Bis(triethyl-ammonium) bis-(μ-pyrazine-2,3-dithiol-ato)bis-(pyrazine-2,3-dithio-lato)diferrate(III) methanol disolvate.

In the title compound, (C(6)H(16)N)(2)[Fe(2)(C(4)H(2)N(2)S(2))(4)]·2CH(4)O, the [Fe(III)(pdt)(2)](-) anion (pdt is pyrazine-2,3-dithiol-ate) forms a centrosymmetric dimer supported by two Fe(III)-S bonds [Fe-S = 2.4787 (4) Å]. In the crystal structure, dimers form a one-dimensional stack along the b axis via π-π stacking inter-actions, the inter-planar separation between adjacent dimers being 3.51 (2) Å. The methanol solvent mol-ecule is involved in two hydrogen bonds in which the hydroxyl group acts as a hydrogen-bond donor to the N atom of a pdt ligand and the O atom acts as an acceptor for the NH group of the triethyl-ammonium cation.

Related literature

For background information, see: Adams (1990 ▶); Frey (2002 ▶); Georgakaki et al. (2003 ▶); Gloaguen et al. (2001 ▶); Liu et al. (2005 ▶); Nicolet et al. (1999 ▶); Peters et al. (1998 ▶); Sakata (2000 ▶); Sun et al. (2005 ▶); Trasatti (1972 ▶); Yamaguchi et al. (2008 ▶). For other iron(III)–dithiol­ene complexes, see: Simao et al. (2006 ▶); Yamaguchi et al. (2008 ▶). For the synthesis, see: Ribas et al. (2004 ▶).

Experimental

Crystal data

(C6H16N)2[Fe2(C4H2N2S2)4]·2CH4O

M = 949.04

Monoclinic,

a = 14.2375 (15) Å

b = 7.9500 (8) Å

c = 17.7456 (18) Å

β = 95.293 (1)°

V = 2000.0 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.19 mm−1

T = 100 (2) K

0.33 × 0.18 × 0.16 mm

Data collection

Bruker SMART APEX CCD-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.695, T max = 0.831

10059 measured reflections

4048 independent reflections

3824 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.054

S = 1.07

4048 reflections

240 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: KENX (Sakai, 2004 ▶); software used to prepare material for publication: SHELXL97, TEXSAN (Molecular Structure Corporation, 2001 ▶), KENX and ORTEPII (Johnson, 1976 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041949/lh2741sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041949/lh2741Isup2.hkl

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

(C6H16N)2[Fe2(C4H2N2S2)4]·2CH4O	F(000) = 988
Mr = 949.04	Dx = 1.576 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7956 reflections
a = 14.2375 (15) Å	θ = 2.3–27.5°
b = 7.9500 (8) Å	µ = 1.19 mm−1
c = 17.7456 (18) Å	T = 100 K
β = 95.293 (1)°	Needles, black
V = 2000.0 (4) Å3	0.33 × 0.18 × 0.16 mm
Z = 2

Bruker SMART APEX CCD-detector diffractometer	4048 independent reflections
Radiation source: rotating anode with a mirror focusing unit	3824 reflections with I > 2σ(I)
graphite	Rint = 0.013
φ and ω scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→17
Tmin = 0.695, Tmax = 0.831	k = −9→9
10059 measured reflections	l = −22→14

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0258P)2 + 1.2723P] where P = (Fo2 + 2Fc2)/3
4048 reflections	(Δ/σ)max = 0.001
240 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data.

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.Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)4.6834 (0.0016) x + 6.8874 (0.0009) y - 7.1795 (0.0020) z = 7.7711 (0.0010)* 0.0655 (0.0002) S1 * -0.0639 (0.0002) S2 * 0.0645 (0.0002) S3 * -0.0661 (0.0002) S4 0.3719 (0.0003) Fe1Rms deviation of fitted atoms = 0.0650Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)5.7097 (0.0038) x + 6.0721 (0.0015) y - 9.5934 (0.0044) z = 7.6443 (0.0017)* 0.0277 (0.0006) S1 * -0.0176 (0.0006) S2 * -0.0098 (0.0012) C1 * -0.0122 (0.0011) C2 * -0.0067 (0.0012) C3 * 0.0190 (0.0011) C4 * -0.0173 (0.0010) N1 * 0.0170 (0.0010) N2 - 3.5344 (0.0008) S1_$2 - 3.4970 (0.0017) C1_$2 - 3.4894 (0.0014) N1_$2Rms deviation of fitted atoms = 0.0170

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	0.404540 (13)	0.93135 (3)	0.023150 (11)	0.01057 (6)
S1	0.54285 (2)	0.79904 (4)	0.029127 (18)	0.01130 (8)
S2	0.35609 (2)	0.79099 (5)	−0.082403 (19)	0.01420 (8)
S3	0.25466 (2)	1.00013 (5)	0.034182 (19)	0.01363 (8)
S4	0.43700 (2)	0.97513 (4)	0.147331 (18)	0.01193 (8)
O1	0.89754 (8)	0.60915 (14)	−0.01530 (6)	0.0209 (2)
H24	0.8767	0.6838	−0.0459	0.031*
N1	0.61230 (9)	0.57967 (15)	−0.06370 (7)	0.0151 (3)
N2	0.44848 (9)	0.57864 (16)	−0.16542 (7)	0.0163 (3)
N3	0.18638 (8)	1.19999 (16)	0.13603 (7)	0.0147 (2)
N4	0.34506 (9)	1.16211 (16)	0.24079 (7)	0.0141 (2)
N5	0.86540 (8)	0.70235 (16)	0.13156 (7)	0.0151 (3)
H20	0.8819	0.6706	0.0841	0.018*
C1	0.53659 (10)	0.67055 (18)	−0.05203 (8)	0.0122 (3)
C2	0.60532 (11)	0.48707 (19)	−0.12700 (9)	0.0171 (3)
H1	0.6571	0.4184	−0.1377	0.021*
C3	0.45350 (10)	0.67025 (18)	−0.10198 (8)	0.0132 (3)
C4	0.52528 (11)	0.48836 (19)	−0.17707 (8)	0.0178 (3)
H2	0.5246	0.4224	−0.2218	0.021*
C5	0.26017 (10)	1.10755 (18)	0.12000 (8)	0.0124 (3)
C6	0.19204 (10)	1.27363 (19)	0.20475 (8)	0.0167 (3)
H3	0.1412	1.3416	0.2179	0.020*
C7	0.34105 (10)	1.09206 (18)	0.17242 (8)	0.0119 (3)
C8	0.26953 (10)	1.25302 (19)	0.25642 (8)	0.0161 (3)
H4	0.2696	1.3047	0.3047	0.019*
C9	0.92078 (11)	0.5916 (2)	0.18858 (8)	0.0181 (3)
H5	0.8909	0.5936	0.2368	0.022*
H6	0.9856	0.6366	0.1985	0.022*
C10	0.92556 (12)	0.4119 (2)	0.16109 (9)	0.0229 (3)
H7	0.8615	0.3687	0.1489	0.034*
H8	0.9583	0.3423	0.2008	0.034*
H9	0.9599	0.4082	0.1158	0.034*
C11	0.76030 (10)	0.6761 (2)	0.13087 (9)	0.0197 (3)
H10	0.7471	0.5538	0.1296	0.024*
H11	0.7289	0.7259	0.0840	0.024*
C12	0.71813 (11)	0.7525 (2)	0.19835 (9)	0.0253 (4)
H13	0.7530	0.7127	0.2451	0.038*
H12	0.6518	0.7189	0.1977	0.038*
H14	0.7223	0.8754	0.1958	0.038*
C13	0.89199 (11)	0.8848 (2)	0.14175 (9)	0.0193 (3)
H16	0.8950	0.9141	0.1961	0.023*
H15	0.8428	0.9557	0.1144	0.023*
C14	0.98672 (13)	0.9219 (2)	0.11225 (10)	0.0283 (4)
H19	1.0362	0.8578	0.1416	0.042*
H18	1.0004	1.0425	0.1173	0.042*
H17	0.9846	0.8894	0.0589	0.042*
C16	0.85896 (13)	0.4489 (2)	−0.03924 (10)	0.0263 (4)
H21	0.8600	0.4378	−0.0942	0.040*
H22	0.7938	0.4406	−0.0260	0.040*
H23	0.8968	0.3588	−0.0139	0.040*

	U11	U22	U33	U12	U13	U23
Fe1	0.01022 (10)	0.01220 (11)	0.00912 (10)	0.00046 (7)	0.00004 (7)	−0.00049 (7)
S1	0.01119 (16)	0.01259 (17)	0.00985 (15)	0.00098 (12)	−0.00040 (12)	−0.00008 (12)
S2	0.01256 (17)	0.01665 (18)	0.01285 (16)	0.00100 (13)	−0.00173 (13)	−0.00337 (13)
S3	0.01063 (16)	0.01853 (19)	0.01144 (16)	0.00053 (13)	−0.00050 (12)	−0.00270 (13)
S4	0.01160 (16)	0.01452 (17)	0.00948 (16)	0.00168 (13)	0.00002 (12)	0.00010 (12)
O1	0.0232 (6)	0.0213 (6)	0.0173 (5)	0.0043 (5)	−0.0036 (4)	−0.0003 (4)
N1	0.0165 (6)	0.0126 (6)	0.0166 (6)	0.0007 (5)	0.0039 (5)	0.0010 (5)
N2	0.0208 (6)	0.0141 (6)	0.0140 (6)	−0.0008 (5)	0.0009 (5)	−0.0018 (5)
N3	0.0138 (6)	0.0149 (6)	0.0156 (6)	−0.0002 (5)	0.0020 (5)	−0.0004 (5)
N4	0.0167 (6)	0.0131 (6)	0.0125 (6)	0.0002 (5)	0.0017 (5)	−0.0004 (5)
N5	0.0136 (6)	0.0187 (7)	0.0124 (6)	0.0002 (5)	−0.0013 (5)	0.0010 (5)
C1	0.0151 (7)	0.0104 (7)	0.0111 (6)	−0.0007 (5)	0.0019 (5)	0.0008 (5)
C2	0.0192 (7)	0.0120 (7)	0.0211 (7)	0.0014 (6)	0.0067 (6)	−0.0012 (6)
C3	0.0156 (7)	0.0109 (7)	0.0132 (6)	−0.0008 (5)	0.0020 (5)	0.0010 (5)
C4	0.0253 (8)	0.0129 (7)	0.0157 (7)	0.0000 (6)	0.0053 (6)	−0.0027 (6)
C5	0.0133 (7)	0.0120 (7)	0.0122 (6)	−0.0016 (5)	0.0023 (5)	0.0011 (5)
C6	0.0164 (7)	0.0158 (7)	0.0183 (7)	0.0017 (6)	0.0043 (6)	−0.0013 (6)
C7	0.0137 (7)	0.0101 (7)	0.0120 (6)	−0.0013 (5)	0.0018 (5)	0.0019 (5)
C8	0.0197 (7)	0.0156 (7)	0.0134 (7)	0.0003 (6)	0.0035 (6)	−0.0017 (5)
C9	0.0147 (7)	0.0233 (8)	0.0155 (7)	0.0015 (6)	−0.0036 (6)	0.0039 (6)
C10	0.0240 (8)	0.0231 (9)	0.0207 (8)	0.0039 (6)	−0.0017 (6)	0.0045 (6)
C11	0.0122 (7)	0.0259 (8)	0.0201 (7)	−0.0001 (6)	−0.0033 (6)	0.0002 (6)
C12	0.0169 (8)	0.0336 (9)	0.0255 (8)	0.0008 (7)	0.0028 (6)	−0.0024 (7)
C13	0.0208 (8)	0.0184 (8)	0.0177 (7)	−0.0012 (6)	−0.0033 (6)	0.0001 (6)
C14	0.0294 (9)	0.0274 (9)	0.0283 (9)	−0.0089 (7)	0.0048 (7)	−0.0002 (7)
C16	0.0303 (9)	0.0248 (9)	0.0228 (8)	0.0009 (7)	−0.0038 (7)	−0.0038 (7)

Fe1—S1	2.2264 (4)	C9—C10	1.513 (2)
Fe1—S3	2.2289 (4)	C11—C12	1.515 (2)
Fe1—S2	2.2341 (4)	C13—C14	1.520 (2)
Fe1—S4	2.2367 (4)	N5—H20	0.9300
Fe1—S1i	2.4787 (4)	C2—H1	0.9500
S1—C1	1.7611 (14)	C4—H2	0.9500
S1—Fe1i	2.4787 (4)	C6—H3	0.9500
S2—C3	1.7477 (15)	C8—H4	0.9500
S3—C5	1.7415 (14)	C9—H5	0.9900
S4—C7	1.7438 (14)	C9—H6	0.9900
O1—C16	1.436 (2)	C10—H7	0.9800
O1—H24	0.8400	C10—H8	0.9800
N1—C1	1.3297 (19)	C10—H9	0.9800
N1—C2	1.339 (2)	C11—H10	0.9900
N2—C3	1.3372 (19)	C11—H11	0.9900
N2—C4	1.340 (2)	C12—H13	0.9800
N3—C5	1.3341 (19)	C12—H12	0.9800
N3—C6	1.3483 (19)	C12—H14	0.9800
N4—C7	1.3315 (18)	C13—H16	0.9900
N4—C8	1.3456 (19)	C13—H15	0.9900
N5—C13	1.506 (2)	C14—H19	0.9800
N5—C9	1.5079 (18)	C14—H18	0.9800
N5—C11	1.5097 (19)	C14—H17	0.9800
C1—C3	1.411 (2)	C16—H21	0.9800
C2—C4	1.379 (2)	C16—H22	0.9800
C5—C7	1.417 (2)	C16—H23	0.9800
C6—C8	1.378 (2)
C1···C1ii	3.493 (3)
S1—Fe1—S3	164.042 (16)	C4—C2—H1	119.0
S1—Fe1—S2	90.420 (15)	N2—C4—H2	118.6
S3—Fe1—S2	88.401 (15)	C2—C4—H2	118.6
S1—Fe1—S4	85.705 (14)	N3—C6—H3	119.1
S3—Fe1—S4	89.299 (14)	C8—C6—H3	119.1
S2—Fe1—S4	157.445 (17)	N4—C8—H4	118.9
S1—Fe1—S1i	97.462 (14)	C6—C8—H4	118.9
S3—Fe1—S1i	98.369 (15)	N5—C9—H5	109.3
S2—Fe1—S1i	101.461 (15)	C10—C9—H5	109.3
S4—Fe1—S1i	101.073 (15)	N5—C9—H6	109.3
C1—S1—Fe1	104.91 (5)	C10—C9—H6	109.3
C1—S1—Fe1i	100.94 (5)	H5—C9—H6	107.9
Fe1—S1—Fe1i	82.538 (14)	C9—C10—H7	109.5
C3—S2—Fe1	104.58 (5)	C9—C10—H8	109.5
C5—S3—Fe1	103.35 (5)	H7—C10—H8	109.5
C7—S4—Fe1	103.82 (5)	C9—C10—H9	109.5
C1—N1—C2	115.52 (13)	H7—C10—H9	109.5
C3—N2—C4	116.15 (13)	H8—C10—H9	109.5
C5—N3—C6	116.71 (12)	N5—C11—H10	108.8
C7—N4—C8	116.39 (12)	C12—C11—H10	108.8
C13—N5—C9	111.84 (11)	N5—C11—H11	108.8
C13—N5—C11	111.85 (12)	C12—C11—H11	108.8
C9—N5—C11	112.41 (12)	H10—C11—H11	107.7
N1—C1—C3	123.08 (13)	C11—C12—H13	109.5
N1—C1—S1	117.51 (11)	C11—C12—H12	109.5
C3—C1—S1	119.40 (11)	H13—C12—H12	109.5
N1—C2—C4	121.97 (14)	C11—C12—H14	109.5
N2—C3—C1	120.42 (13)	H13—C12—H14	109.5
N2—C3—S2	119.00 (11)	H12—C12—H14	109.5
C1—C3—S2	120.58 (11)	N5—C13—H16	109.3
N2—C4—C2	122.84 (14)	C14—C13—H16	109.3
N3—C5—C7	121.06 (13)	N5—C13—H15	109.3
N3—C5—S3	118.93 (11)	C14—C13—H15	109.3
C7—C5—S3	119.98 (11)	H16—C13—H15	108.0
N3—C6—C8	121.84 (14)	C13—C14—H19	109.5
N4—C7—C5	121.71 (13)	C13—C14—H18	109.5
N4—C7—S4	119.13 (11)	H19—C14—H18	109.5
C5—C7—S4	119.14 (11)	C13—C14—H17	109.5
N4—C8—C6	122.20 (13)	H19—C14—H17	109.5
N5—C9—C10	111.80 (12)	H18—C14—H17	109.5
N5—C11—C12	113.75 (12)	O1—C16—H21	109.5
N5—C13—C14	111.52 (13)	O1—C16—H22	109.5
C16—O1—H24	109.5	H21—C16—H22	109.5
C13—N5—H20	106.8	O1—C16—H23	109.5
C9—N5—H20	106.8	H21—C16—H23	109.5
C11—N5—H20	106.8	H22—C16—H23	109.5
N1—C2—H1	119.0
C2—N1—C1—C3	0.5 (2)	Fe1—S3—C5—N3	164.68 (10)
C2—N1—C1—S1	−178.40 (11)	Fe1—S3—C5—C7	−17.12 (12)
Fe1—S1—C1—N1	178.17 (10)	C5—N3—C6—C8	−0.8 (2)
Fe1i—S1—C1—N1	93.07 (11)	C8—N4—C7—C5	−2.2 (2)
Fe1—S1—C1—C3	−0.74 (12)	C8—N4—C7—S4	178.97 (11)
Fe1i—S1—C1—C3	−85.84 (11)	N3—C5—C7—N4	3.2 (2)
C1—N1—C2—C4	0.9 (2)	S3—C5—C7—N4	−174.98 (11)
C4—N2—C3—C1	0.9 (2)	N3—C5—C7—S4	−177.96 (11)
C4—N2—C3—S2	−179.75 (11)	S3—C5—C7—S4	3.87 (16)
N1—C1—C3—N2	−1.4 (2)	Fe1—S4—C7—N4	−169.57 (10)
S1—C1—C3—N2	177.43 (11)	Fe1—S4—C7—C5	11.55 (12)
N1—C1—C3—S2	179.20 (11)	C7—N4—C8—C6	−0.2 (2)
S1—C1—C3—S2	−1.95 (17)	N3—C6—C8—N4	1.8 (2)
Fe1—S2—C3—N2	−175.86 (10)	C13—N5—C9—C10	−156.73 (13)
Fe1—S2—C3—C1	3.53 (12)	C11—N5—C9—C10	76.48 (16)
C3—N2—C4—C2	0.5 (2)	C13—N5—C11—C12	−52.48 (17)
N1—C2—C4—N2	−1.5 (2)	C9—N5—C11—C12	74.31 (17)
C6—N3—C5—C7	−1.5 (2)	C9—N5—C13—C14	75.40 (15)
C6—N3—C5—S3	176.64 (11)	C11—N5—C13—C14	−157.50 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H24···N3i	0.84	1.99	2.8014 (17)	163
N5—H20···O1	0.93	1.86	2.7880 (17)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H24⋯N3i	0.84	1.99	2.8014 (17)	163
N5—H20⋯O1	0.93	1.86	2.7880 (17)	172

Symmetry code: (i) .