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Acta Cryst. (2009). E65, m1600    [ doi:10.1107/S1600536809048065 ]

trans-Bis([mu]-2-hydroxyethanethiolato-[kappa]2S:S)bis[dinitrosyliron(II)](Fe-Fe)

H. M. Lee and S.-J. Chiou

Abstract top

The title complex, [Fe2(C2H5OS)2(NO)4], lies on a crystallographic inversion center. The Fe-Fe distance is characteristic of a metal-metal bond. In the crystal structure, intermolecular O-H...O hydrogen bonds link complex molecules into a two-dimensional network.

Comment top

Roussin's red esters (RREs) are photochemically active NO-release compounds and are expected to become potential NO donor drugs (Dillinger et al. 2007). The title compound is an air-stable and water soluble RRE compound. The molecular structure of the title complex is shown in Fig.1. The molecule lies on a crystallogrphic inversion center. The Fe-Fe distance is characteristic of a M-M bond (Dillinger et al. 2007). In the crystal structure, intermolecular O-H···O hydrogen bonds link complex molecules into a two-dimensional network.

Related literature top

For iron–nitrosyl complexes, see: Chiang et al. (2004); Dillinger et al. (2007); Mazany et al. (1983).

Experimental top

FeSO4.7H2O (5.0 g, 0.018 mol) was added to H2SO4 (4M, 50 ml) at 273K. To the resulting solution, the mixture of NaNO2 (2.0 g, 0.023 mol) and mercaptoethanol (5.0 ml, 0.071 mol) were added. After stirring for 10 min, the solution was kept in refrigerator (277K) for one week. Dark red crystals formed and one was used for this structure determination. Yield: 2.1 g (65%). FTIR (THF): 1809 (w), 1774 (vs), 1748 (s) cm-1 (νNO).

Refinement top

All H atoms were positioned geometrically and refined as riding atoms, with Cmethylene—H = 0.99, O—H = 0.84 Å while Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(O) for all the H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: DIAMOND (Brandenburg, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, showing 50% displacement ellipsoids for non-H atoms. The H atoms are depicted by circles of an arbitrary radius. Unlabeled atoms of the complex are related to labeled atoms by the symmetry operator (2 - x, -y, - z).
[Figure 2] Fig. 2. Part of the crystal structure showing intermolecular hydrogen bonds as dashed lines.
trans-Bis(µ-2-hydroxyethanethiolato- κ2S:S)bis[dinitrosyliron(II)](Fe—Fe) top
Crystal data top
[Fe2(C2H5OS)2(NO)4]F(000) = 776
Mr = 385.98Dx = 2.030 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1286 reflections
a = 16.943 (3) Åθ = 2.4–26.8°
b = 5.0070 (7) ŵ = 2.65 mm−1
c = 14.931 (2) ÅT = 150 K
β = 94.327 (3)°Plate, brown
V = 1263.1 (3) Å30.21 × 0.18 × 0.02 mm
Z = 4
Data collection top
Bruker SMART APEXII
diffractometer		1597 independent reflections
Radiation source: fine-focus sealed tube1240 reflections with I > 2σ
graphiteRint = 0.039
ω scansθmax = 28.7°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −22→22
Tmin = 0.606, Tmax = 0.949k = −6→6
5708 measured reflectionsl = −19→19
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 0.94 w = 1/[σ2(Fo2) + (0.0324P)2]
where P = (Fo2 + 2Fc2)/3
1597 reflections(Δ/σ)max = 0.003
83 parametersΔρmax = 0.52 e Å−3
0 restraintsΔρmin = −0.32 e Å−3
Crystal data top
[Fe2(C2H5OS)2(NO)4]V = 1263.1 (3) Å3
Mr = 385.98Z = 4
Monoclinic, C2/cMo Kα radiation
a = 16.943 (3) ŵ = 2.65 mm−1
b = 5.0070 (7) ÅT = 150 K
c = 14.931 (2) Å0.21 × 0.18 × 0.02 mm
β = 94.327 (3)°
Data collection top
Bruker SMART APEXII
diffractometer		1597 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1240 reflections with I > 2σ
Tmin = 0.606, Tmax = 0.949Rint = 0.039
5708 measured reflectionsθmax = 28.7°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.061Δρmax = 0.52 e Å−3
S = 0.94Δρmin = −0.32 e Å−3
1597 reflectionsAbsolute structure: ?
83 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C10.89173 (13)0.1311 (4)0.14871 (15)0.0189 (5)
H1A0.8810−0.06130.13850.023*
H1B0.91900.15230.20930.023*
C20.81447 (12)0.2848 (5)0.14308 (15)0.0219 (5)
H2A0.82530.47910.14490.026*
H2B0.78360.24360.08580.026*
Fe11.062332 (16)−0.00956 (6)0.06209 (2)0.01677 (10)
N11.06466 (10)−0.2257 (4)0.14697 (12)0.0200 (4)
N21.13967 (11)0.1950 (4)0.05687 (13)0.0216 (4)
O11.07764 (10)−0.3658 (3)0.20944 (11)0.0306 (4)
O21.19777 (10)0.3213 (4)0.06634 (13)0.0370 (5)
O30.77015 (10)0.2112 (3)0.21691 (12)0.0302 (4)
H30.75910.34870.24560.045*
S10.95465 (3)0.25677 (10)0.06417 (4)0.01729 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0256 (11)0.0179 (11)0.0142 (12)−0.0014 (9)0.0070 (8)0.0007 (9)
C20.0243 (11)0.0202 (12)0.0220 (13)−0.0032 (9)0.0071 (9)0.0006 (10)
Fe10.01897 (16)0.01530 (17)0.01622 (17)−0.00062 (13)0.00241 (11)−0.00012 (13)
N10.0220 (9)0.0206 (10)0.0173 (10)−0.0001 (8)0.0012 (7)−0.0025 (8)
N20.0225 (9)0.0206 (10)0.0224 (11)−0.0002 (8)0.0060 (8)−0.0021 (8)
O10.0449 (10)0.0241 (9)0.0220 (10)−0.0008 (8)−0.0020 (8)0.0069 (7)
O20.0276 (9)0.0363 (11)0.0477 (12)−0.0119 (8)0.0069 (8)−0.0058 (9)
O30.0378 (9)0.0235 (9)0.0322 (11)−0.0049 (8)0.0222 (8)−0.0037 (7)
S10.0212 (2)0.0139 (3)0.0174 (3)−0.0006 (2)0.00546 (19)−0.0004 (2)
Geometric parameters (Å, °) top
C1—C21.515 (3)Fe1—N21.6696 (19)
C1—S11.824 (2)Fe1—S1i2.2555 (7)
C1—H1A0.9900Fe1—S12.2619 (6)
C1—H1B0.9900Fe1—Fe1i2.7051 (6)
C2—O31.428 (2)N1—O11.174 (2)
C2—H2A0.9900N2—O21.170 (2)
C2—H2B0.9900O3—H30.8400
Fe1—N11.6650 (19)S1—Fe1i2.2555 (7)
C2—C1—S1109.51 (15)N2—Fe1—S1i110.41 (7)
C2—C1—H1A109.8N1—Fe1—S1110.22 (6)
S1—C1—H1A109.8N2—Fe1—S1106.00 (7)
C2—C1—H1B109.8S1i—Fe1—S1106.43 (2)
S1—C1—H1B109.8N1—Fe1—Fe1i121.14 (6)
H1A—C1—H1B108.2N2—Fe1—Fe1i121.42 (7)
O3—C2—C1109.18 (18)S1i—Fe1—Fe1i53.324 (17)
O3—C2—H2A109.8S1—Fe1—Fe1i53.106 (18)
C1—C2—H2A109.8O1—N1—Fe1170.09 (16)
O3—C2—H2B109.8O2—N2—Fe1169.24 (18)
C1—C2—H2B109.8C2—O3—H3109.5
H2A—C2—H2B108.3C1—S1—Fe1i110.16 (7)
N1—Fe1—N2117.44 (9)C1—S1—Fe1108.68 (7)
N1—Fe1—S1i105.88 (7)Fe1i—S1—Fe173.57 (2)
Symmetry codes: (i) −x+2, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O3ii0.841.972.7950 (14)166
Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Fe1—N11.6650 (19)Fe1—S12.2619 (6)
Fe1—S1i2.2555 (7)Fe1—Fe1i2.7051 (6)
N1—Fe1—N2117.44 (9)N2—Fe1—S1106.00 (7)
N1—Fe1—S1110.22 (6)
Symmetry codes: (i) −x+2, −y, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O3ii0.841.972.7950 (14)166
Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2.
Acknowledgements top

We are grateful to the National Science Council of Taiwan for financial support.

references
References top

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Chiang, C.-Y., Miller, M. L., Reibenspies, J. H. & Darensbourg, M. Y. (2004). J. Am. Chem. Soc. 126, 10867–10867.

Dillinger, S. A. T., Schmalle, H. W., Berke, T. & Fox, H. (2007). Dalton Trans. pp. 3562–3571.

Mazany, A. M., Fackler, J. P. Jr, Gallagher, M. K. & Seyferth, D. (1983). Inorg. Chem. 22, 2593–2596.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.