Hexa-kis-(dimethyl-formamide-κO)manganese(II) μ-oxido-bis-[trichlorido-ferrate(III)].

The title compound, [Mn(C(3)H(7)NO)(6)][Fe(2)Cl(6)O], was obtained unintentionally as a product of an attempted synthesis of heterometallic complexes with Schiff base ligands using manganese powder and FeCl(3)·6H(2)O as starting materials. In the [Fe(2)OCl(6)](2-) anion, the O atom and the Fe atom occupy positions with site symmetry [Formula: see text] and 3, respectively, resulting in a linear Fe-O-Fe angle and a staggered conformation. The octa-hedrally surrounded cation (site symmetry [Formula: see text]) and the [Fe(2)Cl(6)O](2-) anion are alternately stacked along [001].

Related literature

For structures including [Mn(dmf)6]2+ cations, see: Khutornoi et al. (2002 ▶). For stuctures including [Fe(dmf)6]2+, see: Albanati et al. (2007 ▶); Baumgartner (1986 ▶); Li et al. (2007 ▶); Lode & Krautscheid (2000 ▶); Müller et al. (1989 ▶); Qiutian et al. (1983 ▶); Silva et al. (2008 ▶); Young et al. (1989 ▶). For the isostructural complex [Mg(dmf)6][Fe2OCl6], see: Juang et al. (1984 ▶). For bond-valence-sum calculations, see: Brown & Altermatt (1985 ▶). For related direct syntheses, see: Garnovskii et al. (1999 ▶).

Experimental

Crystal data

[Mn(C3H7NO)6][Fe2Cl6O]

M = 833.92

Trigonal,

a = 14.0171 (8) Å

c = 15.3966 (14) Å

V = 2619.8 (3) Å3

Z = 3

Mo Kα radiation

μ = 1.68 mm−1

T = 173 K

0.60 × 0.40 × 0.40 mm

Data collection

Oxford Diffraction Xcalibur/Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.557, T max = 1.000

16066 measured reflections

1624 independent reflections

1323 reflections with I > 2σ(I)

R int = 0.067

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.092

S = 0.98

1624 reflections

68 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.05 e Å−3

Δρmin = −0.37 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2010 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811041523/wm2531sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041523/wm2531Isup2.hkl

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

[Mn(C3H7NO)6][Fe2Cl6O]	Dx = 1.586 Mg m−3
Mr = 833.92	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 2653 reflections
Hall symbol: -R 3	θ = 2.9–32.5°
a = 14.0171 (8) Å	µ = 1.68 mm−1
c = 15.3966 (14) Å	T = 173 K
V = 2619.8 (3) Å3	Block, red
Z = 3	0.60 × 0.40 × 0.40 mm
F(000) = 1281

Oxford Diffraction Xcalibur/Sapphire3 diffractometer	1624 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1323 reflections with I > 2σ(I)
graphite	Rint = 0.067
Detector resolution: 16.1827 pixels mm-1	θmax = 30.0°, θmin = 2.9°
ω scans	h = −19→19
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −19→15
Tmin = 0.557, Tmax = 1.000	l = −20→18
16066 measured reflections

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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ2(Fo2) + (0.0428P)2] where P = (Fo2 + 2Fc2)/3
1624 reflections	(Δ/σ)max < 0.001
68 parameters	Δρmax = 1.05 e Å−3
0 restraints	Δρmin = −0.37 e Å−3
0 constraints

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
Mn1	0.0000	0.0000	0.5000	0.02020 (19)
N1	0.23962 (14)	−0.02345 (15)	0.65588 (11)	0.0223 (4)
Fe1	0.0000	0.0000	0.88467 (3)	0.02113 (16)
O1	0.08798 (13)	−0.06054 (12)	0.57785 (10)	0.0262 (4)
Cl1	0.03397 (5)	−0.12729 (4)	0.82931 (3)	0.02609 (16)
C1	0.15838 (18)	−0.00668 (18)	0.63362 (15)	0.0232 (4)
H1	0.1622 (18)	0.0567 (19)	0.6623 (13)	0.015 (6)*
O1S	0.0000	0.0000	1.0000	0.0282 (8)
C2	0.2521 (2)	−0.1115 (2)	0.61800 (16)	0.0318 (5)
H2A	0.1939	−0.1512	0.5750	0.048*
H2B	0.2467	−0.1626	0.6638	0.048*
H2C	0.3242	−0.0802	0.5897	0.048*
C3	0.3184 (2)	0.0425 (2)	0.72297 (17)	0.0347 (6)
H3A	0.3143	−0.0055	0.7709	0.052*
H3B	0.3010	0.0977	0.7446	0.052*
H3C	0.3929	0.0795	0.6985	0.052*

	U11	U22	U33	U12	U13	U23
Mn1	0.0176 (2)	0.0176 (2)	0.0254 (4)	0.00880 (12)	0.000	0.000
N1	0.0200 (9)	0.0211 (9)	0.0259 (9)	0.0104 (7)	−0.0009 (7)	0.0000 (7)
Fe1	0.02076 (19)	0.02076 (19)	0.0219 (3)	0.01038 (10)	0.000	0.000
O1	0.0238 (8)	0.0209 (8)	0.0340 (9)	0.0112 (7)	−0.0040 (6)	0.0015 (6)
Cl1	0.0271 (3)	0.0233 (3)	0.0303 (3)	0.0145 (2)	0.0021 (2)	0.00083 (19)
C1	0.0209 (11)	0.0185 (10)	0.0296 (11)	0.0093 (9)	0.0026 (8)	0.0041 (8)
O1S	0.0274 (13)	0.0274 (13)	0.030 (2)	0.0137 (6)	0.000	0.000
C2	0.0373 (14)	0.0370 (13)	0.0331 (13)	0.0278 (12)	−0.0034 (10)	−0.0044 (10)
C3	0.0339 (13)	0.0269 (13)	0.0446 (14)	0.0162 (11)	−0.0151 (11)	−0.0065 (10)

Mn1—O1i	2.1736 (15)	Fe1—Cl1	2.2330 (6)
Mn1—O1ii	2.1736 (15)	Fe1—Cl1v	2.2330 (6)
Mn1—O1	2.1736 (15)	O1—C1	1.239 (3)
Mn1—O1iii	2.1736 (15)	C1—H1	0.97 (2)
Mn1—O1iv	2.1736 (15)	O1S—Fe1vi	1.7758 (5)
Mn1—O1v	2.1736 (15)	C2—H2A	0.9800
N1—C1	1.318 (3)	C2—H2B	0.9800
N1—C2	1.453 (3)	C2—H2C	0.9800
N1—C3	1.456 (3)	C3—H3A	0.9800
Fe1—O1S	1.7758 (5)	C3—H3B	0.9800
Fe1—Cl1ii	2.2330 (6)	C3—H3C	0.9800
O1i—Mn1—O1ii	180.00 (6)	O1S—Fe1—Cl1v	112.438 (17)
O1i—Mn1—O1	87.49 (6)	Cl1ii—Fe1—Cl1v	106.348 (19)
O1ii—Mn1—O1	92.51 (6)	Cl1—Fe1—Cl1v	106.348 (19)
O1i—Mn1—O1iii	92.51 (6)	C1—O1—Mn1	125.35 (15)
O1ii—Mn1—O1iii	87.49 (6)	O1—C1—N1	124.6 (2)
O1—Mn1—O1iii	180.00 (7)	O1—C1—H1	122.4 (13)
O1i—Mn1—O1iv	92.51 (6)	N1—C1—H1	112.8 (13)
O1ii—Mn1—O1iv	87.49 (6)	Fe1vi—O1S—Fe1	180.0
O1—Mn1—O1iv	87.49 (6)	N1—C2—H2A	109.5
O1iii—Mn1—O1iv	92.51 (6)	N1—C2—H2B	109.5
O1i—Mn1—O1v	87.49 (6)	H2A—C2—H2B	109.5
O1ii—Mn1—O1v	92.51 (6)	N1—C2—H2C	109.5
O1—Mn1—O1v	92.51 (6)	H2A—C2—H2C	109.5
O1iii—Mn1—O1v	87.49 (6)	H2B—C2—H2C	109.5
O1iv—Mn1—O1v	180.00 (7)	N1—C3—H3A	109.5
C1—N1—C2	121.94 (18)	N1—C3—H3B	109.5
C1—N1—C3	121.34 (19)	H3A—C3—H3B	109.5
C2—N1—C3	116.65 (18)	N1—C3—H3C	109.5
O1S—Fe1—Cl1ii	112.438 (17)	H3A—C3—H3C	109.5
O1S—Fe1—Cl1	112.438 (17)	H3B—C3—H3C	109.5
Cl1ii—Fe1—Cl1	106.348 (19)
O1i—Mn1—O1—C1	169.64 (18)	Mn1—O1—C1—N1	−152.23 (16)
O1ii—Mn1—O1—C1	−10.36 (18)	C2—N1—C1—O1	−2.2 (3)
O1iv—Mn1—O1—C1	77.01 (14)	C3—N1—C1—O1	−179.2 (2)
O1v—Mn1—O1—C1	−102.99 (14)

Table 1

Selected bond lengths (Å)

Mn1—O1	2.1736 (15)
Fe1—O1S	1.7758 (5)
Fe1—Cl1	2.2330 (6)