Hexa­kis­(dimethyl­formamide-κO)manganese(II) (dimethyl­formamide-κO)pentakis(­thio­cyanato­-κN)chromate(III)

Semenaka, V.V.; Nesterova, O.V.; Kokozay, V.N.; Omelchenko, I.V.; Shishkin, O.V.

doi:10.1107/S1600536812023069

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m823

doi:10.1107/S1600536812023069

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Hexakis(dimethylformamide-κO)manganese(II) (dimethylformamide-κO)pentakis(thiocyanato-κN)chromate(III)

Valentyna V. Semenaka,^a ^* Oksana V. Nesterova,^a Vladimir N. Kokozay,^a Irina V. Omelchenko ^b and Oleg V. Shishkin ^b

^aDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, 64 Volodymyrs'ka St., Kyiv 01601, Ukraine, and ^bSTC "Institute for Single Crystals" National Academy of Sciences of Ukraine, 60 Lenina Avenue, Kharkiv 61001, Ukraine
^*Correspondence e-mail: valya.semenaka@gmail.com

(Received 26 April 2012; accepted 20 May 2012; online 26 May 2012)

The title compound, [Mn(C₃H₇NO)₆][Cr(NCS)₅(C₃H₇NO)], was obtained unintentionally as a product of an attempted synthesis of heterometallic complexes based on Reineckes anion using manganese powder, Reineckes salt and 1-(2-hydroxyethyl)tetrazole as starting materials. The crystal structure of the complex consists of an [Mn(dmf)₆]²⁺ cation and a [Cr(NCS)₅(dmf)]²⁻ anion (dmf = dimethylformamide). The Mn^II and Cr^III atoms show a slightly distorted octahedral MnO₆ and CrN₅O coordination geometries with adjacent angles in the range 85.29 (13)–95.96 (14)°.

Related literature

For structures including [Mn(dmf)₆]²⁺ cations, see: Khutornoi et al. (2002 ); Bencini et al. (1992 ). For background to direct synthesis, see: Makhankova (2011 ).

Experimental

Crystal data

[Mn(C₃H₇NO)₆][Cr(NCS)₅(C₃H₇NO)]
M_r = 909.01
Monoclinic, P 2₁ /c
a = 15.327 (3) Å
b = 17.742 (2) Å
c = 17.278 (2) Å
β = 110.36 (2)°
V = 4404.9 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 294 K
0.40 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.735, T_max = 0.922
20206 measured reflections
9620 independent reflections
2863 reflections with I > 2σ(I)
R_int = 0.092

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.100
S = 0.67
9620 reflections
463 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Selected bond lengths (Å)

Cr1—N8	1.969 (4)
Cr1—N9	1.977 (4)
Cr1—N11	1.996 (4)
Cr1—O7	1.999 (3)
Cr1—N7	2.002 (4)
Cr1—N12	2.006 (4)
Mn1—O4	2.133 (4)
Mn1—O3	2.140 (4)
Mn1—O1	2.140 (3)
Mn1—O6	2.143 (3)
Mn1—O5	2.167 (3)
Mn1—O2	2.171 (3)

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812023069/ff2065sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023069/ff2065Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812023069/ff2065Isup3.cdx

checkCIF report

Comment top

Continuing our research on direct synthesis of heterometallic complexes using Reineckes salt, (NH)₄[Cr(NCS)₄(NH₃)₂]_.H₂O, as a source of building blocks or metalloligands (Makhankova, 2011), we present here a new Mn^II/Cr^III complex, which was obtained unintentionally as a product of an attempted reaction of manganese powder, Reineckes salt and 1-(2-hydroxyethyl)tetrazole in dmf (dimethylformamide). The crystal structure of the complex consists of a slightly distorted octahedral [Mn(dmf)₆]²⁺ cation and [Cr(NCS)₅(dmf)]⁺ anion blocks (Fig. 1). Manganese centers have octahedral coordination environment of six oxygen atoms of dmf ligands. The Mn–O bond lengths vary in the range of 2.133 (4) – 2.171 (3) Å that is in good agreement with those in [Mn(dmf)₆][Mo₆Br₈(NCS)₆] [2.152 Å (Khutornoi et al., 2002)]. The cis and trans O–Mn–O bond angles vary from 85.29 (13)° to 95.96 (14)° and from 173.81 (14)° to 175.64 (13)°, respectively. The Cr(III) ions have ON₅ environment formed by N atoms of NCS groups and O atom of dmf that replace NH₃ groups of initial complex anion of Reineckes salt. The Cr–N(O) bond lengths vary from 1.969 (4) to 2.006 (4) Å. The cis and trans N–Cr–N(O) bond angles vary from 86.51 (13)° to 92.83 (16)° and from 175.62 (12)° to 179.24 (17)°, respectively.

Related literature top

For structures including [Mn(dmf)₆]²⁺ cations, see: Khutornoi et al. (2002); Bencini et al. (1992). For background to direct synthesis, see: Makhankova (2011).

Experimental top

Manganese powder (0.069 g, 1.25 mmol), NH₄[Cr(NCS)₄(NH₃)₂]^.H₂O (0.443 g, 1.25 mmol), NH₄NCS (0.095 g, 1.25 mmol), 1-(2-hydroxyethyl)tetrazole (0.5 g, 2.5 mmol) and dmf (20 ml) were heated to 50–60° and stirred magnetically until total dissolution of the manganese was observed (4.2 h). Dark blue crystals suitable for the X-ray crystallographic study were deposited after successive addition of PrⁱOH into the resulting blue solution. The crystals were filtered off, washed with dry PrⁱOH and finally dried in vacuo at room temperature. Yield: 0.17 g. Anal. Calc. for C₂₆H₄₉MnCrN₁₂O₇S₅: Mn, 6.04; Cr, 5.72; C, 34.35; H, 2.86; N, 18.49; S, 17.63. Found: Mn, 6.0; Cr, 5.9; C, 34.5; H, 3.0; N, 18.6; S, 17.7% IR (KBr, cm^-1): 3420(w, br), 2964(sh), 2930(w or m), 2807(w), 2116(sh), 2081(vs), 1688(sh), 1653(vs), 1556(sh), 1496(sh), 1425(sh), 1373(m), 1241(m or sh), 1111(m), 1058(sh), 971(w), 865(w), 708(sh), 673(m), 481(w). The compound is sparingly soluble in dmso and dmf, insoluble in water.

Computing details top

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

Figures top

Fig. 1. Crystal structure of the complex, showing the atom numbering, with 45% probability displacement ellipsoids

Hexakis(dimethylformamide-κO)manganese(II) (dimethylformamide-κO)pentakis(thiocyanato-κN)chromate(III) top

Crystal data top

[Mn(C₃H₇NO)₆][Cr(NCS)₅(C₃H₇NO)]	F(000) = 1896
M_r = 909.01	D_x = 1.371 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 300 reflections
a = 15.327 (3) Å	θ = 3.2–28.5°
b = 17.742 (2) Å	µ = 0.82 mm⁻¹
c = 17.278 (2) Å	T = 294 K
β = 110.36 (2)°	Block, blue
V = 4404.9 (11) Å³	0.40 × 0.20 × 0.10 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	9620 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2863 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.092
Detector resolution: 16.1827 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
ω scans	h = −19→19
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −23→22
T_min = 0.735, T_max = 0.922	l = −12→22
20206 measured reflections

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 0.67	w = 1/[σ²(F_o²) + (0.0294P)²] where P = (F_o² + 2F_c²)/3
9620 reflections	(Δ/σ)_max < 0.001
463 parameters	Δρ_max = 0.85 e Å⁻³
4 restraints	Δρ_min = −0.57 e Å⁻³
104 constraints

Crystal data top

[Mn(C₃H₇NO)₆][Cr(NCS)₅(C₃H₇NO)]	V = 4404.9 (11) Å³
M_r = 909.01	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.327 (3) Å	µ = 0.82 mm⁻¹
b = 17.742 (2) Å	T = 294 K
c = 17.278 (2) Å	0.40 × 0.20 × 0.10 mm
β = 110.36 (2)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	9620 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	2863 reflections with I > 2σ(I)
T_min = 0.735, T_max = 0.922	R_int = 0.092
20206 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	4 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 0.67	Δρ_max = 0.85 e Å⁻³
9620 reflections	Δρ_min = −0.57 e Å⁻³
463 parameters

Special details top

Experimental. Absorption correction: CrysAlis RED (Oxford Diffraction, 2010) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Cr1	0.22880 (5)	0.21566 (4)	0.23165 (5)	0.0298 (2)
Mn1	0.70617 (5)	0.21884 (4)	0.26170 (5)	0.0372 (2)
N1	0.8824 (3)	0.0894 (2)	0.1622 (2)	0.0450 (12)
N2	0.4621 (3)	0.0800 (2)	0.1678 (3)	0.0393 (11)
N3	0.6171 (3)	0.3210 (2)	0.4454 (3)	0.0520 (13)
N4	0.9826 (3)	0.3188 (2)	0.3868 (2)	0.0329 (10)
N6	0.7430 (3)	0.4134 (2)	0.1329 (3)	0.0361 (10)
N7	0.1901 (3)	0.1206 (2)	0.1662 (2)	0.0315 (10)
N8	0.1676 (3)	0.1834 (2)	0.3092 (2)	0.0340 (10)
N9	0.2747 (3)	0.3103 (2)	0.2927 (3)	0.0423 (12)
N10	0.3868 (3)	0.3073 (2)	0.1029 (2)	0.0329 (10)
N11	0.3458 (3)	0.1635 (2)	0.2994 (2)	0.0357 (11)
N12	0.1107 (3)	0.2669 (2)	0.1626 (2)	0.0353 (11)
O1	0.7688 (2)	0.14527 (17)	0.1978 (2)	0.0477 (10)
O2	0.5714 (2)	0.17089 (17)	0.1918 (2)	0.0441 (9)
O3	0.6391 (3)	0.2817 (2)	0.3308 (3)	0.0773 (13)
O4	0.8408 (2)	0.2668 (2)	0.3198 (2)	0.0544 (11)
O5	0.7315 (2)	0.12866 (18)	0.35140 (19)	0.0438 (9)
O6	0.6900 (2)	0.30489 (18)	0.1707 (2)	0.0447 (9)
O7	0.2835 (2)	0.24700 (16)	0.14712 (19)	0.0387 (9)
S1	0.15171 (9)	−0.02018 (7)	0.08949 (9)	0.0478 (4)
S2	0.06542 (10)	0.13086 (8)	0.40395 (9)	0.0548 (4)
S3	0.38322 (11)	0.43885 (8)	0.35746 (10)	0.0648 (5)
S4	0.46635 (9)	0.06510 (8)	0.41462 (9)	0.0527 (4)
S5	−0.06415 (10)	0.32690 (9)	0.08380 (9)	0.0639 (5)
C1	0.8415 (5)	0.1480 (4)	0.1847 (4)	0.0816 (15)
H1A	0.8712	0.1944	0.1908	0.098*
C2	0.9712 (4)	0.0939 (3)	0.1524 (4)	0.077 (2)
H2A	0.9950	0.1443	0.1642	0.115*
H2B	0.9647	0.0811	0.0967	0.115*
H2C	1.0136	0.0594	0.1898	0.115*
C3	0.8435 (4)	0.0154 (3)	0.1565 (4)	0.1045 (19)
H3A	0.7820	0.0187	0.1591	0.157*
H3B	0.8820	−0.0149	0.2014	0.157*
H3C	0.8402	−0.0072	0.1051	0.157*
C4	0.5363 (4)	0.1137 (3)	0.2144 (3)	0.0405 (13)
H4A	0.5658	0.0952	0.2675	0.049*
C5	0.4271 (4)	0.0114 (3)	0.1972 (4)	0.0868 (15)
H5A	0.4554	0.0077	0.2561	0.130*
H5B	0.4426	−0.0325	0.1720	0.130*
H5C	0.3608	0.0146	0.1823	0.130*
C6	0.4090 (4)	0.1043 (3)	0.0861 (3)	0.0569 (16)
H6A	0.4339	0.1509	0.0747	0.085*
H6B	0.3454	0.1116	0.0818	0.085*
H6C	0.4119	0.0668	0.0471	0.085*
N5	0.8034 (3)	0.0143 (3)	0.3822 (2)	0.0483 (12)
C7	0.6621 (4)	0.3234 (3)	0.3923 (3)	0.0816 (15)
H7A	0.7114	0.3568	0.4012	0.098*
C8	0.5470 (4)	0.2770 (3)	0.4630 (5)	0.1045 (19)
H8A	0.5281	0.2358	0.4248	0.157*
H8B	0.4941	0.3083	0.4578	0.157*
H8C	0.5721	0.2577	0.5183	0.157*
C9	0.6448 (4)	0.3856 (3)	0.5001 (3)	0.0868 (15)
H9A	0.6959	0.4108	0.4912	0.130*
H9B	0.6634	0.3689	0.5564	0.130*
H9C	0.5933	0.4198	0.4888	0.130*
C10	0.9062 (4)	0.2806 (3)	0.3830 (3)	0.0426 (14)
H10A	0.9024	0.2632	0.4325	0.051*
C11	1.0567 (4)	0.3337 (3)	0.4630 (3)	0.0706 (19)
H11A	1.0388	0.3172	0.5083	0.106*
H11B	1.0694	0.3868	0.4679	0.106*
H11C	1.1116	0.3070	0.4639	0.106*
C12	0.9917 (4)	0.3480 (3)	0.3130 (3)	0.0528 (15)
H12A	0.9434	0.3277	0.2659	0.079*
H12B	1.0513	0.3341	0.3107	0.079*
H12C	0.9867	0.4020	0.3127	0.079*
C16	0.7301 (3)	0.3674 (3)	0.1886 (3)	0.0398 (14)
H16A	0.7518	0.3824	0.2436	0.048*
C17	0.7130 (3)	0.3912 (3)	0.0463 (3)	0.0555 (16)
H17A	0.6964	0.3388	0.0413	0.083*
H17B	0.7628	0.3994	0.0257	0.083*
H17C	0.6601	0.4208	0.0150	0.083*
C18	0.7886 (4)	0.4847 (2)	0.1548 (3)	0.0536 (15)
H18A	0.8060	0.4923	0.2132	0.080*
H18B	0.7471	0.5242	0.1260	0.080*
H18C	0.8433	0.4855	0.1397	0.080*
C19	0.8004 (4)	0.0875 (3)	0.3649 (3)	0.0493 (15)
H19A	0.8545	0.1096	0.3629	0.059*
C20	0.8854 (4)	−0.0308 (3)	0.3888 (3)	0.0727 (19)
H20A	0.9328	0.0012	0.3823	0.109*
H20B	0.8689	−0.0686	0.3465	0.109*
H20C	0.9082	−0.0546	0.4420	0.109*
C21	0.7238 (4)	−0.0250 (3)	0.3849 (3)	0.074 (2)
H21A	0.6763	0.0106	0.3842	0.110*
H21B	0.7404	−0.0545	0.4345	0.110*
H21C	0.7008	−0.0576	0.3378	0.110*
C22	0.1741 (3)	0.0613 (3)	0.1342 (3)	0.0325 (12)
C23	0.1256 (3)	0.1623 (2)	0.3479 (3)	0.0297 (12)
C24	0.3185 (4)	0.3642 (3)	0.3215 (3)	0.0420 (14)
C25	0.3606 (4)	0.2789 (3)	0.1597 (3)	0.0421 (13)
H25A	0.4015	0.2822	0.2139	0.050*
C26	0.4764 (3)	0.3431 (3)	0.1240 (3)	0.0424 (13)
H26A	0.5055	0.3450	0.1830	0.064*
H26B	0.4685	0.3935	0.1022	0.064*
H26C	0.5148	0.3149	0.1009	0.064*
C27	0.3291 (3)	0.3023 (3)	0.0172 (3)	0.0440 (14)
H27A	0.2659	0.2927	0.0128	0.066*
H27B	0.3508	0.2619	−0.0085	0.066*
H27C	0.3322	0.3489	−0.0100	0.066*
C28	0.3953 (3)	0.1229 (3)	0.3477 (3)	0.0314 (12)
C29	0.0390 (4)	0.2920 (3)	0.1304 (3)	0.0383 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr1	0.0311 (4)	0.0319 (4)	0.0270 (5)	0.0015 (4)	0.0110 (4)	0.0068 (4)
Mn1	0.0416 (5)	0.0327 (4)	0.0430 (5)	−0.0013 (4)	0.0221 (4)	−0.0004 (5)
N1	0.026 (2)	0.060 (3)	0.051 (3)	0.000 (2)	0.016 (2)	−0.020 (3)
N2	0.043 (3)	0.038 (3)	0.034 (3)	−0.010 (2)	0.011 (2)	−0.001 (2)
N3	0.041 (3)	0.088 (3)	0.036 (3)	0.024 (3)	0.025 (2)	0.012 (3)
N4	0.042 (3)	0.023 (2)	0.028 (3)	−0.009 (2)	0.006 (2)	−0.002 (2)
N6	0.033 (2)	0.029 (2)	0.045 (3)	−0.001 (2)	0.012 (2)	0.011 (2)
N7	0.028 (2)	0.041 (2)	0.026 (3)	0.004 (2)	0.009 (2)	0.009 (2)
N8	0.029 (2)	0.045 (3)	0.028 (3)	0.009 (2)	0.012 (2)	0.001 (2)
N9	0.049 (3)	0.037 (3)	0.037 (3)	0.004 (2)	0.010 (2)	0.006 (2)
N10	0.036 (3)	0.039 (3)	0.030 (3)	−0.002 (2)	0.018 (2)	0.013 (2)
N11	0.038 (3)	0.041 (3)	0.030 (3)	0.001 (2)	0.014 (2)	0.004 (2)
N12	0.042 (3)	0.032 (3)	0.033 (3)	0.002 (2)	0.014 (2)	0.003 (2)
O1	0.043 (2)	0.057 (2)	0.051 (3)	0.001 (2)	0.027 (2)	−0.004 (2)
O2	0.049 (2)	0.0298 (18)	0.055 (3)	−0.0079 (19)	0.021 (2)	0.0002 (19)
O3	0.082 (3)	0.059 (2)	0.083 (3)	−0.003 (2)	0.018 (3)	−0.047 (3)
O4	0.043 (2)	0.055 (3)	0.050 (3)	−0.011 (2)	−0.004 (2)	0.007 (2)
O5	0.047 (2)	0.048 (2)	0.031 (2)	−0.011 (2)	0.007 (2)	0.0022 (19)
O6	0.034 (2)	0.040 (2)	0.053 (3)	−0.0068 (18)	0.0061 (18)	0.0076 (19)
O7	0.040 (2)	0.0407 (19)	0.041 (2)	−0.0003 (18)	0.0208 (18)	0.0063 (17)
S1	0.0461 (9)	0.0402 (8)	0.0479 (10)	−0.0033 (8)	0.0047 (8)	−0.0079 (8)
S2	0.0556 (10)	0.0605 (9)	0.0643 (11)	0.0111 (8)	0.0410 (9)	0.0229 (9)
S3	0.0703 (11)	0.0513 (9)	0.0672 (12)	−0.0134 (9)	0.0169 (10)	−0.0068 (9)
S4	0.0452 (9)	0.0624 (9)	0.0395 (9)	0.0171 (8)	0.0008 (7)	0.0036 (8)
S5	0.0514 (10)	0.0932 (12)	0.0425 (10)	0.0329 (10)	0.0104 (8)	−0.0002 (9)
C1	0.059 (3)	0.084 (4)	0.095 (4)	−0.006 (3)	0.019 (3)	0.003 (3)
C2	0.061 (4)	0.088 (5)	0.088 (5)	−0.001 (4)	0.035 (4)	−0.036 (4)
C3	0.099 (4)	0.053 (3)	0.187 (6)	0.004 (3)	0.083 (4)	0.008 (3)
C4	0.035 (3)	0.043 (3)	0.043 (4)	0.001 (3)	0.014 (3)	−0.008 (3)
C5	0.073 (3)	0.087 (3)	0.082 (4)	−0.012 (3)	0.003 (3)	0.001 (3)
C6	0.054 (4)	0.058 (4)	0.052 (4)	0.004 (3)	0.009 (3)	−0.002 (3)
N5	0.060 (3)	0.051 (3)	0.036 (3)	−0.011 (3)	0.019 (3)	0.009 (3)
C7	0.059 (3)	0.084 (4)	0.095 (4)	−0.006 (3)	0.019 (3)	0.003 (3)
C8	0.099 (4)	0.053 (3)	0.187 (6)	0.004 (3)	0.083 (4)	0.008 (3)
C9	0.073 (3)	0.087 (3)	0.082 (4)	−0.012 (3)	0.003 (3)	0.001 (3)
C10	0.072 (4)	0.024 (3)	0.041 (4)	0.003 (3)	0.030 (3)	0.012 (3)
C11	0.074 (4)	0.061 (4)	0.046 (4)	−0.032 (4)	−0.019 (3)	0.008 (3)
C12	0.056 (4)	0.046 (3)	0.056 (4)	−0.009 (3)	0.019 (3)	0.001 (3)
C16	0.028 (3)	0.055 (4)	0.043 (4)	0.010 (3)	0.022 (3)	0.005 (3)
C17	0.042 (3)	0.068 (4)	0.042 (4)	−0.012 (3)	−0.004 (3)	0.010 (3)
C18	0.061 (4)	0.029 (3)	0.072 (4)	−0.002 (3)	0.024 (3)	0.004 (3)
C19	0.055 (4)	0.041 (4)	0.040 (4)	−0.019 (3)	0.002 (3)	0.008 (3)
C20	0.101 (5)	0.055 (4)	0.060 (5)	0.010 (4)	0.026 (4)	0.009 (4)
C21	0.111 (6)	0.062 (4)	0.042 (4)	−0.035 (4)	0.019 (4)	−0.001 (3)
C22	0.023 (3)	0.048 (3)	0.022 (3)	0.006 (3)	0.002 (2)	0.011 (3)
C23	0.028 (3)	0.029 (3)	0.024 (3)	0.009 (2)	−0.001 (2)	−0.002 (2)
C24	0.054 (4)	0.041 (3)	0.035 (4)	0.003 (3)	0.019 (3)	0.010 (3)
C25	0.041 (3)	0.031 (3)	0.053 (4)	0.003 (3)	0.014 (3)	−0.004 (3)
C26	0.030 (3)	0.055 (3)	0.038 (3)	−0.007 (3)	0.008 (3)	−0.001 (3)
C27	0.035 (3)	0.056 (3)	0.038 (4)	0.006 (3)	0.009 (3)	0.008 (3)
C28	0.031 (3)	0.036 (3)	0.031 (3)	−0.002 (3)	0.015 (3)	−0.005 (3)
C29	0.054 (4)	0.035 (3)	0.029 (3)	0.011 (3)	0.019 (3)	0.002 (3)

Geometric parameters (Å, º) top

Cr1—N8	1.969 (4)	C2—H2C	0.9600
Cr1—N9	1.977 (4)	C3—H3A	0.9600
Cr1—N11	1.996 (4)	C3—H3B	0.9600
Cr1—O7	1.999 (3)	C3—H3C	0.9600
Cr1—N7	2.002 (4)	C4—H4A	0.9300
Cr1—N12	2.006 (4)	C5—H5A	0.9600
Mn1—O4	2.133 (4)	C5—H5B	0.9600
Mn1—O3	2.140 (4)	C5—H5C	0.9600
Mn1—O1	2.140 (3)	C6—H6A	0.9600
Mn1—O6	2.143 (3)	C6—H6B	0.9600
Mn1—O5	2.167 (3)	C6—H6C	0.9600
Mn1—O2	2.171 (3)	N5—C19	1.329 (6)
N1—C1	1.340 (7)	N5—C21	1.421 (6)
N1—C2	1.430 (6)	N5—C20	1.460 (6)
N1—C3	1.432 (6)	C7—H7A	0.9300
N2—C4	1.290 (6)	C8—H8A	0.9600
N2—C6	1.428 (6)	C8—H8B	0.9600
N2—C5	1.488 (6)	C8—H8C	0.9600
N3—C7	1.326 (2)	C9—H9A	0.9600
N3—C8	1.444 (2)	C9—H9B	0.9600
N3—C9	1.451 (2)	C9—H9C	0.9600
N4—C10	1.334 (6)	C10—H10A	0.9300
N4—C12	1.428 (5)	C11—H11A	0.9600
N4—C11	1.434 (6)	C11—H11B	0.9600
N6—C16	1.328 (5)	C11—H11C	0.9600
N6—C18	1.432 (5)	C12—H12A	0.9600
N6—C17	1.457 (5)	C12—H12B	0.9600
N7—C22	1.174 (5)	C12—H12C	0.9600
N8—C23	1.142 (5)	C16—H16A	0.9300
N9—C24	1.174 (5)	C17—H17A	0.9600
N10—C25	1.284 (5)	C17—H17B	0.9600
N10—C27	1.440 (5)	C17—H17C	0.9600
N10—C26	1.441 (5)	C18—H18A	0.9600
N11—C28	1.162 (5)	C18—H18B	0.9600
N12—C29	1.136 (5)	C18—H18C	0.9600
O1—C1	1.213 (6)	C19—H19A	0.9300
O2—C4	1.270 (5)	C20—H20A	0.9600
O3—C7	1.242 (2)	C20—H20B	0.9600
O4—C10	1.223 (6)	C20—H20C	0.9600
O5—C19	1.238 (6)	C21—H21A	0.9600
O6—C16	1.254 (5)	C21—H21B	0.9600
O7—C25	1.260 (5)	C21—H21C	0.9600
S1—C22	1.618 (5)	C25—H25A	0.9300
S2—C23	1.649 (5)	C26—H26A	0.9600
S3—C24	1.642 (6)	C26—H26B	0.9600
S4—C28	1.642 (5)	C26—H26C	0.9600
S5—C29	1.626 (6)	C27—H27A	0.9600
C1—H1A	0.9300	C27—H27B	0.9600
C2—H2A	0.9600	C27—H27C	0.9600
C2—H2B	0.9600

N8—Cr1—N9	92.83 (16)	N2—C6—H6C	109.5
N8—Cr1—N11	90.52 (15)	H6A—C6—H6C	109.5
N9—Cr1—N11	90.03 (16)	H6B—C6—H6C	109.5
N8—Cr1—O7	176.41 (15)	C19—N5—C21	121.6 (5)
N9—Cr1—O7	89.51 (14)	C19—N5—C20	121.0 (5)
N11—Cr1—O7	92.20 (14)	C21—N5—C20	117.0 (5)
N8—Cr1—N7	91.22 (15)	O3—C7—N3	120.8 (5)
N9—Cr1—N7	175.62 (15)	O3—C7—H7A	119.6
N11—Cr1—N7	88.27 (15)	N3—C7—H7A	119.6
O7—Cr1—N7	86.51 (13)	N3—C8—H8A	109.5
N8—Cr1—N12	89.55 (15)	N3—C8—H8B	109.5
N9—Cr1—N12	90.72 (16)	H8A—C8—H8B	109.5
N11—Cr1—N12	179.24 (17)	N3—C8—H8C	109.5
O7—Cr1—N12	87.70 (14)	H8A—C8—H8C	109.5
N7—Cr1—N12	90.97 (15)	H8B—C8—H8C	109.5
O4—Mn1—O3	95.96 (14)	N3—C9—H9A	109.5
O4—Mn1—O1	87.26 (14)	N3—C9—H9B	109.5
O3—Mn1—O1	173.81 (14)	H9A—C9—H9B	109.5
O4—Mn1—O6	84.69 (13)	N3—C9—H9C	109.5
O3—Mn1—O6	94.73 (14)	H9A—C9—H9C	109.5
O1—Mn1—O6	90.83 (12)	H9B—C9—H9C	109.5
O4—Mn1—O5	93.14 (13)	O4—C10—N4	125.3 (5)
O3—Mn1—O5	89.24 (15)	O4—C10—H10A	117.3
O1—Mn1—O5	85.29 (13)	N4—C10—H10A	117.3
O6—Mn1—O5	175.64 (13)	N4—C11—H11A	109.5
O4—Mn1—O2	174.71 (14)	N4—C11—H11B	109.5
O3—Mn1—O2	88.00 (13)	H11A—C11—H11B	109.5
O1—Mn1—O2	89.13 (12)	N4—C11—H11C	109.5
O6—Mn1—O2	91.51 (13)	H11A—C11—H11C	109.5
O5—Mn1—O2	90.41 (12)	H11B—C11—H11C	109.5
C1—N1—C2	123.5 (5)	N4—C12—H12A	109.5
C1—N1—C3	120.3 (4)	N4—C12—H12B	109.5
C2—N1—C3	115.8 (4)	H12A—C12—H12B	109.5
C4—N2—C6	123.5 (4)	N4—C12—H12C	109.5
C4—N2—C5	120.7 (5)	H12A—C12—H12C	109.5
C6—N2—C5	115.8 (4)	H12B—C12—H12C	109.5
C7—N3—C8	140.2 (5)	O6—C16—N6	123.2 (5)
C7—N3—C9	108.7 (4)	O6—C16—H16A	118.4
C8—N3—C9	111.1 (4)	N6—C16—H16A	118.4
C10—N4—C12	119.9 (4)	N6—C17—H17A	109.5
C10—N4—C11	122.7 (4)	N6—C17—H17B	109.5
C12—N4—C11	117.4 (4)	H17A—C17—H17B	109.5
C16—N6—C18	122.2 (5)	N6—C17—H17C	109.5
C16—N6—C17	120.4 (4)	H17A—C17—H17C	109.5
C18—N6—C17	117.4 (4)	H17B—C17—H17C	109.5
C22—N7—Cr1	173.3 (4)	N6—C18—H18A	109.5
C23—N8—Cr1	173.6 (4)	N6—C18—H18B	109.5
C24—N9—Cr1	164.1 (4)	H18A—C18—H18B	109.5
C25—N10—C27	121.2 (4)	N6—C18—H18C	109.5
C25—N10—C26	120.2 (4)	H18A—C18—H18C	109.5
C27—N10—C26	118.5 (4)	H18B—C18—H18C	109.5
C28—N11—Cr1	159.7 (4)	O5—C19—N5	125.4 (5)
C29—N12—Cr1	171.1 (4)	O5—C19—H19A	117.3
C1—O1—Mn1	132.7 (4)	N5—C19—H19A	117.3
C4—O2—Mn1	124.3 (3)	N5—C20—H20A	109.5
C7—O3—Mn1	137.7 (4)	N5—C20—H20B	109.5
C10—O4—Mn1	149.2 (4)	H20A—C20—H20B	109.5
C19—O5—Mn1	120.0 (3)	N5—C20—H20C	109.5
C16—O6—Mn1	121.9 (3)	H20A—C20—H20C	109.5
C25—O7—Cr1	127.3 (3)	H20B—C20—H20C	109.5
O1—C1—N1	125.3 (6)	N5—C21—H21A	109.5
O1—C1—H1A	117.4	N5—C21—H21B	109.5
N1—C1—H1A	117.4	H21A—C21—H21B	109.5
N1—C2—H2A	109.5	N5—C21—H21C	109.5
N1—C2—H2B	109.5	H21A—C21—H21C	109.5
H2A—C2—H2B	109.5	H21B—C21—H21C	109.5
N1—C2—H2C	109.5	N7—C22—S1	179.7 (6)
H2A—C2—H2C	109.5	N8—C23—S2	179.3 (4)
H2B—C2—H2C	109.5	N9—C24—S3	176.3 (5)
N1—C3—H3A	109.5	O7—C25—N10	124.6 (5)
N1—C3—H3B	109.5	O7—C25—H25A	117.7
H3A—C3—H3B	109.5	N10—C25—H25A	117.7
N1—C3—H3C	109.5	N10—C26—H26A	109.5
H3A—C3—H3C	109.5	N10—C26—H26B	109.5
H3B—C3—H3C	109.5	H26A—C26—H26B	109.5
O2—C4—N2	123.6 (5)	N10—C26—H26C	109.5
O2—C4—H4A	118.2	H26A—C26—H26C	109.5
N2—C4—H4A	118.2	H26B—C26—H26C	109.5
N2—C5—H5A	109.5	N10—C27—H27A	109.5
N2—C5—H5B	109.5	N10—C27—H27B	109.5
H5A—C5—H5B	109.5	H27A—C27—H27B	109.5
N2—C5—H5C	109.5	N10—C27—H27C	109.5
H5A—C5—H5C	109.5	H27A—C27—H27C	109.5
H5B—C5—H5C	109.5	H27B—C27—H27C	109.5
N2—C6—H6A	109.5	N11—C28—S4	178.8 (4)
N2—C6—H6B	109.5	N12—C29—S5	179.3 (5)
H6A—C6—H6B	109.5

N8—Cr1—N9—C24	150.7 (15)	O3—Mn1—O6—C16	65.4 (3)
N11—Cr1—N9—C24	60.1 (15)	O1—Mn1—O6—C16	−117.3 (3)
O7—Cr1—N9—C24	−32.1 (15)	O2—Mn1—O6—C16	153.5 (3)
N12—Cr1—N9—C24	−119.7 (15)	N9—Cr1—O7—C25	40.3 (4)
N8—Cr1—N11—C28	17.6 (11)	N11—Cr1—O7—C25	−49.7 (4)
N9—Cr1—N11—C28	110.4 (11)	N7—Cr1—O7—C25	−137.9 (4)
O7—Cr1—N11—C28	−160.1 (11)	N12—Cr1—O7—C25	131.0 (4)
N7—Cr1—N11—C28	−73.6 (11)	Mn1—O1—C1—N1	162.0 (4)
O4—Mn1—O1—C1	−18.3 (5)	C2—N1—C1—O1	−175.8 (6)
O6—Mn1—O1—C1	66.3 (5)	C3—N1—C1—O1	−3.7 (10)
O5—Mn1—O1—C1	−111.7 (5)	Mn1—O2—C4—N2	−170.7 (3)
O2—Mn1—O1—C1	157.8 (5)	C6—N2—C4—O2	−2.0 (7)
O3—Mn1—O2—C4	−85.0 (3)	C5—N2—C4—O2	177.5 (4)
O1—Mn1—O2—C4	89.5 (3)	Mn1—O3—C7—N3	−142.2 (4)
O6—Mn1—O2—C4	−179.7 (3)	C8—N3—C7—O3	8.1 (11)
O5—Mn1—O2—C4	4.2 (3)	C9—N3—C7—O3	−168.0 (5)
O4—Mn1—O3—C7	−10.6 (6)	Mn1—O4—C10—N4	−177.5 (4)
O6—Mn1—O3—C7	−95.8 (6)	C12—N4—C10—O4	1.0 (7)
O5—Mn1—O3—C7	82.5 (6)	C11—N4—C10—O4	179.5 (5)
O2—Mn1—O3—C7	172.9 (6)	Mn1—O6—C16—N6	160.9 (3)
O3—Mn1—O4—C10	55.6 (7)	C18—N6—C16—O6	179.7 (4)
O1—Mn1—O4—C10	−119.1 (7)	C17—N6—C16—O6	−2.2 (6)
O6—Mn1—O4—C10	149.8 (7)	Mn1—O5—C19—N5	−144.6 (4)
O5—Mn1—O4—C10	−34.0 (7)	C21—N5—C19—O5	1.4 (8)
O4—Mn1—O5—C19	−54.4 (4)	C20—N5—C19—O5	173.6 (5)
O3—Mn1—O5—C19	−150.4 (4)	Cr1—O7—C25—N10	−169.8 (3)
O1—Mn1—O5—C19	32.6 (4)	C27—N10—C25—O7	−2.2 (7)
O2—Mn1—O5—C19	121.7 (4)	C26—N10—C25—O7	179.5 (4)
O4—Mn1—O6—C16	−30.2 (3)	Cr1—N12—C29—S5	−77 (43)

Experimental details

Crystal data
Chemical formula	[Mn(C₃H₇NO)₆][Cr(NCS)₅(C₃H₇NO)]
M_r	909.01
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	15.327 (3), 17.742 (2), 17.278 (2)
β (°)	110.36 (2)
V (Å³)	4404.9 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.40 × 0.20 × 0.10

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010)
T_min, T_max	0.735, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	20206, 9620, 2863
R_int	0.092
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.100, 0.67
No. of reflections	9620
No. of parameters	463
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.57

Computer programs: CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), XP in SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cr1—N8	1.969 (4)	Mn1—O4	2.133 (4)
Cr1—N9	1.977 (4)	Mn1—O3	2.140 (4)
Cr1—N11	1.996 (4)	Mn1—O1	2.140 (3)
Cr1—O7	1.999 (3)	Mn1—O6	2.143 (3)
Cr1—N7	2.002 (4)	Mn1—O5	2.167 (3)
Cr1—N12	2.006 (4)	Mn1—O2	2.171 (3)

Acknowledgements

We thank Viktoriya V. Dyakonenko for the data collection.

References

Bencini, A., Cecconi, F., Ghilardi, C. A., Midollini, S., Nuzzi, F. N. & Orlandini, A. (1992). Inorg. Chem. 31, 5339–5342. CSD CrossRef CAS Web of Science Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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