trans-Bis[2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole-κ(2) N (2),N (3)]bis-(methanol-κO)iron(II) bis-(perchlorate).

The title compound, [Fe(C12H8N4S)2(CH3OH)2](ClO4)2, crystallized in the solvent-free form from a methanol solution. The Fe(II) ion is located on a centre of inversion. The distorted N4O2 octa-hedral coordination geometry is formed by two N,N'-chelating equatorial 2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole ligands and axially coordinating methanol coligands, resulting in the mononuclear trans-(N (2),N (3),O)2 coordination mode. The methanol co-ligand is involved in a hydrogen bond to the perchlorate counter-ion.

Related literature

For other 3d metal structures of 2,5-bis­(pyridin-2-yl)-1,3,4-thia­diazole, see: Klingele et al. (2010 ▶, 2012 ▶); Bentiss, Lagrenee, Mentre et al. (2004 ▶); Bentiss, Lagrenee, Vezin et al. (2004 ▶); Zheng et al. (2006 ▶); Bentiss et al. (2002 ▶); Wan et al. (2007 ▶). For related compounds, see: Guionneau et al. (2004 ▶). For the bridging capability of 4,4′-bispyridine-N,N′-dioxide, see: Jia et al. (2008 ▶).

Experimental

Crystal data

[Fe(C12H8N4S)2(CH4O)2](ClO4)2

M = 799.40

Triclinic,

a = 8.8410 (3) Å

b = 9.5579 (4) Å

c = 9.5875 (4) Å

α = 87.169 (2)°

β = 88.945 (2)°

γ = 74.735 (2)°

V = 780.61 (5) Å3

Z = 1

Mo Kα radiation

μ = 0.86 mm−1

T = 100 K

0.18 × 0.08 × 0.03 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.861, T max = 0.975

18025 measured reflections

3128 independent reflections

2789 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.062

S = 1.05

3128 reflections

227 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: OLEX2.refine (Puschmann et al., 2013 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and OLEX2.refine (Puschmann et al., 2013 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2011 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681401277X/lr2128sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401277X/lr2128Isup2.hkl

CCDC reference: 1006207

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Fe(C12H8N4S)2(CH4O)2](ClO4)2	Z = 1
Mr = 799.40	F(000) = 408
Triclinic, P1	Dx = 1.701 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8410 (3) Å	Cell parameters from 9969 reflections
b = 9.5579 (4) Å	θ = 2.2–30.5°
c = 9.5875 (4) Å	µ = 0.86 mm−1
α = 87.169 (2)°	T = 100 K
β = 88.945 (2)°	Plate, red
γ = 74.735 (2)°	0.18 × 0.08 × 0.03 mm
V = 780.61 (5) Å3

Bruker APEXII CCD area-detector diffractometer	3128 independent reflections
Radiation source: microfocus sealed tube	2789 reflections with I > 2σ(I)
Multilayer mirror optics monochromator	Rint = 0.019
φ and ω scans	θmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
Tmin = 0.861, Tmax = 0.975	k = −11→11
18025 measured reflections	l = −11→11

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0172P)2 + 0.9493P] where P = (Fo2 + 2Fc2)/3
3128 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

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	0.0000	1.0000	0.0000	0.01139 (10)
S1	0.22171 (5)	0.51392 (5)	0.06646 (5)	0.01390 (11)
N1	0.18464 (17)	0.89318 (16)	−0.14602 (15)	0.0128 (3)
N2	0.05730 (17)	0.77550 (16)	0.07183 (16)	0.0131 (3)
N3	−0.00347 (18)	0.70371 (17)	0.17709 (16)	0.0144 (3)
N4	0.14375 (19)	0.33511 (17)	0.30380 (17)	0.0171 (3)
C1	0.2469 (2)	0.9547 (2)	−0.25294 (19)	0.0154 (4)
H1	0.2034	1.0550	−0.2760	0.018*
C2	0.3724 (2)	0.8783 (2)	−0.33180 (19)	0.0162 (4)
H2	0.4130	0.9255	−0.4075	0.019*
C3	0.4371 (2)	0.7330 (2)	−0.2986 (2)	0.0154 (4)
H3	0.5228	0.6786	−0.3510	0.018*
C4	0.3748 (2)	0.6677 (2)	−0.18715 (19)	0.0138 (4)
H4	0.4174	0.5679	−0.1617	0.017*
C5	0.2495 (2)	0.75062 (19)	−0.11400 (18)	0.0115 (4)
C6	0.1740 (2)	0.69113 (19)	0.00391 (18)	0.0118 (4)
C7	0.0705 (2)	0.5668 (2)	0.18660 (19)	0.0131 (4)
C8	0.0312 (2)	0.4599 (2)	0.28666 (19)	0.0131 (4)
C9	−0.1131 (2)	0.4898 (2)	0.35465 (19)	0.0158 (4)
H9	−0.1888	0.5801	0.3387	0.019*
C10	−0.1429 (2)	0.3835 (2)	0.4465 (2)	0.0186 (4)
H10	−0.2402	0.3992	0.4949	0.022*
C11	−0.0285 (2)	0.2540 (2)	0.4665 (2)	0.0200 (4)
H11	−0.0462	0.1794	0.5288	0.024*
C12	0.1125 (2)	0.2350 (2)	0.3942 (2)	0.0201 (4)
H12	0.1908	0.1463	0.4098	0.024*
C20	−0.2991 (2)	0.9010 (2)	−0.0662 (2)	0.0234 (5)
H20A	−0.3466	0.8617	−0.1416	0.035*
H20B	−0.3792	0.9775	−0.0223	0.035*
H20C	−0.2552	0.8232	0.0036	0.035*
O20	−0.17589 (15)	0.96075 (15)	−0.12275 (15)	0.0173 (3)
H20	−0.212 (3)	1.021 (3)	−0.179 (3)	0.026*
Cl10	−0.46099 (5)	1.25579 (5)	−0.29619 (5)	0.01521 (11)
O11	−0.30426 (17)	1.16340 (19)	−0.32171 (16)	0.0353 (4)
O12	−0.47275 (19)	1.39590 (16)	−0.36152 (17)	0.0320 (4)
O13	−0.57261 (18)	1.19384 (18)	−0.35684 (18)	0.0339 (4)
O14	−0.48818 (18)	1.26721 (19)	−0.14843 (15)	0.0327 (4)

	U11	U22	U33	U12	U13	U23
Fe1	0.01072 (18)	0.00969 (19)	0.01282 (19)	−0.00126 (14)	0.00130 (14)	0.00030 (14)
S1	0.0141 (2)	0.0101 (2)	0.0162 (2)	−0.00128 (17)	0.00275 (17)	0.00076 (18)
N1	0.0137 (8)	0.0124 (8)	0.0118 (8)	−0.0027 (6)	0.0007 (6)	−0.0007 (6)
N2	0.0133 (7)	0.0125 (8)	0.0128 (8)	−0.0024 (6)	0.0018 (6)	0.0005 (6)
N3	0.0159 (8)	0.0134 (8)	0.0136 (8)	−0.0042 (6)	0.0017 (6)	0.0012 (6)
N4	0.0202 (8)	0.0136 (8)	0.0171 (8)	−0.0041 (7)	0.0023 (7)	0.0009 (7)
C1	0.0184 (9)	0.0129 (9)	0.0153 (9)	−0.0048 (8)	0.0005 (7)	−0.0001 (7)
C2	0.0177 (9)	0.0198 (10)	0.0134 (9)	−0.0090 (8)	0.0025 (7)	−0.0020 (8)
C3	0.0124 (9)	0.0184 (10)	0.0163 (9)	−0.0047 (7)	0.0026 (7)	−0.0070 (8)
C4	0.0137 (9)	0.0115 (9)	0.0157 (9)	−0.0021 (7)	−0.0010 (7)	−0.0026 (7)
C5	0.0119 (8)	0.0128 (9)	0.0104 (8)	−0.0041 (7)	−0.0022 (7)	−0.0014 (7)
C6	0.0117 (8)	0.0109 (9)	0.0126 (9)	−0.0026 (7)	−0.0025 (7)	−0.0009 (7)
C7	0.0115 (9)	0.0152 (9)	0.0127 (9)	−0.0036 (7)	−0.0007 (7)	−0.0015 (7)
C8	0.0159 (9)	0.0129 (9)	0.0118 (9)	−0.0060 (7)	−0.0007 (7)	−0.0015 (7)
C9	0.0152 (9)	0.0170 (10)	0.0161 (9)	−0.0057 (8)	−0.0035 (7)	−0.0003 (8)
C10	0.0184 (10)	0.0262 (11)	0.0153 (10)	−0.0130 (8)	0.0002 (8)	−0.0026 (8)
C11	0.0301 (11)	0.0198 (10)	0.0144 (10)	−0.0145 (9)	0.0005 (8)	0.0011 (8)
C12	0.0272 (11)	0.0131 (10)	0.0189 (10)	−0.0037 (8)	−0.0001 (8)	0.0015 (8)
C20	0.0144 (10)	0.0255 (11)	0.0320 (12)	−0.0074 (8)	0.0032 (8)	−0.0068 (9)
O20	0.0145 (7)	0.0178 (7)	0.0192 (7)	−0.0037 (6)	−0.0026 (5)	0.0009 (6)
Cl10	0.0138 (2)	0.0166 (2)	0.0151 (2)	−0.00390 (17)	0.00130 (17)	0.00016 (18)
O11	0.0177 (8)	0.0490 (11)	0.0267 (9)	0.0102 (7)	0.0051 (6)	0.0129 (8)
O12	0.0452 (10)	0.0162 (8)	0.0349 (9)	−0.0095 (7)	0.0194 (7)	−0.0019 (7)
O13	0.0289 (9)	0.0383 (10)	0.0423 (10)	−0.0201 (7)	0.0035 (7)	−0.0160 (8)
O14	0.0312 (9)	0.0527 (11)	0.0135 (7)	−0.0105 (8)	0.0059 (6)	−0.0004 (7)

Fe1—O20	2.0886 (13)	C1—C2	1.391 (3)
Fe1—O20i	2.0886 (13)	C2—C3	1.379 (3)
Fe1—N2i	2.1516 (15)	C3—C4	1.389 (3)
Fe1—N2	2.1516 (15)	C4—C5	1.382 (3)
Fe1—N1i	2.2015 (15)	C5—C6	1.468 (2)
Fe1—N1	2.2015 (15)	C7—C8	1.471 (2)
S1—C6	1.7144 (18)	C8—C9	1.389 (3)
S1—C7	1.7364 (19)	C9—C10	1.386 (3)
N1—C1	1.338 (2)	C10—C11	1.384 (3)
N1—C5	1.354 (2)	C11—C12	1.389 (3)
N2—C6	1.315 (2)	C20—O20	1.443 (2)
N2—N3	1.372 (2)	Cl10—O13	1.4232 (15)
N3—C7	1.299 (2)	Cl10—O12	1.4292 (15)
N4—C12	1.339 (2)	Cl10—O14	1.4372 (15)
N4—C8	1.342 (2)	Cl10—O11	1.4574 (15)
O20—Fe1—O20i	180.00 (4)	C2—C3—C4	118.88 (17)
O20—Fe1—N2i	91.48 (6)	C5—C4—C3	118.73 (17)
O20i—Fe1—N2i	88.52 (6)	N1—C5—C4	122.90 (16)
O20—Fe1—N2	88.52 (6)	N1—C5—C6	114.25 (16)
O20i—Fe1—N2	91.48 (6)	C4—C5—C6	122.85 (16)
N2i—Fe1—N2	180.0	N2—C6—C5	120.39 (16)
O20—Fe1—N1i	87.99 (5)	N2—C6—S1	113.48 (13)
O20i—Fe1—N1i	92.01 (5)	C5—C6—S1	126.13 (14)
N2i—Fe1—N1i	76.37 (6)	N3—C7—C8	124.64 (17)
N2—Fe1—N1i	103.63 (6)	N3—C7—S1	114.73 (13)
O20—Fe1—N1	92.01 (5)	C8—C7—S1	120.61 (14)
O20i—Fe1—N1	87.99 (5)	N4—C8—C9	124.49 (17)
N2i—Fe1—N1	103.63 (6)	N4—C8—C7	114.70 (16)
N2—Fe1—N1	76.37 (6)	C9—C8—C7	120.81 (17)
N1i—Fe1—N1	180.0	C10—C9—C8	117.74 (18)
C6—S1—C7	86.84 (9)	C11—C10—C9	118.93 (18)
C1—N1—C5	117.61 (16)	C10—C11—C12	118.91 (18)
C1—N1—Fe1	127.76 (12)	N4—C12—C11	123.43 (19)
C5—N1—Fe1	114.39 (11)	C20—O20—Fe1	123.03 (12)
C6—N2—N3	113.63 (15)	O13—Cl10—O12	109.10 (10)
C6—N2—Fe1	114.27 (12)	O13—Cl10—O14	110.30 (10)
N3—N2—Fe1	132.09 (12)	O12—Cl10—O14	110.33 (10)
C7—N3—N2	111.33 (15)	O13—Cl10—O11	108.75 (10)
C12—N4—C8	116.48 (17)	O12—Cl10—O11	108.62 (9)
N1—C1—C2	122.82 (17)	O14—Cl10—O11	109.71 (9)
C3—C2—C1	119.05 (17)
O20—Fe1—N1—C1	92.67 (15)	Fe1—N2—C6—C5	−2.5 (2)
O20i—Fe1—N1—C1	−87.33 (15)	N3—N2—C6—S1	−0.96 (19)
N2i—Fe1—N1—C1	0.65 (16)	Fe1—N2—C6—S1	178.04 (8)
N2—Fe1—N1—C1	−179.35 (16)	N1—C5—C6—N2	−2.2 (2)
O20—Fe1—N1—C5	−93.28 (12)	C4—C5—C6—N2	178.55 (16)
O20i—Fe1—N1—C5	86.72 (12)	N1—C5—C6—S1	177.18 (13)
N2i—Fe1—N1—C5	174.71 (12)	C4—C5—C6—S1	−2.0 (3)
N2—Fe1—N1—C5	−5.29 (12)	C7—S1—C6—N2	0.74 (14)
O20—Fe1—N2—C6	96.46 (13)	C7—S1—C6—C5	−178.71 (16)
O20i—Fe1—N2—C6	−83.54 (13)	N2—N3—C7—C8	−178.46 (16)
N1i—Fe1—N2—C6	−175.97 (12)	N2—N3—C7—S1	−0.07 (19)
N1—Fe1—N2—C6	4.03 (12)	C6—S1—C7—N3	−0.37 (15)
O20—Fe1—N2—N3	−84.78 (15)	C6—S1—C7—C8	178.09 (15)
O20i—Fe1—N2—N3	95.22 (15)	C12—N4—C8—C9	−0.7 (3)
N1i—Fe1—N2—N3	2.79 (16)	C12—N4—C8—C7	179.92 (17)
N1—Fe1—N2—N3	−177.21 (16)	N3—C7—C8—N4	−163.82 (17)
C6—N2—N3—C7	0.7 (2)	S1—C7—C8—N4	17.9 (2)
Fe1—N2—N3—C7	−178.11 (13)	N3—C7—C8—C9	16.8 (3)
C5—N1—C1—C2	0.7 (3)	S1—C7—C8—C9	−161.50 (14)
Fe1—N1—C1—C2	174.61 (13)	N4—C8—C9—C10	0.0 (3)
N1—C1—C2—C3	−0.5 (3)	C7—C8—C9—C10	179.33 (17)
C1—C2—C3—C4	−0.1 (3)	C8—C9—C10—C11	0.3 (3)
C2—C3—C4—C5	0.3 (3)	C9—C10—C11—C12	0.1 (3)
C1—N1—C5—C4	−0.4 (3)	C8—N4—C12—C11	1.2 (3)
Fe1—N1—C5—C4	−175.14 (13)	C10—C11—C12—N4	−0.9 (3)
C1—N1—C5—C6	−179.67 (15)	N2i—Fe1—O20—C20	−124.06 (14)
Fe1—N1—C5—C6	5.64 (19)	N2—Fe1—O20—C20	55.94 (14)
C3—C4—C5—N1	−0.1 (3)	N1i—Fe1—O20—C20	−47.76 (14)
C3—C4—C5—C6	179.08 (16)	N1—Fe1—O20—C20	132.24 (14)
N3—N2—C6—C5	178.53 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O20—H20···O11	0.78 (3)	1.91 (3)	2.690 (2)	178 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O20—H20⋯O11	0.78 (3)	1.91 (3)	2.690 (2)	178 (3)