Tetra­quabis(5-fluoro­saccharinato)nickel(II)

In the centrosymmetric title complex, [Ni(C₇H₃FNO₃S)₂(H₂O)₄], the Ni^II atom exhibits a slightly distorted trans-NiN₂O₄ octa­hedral coordination. The nitro­gen donors are provided by two 5-fluoro­saccharinate ligands and the oxygen donors are provided by four water mol­ecules. The crystal structure features O—H...O and bifurcated O—H...(F,O) hydrogen bonds, the latter involving the F atom of the 5-fluoro­saccharinate ligand.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.024
• wR factor = 0.065
• Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   150.000
            Value of melting point given =     0.000
PLAT432_ALERT_2_C Short Inter X...Y Contact  O3     ..  C4      ..       2.94 Ang.
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.89
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5A    ..  F1      ..       2.59 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.895
            Tmax scaled      0.895 Tmin scaled      0.794
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The study of metal saccharinate complexes has been of current interest with respect to their incorporation into novel coordination polymers (Falvello et al., 2001). As a continuation of our own efforts in this area (Khalil et al., 2005), we have deemed it worthwhile to explore the solid state structures of metal organic compounds containing fluorinated saccharinates. The choice of fluorinated saccharinates stems from the novel types of interactions in which carbon bound fluorine may participate (Plenio, 1997). Our initial studies have led to the preparation of the title nickel complex (I) that contains 5-fluorosaccharinate (5-fsacch) as an anionic ligand.

The crystal structure of (I) consists of monomeric Ni(5-fsacch)₂(H₂O)₄ molecular units, as shown in Figure 1. The Ni^II atom, which lies on an inversion center, is octahedrally coordinated by a pair of trans N atoms from two equivalent 5-fsacch ligands, and by four O atoms from two pairs that contain equivalent water molecules (Table 1).

The average Ni—N and Ni—O bond distances in (I) are 2.086 Å (1) and 2.076 (2) Å, respectively. By comparison to a similar structure, in (I) the average Ni—N distance is shorter whereas the average Ni—O distance is longer than their corresponding values in the previously reported nickel saccharinate complex, namely Ni(sacch)₂(H₂O)₄.2(H₂O) (II) (sacch = saccharinate) (Haider et al., 1983). In (II) the average Ni—N distance is 2.154 (1) Å, while the average Ni—O distance is 2.069 (2) Å. All angles in (I) are normal and are comparable to their corresponding values in (II).

The crystal structure in (I) features extensive hydrogen bonding (Table 2) in which both the carbonyl and sulfonyl O atoms of 5-fsacch, as well its carbon bound fluorine, act as hydrogen bond acceptors for the water H atoms, as shown in Fig. 2. This hydrogen bonding scheme is different from that of (II) for two major reasons. First, there is the presence of the previously mentioned C—F···H hydrogen bonding in (I) that is obviously absent in (II). Second, in (II) there exists hydrogen bonding involving lattice water molecules, which because of their absence in (I) precludes such interactions.

Related literature

For a related structure; see: Haider et al. (1983). For background, see: Falvello et al. (2001); Khalil et al. (2005); Plenio (1997).

S2. Experimental

All chemicals and solvents were purchased from commercial sources and used without further purification. The synthesis of sodium 5-fluorosaccharinate will be described elsewhere. A 10 ml solution of sodium 5-fluorosaccharinate (0.10 mmol) was added dropwise to a 10.0 ml solution of nickel(II) chloride tetrahydrate (0.050 mmol). Light blue, block-like crystals of (I) were formed in about three weeks by slow evaporation after the solution volume was reduced to 5.0 ml under ambient conditions.

S3. Refinement

Hydrogen atoms bonded to carbon were placed in geometrically idealized positions and included as riding atoms with refined isotropic displacement parameters. The water H atoms were located in difference maps and refined freely.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The coordination environment of Ni(II) in (I), with the atom-labeling scheme. The H atoms of 5-fsacch are omitted for clarity. Displacement ellipsoids for nonhydrogen atoms are drawn at the 50% probability level. Hydrogen bonds are represented by dashed lines.
	Fig. 2. View of the crystal packing in (I). All H atoms except for those of water are omitted for clarity. Hydrogen bonds are represented by dashed lines.

Tetraquabis(5-fluorosaccharinato)nickel(II)

Crystal data

[Ni(C7H3FNO3S)2(H2O)4]	Z = 1
Mr = 531.10	F(000) = 270
Triclinic, P1	Dx = 1.942 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9649 (3) Å	Cell parameters from 4507 reflections
b = 8.0484 (3) Å	θ = 2.4–26.4°
c = 9.5877 (4) Å	µ = 1.38 mm^−1
α = 101.780 (1)°	T = 150 K
β = 105.983 (1)°	Block, light blue
γ = 110.973 (1)°	0.22 × 0.18 × 0.08 mm
V = 454.18 (3) Å^3

Data collection

Bruker SMART APEX CCD diffractometer	1858 independent reflections
Radiation source: fine-focus sealed tube	1769 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 26.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −8→8
Tmin = 0.887, Tmax = 1.000	k = −10→10
6861 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Hydrogen site location: mixed
wR(F^2) = 0.065	Only H-atom displacement parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0376P)^2 + 0.2342P] where P = (Fo^2 + 2Fc^2)/3
1858 reflections	(Δ/σ)max < 0.001
161 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.01450 (11)
S1	−0.01342 (6)	0.32955 (6)	0.24583 (5)	0.01495 (12)
C1	0.2752 (3)	0.2997 (2)	0.1523 (2)	0.0176 (4)
C2	0.0749 (3)	0.2377 (2)	0.0098 (2)	0.0164 (3)
C3	0.0542 (3)	0.1736 (2)	−0.1416 (2)	0.0179 (3)
H3	0.1724	0.1621	−0.1670	0.020 (5)*
C4	−0.1482 (3)	0.1274 (2)	−0.2531 (2)	0.0179 (3)
C5	−0.3263 (3)	0.1414 (3)	−0.2223 (2)	0.0217 (4)
H5	−0.4613	0.1090	−0.3041	0.036 (6)*
C6	−0.3043 (3)	0.2036 (3)	−0.0695 (2)	0.0209 (4)
H6	−0.4232	0.2132	−0.0438	0.026 (6)*
C7	−0.1013 (3)	0.2507 (2)	0.04337 (19)	0.0169 (3)
F1	−0.17280 (17)	0.06728 (16)	−0.40248 (12)	0.0230 (2)
N1	0.2420 (2)	0.3605 (2)	0.28345 (17)	0.0172 (3)
O1	0.4490 (2)	0.2954 (2)	0.15047 (15)	0.0258 (3)
O2	−0.1302 (2)	0.18308 (18)	0.29833 (15)	0.0210 (3)
O3	−0.01877 (19)	0.50819 (17)	0.30498 (14)	0.0193 (3)
O4	0.2988 (2)	0.3398 (2)	0.59836 (16)	0.0197 (3)
H4A	0.190 (5)	0.249 (4)	0.535 (4)	0.048 (8)*
H4B	0.254 (5)	0.396 (4)	0.646 (3)	0.043 (8)*
O5	0.4047 (2)	0.71025 (18)	0.54925 (17)	0.0187 (3)
H5A	0.284 (5)	0.685 (4)	0.490 (3)	0.046 (8)*
H5B	0.412 (4)	0.742 (4)	0.637 (3)	0.039 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01254 (16)	0.01878 (18)	0.01260 (17)	0.00792 (13)	0.00498 (12)	0.00392 (12)
S1	0.0128 (2)	0.0187 (2)	0.0134 (2)	0.00758 (17)	0.00549 (16)	0.00357 (17)
C1	0.0179 (8)	0.0214 (9)	0.0152 (8)	0.0101 (7)	0.0070 (7)	0.0056 (7)
C2	0.0156 (8)	0.0175 (8)	0.0163 (9)	0.0077 (7)	0.0058 (7)	0.0058 (7)
C3	0.0183 (8)	0.0192 (8)	0.0183 (9)	0.0092 (7)	0.0086 (7)	0.0066 (7)
C4	0.0228 (8)	0.0174 (8)	0.0126 (8)	0.0079 (7)	0.0073 (7)	0.0043 (7)
C5	0.0173 (8)	0.0242 (9)	0.0189 (9)	0.0081 (7)	0.0031 (7)	0.0052 (7)
C6	0.0168 (8)	0.0261 (9)	0.0190 (9)	0.0096 (7)	0.0070 (7)	0.0052 (7)
C7	0.0180 (8)	0.0181 (8)	0.0135 (8)	0.0079 (7)	0.0063 (7)	0.0030 (7)
F1	0.0246 (5)	0.0294 (6)	0.0125 (5)	0.0113 (5)	0.0064 (4)	0.0040 (4)
N1	0.0129 (6)	0.0241 (8)	0.0148 (7)	0.0100 (6)	0.0050 (6)	0.0040 (6)
O1	0.0188 (6)	0.0437 (8)	0.0177 (7)	0.0188 (6)	0.0073 (5)	0.0061 (6)
O2	0.0216 (6)	0.0228 (7)	0.0200 (7)	0.0090 (5)	0.0109 (5)	0.0073 (5)
O3	0.0170 (6)	0.0202 (6)	0.0196 (6)	0.0096 (5)	0.0062 (5)	0.0030 (5)
O4	0.0184 (6)	0.0213 (7)	0.0188 (7)	0.0082 (6)	0.0087 (6)	0.0044 (6)
O5	0.0170 (6)	0.0229 (7)	0.0163 (7)	0.0105 (5)	0.0060 (5)	0.0042 (5)

Geometric parameters (Å, º)

Ni1—O5^i	2.0440 (13)	C2—C3	1.385 (2)
Ni1—O5	2.0440 (13)	C3—C4	1.379 (2)
Ni1—N1	2.0856 (14)	C3—H3	0.9500
Ni1—N1^i	2.0856 (14)	C4—F1	1.355 (2)
Ni1—O4	2.1084 (13)	C4—C5	1.388 (2)
Ni1—O4^i	2.1084 (13)	C5—C6	1.394 (3)
S1—O2	1.4443 (13)	C5—H5	0.9500
S1—O3	1.4515 (13)	C6—C7	1.385 (2)
S1—N1	1.6277 (14)	C6—H6	0.9500
S1—C7	1.7635 (17)	O4—H4A	0.81 (3)
C1—O1	1.228 (2)	O4—H4B	0.78 (3)
C1—N1	1.366 (2)	O5—H5A	0.80 (3)
C1—C2	1.495 (2)	O5—H5B	0.81 (3)
C2—C7	1.385 (2)
O5^i—Ni1—O5	180.0	C3—C2—C1	127.30 (15)
O5^i—Ni1—N1	87.50 (6)	C4—C3—C2	116.09 (15)
O5—Ni1—N1	92.50 (6)	C4—C3—H3	122.0
O5^i—Ni1—N1^i	92.50 (6)	C2—C3—H3	122.0
O5—Ni1—N1^i	87.50 (6)	F1—C4—C3	117.60 (15)
N1—Ni1—N1^i	180.0	F1—C4—C5	118.11 (16)
O5^i—Ni1—O4	88.53 (5)	C3—C4—C5	124.28 (17)
O5—Ni1—O4	91.47 (5)	C4—C5—C6	119.03 (16)
N1—Ni1—O4	90.65 (6)	C4—C5—H5	120.5
N1^i—Ni1—O4	89.35 (6)	C6—C5—H5	120.5
O5^i—Ni1—O4^i	91.47 (5)	C7—C6—C5	117.06 (16)
O5—Ni1—O4^i	88.53 (5)	C7—C6—H6	121.5
N1—Ni1—O4^i	89.35 (6)	C5—C6—H6	121.5
N1^i—Ni1—O4^i	90.65 (6)	C2—C7—C6	122.86 (16)
O4—Ni1—O4^i	180.0	C2—C7—S1	107.03 (13)
O2—S1—O3	114.08 (7)	C6—C7—S1	130.10 (13)
O2—S1—N1	110.96 (8)	C1—N1—S1	111.66 (12)
O3—S1—N1	110.42 (7)	C1—N1—Ni1	122.66 (11)
O2—S1—C7	111.32 (8)	S1—N1—Ni1	125.40 (8)
O3—S1—C7	112.14 (8)	Ni1—O4—H4A	113 (2)
N1—S1—C7	96.63 (8)	Ni1—O4—H4B	113 (2)
O1—C1—N1	124.25 (16)	H4A—O4—H4B	106 (3)
O1—C1—C2	123.43 (16)	Ni1—O5—H5A	113 (2)
N1—C1—C2	112.32 (14)	Ni1—O5—H5B	113.5 (19)
C7—C2—C3	120.66 (16)	H5A—O5—H5B	110 (3)
C7—C2—C1	112.04 (15)
O1—C1—C2—C7	177.99 (17)	O3—S1—C7—C6	−61.72 (19)
N1—C1—C2—C7	−1.9 (2)	N1—S1—C7—C6	−176.96 (18)
O1—C1—C2—C3	−2.1 (3)	O1—C1—N1—S1	−174.70 (15)
N1—C1—C2—C3	178.04 (16)	C2—C1—N1—S1	5.15 (19)
C7—C2—C3—C4	0.8 (3)	O1—C1—N1—Ni1	11.1 (3)
C1—C2—C3—C4	−179.07 (16)	C2—C1—N1—Ni1	−169.10 (11)
C2—C3—C4—F1	178.87 (14)	O2—S1—N1—C1	110.32 (13)
C2—C3—C4—C5	0.0 (3)	O3—S1—N1—C1	−122.18 (13)
F1—C4—C5—C6	−179.76 (16)	C7—S1—N1—C1	−5.56 (14)
C3—C4—C5—C6	−0.9 (3)	O2—S1—N1—Ni1	−75.62 (11)
C4—C5—C6—C7	0.9 (3)	O3—S1—N1—Ni1	51.87 (12)
C3—C2—C7—C6	−0.7 (3)	C7—S1—N1—Ni1	168.50 (10)
C1—C2—C7—C6	179.18 (16)	O5^i—Ni1—N1—C1	−48.82 (14)
C3—C2—C7—S1	178.11 (14)	O5—Ni1—N1—C1	131.18 (14)
C1—C2—C7—S1	−1.98 (18)	O4—Ni1—N1—C1	−137.32 (14)
C5—C6—C7—C2	−0.2 (3)	O4^i—Ni1—N1—C1	42.68 (14)
C5—C6—C7—S1	−178.74 (14)	O5^i—Ni1—N1—S1	137.74 (10)
O2—S1—C7—C2	−111.27 (13)	O5—Ni1—N1—S1	−42.26 (10)
O3—S1—C7—C2	119.56 (12)	O4—Ni1—N1—S1	49.24 (10)
N1—S1—C7—C2	4.32 (14)	O4^i—Ni1—N1—S1	−130.76 (10)
O2—S1—C7—C6	67.46 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2	0.81 (3)	2.51 (3)	3.1436 (19)	137 (3)
O4—H4A···F1^ii	0.81 (3)	2.54 (3)	3.0910 (19)	127 (3)
O4—H4B···O3^iii	0.78 (3)	2.17 (3)	2.8985 (18)	158 (3)
O5—H5A···O3	0.80 (3)	2.10 (3)	2.8346 (18)	155 (3)
O5—H5A···F1^iv	0.80 (3)	2.59 (3)	3.1050 (17)	124 (2)
O5—H5B···O1^i	0.81 (3)	2.13 (3)	2.793 (2)	139 (2)
O5—H5B···O2^iii	0.81 (3)	2.44 (3)	2.9541 (18)	122 (2)

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