cis-Difluoridobis(1,10-phenanthroline)chromium(III) perchlorate monohydrate

Birk, T.; Bendix, J.; Weihe, H.

doi:10.1107/S1600536808001153

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m369-m370

doi:10.1107/S1600536808001153

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cis-Difluoridobis(1,10-phenanthroline)chromium(III) perchlorate monohydrate

Torben Birk,^a ^* Jesper Bendix ^a and Högni Weihe ^a

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

(Received 5 January 2008; accepted 11 January 2008; online 16 January 2008)

The title complex, [CrF₂(C₁₂H₈N₂)₂]ClO₄·H₂O, displays a slightly distorted octahedral coordination geometry around the central chromium(III) ion. The Cr environment is composed of a cis arrangement of two 1,10-phenanthroline [average Cr^III—N = 2.0726 (10) Å] and two fluoride [average Cr^III—F = 1.8533 (6) Å] ligands. The water molecule forms a hydrogen bond to fluorine in a neighbouring cation.

Related literature

For details of the general synthesis of amine-containing difluorido complexes of chromium(III), see: Glerup et al. (1970 ). For the structure of the analogous 2,2′-bipyridine complex, see: Yamaguchi-Terasaki et al. (2007 ). For related literature, see: Brenčič et al. (1981 , 1987 ); Delavar & Staples (1981 ); Kaizaki & Takemoto (1990 ); Kane-Maguire et al. (1986 ).

Experimental

Crystal data

[CrF₂(C₁₂H₈N₂)₂]ClO₄·H₂O
M_r = 567.87
Triclinic, $[P \overline 1]$
a = 7.6930 (10) Å
b = 9.4640 (8) Å
c = 16.0610 (17) Å
α = 79.750 (7)°
β = 83.228 (12)°
γ = 88.115 (8)°
V = 1142.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 122 (1) K
0.44 × 0.41 × 0.16 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: Gaussian integration (Coppens, 1970 ) T_min = 0.794, T_max = 0.913
28606 measured reflections
4014 independent reflections
3851 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.145
S = 1.41
4014 reflections
329 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cr1—F2	1.8444 (10)
Cr1—F1	1.8621 (10)
Cr1—N4	2.0566 (15)
Cr1—N2	2.0607 (15)
Cr1—N3	2.0797 (16)
Cr1—N1	2.0934 (15)

F2—Cr1—F1	95.92 (5)
F2—Cr1—N4	92.33 (5)
F1—Cr1—N4	91.42 (5)
F2—Cr1—N2	91.83 (6)
F1—Cr1—N2	91.86 (5)
N4—Cr1—N2	174.40 (5)
F2—Cr1—N3	89.38 (5)
F1—Cr1—N3	170.08 (5)
N4—Cr1—N3	79.95 (6)
N2—Cr1—N3	96.36 (6)
F2—Cr1—N1	170.54 (5)
F1—Cr1—N1	88.67 (5)
N4—Cr1—N1	95.83 (6)
N2—Cr1—N1	79.72 (6)
N3—Cr1—N1	87.34 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5B⋯F1ⁱ	1.03	1.69	2.7183 (19)	175
Symmetry code: (i) x-1, y, z.

Data collection: COLLECT (Nonius, 1999 ); 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: 10.1107/S1600536808001153/wk2075sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001153/wk2075Isup2.hkl

checkCIF report

Comment top

Difluoro complexes of chromium(III) with various amine ligands have received a steady interest in the literature. Areas of interest have been e.g. kinetic behavior (Delavar & Staples, 1981), solvatochromism (Kaizaki & Takemoto, 1990) and photochemical/photophysical properties (Kane-Maguire et al., 1986). From a synthetic point of view simple fluoro containing complexes exhibit some advantageous properties for synthesis in non-acidic media. The strong coordination of the small and basic fluoro ligand makes it suitable as an "inorganic" protection group, easily removed and substituted by other ligands. Only a limited number of complexes belonging to this group have been structural characterized e.g. cis-[Cr(NH₃)₄F₂]ClO₄ (Brenčič et al., 1981), cis-[Cr(en)₂F₂]ClO₄ ^. NaClOO₄ ^. H₂O (Brenčič et al., 1987) and cis-[Cr(bipy)₂F₂]ClO₄ (Yamaguchi-Terasaki et al., 2007). In this report we present the crystal structure of cis-Difluoro(1,10-phenanthroline)chromium(III) perchlorate monohydrate (1).

The structure of (1) shows a octahedral coordination geometry around the central chromium(III) ion consisting of a cis arrangment of two fluorine and two nitrogen ligator atoms (Figure 1). Comparison of the Cr—N bond distances in trans position relative to the fluoro ligand [N₁: 2.0934 (15) Å and N₃: 2.0797 (16) Å] show a slightly elongation compared to the corresponding in cis postion [N₂: 2.0607 (15) Å and N₄: 2.0566 (15) Å]. This pattern of bond lengths are similar to that found in the analogous bipyridine complex cis-Difluoro(2,2'-bipyridine)chromium(III) perchlorate, cis-[Cr(bipy)₂F₂]ClO₄.

The overall crystal packing is predominately determined by the approximately perpendicular orientation of the two planar 1,10-phenanthroline ligands [N₃—Cr—N₁:87.34 (6) °, N₃—Cr—N₂: 96.36 (6) °] and the presence of crystal water connecting each asymmetric unit with another through hydrogen bonding from water to fluorine (Figure 2).

Related literature top

For details of the general synthesis of amine-containing difluoro complexes of chromium(III), see Glerup et al. (1970). For the structure of the analogue 2,2'-bipyridine complex, see Yamaguchi-Terasaki et al. (2007).

For related literature, see: Brenčič et al. (1981, 1987); Delavar & Staples (1981); Kaizaki & Takemoto (1990); Kane-Maguire, Wallace & Speece (1986).

Experimental top

The title complex was synthesized by reflux of trans-difluorotetrakis(pyridine)chromium(III) perchlorate and 1,10-phenanthroline in 2-methoxyethanol according to the published method (Glerup et al., 1970).

Crystal suitable for X-ray diffraction were obtained by the following method: 0.208 g of the compound was dissolved in a solution of water/acetonitrile (20 ml/10 ml) and filtered though a filter paper into a small beaker. The beaker was covered with a lid of paper and left undisturbed at room temperature for crystallization (ca 3–5 days). The crystals was harvested by gently scratching with a spatula and washed with the mother liquid.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: COLLECT (Nonius, 1999); 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 and atom labeling scheme of cis-[Cr(phen)₂F₂]ClO₄^. H₂O. Displacement ellipsoids are drawn at 50% probability. H atoms with arbitrary radii.
	Fig. 2. The crystal packing in cis-[Cr(phen)₂F₂]ClO₄^.H₂O. Displacement ellipsoids are drawn at 50% probability. H atoms except the one originated from cystal water have been omitted.

cis-Difluorido(1,10-phenanthroline)chromium(III) perchlorate monohydrate top

Crystal data top

[CrF₂(C₁₂H₈N₂)₂]ClO₄·H₂O	Z = 2
M_r = 567.87	F(000) = 578
Triclinic, P1	D_x = 1.651 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.693 (1) Å	Cell parameters from 26598 reflections
b = 9.4640 (8) Å	θ = 2.3–25.0°
c = 16.0610 (17) Å	µ = 0.68 mm⁻¹
α = 79.750 (7)°	T = 122 K
β = 83.228 (12)°	Block, red
γ = 88.115 (8)°	0.44 × 0.41 × 0.16 mm
V = 1142.6 (2) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	4014 independent reflections
Radiation source: fine-focus sealed tube	3851 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: gaussian integration (Coppens, 1970)	h = −9→9
T_min = 0.794, T_max = 0.913	k = −11→11
28606 measured reflections	l = −18→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.145	(Δ/σ)_max = 0.078
S = 1.41	Δρ_max = 0.79 e Å⁻³
4014 reflections	Δρ_min = −0.51 e Å⁻³
329 parameters

Crystal data top

[CrF₂(C₁₂H₈N₂)₂]ClO₄·H₂O	γ = 88.115 (8)°
M_r = 567.87	V = 1142.6 (2) Å³
Triclinic, P1	Z = 2
a = 7.693 (1) Å	Mo Kα radiation
b = 9.4640 (8) Å	µ = 0.68 mm⁻¹
c = 16.0610 (17) Å	T = 122 K
α = 79.750 (7)°	0.44 × 0.41 × 0.16 mm
β = 83.228 (12)°

Data collection top

Nonius KappaCCD area-detector diffractometer	4014 independent reflections
Absorption correction: gaussian integration (Coppens, 1970)	3851 reflections with I > 2σ(I)
T_min = 0.794, T_max = 0.913	R_int = 0.025
28606 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.41	Δρ_max = 0.79 e Å⁻³
4014 reflections	Δρ_min = −0.51 e Å⁻³
329 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cr1	0.86046 (3)	0.55137 (3)	0.266315 (15)	0.01130 (17)
Cl1	0.42169 (6)	0.04581 (5)	0.27329 (3)	0.02027 (19)
F1	1.08731 (13)	0.60734 (11)	0.22192 (6)	0.0170 (3)
F2	0.92467 (13)	0.41293 (11)	0.35383 (6)	0.0175 (3)
N1	0.76931 (19)	0.68048 (16)	0.16003 (9)	0.0124 (3)
N3	0.6003 (2)	0.52586 (16)	0.31812 (9)	0.0136 (3)
N4	0.83917 (19)	0.70717 (16)	0.34149 (9)	0.0146 (3)
N2	0.8597 (2)	0.40348 (16)	0.18644 (10)	0.0144 (3)
C12	0.7592 (2)	0.60779 (19)	0.09479 (11)	0.0137 (4)
C1	0.7256 (2)	0.81930 (19)	0.14890 (12)	0.0171 (4)
H1	0.7315	0.8707	0.1942	0.020*
C24	0.5533 (2)	0.61063 (18)	0.37709 (10)	0.0138 (4)
C23	0.6826 (2)	0.70727 (19)	0.39112 (10)	0.0139 (4)
C13	0.4814 (2)	0.43556 (19)	0.30366 (12)	0.0173 (4)
H13	0.5134	0.3751	0.2629	0.021*
C15	0.2655 (2)	0.5115 (2)	0.40692 (12)	0.0197 (4)
H15	0.1510	0.5056	0.4367	0.024*
C11	0.8100 (2)	0.45883 (19)	0.10871 (11)	0.0140 (4)
C10	0.9151 (2)	0.26736 (19)	0.20079 (12)	0.0191 (4)
H10	0.9493	0.2277	0.2551	0.023*
C18	0.4782 (3)	0.7862 (2)	0.50181 (12)	0.0202 (4)
H18	0.4531	0.8434	0.5448	0.024*
C22	0.9635 (2)	0.7957 (2)	0.35158 (12)	0.0183 (4)
H22	1.0730	0.7964	0.3173	0.022*
C7	0.8106 (2)	0.3795 (2)	0.04286 (12)	0.0171 (4)
C19	0.6457 (2)	0.79451 (19)	0.45241 (11)	0.0164 (4)
C9	0.9245 (3)	0.1812 (2)	0.13812 (13)	0.0224 (4)
H9	0.9671	0.0851	0.1497	0.027*
C20	0.7809 (3)	0.8874 (2)	0.46210 (12)	0.0208 (4)
H20	0.7628	0.9482	0.5035	0.025*
C8	0.8722 (3)	0.2354 (2)	0.05988 (13)	0.0212 (4)
H8	0.8771	0.1771	0.0173	0.025*
C3	0.6631 (2)	0.8201 (2)	0.00597 (12)	0.0204 (4)
H3	0.6278	0.8691	−0.0464	0.024*
C21	0.9360 (3)	0.8881 (2)	0.41136 (13)	0.0231 (4)
H21	1.0260	0.9512	0.4168	0.028*
C17	0.3534 (2)	0.6962 (2)	0.48787 (12)	0.0201 (4)
H17	0.2421	0.6933	0.5207	0.024*
C2	0.6715 (3)	0.8918 (2)	0.07198 (12)	0.0214 (4)
H2	0.6406	0.9908	0.0661	0.026*
C6	0.7569 (2)	0.4481 (2)	−0.03680 (12)	0.0198 (4)
H6	0.7560	0.3946	−0.0815	0.024*
C5	0.7068 (3)	0.5882 (2)	−0.05005 (12)	0.0205 (4)
H5	0.6709	0.6311	−0.1035	0.025*
C4	0.7071 (2)	0.6730 (2)	0.01613 (11)	0.0168 (4)
C16	0.3878 (2)	0.6065 (2)	0.42455 (11)	0.0164 (4)
C14	0.3132 (2)	0.4267 (2)	0.34592 (12)	0.0205 (4)
H14	0.2312	0.3630	0.3333	0.025*
O3	0.3942 (2)	−0.10036 (16)	0.26532 (11)	0.0357 (4)
O2	0.5918 (3)	0.0563 (2)	0.29920 (14)	0.0537 (5)
O4	0.2950 (3)	0.0879 (2)	0.33573 (14)	0.0617 (7)
O1	0.4169 (4)	0.1381 (2)	0.19353 (12)	0.0641 (7)
O5	0.1662 (2)	0.87161 (16)	0.12962 (9)	0.0286 (4)*
H5A	0.2568	0.9069	0.1647	0.034*
H5B	0.1306	0.7742	0.1664	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr1	0.0102 (2)	0.0141 (2)	0.0097 (2)	−0.00101 (14)	0.00002 (14)	−0.00270 (15)
Cl1	0.0265 (3)	0.0206 (3)	0.0139 (3)	0.0005 (2)	−0.0013 (2)	−0.0043 (2)
F1	0.0123 (5)	0.0210 (6)	0.0168 (6)	−0.0029 (4)	0.0026 (4)	−0.0030 (4)
F2	0.0128 (5)	0.0227 (6)	0.0152 (5)	−0.0009 (4)	−0.0013 (4)	0.0017 (4)
N1	0.0098 (7)	0.0129 (7)	0.0140 (7)	−0.0007 (6)	0.0019 (6)	−0.0029 (6)
N3	0.0110 (7)	0.0157 (7)	0.0139 (7)	−0.0005 (6)	−0.0028 (5)	−0.0011 (6)
N4	0.0136 (8)	0.0185 (8)	0.0117 (7)	−0.0003 (6)	−0.0011 (6)	−0.0024 (6)
N2	0.0140 (8)	0.0136 (8)	0.0154 (8)	−0.0016 (6)	0.0019 (6)	−0.0038 (6)
C12	0.0090 (8)	0.0195 (9)	0.0125 (9)	−0.0024 (7)	0.0010 (7)	−0.0038 (7)
C1	0.0124 (9)	0.0166 (9)	0.0224 (10)	0.0005 (7)	−0.0003 (7)	−0.0051 (7)
C24	0.0128 (9)	0.0153 (8)	0.0114 (8)	0.0024 (7)	−0.0023 (6)	0.0027 (7)
C23	0.0146 (9)	0.0161 (8)	0.0107 (8)	0.0029 (7)	−0.0030 (7)	−0.0010 (7)
C13	0.0182 (9)	0.0174 (9)	0.0164 (9)	−0.0010 (7)	−0.0055 (7)	−0.0008 (7)
C15	0.0110 (9)	0.0219 (9)	0.0217 (10)	0.0009 (7)	−0.0006 (7)	0.0073 (7)
C11	0.0102 (8)	0.0181 (9)	0.0139 (9)	−0.0024 (7)	0.0015 (7)	−0.0046 (7)
C10	0.0183 (9)	0.0150 (9)	0.0231 (10)	−0.0012 (7)	−0.0011 (8)	−0.0010 (7)
C18	0.0239 (10)	0.0233 (10)	0.0127 (9)	0.0108 (8)	−0.0020 (7)	−0.0030 (7)
C22	0.0144 (9)	0.0245 (10)	0.0171 (9)	−0.0034 (8)	−0.0022 (7)	−0.0056 (7)
C7	0.0129 (9)	0.0209 (9)	0.0183 (9)	−0.0049 (7)	0.0032 (7)	−0.0080 (7)
C19	0.0206 (10)	0.0170 (9)	0.0113 (9)	0.0027 (7)	−0.0047 (7)	−0.0001 (7)
C9	0.0221 (10)	0.0138 (9)	0.0307 (11)	−0.0008 (8)	0.0029 (8)	−0.0061 (8)
C20	0.0265 (10)	0.0226 (10)	0.0164 (9)	0.0025 (8)	−0.0071 (8)	−0.0097 (7)
C8	0.0193 (10)	0.0206 (10)	0.0249 (10)	−0.0043 (8)	0.0057 (8)	−0.0121 (8)
C3	0.0167 (9)	0.0250 (10)	0.0183 (9)	0.0010 (8)	−0.0031 (7)	0.0000 (8)
C21	0.0255 (11)	0.0230 (10)	0.0242 (10)	−0.0055 (8)	−0.0084 (8)	−0.0082 (8)
C17	0.0149 (9)	0.0244 (10)	0.0168 (9)	0.0086 (8)	0.0036 (7)	0.0030 (7)
C2	0.0206 (10)	0.0162 (9)	0.0268 (10)	0.0016 (8)	−0.0035 (8)	−0.0014 (8)
C6	0.0162 (9)	0.0297 (10)	0.0158 (9)	−0.0030 (8)	0.0006 (7)	−0.0111 (8)
C5	0.0179 (10)	0.0323 (11)	0.0121 (9)	−0.0025 (8)	−0.0020 (7)	−0.0054 (8)
C4	0.0108 (8)	0.0218 (9)	0.0169 (9)	−0.0012 (7)	0.0003 (7)	−0.0017 (7)
C16	0.0124 (9)	0.0183 (9)	0.0152 (9)	0.0042 (7)	−0.0016 (7)	0.0054 (7)
C14	0.0144 (9)	0.0181 (9)	0.0276 (10)	−0.0027 (7)	−0.0079 (8)	0.0033 (8)
O3	0.0323 (9)	0.0276 (8)	0.0520 (10)	−0.0016 (7)	−0.0062 (7)	−0.0190 (7)
O2	0.0472 (12)	0.0437 (10)	0.0732 (13)	−0.0143 (9)	−0.0298 (10)	−0.0008 (10)
O4	0.0711 (15)	0.0491 (11)	0.0621 (13)	−0.0118 (10)	0.0385 (11)	−0.0304 (10)
O1	0.111 (2)	0.0517 (12)	0.0274 (10)	0.0159 (12)	−0.0227 (11)	0.0056 (8)

Geometric parameters (Å, º) top

Cr1—F2	1.8444 (10)	C11—C7	1.401 (3)
Cr1—F1	1.8621 (10)	C10—C9	1.398 (3)
Cr1—N4	2.0566 (15)	C10—H10	0.9501
Cr1—N2	2.0607 (15)	C18—C17	1.367 (3)
Cr1—N3	2.0797 (16)	C18—C19	1.428 (3)
Cr1—N1	2.0934 (15)	C18—H18	0.9501
Cl1—O4	1.4144 (17)	C22—C21	1.404 (3)
Cl1—O1	1.4200 (18)	C22—H22	0.9501
Cl1—O2	1.4310 (19)	C7—C8	1.419 (3)
Cl1—O3	1.4365 (15)	C7—C6	1.429 (3)
N1—C1	1.331 (2)	C19—C20	1.423 (3)
N1—C12	1.363 (2)	C9—C8	1.371 (3)
N3—C13	1.339 (2)	C9—H9	0.9500
N3—C24	1.357 (2)	C20—C21	1.362 (3)
N4—C22	1.335 (2)	C20—H20	0.9500
N4—C23	1.364 (2)	C8—H8	0.9500
N2—C10	1.333 (2)	C3—C2	1.365 (3)
N2—C11	1.359 (2)	C3—C4	1.406 (3)
C12—C4	1.401 (3)	C3—H3	0.9500
C12—C11	1.436 (3)	C21—H21	0.9500
C1—C2	1.404 (3)	C17—C16	1.433 (3)
C1—H1	0.9501	C17—H17	0.9500
C24—C16	1.403 (3)	C2—H2	0.9500
C24—C23	1.436 (2)	C6—C5	1.355 (3)
C23—C19	1.393 (3)	C6—H6	0.9499
C13—C14	1.386 (3)	C5—C4	1.442 (3)
C13—H13	0.9501	C5—H5	0.9500
C15—C14	1.384 (3)	C14—H14	0.9500
C15—C16	1.407 (3)	O5—H5A	1.0444
C15—H15	0.9500	O5—H5B	1.0283

F2—Cr1—F1	95.92 (5)	C7—C11—C12	119.83 (16)
F2—Cr1—N4	92.33 (5)	N2—C10—C9	121.87 (17)
F1—Cr1—N4	91.42 (5)	N2—C10—H10	119.1
F2—Cr1—N2	91.83 (6)	C9—C10—H10	119.0
F1—Cr1—N2	91.86 (5)	C17—C18—C19	120.56 (17)
N4—Cr1—N2	174.40 (5)	C17—C18—H18	119.6
F2—Cr1—N3	89.38 (5)	C19—C18—H18	119.9
F1—Cr1—N3	170.08 (5)	N4—C22—C21	121.54 (17)
N4—Cr1—N3	79.95 (6)	N4—C22—H22	119.2
N2—Cr1—N3	96.36 (6)	C21—C22—H22	119.3
F2—Cr1—N1	170.54 (5)	C11—C7—C8	116.47 (17)
F1—Cr1—N1	88.67 (5)	C11—C7—C6	119.10 (17)
N4—Cr1—N1	95.83 (6)	C8—C7—C6	124.39 (17)
N2—Cr1—N1	79.72 (6)	C23—C19—C20	116.89 (17)
N3—Cr1—N1	87.34 (6)	C23—C19—C18	119.31 (17)
O4—Cl1—O1	111.05 (15)	C20—C19—C18	123.80 (17)
O4—Cl1—O2	108.77 (15)	C8—C9—C10	119.92 (17)
O1—Cl1—O2	107.61 (15)	C8—C9—H9	120.0
O4—Cl1—O3	110.09 (11)	C10—C9—H9	120.1
O1—Cl1—O3	110.47 (12)	C21—C20—C19	119.31 (17)
O2—Cl1—O3	108.78 (11)	C21—C20—H20	120.5
C1—N1—C12	118.50 (15)	C19—C20—H20	120.1
C1—N1—Cr1	128.82 (12)	C9—C8—C7	119.61 (18)
C12—N1—Cr1	112.66 (11)	C9—C8—H8	120.3
C13—N3—C24	118.21 (16)	C7—C8—H8	120.1
C13—N3—Cr1	129.08 (13)	C2—C3—C4	119.46 (17)
C24—N3—Cr1	112.64 (12)	C2—C3—H3	120.2
C22—N4—C23	118.54 (16)	C4—C3—H3	120.3
C22—N4—Cr1	127.53 (13)	C20—C21—C22	120.31 (18)
C23—N4—Cr1	113.65 (12)	C20—C21—H21	119.8
C10—N2—C11	118.64 (16)	C22—C21—H21	119.9
C10—N2—Cr1	127.12 (13)	C18—C17—C16	121.10 (17)
C11—N2—Cr1	113.99 (12)	C18—C17—H17	119.4
N1—C12—C4	122.95 (16)	C16—C17—H17	119.6
N1—C12—C11	116.89 (15)	C3—C2—C1	120.06 (17)
C4—C12—C11	120.14 (16)	C3—C2—H2	120.1
N1—C1—C2	121.76 (17)	C1—C2—H2	119.8
N1—C1—H1	119.1	C5—C6—C7	121.37 (17)
C2—C1—H1	119.2	C5—C6—H6	119.2
N3—C24—C16	123.29 (17)	C7—C6—H6	119.5
N3—C24—C23	117.20 (16)	C6—C5—C4	120.78 (17)
C16—C24—C23	119.51 (17)	C6—C5—H5	119.7
N4—C23—C19	123.39 (16)	C4—C5—H5	119.5
N4—C23—C24	116.13 (16)	C12—C4—C3	117.27 (17)
C19—C23—C24	120.48 (17)	C12—C4—C5	118.77 (17)
N3—C13—C14	122.54 (18)	C3—C4—C5	123.94 (17)
N3—C13—H13	118.9	C24—C16—C15	116.91 (17)
C14—C13—H13	118.6	C24—C16—C17	119.01 (17)
C14—C15—C16	119.58 (17)	C15—C16—C17	124.08 (17)
C14—C15—H15	120.1	C15—C14—C13	119.45 (17)
C16—C15—H15	120.3	C15—C14—H14	120.1
N2—C11—C7	123.46 (17)	C13—C14—H14	120.4
N2—C11—C12	116.68 (16)	H5A—O5—H5B	101.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···F1ⁱ	1.03	1.69	2.7183 (19)	175

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[CrF₂(C₁₂H₈N₂)₂]ClO₄·H₂O
M_r	567.87
Crystal system, space group	Triclinic, P1
Temperature (K)	122
a, b, c (Å)	7.693 (1), 9.4640 (8), 16.0610 (17)
α, β, γ (°)	79.750 (7), 83.228 (12), 88.115 (8)
V (Å³)	1142.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.44 × 0.41 × 0.16

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Gaussian integration (Coppens, 1970)
T_min, T_max	0.794, 0.913
No. of measured, independent and observed [I > 2σ(I)] reflections	28606, 4014, 3851
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.145, 1.41
No. of reflections	4014
No. of parameters	329
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.51

Computer programs: COLLECT (Nonius, 1999), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected geometric parameters (Å, º) top

Cr1—F2	1.8444 (10)	Cr1—N2	2.0607 (15)
Cr1—F1	1.8621 (10)	Cr1—N3	2.0797 (16)
Cr1—N4	2.0566 (15)	Cr1—N1	2.0934 (15)

F2—Cr1—F1	95.92 (5)	N4—Cr1—N3	79.95 (6)
F2—Cr1—N4	92.33 (5)	N2—Cr1—N3	96.36 (6)
F1—Cr1—N4	91.42 (5)	F2—Cr1—N1	170.54 (5)
F2—Cr1—N2	91.83 (6)	F1—Cr1—N1	88.67 (5)
F1—Cr1—N2	91.86 (5)	N4—Cr1—N1	95.83 (6)
N4—Cr1—N2	174.40 (5)	N2—Cr1—N1	79.72 (6)
F2—Cr1—N3	89.38 (5)	N3—Cr1—N1	87.34 (6)
F1—Cr1—N3	170.08 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···F1ⁱ	1.029	1.692	2.7183 (19)	174.84

Symmetry code: (i) x−1, y, z.

Acknowledgements

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

References

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