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

The title complex, [CrF(2)(C(12)H(8)N(2))(2)]ClO(4)·H(2)O, displays a slightly distorted octa-hedral 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 = 567.87

Triclinic,

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[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.145

S = 1.41

4014 reflections

329 parameters

H-atom parameters constrained

Δρmax = 0.79 e Å−3

Δρmin = −0.51 e Å−3

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001153/wk2075sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[CrF2(C12H8N2)2]ClO4·H2O	Z = 2
Mr = 567.87	F000 = 578
Triclinic, P1	Dx = 1.651 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 7.6930 (10) Å	Cell parameters from 26598 reflections
b = 9.4640 (8) Å	θ = 2.3–25.0º
c = 16.0610 (17) Å	µ = 0.68 mm−1
α = 79.750 (7)º	T = 122 (1) K
β = 83.228 (12)º	Block, red
γ = 88.115 (8)º	0.44 × 0.41 × 0.16 mm
V = 1142.6 (2) Å3

Nonius KappaCCD area-detector diffractometer	4014 independent reflections
Radiation source: fine-focus sealed tube	3851 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.025
T = 122.0(10) K	θmax = 25.0º
ω and φ scans	θmin = 2.3º
Absorption correction: gaussian integration(Coppens, 1970)	h = −9→9
Tmin = 0.794, Tmax = 0.913	k = −11→11
28606 measured reflections	l = −18→19

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.031	(Δ/σ)max = 0.078
wR(F2) = 0.145	Δρmax = 0.79 e Å−3
S = 1.41	Δρmin = −0.51 e Å−3
4014 reflections	Extinction correction: none
329 parameters

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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
?—?—?—?	?

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

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) .