Bis(μ-4-fluoro-2,6-diformyl-phenolato)bis-[diaqua-nickel(II)] dichloride.

In the title dinuclear nickel(II) complex, [Ni(2)(C(8)H(4)FO(3))(2)(H(2)O)(4)]Cl(2), synthesized by the reaction between 4-fluoro-2,6-diformyl-phenol and nickel(II) chloride in methanol, the coordination cation is located on an inversion center and the Ni(II) atom adopts a slightly distorted octa-hedral coordination geometry. The two Ni atoms are bridged by two phenolate O atoms and the intra-molecular Ni⋯Ni distance is 3.0751 (9) Å. The crystal structure is stabilized by O-H⋯Cl hydrogen bonds.

Related literature

For the synthesis of related compounds and their properties, see: Thompson et al. (1996 ▶); Zhou et al. (2005 ▶); Raimondi et al. (2004 ▶); Taniguchi (1984 ▶); Mohanta et al. (1998 ▶); Wang et al. (1997 ▶). For related structures, see: Adhikary et al. (1987 ▶); Zhou et al. (2007 ▶).

Experimental

Crystal data

[Ni2(C8H4FO3)2(H2O)4]Cl2

M = 594.61

Monoclinic,

a = 8.3299 (14) Å

b = 13.576 (2) Å

c = 9.9965 (17) Å

β = 114.623 (3)°

V = 1027.6 (3) Å3

Z = 2

Mo Kα radiation

μ = 2.16 mm−1

T = 291 K

0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.603, T max = 0.672

5827 measured reflections

2018 independent reflections

1708 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.119

S = 1.05

2018 reflections

157 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.94 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810016284/gk2267sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016284/gk2267Isup2.hkl

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

[Ni2(C8H4FO3)2(H2O)4]Cl2	F(000) = 600
Mr = 594.61	Dx = 1.922 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3902 reflections
a = 8.3299 (14) Å	θ = 2.2–28.0°
b = 13.576 (2) Å	µ = 2.16 mm−1
c = 9.9965 (17) Å	T = 291 K
β = 114.623 (3)°	Block, green
V = 1027.6 (3) Å3	0.26 × 0.22 × 0.20 mm
Z = 2

Bruker SMART APEX CCD diffractometer	2018 independent reflections
Radiation source: sealed tube	1708 reflections with I > 2σ(I)
graphite	Rint = 0.041
phi and ω scans	θmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→7
Tmin = 0.603, Tmax = 0.672	k = −15→16
5827 measured reflections	l = −8→12

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.06P)2 + 1.99P] where P = (Fo2 + 2Fc2)/3
2018 reflections	(Δ/σ)max < 0.001
157 parameters	Δρmax = 0.42 e Å−3
4 restraints	Δρmin = −0.94 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.2077 (6)	0.3085 (3)	0.2584 (5)	0.0349 (11)
H1	0.1159	0.2647	0.2095	0.042*
C2	0.2373 (6)	0.3811 (3)	0.1689 (5)	0.0281 (9)
C3	0.1336 (6)	0.3705 (3)	0.0166 (5)	0.0331 (10)
H3	0.0559	0.3178	−0.0182	0.040*
C4	0.1475 (7)	0.4376 (4)	−0.0792 (5)	0.0401 (12)
C5	0.2548 (7)	0.5179 (4)	−0.0329 (5)	0.0370 (11)
H5	0.2609	0.5630	−0.1007	0.044*
C6	0.3552 (6)	0.5318 (3)	0.1172 (5)	0.0276 (9)
C7	0.3474 (5)	0.4643 (3)	0.2223 (5)	0.0228 (8)
C8	0.4651 (6)	0.6193 (4)	0.1539 (6)	0.0356 (11)
H8	0.4680	0.6545	0.0752	0.043*
Cl1	0.16724 (17)	0.66791 (9)	0.64475 (15)	0.0406 (3)
F1	0.0499 (5)	0.4245 (3)	−0.2256 (3)	0.0555 (9)
Ni1	0.43045 (7)	0.40202 (4)	0.53212 (6)	0.02194 (18)
O1	0.2874 (4)	0.2955 (2)	0.3923 (4)	0.0318 (7)
O2	0.4438 (4)	0.4760 (2)	0.3627 (3)	0.0249 (6)
O3	0.5544 (5)	0.6519 (2)	0.2770 (4)	0.0351 (8)
O4	0.1900 (5)	0.4629 (3)	0.4960 (4)	0.0415 (8)
H4A	0.201 (8)	0.502 (4)	0.565 (5)	0.050*
H4B	0.116 (6)	0.417 (3)	0.484 (7)	0.050*
O5	0.6594 (5)	0.3234 (3)	0.5759 (4)	0.0402 (8)
H5C	0.725 (7)	0.313 (4)	0.6662 (18)	0.048*
H5A	0.717 (7)	0.354 (4)	0.535 (6)	0.048*

	U11	U22	U33	U12	U13	U23
C1	0.034 (2)	0.032 (2)	0.034 (3)	−0.0109 (19)	0.008 (2)	−0.002 (2)
C2	0.024 (2)	0.025 (2)	0.035 (2)	−0.0003 (17)	0.0122 (18)	−0.0051 (18)
C3	0.028 (2)	0.032 (2)	0.034 (3)	0.0002 (19)	0.0079 (19)	−0.010 (2)
C4	0.050 (3)	0.042 (3)	0.019 (2)	0.012 (2)	0.006 (2)	−0.001 (2)
C5	0.055 (3)	0.035 (3)	0.018 (2)	0.001 (2)	0.012 (2)	0.0028 (19)
C6	0.031 (2)	0.027 (2)	0.024 (2)	−0.0020 (17)	0.0109 (17)	0.0029 (17)
C7	0.0206 (19)	0.0228 (19)	0.028 (2)	0.0044 (15)	0.0127 (17)	0.0059 (17)
C8	0.039 (3)	0.036 (3)	0.036 (3)	0.004 (2)	0.020 (2)	0.011 (2)
Cl1	0.0417 (7)	0.0394 (6)	0.0449 (7)	0.0017 (5)	0.0222 (6)	−0.0033 (5)
F1	0.066 (2)	0.0570 (19)	0.0244 (15)	−0.0102 (17)	−0.0007 (14)	−0.0047 (14)
Ni1	0.0241 (3)	0.0209 (3)	0.0230 (3)	−0.0028 (2)	0.0120 (2)	0.0000 (2)
O1	0.0358 (16)	0.0266 (16)	0.0336 (18)	−0.0065 (13)	0.0149 (14)	−0.0018 (13)
O2	0.0303 (15)	0.0256 (14)	0.0188 (14)	−0.0044 (12)	0.0103 (12)	0.0019 (11)
O3	0.0455 (19)	0.0349 (18)	0.0282 (18)	−0.0055 (15)	0.0186 (15)	0.0046 (14)
O4	0.0335 (18)	0.040 (2)	0.053 (2)	0.0004 (15)	0.0196 (17)	−0.0023 (17)
O5	0.0359 (18)	0.051 (2)	0.0361 (19)	0.0158 (16)	0.0178 (15)	0.0147 (17)

C1—O1	1.234 (6)	C8—O3	1.226 (6)
C1—C2	1.421 (7)	C8—H8	0.9300
C1—H1	0.9300	Ni1—O3i	1.998 (3)
C2—C3	1.410 (6)	Ni1—O2i	2.007 (3)
C2—C7	1.412 (6)	Ni1—O2	2.012 (3)
C3—C4	1.361 (7)	Ni1—O1	2.019 (3)
C3—H3	0.9300	Ni1—O4	2.054 (4)
C4—F1	1.358 (5)	Ni1—O5	2.067 (3)
C4—C5	1.364 (7)	O2—Ni1i	2.007 (3)
C5—C6	1.393 (6)	O3—Ni1i	1.998 (3)
C5—H5	0.9300	O4—H4A	0.85 (5)
C6—C7	1.416 (6)	O4—H4B	0.85 (5)
C6—C8	1.450 (6)	O5—H5C	0.85 (2)
C7—O2	1.304 (5)	O5—H5A	0.86 (6)
O1—C1—C2	128.7 (4)	O3i—Ni1—O2	169.53 (13)
O1—C1—H1	115.6	O2i—Ni1—O2	80.18 (13)
C2—C1—H1	115.6	O3i—Ni1—O1	100.54 (14)
C3—C2—C1	114.8 (4)	O2i—Ni1—O1	169.22 (12)
C3—C2—C7	119.9 (4)	O2—Ni1—O1	89.91 (13)
C1—C2—C7	125.0 (4)	O3i—Ni1—O4	89.11 (15)
C4—C3—C2	119.9 (4)	O2i—Ni1—O4	91.02 (14)
C4—C3—H3	120.1	O2—Ni1—O4	92.46 (14)
C2—C3—H3	120.1	O1—Ni1—O4	85.14 (14)
F1—C4—C3	118.9 (5)	O3i—Ni1—O5	85.59 (15)
F1—C4—C5	118.9 (5)	O2i—Ni1—O5	94.66 (15)
C3—C4—C5	122.2 (4)	O2—Ni1—O5	93.79 (13)
C4—C5—C6	119.2 (5)	O1—Ni1—O5	90.19 (15)
C4—C5—H5	120.4	O4—Ni1—O5	172.19 (15)
C6—C5—H5	120.4	C1—O1—Ni1	123.0 (3)
C5—C6—C7	121.3 (4)	C7—O2—Ni1i	128.1 (3)
C5—C6—C8	114.5 (4)	C7—O2—Ni1	128.3 (3)
C7—C6—C8	124.1 (4)	Ni1i—O2—Ni1	99.82 (13)
O2—C7—C2	121.1 (4)	C8—O3—Ni1i	126.6 (3)
O2—C7—C6	121.5 (4)	Ni1—O4—H4A	110 (4)
C2—C7—C6	117.4 (4)	Ni1—O4—H4B	109 (4)
O3—C8—C6	127.3 (4)	H4A—O4—H4B	114 (6)
O3—C8—H8	116.4	Ni1—O5—H5C	116 (4)
C6—C8—H8	116.4	Ni1—O5—H5A	108 (4)
O3i—Ni1—O2i	89.45 (13)	H5C—O5—H5A	111 (6)
O1—C1—C2—C3	174.3 (5)	O3i—Ni1—O1—C1	161.0 (4)
O1—C1—C2—C7	−11.6 (8)	O2i—Ni1—O1—C1	3.4 (9)
C1—C2—C3—C4	178.2 (5)	O2—Ni1—O1—C1	−19.6 (4)
C7—C2—C3—C4	3.7 (7)	O4—Ni1—O1—C1	72.9 (4)
C2—C3—C4—F1	178.3 (4)	O5—Ni1—O1—C1	−113.4 (4)
C2—C3—C4—C5	−2.4 (8)	C2—C7—O2—Ni1i	−166.2 (3)
F1—C4—C5—C6	180.0 (5)	C6—C7—O2—Ni1i	16.8 (6)
C3—C4—C5—C6	0.7 (8)	C2—C7—O2—Ni1	−12.6 (5)
C4—C5—C6—C7	−0.3 (8)	C6—C7—O2—Ni1	170.5 (3)
C4—C5—C6—C8	179.7 (5)	O3i—Ni1—O2—C7	−167.1 (7)
C3—C2—C7—O2	179.7 (4)	O2i—Ni1—O2—C7	−159.3 (4)
C1—C2—C7—O2	5.8 (7)	O1—Ni1—O2—C7	16.5 (3)
C3—C2—C7—C6	−3.3 (6)	O4—Ni1—O2—C7	−68.7 (3)
C1—C2—C7—C6	−177.1 (4)	O5—Ni1—O2—C7	106.7 (3)
C5—C6—C7—O2	178.6 (4)	O3i—Ni1—O2—Ni1i	−7.8 (8)
C8—C6—C7—O2	−1.4 (7)	O2i—Ni1—O2—Ni1i	0.0
C5—C6—C7—C2	1.6 (6)	O1—Ni1—O2—Ni1i	175.74 (14)
C8—C6—C7—C2	−178.4 (4)	O4—Ni1—O2—Ni1i	90.61 (15)
C5—C6—C8—O3	173.9 (5)	O5—Ni1—O2—Ni1i	−94.08 (16)
C7—C6—C8—O3	−6.1 (8)	C6—C8—O3—Ni1i	−2.9 (7)
C2—C1—O1—Ni1	21.3 (7)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···Cl1	0.85 (5)	2.44 (3)	3.198 (4)	149 (6)
O4—H4B···Cl1ii	0.85 (5)	2.45 (3)	3.241 (4)	154 (5)
O5—H5C···Cl1iii	0.85 (2)	2.61 (4)	3.313 (4)	141 (5)
O5—H5A···Cl1i	0.86 (6)	2.39 (4)	3.101 (4)	142 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯Cl1	0.85 (5)	2.44 (3)	3.198 (4)	149 (6)
O4—H4B⋯Cl1i	0.85 (5)	2.45 (3)	3.241 (4)	154 (5)
O5—H5C⋯Cl1ii	0.85 (2)	2.61 (4)	3.313 (4)	141 (5)
O5—H5A⋯Cl1iii	0.86 (6)	2.39 (4)	3.101 (4)	142 (5)

Symmetry codes: (i) ; (ii) ; (iii) .