trans-Bis(μ-2-hydroxy­ethanethiol­ato-κ2S:S)bis­[dinitro­syliron(II)](Fe—Fe)

Lee, H.M.; Chiou, S.-J.

doi:10.1107/S1600536809048065

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1600

doi:10.1107/S1600536809048065

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trans-Bis(μ-2-hydroxyethanethiolato-κ²S:S)bis[dinitrosyliron(II)](Fe—Fe)

Hon Man Lee ^a and Show-Jen Chiou ^b ^*

^aDepartment of Chemistry, National Changhua University of Education, Changhua, Taiwan 50058, and ^bDepartment of Applied Chemistry, National Chiayi University, 300 Syuefu Road, Chiayi City 60004, Taiwan
^*Correspondence e-mail: genechiou@mail.ncyu.edu.tw

(Received 26 October 2009; accepted 12 November 2009; online 18 November 2009)

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.

Related literature

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

Experimental

Crystal data

[Fe₂(C₂H₅OS)₂(NO)₄]
M_r = 385.98
Monoclinic, C 2/c
a = 16.943 (3) Å
b = 5.0070 (7) Å
c = 14.931 (2) Å
β = 94.327 (3)°
V = 1263.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.65 mm⁻¹
T = 150 K
0.21 × 0.18 × 0.02 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.606, T_max = 0.949
5708 measured reflections
1597 independent reflections
1240 reflections with I > 2σ
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.061
S = 0.94
1597 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe1—N1	1.6650 (19)
Fe1—S1ⁱ	2.2555 (7)
Fe1—S1	2.2619 (6)
Fe1—Fe1ⁱ	2.7051 (6)

N1—Fe1—N2	117.44 (9)
N1—Fe1—S1	110.22 (6)
N2—Fe1—S1	106.00 (7)
Symmetry code: (i) -x+2, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O3ⁱⁱ	0.84	1.97	2.7950 (14)	166
Symmetry code: (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (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: DIAMOND (Brandenburg, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048065/lh2939sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048065/lh2939Isup2.hkl

checkCIF report

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).

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

	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).
	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
M_r = 385.98	D_x = 2.030 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1286 reflections
a = 16.943 (3) Å	θ = 2.4–26.8°
b = 5.0070 (7) Å	µ = 2.65 mm⁻¹
c = 14.931 (2) Å	T = 150 K
β = 94.327 (3)°	Plate, brown
V = 1263.1 (3) Å³	0.21 × 0.18 × 0.02 mm
Z = 4

Data collection top

Bruker SMART APEXII diffractometer	1597 independent reflections
Radiation source: fine-focus sealed tube	1240 reflections with I > 2σ
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 28.7°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→22
T_min = 0.606, T_max = 0.949	k = −6→6
5708 measured reflections	l = −19→19

Refinement top

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0324P)²] where P = (F_o² + 2F_c²)/3
1597 reflections	(Δ/σ)_max = 0.003
83 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Fe₂(C₂H₅OS)₂(NO)₄]	V = 1263.1 (3) Å³
M_r = 385.98	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.943 (3) Å	µ = 2.65 mm⁻¹
b = 5.0070 (7) Å	T = 150 K
c = 14.931 (2) Å	0.21 × 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
T_min = 0.606, T_max = 0.949	R_int = 0.039
5708 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 0.94	Δρ_max = 0.52 e Å⁻³
1597 reflections	Δρ_min = −0.32 e Å⁻³
83 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.89173 (13)	0.1311 (4)	0.14871 (15)	0.0189 (5)
H1A	0.8810	−0.0613	0.1385	0.023*
H1B	0.9190	0.1523	0.2093	0.023*
C2	0.81447 (12)	0.2848 (5)	0.14308 (15)	0.0219 (5)
H2A	0.8253	0.4791	0.1449	0.026*
H2B	0.7836	0.2436	0.0858	0.026*
Fe1	1.062332 (16)	−0.00956 (6)	0.06209 (2)	0.01677 (10)
N1	1.06466 (10)	−0.2257 (4)	0.14697 (12)	0.0200 (4)
N2	1.13967 (11)	0.1950 (4)	0.05687 (13)	0.0216 (4)
O1	1.07764 (10)	−0.3658 (3)	0.20944 (11)	0.0306 (4)
O2	1.19777 (10)	0.3213 (4)	0.06634 (13)	0.0370 (5)
O3	0.77015 (10)	0.2112 (3)	0.21691 (12)	0.0302 (4)
H3	0.7591	0.3487	0.2456	0.045*
S1	0.95465 (3)	0.25677 (10)	0.06417 (4)	0.01729 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0256 (11)	0.0179 (11)	0.0142 (12)	−0.0014 (9)	0.0070 (8)	0.0007 (9)
C2	0.0243 (11)	0.0202 (12)	0.0220 (13)	−0.0032 (9)	0.0071 (9)	0.0006 (10)
Fe1	0.01897 (16)	0.01530 (17)	0.01622 (17)	−0.00062 (13)	0.00241 (11)	−0.00012 (13)
N1	0.0220 (9)	0.0206 (10)	0.0173 (10)	−0.0001 (8)	0.0012 (7)	−0.0025 (8)
N2	0.0225 (9)	0.0206 (10)	0.0224 (11)	−0.0002 (8)	0.0060 (8)	−0.0021 (8)
O1	0.0449 (10)	0.0241 (9)	0.0220 (10)	−0.0008 (8)	−0.0020 (8)	0.0069 (7)
O2	0.0276 (9)	0.0363 (11)	0.0477 (12)	−0.0119 (8)	0.0069 (8)	−0.0058 (9)
O3	0.0378 (9)	0.0235 (9)	0.0322 (11)	−0.0049 (8)	0.0222 (8)	−0.0037 (7)
S1	0.0212 (2)	0.0139 (3)	0.0174 (3)	−0.0006 (2)	0.00546 (19)	−0.0004 (2)

Geometric parameters (Å, º) top

C1—C2	1.515 (3)	Fe1—N2	1.6696 (19)
C1—S1	1.824 (2)	Fe1—S1ⁱ	2.2555 (7)
C1—H1A	0.9900	Fe1—S1	2.2619 (6)
C1—H1B	0.9900	Fe1—Fe1ⁱ	2.7051 (6)
C2—O3	1.428 (2)	N1—O1	1.174 (2)
C2—H2A	0.9900	N2—O2	1.170 (2)
C2—H2B	0.9900	O3—H3	0.8400
Fe1—N1	1.6650 (19)	S1—Fe1ⁱ	2.2555 (7)

C2—C1—S1	109.51 (15)	N2—Fe1—S1ⁱ	110.41 (7)
C2—C1—H1A	109.8	N1—Fe1—S1	110.22 (6)
S1—C1—H1A	109.8	N2—Fe1—S1	106.00 (7)
C2—C1—H1B	109.8	S1ⁱ—Fe1—S1	106.43 (2)
S1—C1—H1B	109.8	N1—Fe1—Fe1ⁱ	121.14 (6)
H1A—C1—H1B	108.2	N2—Fe1—Fe1ⁱ	121.42 (7)
O3—C2—C1	109.18 (18)	S1ⁱ—Fe1—Fe1ⁱ	53.324 (17)
O3—C2—H2A	109.8	S1—Fe1—Fe1ⁱ	53.106 (18)
C1—C2—H2A	109.8	O1—N1—Fe1	170.09 (16)
O3—C2—H2B	109.8	O2—N2—Fe1	169.24 (18)
C1—C2—H2B	109.8	C2—O3—H3	109.5
H2A—C2—H2B	108.3	C1—S1—Fe1ⁱ	110.16 (7)
N1—Fe1—N2	117.44 (9)	C1—S1—Fe1	108.68 (7)
N1—Fe1—S1ⁱ	105.88 (7)	Fe1ⁱ—S1—Fe1	73.57 (2)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O3ⁱⁱ	0.84	1.97	2.7950 (14)	166

Symmetry code: (ii) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Fe₂(C₂H₅OS)₂(NO)₄]
M_r	385.98
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	16.943 (3), 5.0070 (7), 14.931 (2)
β (°)	94.327 (3)
V (Å³)	1263.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.65
Crystal size (mm)	0.21 × 0.18 × 0.02

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.606, 0.949
No. of measured, independent and observed (I > 2σ) reflections	5708, 1597, 1240
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.061, 0.94
No. of reflections	1597
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.32

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Selected geometric parameters (Å, º) top

Fe1—N1	1.6650 (19)	Fe1—S1	2.2619 (6)
Fe1—S1ⁱ	2.2555 (7)	Fe1—Fe1ⁱ	2.7051 (6)

N1—Fe1—N2	117.44 (9)	N2—Fe1—S1	106.00 (7)
N1—Fe1—S1	110.22 (6)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O3ⁱⁱ	0.84	1.97	2.7950 (14)	165.8

Symmetry code: (ii) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

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

References

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