Dicarbon-yl(pyrazine-1,3-dithiol-ato-κS,S')bis-(trimethyl-phosphane-κP)iron(II).

The title compound, [Fe(C(4)H(2)N(2)S(2))(C(3)H(9)P)(2)(CO)(2)], was obtained as a mononuclear by-product during the treatment of [Fe(2)(μ-S(2)C(4)N(2)H(2))(CO)(6)] in excess trimethyl-phosphane. The Fe atom is six-coordinated by two thiol-ate S atoms, two phosphane P atoms and two carbonyl C atoms in a distorted octa-hedral geometry. The average Fe-C(O) distance (1.771 Å) is relatively shorter than that of its parent hexa-carbonyl-diiron compound, and differs by 0.511 Å from the average Fe-P(Me)(3) distance. The five-membered FeC(2)S(2) chelate ring plane is close to being perpendicular to the P/Fe/P plane [86.5 (2)°].

Related literature

For general background to iron sulfides, see: Cody et al. (2000 ▶); Georgakaki et al. (2003 ▶); Capon et al. (2005 ▶); Song (2005 ▶); Li et al. (2005 ▶); Liu & Xiao (2011 ▶). For related structures and the synthesis, see: Durgaprasad et al. (2011 ▶).

Experimental

Crystal data

[Fe(C4H2N2S2)(C3H9P)2(CO)2]

M = 406.21

Orthorhombic,

a = 12.2078 (10) Å

b = 11.951 (1) Å

c = 25.326 (2) Å

V = 3694.9 (5) Å3

Z = 8

Mo Kα radiation

μ = 1.22 mm−1

T = 273 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.711, T max = 0.793

18679 measured reflections

3628 independent reflections

3166 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.073

S = 1.09

3628 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.56 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811048574/kp2368sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048574/kp2368Isup2.hkl

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

[Fe(C4H2N2S2)(C3H9P)2(CO)2]	F(000) = 1680
Mr = 406.21	Dx = 1.460 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9947 reflections
a = 12.2078 (10) Å	θ = 2.3–27.5°
b = 11.951 (1) Å	µ = 1.22 mm−1
c = 25.326 (2) Å	T = 273 K
V = 3694.9 (5) Å3	Block, orange
Z = 8	0.30 × 0.25 × 0.20 mm

Bruker APEXII CCD area-detector diffractometer	3628 independent reflections
Radiation source: fine-focus sealed tube	3166 reflections with I > 2σ(I)
graphite	Rint = 0.025
phi and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −15→14
Tmin = 0.711, Tmax = 0.793	k = −14→8
18679 measured reflections	l = −31→31

Refinement on F2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.029	w = 1/[σ2(Fo2) + (0.0363P)2 + 1.1092P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.073	(Δ/σ)max = 0.001
S = 1.09	Δρmax = 0.30 e Å−3
3628 reflections	Δρmin = −0.56 e Å−3
190 parameters

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.

	x	y	z	Uiso*/Ueq
Fe1	0.374999 (19)	0.76447 (2)	0.389085 (10)	0.03519 (9)
S1	0.38945 (4)	0.57419 (4)	0.37296 (2)	0.04420 (13)
P2	0.39648 (4)	0.71975 (5)	0.47615 (2)	0.04635 (14)
S2	0.56151 (4)	0.78108 (4)	0.37704 (2)	0.05021 (14)
P1	0.35858 (4)	0.80265 (5)	0.30127 (2)	0.04756 (14)
O1	0.13778 (12)	0.74340 (14)	0.39685 (7)	0.0643 (4)
C7	0.23021 (16)	0.75098 (15)	0.39447 (7)	0.0430 (4)
C9	0.60519 (15)	0.64370 (18)	0.36700 (7)	0.0446 (4)
O2	0.38260 (15)	1.00089 (14)	0.41494 (8)	0.0817 (5)
C10	0.53051 (15)	0.55283 (16)	0.36640 (6)	0.0407 (4)
N1	0.56545 (15)	0.44788 (15)	0.36180 (6)	0.0519 (4)
C8	0.37676 (16)	0.90822 (17)	0.40424 (9)	0.0502 (5)
C12	0.74509 (18)	0.5207 (2)	0.35593 (9)	0.0667 (7)
H12A	0.8193	0.5059	0.3516	0.080*
C11	0.6742 (2)	0.4338 (2)	0.35706 (7)	0.0589 (6)
H11A	0.7018	0.3615	0.3545	0.071*
C6	0.52289 (18)	0.6505 (2)	0.49459 (9)	0.0626 (6)
H6A	0.5227	0.6361	0.5319	0.094*
H6B	0.5839	0.6978	0.4859	0.094*
H6C	0.5291	0.5811	0.4757	0.094*
N2	0.71250 (14)	0.62810 (18)	0.36084 (7)	0.0612 (5)
C2	0.2200 (2)	0.8015 (3)	0.27602 (9)	0.0830 (9)
H2B	0.2208	0.8183	0.2390	0.125*
H2C	0.1772	0.8567	0.2943	0.125*
H2D	0.1883	0.7289	0.2814	0.125*
C3	0.4080 (3)	0.9401 (3)	0.28305 (11)	0.0997 (11)
H3A	0.3988	0.9508	0.2457	0.150*
H3B	0.4842	0.9463	0.2919	0.150*
H3C	0.3671	0.9961	0.3018	0.150*
C4	0.29368 (19)	0.6241 (2)	0.50169 (9)	0.0728 (7)
H4A	0.3080	0.6093	0.5383	0.109*
H4B	0.2963	0.5552	0.4822	0.109*
H4C	0.2224	0.6571	0.4981	0.109*
C1	0.4288 (2)	0.7111 (3)	0.25558 (10)	0.0827 (8)
H1B	0.4155	0.7358	0.2201	0.124*
H1C	0.4021	0.6361	0.2598	0.124*
H1D	0.5060	0.7129	0.2626	0.124*
C5	0.3912 (3)	0.8351 (3)	0.52247 (11)	0.0983 (11)
H5A	0.4011	0.8073	0.5577	0.147*
H5B	0.3213	0.8716	0.5199	0.147*
H5C	0.4483	0.8876	0.5144	0.147*

	U11	U22	U33	U12	U13	U23
Fe1	0.03369 (15)	0.03112 (15)	0.04075 (16)	0.00071 (9)	−0.00012 (10)	0.00066 (10)
S1	0.0391 (2)	0.0349 (2)	0.0586 (3)	−0.00252 (18)	0.00205 (19)	−0.0062 (2)
P2	0.0529 (3)	0.0452 (3)	0.0409 (3)	0.0026 (2)	−0.0055 (2)	−0.0013 (2)
S2	0.0355 (2)	0.0422 (3)	0.0729 (3)	−0.0058 (2)	0.0009 (2)	0.0035 (2)
P1	0.0472 (3)	0.0532 (3)	0.0423 (3)	−0.0029 (2)	−0.0002 (2)	0.0065 (2)
O1	0.0383 (8)	0.0691 (11)	0.0856 (12)	0.0028 (7)	0.0084 (7)	0.0101 (9)
C7	0.0424 (11)	0.0387 (10)	0.0479 (10)	0.0035 (8)	0.0032 (8)	0.0037 (8)
C9	0.0377 (9)	0.0518 (11)	0.0442 (10)	0.0056 (8)	0.0000 (7)	0.0026 (9)
O2	0.0976 (14)	0.0380 (9)	0.1097 (15)	0.0031 (8)	−0.0022 (11)	−0.0105 (9)
C10	0.0428 (10)	0.0435 (10)	0.0358 (9)	0.0075 (8)	0.0015 (7)	−0.0015 (8)
N1	0.0616 (11)	0.0483 (10)	0.0458 (9)	0.0136 (8)	0.0018 (7)	−0.0040 (7)
C8	0.0510 (11)	0.0384 (11)	0.0613 (12)	0.0032 (8)	−0.0005 (9)	0.0009 (9)
C12	0.0460 (12)	0.0879 (19)	0.0661 (14)	0.0269 (13)	0.0043 (10)	0.0017 (13)
C11	0.0665 (14)	0.0675 (15)	0.0428 (10)	0.0308 (13)	0.0019 (9)	−0.0026 (10)
C6	0.0600 (13)	0.0693 (15)	0.0584 (12)	0.0014 (11)	−0.0192 (10)	0.0096 (11)
N2	0.0382 (9)	0.0730 (13)	0.0723 (12)	0.0083 (9)	0.0024 (8)	0.0048 (10)
C2	0.0597 (14)	0.135 (3)	0.0548 (13)	0.0022 (16)	−0.0134 (11)	0.0142 (15)
C3	0.152 (3)	0.081 (2)	0.0660 (16)	−0.043 (2)	−0.0189 (17)	0.0327 (15)
C4	0.0638 (14)	0.099 (2)	0.0552 (12)	−0.0068 (14)	0.0009 (11)	0.0253 (13)
C1	0.0862 (18)	0.112 (2)	0.0493 (13)	0.0191 (17)	0.0164 (12)	−0.0033 (14)
C5	0.160 (3)	0.076 (2)	0.0591 (15)	0.0244 (19)	−0.0146 (17)	−0.0217 (14)

Fe1—C8	1.761 (2)	C12—C11	1.352 (4)
Fe1—C7	1.780 (2)	C12—H12A	0.9300
Fe1—P1	2.2793 (6)	C11—H11A	0.9300
Fe1—P2	2.2840 (6)	C6—H6A	0.9600
Fe1—S2	2.3058 (6)	C6—H6B	0.9600
Fe1—S1	2.3170 (6)	C6—H6C	0.9600
S1—C10	1.7488 (18)	C2—H2B	0.9600
P2—C5	1.811 (3)	C2—H2C	0.9600
P2—C6	1.812 (2)	C2—H2D	0.9600
P2—C4	1.817 (2)	C3—H3A	0.9600
S2—C9	1.745 (2)	C3—H3B	0.9600
P1—C1	1.808 (2)	C3—H3C	0.9600
P1—C2	1.809 (2)	C4—H4A	0.9600
P1—C3	1.810 (3)	C4—H4B	0.9600
O1—C7	1.134 (2)	C4—H4C	0.9600
C9—N2	1.332 (2)	C1—H1B	0.9600
C9—C10	1.418 (3)	C1—H1C	0.9600
O2—C8	1.142 (3)	C1—H1D	0.9600
C10—N1	1.330 (3)	C5—H5A	0.9600
N1—C11	1.343 (3)	C5—H5B	0.9600
C12—N2	1.349 (3)	C5—H5C	0.9600
C8—Fe1—C7	94.81 (9)	N1—C11—C12	122.6 (2)
C8—Fe1—P1	91.05 (7)	N1—C11—H11A	118.7
C7—Fe1—P1	90.32 (6)	C12—C11—H11A	118.7
C8—Fe1—P2	90.95 (7)	P2—C6—H6A	109.5
C7—Fe1—P2	91.08 (6)	P2—C6—H6B	109.5
P1—Fe1—P2	177.45 (2)	H6A—C6—H6B	109.5
C8—Fe1—S2	86.14 (6)	P2—C6—H6C	109.5
C7—Fe1—S2	176.78 (6)	H6A—C6—H6C	109.5
P1—Fe1—S2	86.58 (2)	H6B—C6—H6C	109.5
P2—Fe1—S2	91.98 (2)	C9—N2—C12	115.7 (2)
C8—Fe1—S1	174.39 (7)	P1—C2—H2B	109.5
C7—Fe1—S1	90.01 (6)	P1—C2—H2C	109.5
P1—Fe1—S1	91.79 (2)	H2B—C2—H2C	109.5
P2—Fe1—S1	86.09 (2)	P1—C2—H2D	109.5
S2—Fe1—S1	89.198 (19)	H2B—C2—H2D	109.5
C10—S1—Fe1	103.59 (7)	H2C—C2—H2D	109.5
C5—P2—C6	102.18 (13)	P1—C3—H3A	109.5
C5—P2—C4	102.93 (15)	P1—C3—H3B	109.5
C6—P2—C4	102.08 (12)	H3A—C3—H3B	109.5
C5—P2—Fe1	116.29 (10)	P1—C3—H3C	109.5
C6—P2—Fe1	116.96 (8)	H3A—C3—H3C	109.5
C4—P2—Fe1	114.31 (8)	H3B—C3—H3C	109.5
C9—S2—Fe1	103.89 (7)	P2—C4—H4A	109.5
C1—P1—C2	102.28 (13)	P2—C4—H4B	109.5
C1—P1—C3	103.18 (15)	H4A—C4—H4B	109.5
C2—P1—C3	103.19 (14)	P2—C4—H4C	109.5
C1—P1—Fe1	117.49 (9)	H4A—C4—H4C	109.5
C2—P1—Fe1	115.19 (8)	H4B—C4—H4C	109.5
C3—P1—Fe1	113.66 (9)	P1—C1—H1B	109.5
O1—C7—Fe1	178.51 (19)	P1—C1—H1C	109.5
N2—C9—C10	121.58 (19)	H1B—C1—H1C	109.5
N2—C9—S2	116.69 (17)	P1—C1—H1D	109.5
C10—C9—S2	121.72 (14)	H1B—C1—H1D	109.5
N1—C10—C9	121.13 (17)	H1C—C1—H1D	109.5
N1—C10—S1	117.51 (15)	P2—C5—H5A	109.5
C9—C10—S1	121.35 (14)	P2—C5—H5B	109.5
C10—N1—C11	116.28 (19)	H5A—C5—H5B	109.5
O2—C8—Fe1	176.9 (2)	P2—C5—H5C	109.5
N2—C12—C11	122.7 (2)	H5A—C5—H5C	109.5
N2—C12—H12A	118.7	H5B—C5—H5C	109.5
C11—C12—H12A	118.7
C8—Fe1—S1—C10	−29.4 (8)	S2—Fe1—P1—C2	178.35 (12)
C7—Fe1—S1—C10	−178.74 (8)	S1—Fe1—P1—C2	89.26 (12)
P1—Fe1—S1—C10	90.93 (6)	C8—Fe1—P1—C3	23.20 (15)
P2—Fe1—S1—C10	−87.66 (6)	C7—Fe1—P1—C3	118.01 (15)
S2—Fe1—S1—C10	4.37 (6)	P2—Fe1—P1—C3	−118.6 (5)
C8—Fe1—P2—C5	6.40 (15)	S2—Fe1—P1—C3	−62.87 (13)
C7—Fe1—P2—C5	−88.43 (14)	S1—Fe1—P1—C3	−151.96 (13)
P1—Fe1—P2—C5	148.2 (5)	C8—Fe1—C7—O1	78 (8)
S2—Fe1—P2—C5	92.57 (13)	P1—Fe1—C7—O1	−13 (8)
S1—Fe1—P2—C5	−178.37 (13)	P2—Fe1—C7—O1	169 (8)
C8—Fe1—P2—C6	−114.62 (11)	S2—Fe1—C7—O1	−29 (9)
C7—Fe1—P2—C6	150.55 (11)	S1—Fe1—C7—O1	−105 (8)
P1—Fe1—P2—C6	27.1 (5)	Fe1—S2—C9—N2	−177.54 (14)
S2—Fe1—P2—C6	−28.45 (9)	Fe1—S2—C9—C10	1.34 (16)
S1—Fe1—P2—C6	60.61 (9)	N2—C9—C10—N1	2.8 (3)
C8—Fe1—P2—C4	126.20 (12)	S2—C9—C10—N1	−176.04 (14)
C7—Fe1—P2—C4	31.37 (12)	N2—C9—C10—S1	−178.48 (14)
P1—Fe1—P2—C4	−92.0 (5)	S2—C9—C10—S1	2.7 (2)
S2—Fe1—P2—C4	−147.63 (10)	Fe1—S1—C10—N1	173.69 (13)
S1—Fe1—P2—C4	−58.57 (10)	Fe1—S1—C10—C9	−5.10 (16)
C8—Fe1—S2—C9	173.53 (10)	C9—C10—N1—C11	−0.9 (3)
C7—Fe1—S2—C9	−79.2 (11)	S1—C10—N1—C11	−179.71 (13)
P1—Fe1—S2—C9	−95.18 (7)	C7—Fe1—C8—O2	153 (4)
P2—Fe1—S2—C9	82.72 (7)	P1—Fe1—C8—O2	−117 (4)
S1—Fe1—S2—C9	−3.34 (7)	P2—Fe1—C8—O2	62 (4)
C8—Fe1—P1—C1	143.77 (13)	S2—Fe1—C8—O2	−30 (4)
C7—Fe1—P1—C1	−121.41 (13)	S1—Fe1—C8—O2	4(5)
P2—Fe1—P1—C1	2.0 (5)	C10—N1—C11—C12	−1.2 (3)
S2—Fe1—P1—C1	57.70 (12)	N2—C12—C11—N1	1.8 (3)
S1—Fe1—P1—C1	−31.39 (12)	C10—C9—N2—C12	−2.2 (3)
C8—Fe1—P1—C2	−95.58 (14)	S2—C9—N2—C12	176.63 (16)
C7—Fe1—P1—C2	−0.76 (13)	C11—C12—N2—C9	0.1 (3)
P2—Fe1—P1—C2	122.7 (5)

Table 1

Selected bond lengths (Å)

Fe1—C8	1.761 (2)
Fe1—C7	1.780 (2)
Fe1—P1	2.2793 (6)
Fe1—P2	2.2840 (6)
Fe1—S2	2.3058 (6)
Fe1—S1	2.3170 (6)