20	0.54167 (15)	−0.06375 (13)	0.73489 (13)	0.0162 (3)
H20	0.5130	−0.1192	0.8061	0.019*
C4	−0.02135 (16)	0.28464 (15)	1.02335 (14)	0.0215 (3)
H4	−0.1196	0.2867	1.0187	0.026*
O11	0.02074 (14)	0.86579 (11)	0.52039 (12)	0.0325 (3)
C2	0.16777 (17)	0.34562 (14)	1.09959 (14)	0.0213 (3)
H2	0.2005	0.3883	1.1490	0.026*
C14	0.43510 (16)	0.32978 (14)	0.50111 (13)	0.0183 (3)
H14	0.4903	0.3131	0.4302	0.022*
C18	0.69355 (16)	−0.01741 (14)	0.54925 (14)	0.0203 (3)
H18	0.7703	−0.0392	0.4925	0.024*
C9	−0.00262 (17)	−0.01809 (14)	0.75276 (13)	0.0205 (3)
H9	−0.0162	−0.0742	0.7078	0.025*
C15	0.43247 (14)	0.24527 (12)	0.60527 (12)	0.0132 (3)
C8	−0.11776 (17)	0.04497 (15)	0.80722 (14)	0.0229 (3)
H8	−0.2118	0.0340	0.7984	0.028*
C7	−0.09549 (16)	0.12434 (14)	0.87471 (13)	0.0195 (3)
H7	−0.1739	0.1667	0.9140	0.023*
O10	−0.03306 (19)	0.66919 (14)	0.61505 (13)	0.0487 (4)
C17	0.62360 (16)	0.09676 (14)	0.52947 (13)	0.0180 (3)
H17	0.6506	0.1535	0.4588	0.022*
C3	0.02397 (17)	0.34882 (15)	1.09551 (15)	0.0247 (3)
H3	−0.0432	0.3944	1.1416	0.030*
C19	0.65089 (16)	−0.09956 (13)	0.65221 (14)	0.0191 (3)
H19	0.6957	−0.1789	0.6658	0.023*
Cl40	0.60695 (4)	0.35453 (3)	0.15860 (3)	0.01724 (8)
O4	0.61978 (13)	0.29094 (12)	0.06429 (11)	0.0284 (3)
O5	0.45771 (12)	0.37385 (12)	0.20582 (11)	0.0296 (3)
O6	0.67943 (14)	0.28330 (12)	0.25003 (11)	0.0322 (3)
O7	0.66883 (17)	0.46781 (12)	0.11571 (13)	0.0397 (3)
F1	0.36386 (9)	−0.01840 (7)	0.96103 (7)	0.01657 (17)
O2	0.37076 (13)	0.62663 (10)	0.21825 (10)	0.0241 (2)
H2A	0.2792	0.6097	0.2348	0.029*
H2B	0.4116	0.5629	0.1987	0.029*
O3	0.08500 (14)	0.57629 (12)	0.26794 (11)	0.0298 (3)
H3A	0.0722	0.5022	0.3148	0.036*
H3B	0.0491	0.6222	0.3174	0.036*
O1	0.52507 (10)	0.17280 (9)	0.88317 (9)	0.0153 (2)
H1A	0.5620	0.1268	0.9357	0.018*
H1B	0.5629	0.2360	0.8503	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr1	0.00962 (10)	0.01015 (11)	0.00923 (10)	−0.00046 (7)	−0.00176 (7)	−0.00038 (8)
Cl2	0.0299 (2)	0.01514 (16)	0.01916 (17)	0.00224 (13)	−0.00580 (14)	−0.00367 (13)
N3	0.0114 (5)	0.0123 (5)	0.0118 (5)	−0.0013 (4)	−0.0029 (4)	−0.0014 (4)
N1	0.0133 (5)	0.0134 (5)	0.0104 (5)	−0.0010 (4)	−0.0017 (4)	−0.0013 (4)
N2	0.0130 (5)	0.0134 (5)	0.0106 (5)	−0.0018 (4)	−0.0022 (4)	−0.0003 (4)
N4	0.0117 (5)	0.0124 (5)	0.0137 (5)	−0.0012 (4)	−0.0017 (4)	−0.0024 (4)
O9	0.0434 (8)	0.0351 (7)	0.0369 (7)	0.0189 (6)	−0.0020 (6)	−0.0098 (6)
C11	0.0157 (6)	0.0138 (6)	0.0169 (7)	0.0003 (5)	−0.0027 (5)	−0.0024 (5)
C10	0.0188 (7)	0.0169 (7)	0.0143 (6)	−0.0024 (5)	−0.0019 (5)	−0.0037 (5)
C5	0.0136 (6)	0.0150 (6)	0.0122 (6)	−0.0015 (5)	−0.0020 (5)	−0.0010 (5)
C6	0.0135 (6)	0.0147 (6)	0.0116 (6)	−0.0014 (5)	−0.0019 (5)	−0.0005 (5)
C16	0.0132 (6)	0.0142 (6)	0.0135 (6)	−0.0024 (5)	−0.0031 (5)	−0.0030 (5)
O8	0.0470 (8)	0.0426 (8)	0.0440 (8)	−0.0172 (7)	−0.0238 (7)	−0.0032 (6)
C12	0.0193 (7)	0.0132 (6)	0.0235 (7)	0.0005 (5)	−0.0063 (6)	0.0007 (6)
C1	0.0174 (7)	0.0180 (7)	0.0145 (6)	−0.0028 (5)	−0.0035 (5)	−0.0034 (5)
C13	0.0237 (7)	0.0173 (7)	0.0173 (7)	−0.0033 (6)	−0.0069 (6)	0.0047 (5)
C20	0.0167 (7)	0.0129 (6)	0.0187 (7)	−0.0010 (5)	−0.0034 (5)	−0.0025 (5)
C4	0.0147 (7)	0.0274 (8)	0.0234 (8)	0.0011 (6)	−0.0016 (6)	−0.0101 (6)
O11	0.0370 (7)	0.0230 (6)	0.0415 (7)	0.0011 (5)	−0.0069 (6)	−0.0164 (5)
C2	0.0241 (8)	0.0235 (7)	0.0192 (7)	−0.0025 (6)	−0.0030 (6)	−0.0108 (6)
C14	0.0212 (7)	0.0194 (7)	0.0131 (7)	−0.0034 (6)	−0.0017 (5)	−0.0004 (5)
C18	0.0157 (7)	0.0249 (8)	0.0206 (7)	0.0010 (6)	0.0002 (6)	−0.0093 (6)
C9	0.0234 (8)	0.0226 (7)	0.0182 (7)	−0.0079 (6)	−0.0048 (6)	−0.0058 (6)
C15	0.0129 (6)	0.0139 (6)	0.0131 (6)	−0.0028 (5)	−0.0023 (5)	−0.0020 (5)
C8	0.0164 (7)	0.0304 (8)	0.0242 (8)	−0.0076 (6)	−0.0048 (6)	−0.0062 (6)
C7	0.0132 (7)	0.0251 (7)	0.0205 (7)	−0.0025 (6)	−0.0015 (5)	−0.0058 (6)
O10	0.0745 (11)	0.0352 (8)	0.0266 (7)	−0.0070 (7)	0.0050 (7)	0.0049 (6)
C17	0.0164 (7)	0.0208 (7)	0.0156 (7)	−0.0025 (5)	0.0006 (5)	−0.0033 (5)
C3	0.0224 (8)	0.0286 (8)	0.0247 (8)	0.0030 (6)	0.0003 (6)	−0.0149 (7)
C19	0.0175 (7)	0.0161 (7)	0.0244 (8)	0.0031 (5)	−0.0040 (6)	−0.0074 (6)
Cl40	0.01915 (17)	0.01732 (16)	0.01546 (16)	−0.00394 (12)	−0.00042 (12)	−0.00447 (12)
O4	0.0287 (6)	0.0368 (7)	0.0245 (6)	−0.0081 (5)	0.0006 (5)	−0.0180 (5)
O5	0.0193 (6)	0.0376 (7)	0.0300 (6)	0.0045 (5)	0.0003 (5)	−0.0095 (5)
O6	0.0287 (6)	0.0422 (7)	0.0226 (6)	0.0053 (5)	−0.0068 (5)	−0.0023 (5)
O7	0.0553 (9)	0.0245 (6)	0.0397 (8)	−0.0214 (6)	−0.0010 (7)	−0.0043 (6)
F1	0.0164 (4)	0.0153 (4)	0.0157 (4)	−0.0020 (3)	−0.0043 (3)	0.0034 (3)
O2	0.0263 (6)	0.0159 (5)	0.0277 (6)	−0.0039 (4)	−0.0016 (5)	−0.0003 (4)
O3	0.0345 (7)	0.0294 (6)	0.0262 (6)	−0.0073 (5)	0.0015 (5)	−0.0100 (5)
O1	0.0143 (5)	0.0140 (5)	0.0170 (5)	−0.0037 (4)	−0.0067 (4)	0.0031 (4)

Geometric parameters (Å, º) top

Cr1—F1	1.8614 (8)	C13—C14	1.390 (2)
Cr1—O1	1.9579 (10)	C13—H13	0.9500
Cr1—N1	2.0501 (12)	C20—C19	1.386 (2)
Cr1—N2	2.0456 (12)	C20—H20	0.9500
Cr1—N3	2.0545 (12)	C4—C3	1.390 (2)
Cr1—N4	2.0571 (12)	C4—H4	0.9500
Cl2—O11	1.4311 (12)	C2—C3	1.383 (2)
Cl2—O8	1.4369 (14)	C2—H2	0.9500
Cl2—O10	1.4400 (14)	C14—C15	1.3841 (19)
Cl2—O9	1.4421 (14)	C14—H14	0.9500
N3—C11	1.3431 (18)	C18—C19	1.388 (2)
N3—C15	1.3595 (18)	C18—C17	1.388 (2)
N1—C1	1.3460 (18)	C18—H18	0.9500
N1—C5	1.3573 (18)	C9—C8	1.383 (2)
N2—C10	1.3408 (18)	C9—H9	0.9500
N2—C6	1.3589 (18)	C8—C7	1.387 (2)
N4—C20	1.3458 (18)	C8—H8	0.9500
N4—C16	1.3548 (18)	C7—H7	0.9500
C11—C12	1.385 (2)	C17—H17	0.9500
C11—H11	0.9500	C3—H3	0.9500
C10—C9	1.387 (2)	C19—H19	0.9500
C10—H10	0.9500	Cl40—O7	1.4316 (13)
C5—C4	1.385 (2)	Cl40—O4	1.4382 (12)
C5—C6	1.4764 (19)	Cl40—O6	1.4392 (12)
C6—C7	1.386 (2)	Cl40—O5	1.4470 (12)
C16—C17	1.388 (2)	O2—H2A	0.8959
C16—C15	1.4769 (19)	O2—H2B	0.8435
C12—C13	1.381 (2)	O3—H3A	0.9096
C12—H12	0.9500	O3—H3B	0.8684
C1—C2	1.384 (2)	O1—H1A	0.8255
C1—H1	0.9500	O1—H1B	0.8276

F1—Cr1—O1	90.26 (4)	N1—C1—H1	119.0
F1—Cr1—N2	89.57 (4)	C2—C1—H1	119.0
O1—Cr1—N2	172.88 (5)	C12—C13—C14	119.24 (13)
F1—Cr1—N1	94.23 (4)	C12—C13—H13	120.4
O1—Cr1—N1	93.41 (5)	C14—C13—H13	120.4
N2—Cr1—N1	79.51 (5)	N4—C20—C19	121.80 (13)
F1—Cr1—N3	172.26 (4)	N4—C20—H20	119.1
O1—Cr1—N3	90.13 (4)	C19—C20—H20	119.1
N2—Cr1—N3	90.99 (5)	C5—C4—C3	119.00 (14)
N1—Cr1—N3	93.46 (5)	C5—C4—H4	120.5
F1—Cr1—N4	93.04 (4)	C3—C4—H4	120.5
O1—Cr1—N4	88.50 (5)	C3—C2—C1	119.02 (14)
N2—Cr1—N4	98.62 (5)	C3—C2—H2	120.5
N1—Cr1—N4	172.47 (5)	C1—C2—H2	120.5
N3—Cr1—N4	79.24 (5)	C15—C14—C13	119.05 (14)
O11—Cl2—O8	109.72 (9)	C15—C14—H14	120.5
O11—Cl2—O10	109.32 (9)	C13—C14—H14	120.5
O8—Cl2—O10	110.21 (10)	C19—C18—C17	119.71 (14)
O11—Cl2—O9	108.75 (9)	C19—C18—H18	120.1
O8—Cl2—O9	108.89 (9)	C17—C18—H18	120.1
O10—Cl2—O9	109.91 (9)	C8—C9—C10	118.43 (14)
C11—N3—C15	118.59 (12)	C8—C9—H9	120.8
C11—N3—Cr1	126.26 (10)	C10—C9—H9	120.8
C15—N3—Cr1	115.12 (9)	N3—C15—C14	121.69 (13)
C1—N1—C5	119.17 (12)	N3—C15—C16	114.74 (12)
C1—N1—Cr1	125.61 (10)	C14—C15—C16	123.57 (13)
C5—N1—Cr1	115.10 (9)	C9—C8—C7	119.79 (14)
C10—N2—C6	119.20 (12)	C9—C8—H8	120.1
C10—N2—Cr1	125.76 (10)	C7—C8—H8	120.1
C6—N2—Cr1	115.04 (9)	C6—C7—C8	118.95 (14)
C20—N4—C16	119.50 (12)	C6—C7—H7	120.5
C20—N4—Cr1	124.11 (10)	C8—C7—H7	120.5
C16—N4—Cr1	114.77 (9)	C16—C17—C18	118.73 (14)
N3—C11—C12	122.47 (13)	C16—C17—H17	120.6
N3—C11—H11	118.8	C18—C17—H17	120.6
C12—C11—H11	118.8	C2—C3—C4	119.37 (14)
N2—C10—C9	122.31 (14)	C2—C3—H3	120.3
N2—C10—H10	118.8	C4—C3—H3	120.3
C9—C10—H10	118.8	C20—C19—C18	118.75 (14)
N1—C5—C4	121.45 (13)	C20—C19—H19	120.6
N1—C5—C6	114.70 (12)	C18—C19—H19	120.6
C4—C5—C6	123.83 (13)	O7—Cl40—O4	109.83 (8)
N2—C6—C7	121.27 (13)	O7—Cl40—O6	109.51 (9)
N2—C6—C5	115.05 (12)	O4—Cl40—O6	109.40 (8)
C7—C6—C5	123.61 (13)	O7—Cl40—O5	110.01 (9)
N4—C16—C17	121.47 (13)	O4—Cl40—O5	108.98 (8)
N4—C16—C15	114.56 (12)	O6—Cl40—O5	109.10 (8)
C17—C16—C15	123.93 (13)	H2A—O2—H2B	101.9
C13—C12—C11	118.88 (14)	H3A—O3—H3B	100.6
C13—C12—H12	120.6	Cr1—O1—H1A	116.4
C11—C12—H12	120.6	Cr1—O1—H1B	125.2
N1—C1—C2	121.96 (14)	H1A—O1—H1B	118.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F1ⁱ	0.83	1.73	2.5482 (13)	174
O1—H1B···O2ⁱⁱ	0.83	1.73	2.5548 (15)	176
O2—H2A···O3	0.90	1.89	2.7887 (18)	179
O2—H2B···O5	0.84	2.14	2.9380 (17)	158
O3—H3A···O10ⁱⁱⁱ	0.91	2.00	2.890 (2)	167
O3—H3B···O8	0.87	2.19	3.050 (2)	168
O3—H3B···O9	0.87	2.48	3.123 (2)	132

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

Experimental details

Crystal data
Chemical formula	[CrF(C₁₀H₈N₂)₂(H₂O)](ClO₄)₂·2H₂O
M_r	636.32
Crystal system, space group	Triclinic, P1
Temperature (K)	122
a, b, c (Å)	9.577 (1), 11.4050 (6), 11.8150 (11)
α, β, γ (°)	77.273 (6), 79.427 (9), 83.590 (5)
V (Å³)	1234.01 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.41 × 0.24 × 0.14

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Gaussian (Coppens, 1970)
T_min, T_max	0.805, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	27824, 5691, 5244
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.070, 1.03
No. of reflections	5691
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.42

Computer programs: COLLECT (Nonius, 1998), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top

Cr1—F1	1.8614 (8)	Cr1—N2	2.0456 (12)
Cr1—O1	1.9579 (10)	Cr1—N3	2.0545 (12)
Cr1—N1	2.0501 (12)	Cr1—N4	2.0571 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F1ⁱ	0.83	1.73	2.5482 (13)	174
O1—H1B···O2ⁱⁱ	0.83	1.73	2.5548 (15)	176
O2—H2A···O3	0.90	1.89	2.7887 (18)	179
O2—H2B···O5	0.84	2.14	2.9380 (17)	158
O3—H3A···O10ⁱⁱⁱ	0.91	2.00	2.890 (2)	167
O3—H3B···O8	0.87	2.19	3.050 (2)	168
O3—H3B···O9	0.87	2.48	3.123 (2)	132

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

M—F bond distances (Å) for related cis/trans-[M(L)₂F₂]⁺ complexes top

(I)	(II)	(III)	(IV)	(V)
1.8621 (10)	1.8541 (10)	1.887 (6)	1.887 (5)	1.7389 (15)
1.8444 (10)	1.8409 (10)	1.878 (6)	1.868 (4)	1.7232 (15)

Notes: (I) cis-[Cr(phen)₂F₂]ClO₄.H₂O (Birk et al., 2008); (II) cis-[Cr(bipy)₂F₂]ClO₄.H₂O (Yamaguchi-Terasaki et al., 2007); (III) trans-[Cr(en)₂F₂]ClO₄ (Brenčič & Leban, 1981); (IV) cis-[Cr(en)₂F₂]ClO₄.NaClO₄.H₂O (Brenčič et al., 1987); (V) cis-[V(bipy)₂F₂]BF₄ (Kavitha et al., 2005). en = ethane-1,2-diamine; bipy = 2,2'-bipyridine; phen = 1,10-phenanthroline.

Acknowledgements

The authors are gratful to Mr Flemming Hansen (Centre of Crystallographic Studies, University of Copenhagen) for collecting the X-ray diffraction data.

References

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