cis-Aqua-bis(2,2'-bipyridine-κN,N')fluoridochromium(III) bis-(perchlorate) dihydrate.

The title mixed aqua-fluoride complex, [CrF(C(10)H(8)N(2))(2)(H(2)O)](ClO(4))(2)·2H(2)O, has been synthesized by aqua-tion of the corresponding difluoride complex using lanthan-ide(III) ions as F(-) acceptors. The complex crystallizes with a Cr(III) ion at the center of a distorted octa-hedral coordination polyhedron with a cis arrangement of ligands. The crystal packing shows a hydrogen-bonding pattern involving water mol-ecules, 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 = 636.32

Triclinic,

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[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.070

S = 1.03

5691 reflections

352 parameters

H-atom parameters constrained

Δρmax = 0.55 e Å−3

Δρmin = −0.42 e Å−3

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.

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000127/hy2268Isup2.hkl

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

[CrF(C10H8N2)2(H2O)](ClO4)2·2H2O	Z = 2
Mr = 636.32	F(000) = 650
Triclinic, P1	Dx = 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

Nonius KappaCCD diffractometer	5691 independent reflections
Radiation source: fine-focus sealed tube	5244 reflections with I > 2σ(I)
graphite	Rint = 0.021
ω and φ scans	θmax = 27.6°, θmin = 1.8°
Absorption correction: gaussian (Coppens, 1970)	h = −12→12
Tmin = 0.805, Tmax = 0.925	k = −14→11
27824 measured reflections	l = −15→15

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(Fo2) + (0.0294P)2 + 1.0724P] where P = (Fo2 + 2Fc2)/3
5691 reflections	(Δ/σ)max = 0.001
352 parameters	Δρmax = 0.55 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

	x	y	z	Uiso*/Ueq
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*

	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)

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

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

(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)

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) ; (ii) ; (iii) .

Table 3

M—F bond distances (Å) for related cis/-[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.