Bis{μ2-2-[(2-hy­droxy­eth­yl)(meth­yl)amino]­ethano­lato}bis­(μ3-N-methyl-2,2′-aza­nediyldiethano­lato)tetra­kis­(thio­cyan­atato-κN)dichromium(III)dimanganese(II) dimethyl­formamide tetra­solvate

Semenaka, V.V.; Nesterova, O.V.; Kokozay, V.N.; Zubatyuk, R.I.; Shishkin, O.V.

doi:10.1107/S1600536811049336

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1864-m1865

https://doi.org/10.1107/S1600536811049336

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Bis{μ₂-2-[(2-hydroxyethyl)(methyl)amino]ethanolato}bis(μ₃-N-methyl-2,2′-azanediyldiethanolato)tetrakis(thiocyanatato-κN)dichromium(III)dimanganese(II) dimethylformamide tetrasolvate

Valentyna V. Semenaka,^a ^* Oksana V. Nesterova,^a Volodymyr N. Kokozay,^a Roman I. Zubatyuk ^b and Oleg V. Shishkin ^b

^aDepartment of Inorganic Chemistry,Taras Shevchenko National University of Kyiv, Volodymyrs'ka St. 64, 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 10 October 2011; accepted 18 November 2011; online 30 November 2011)

The heterometallic title complex, [Cr₂Mn₂(C₅H₁₁NO₂)₂(C₅H₁₂NO₂)₂(NCS)₄]·4C₃H₇NO, was prepared using manganese powder, Reineckes salt, ammonium thiocyanate and a non-aqueous solution of N-methyldiethanolamine in air. The centrosymmetric molecular structure of the complex is based on a tetranuclear {Mn₂Cr₂(μ-O)₆} core. The tetranuclear complex molecule and the two uncoordinated dimethylformamide molecules are linked by O—H⋯O hydrogen bonds, while the two other molecules of dimethylformamide do not participate in hydrogen bonding.

Related literature

For background to polynuclear chromium-containing complexes, see: McInnes et al. (2005 ); Affronte et al. (2005 ). For the use of amino alcohols with versatile bridging modes in generating such metal clusters, see: Langley et al. (2009 ); Ferguson et al. (2008 ); Saalfrank et al. (2001 ). For background to direct synthesis, see: Kokozay & Shevchenko (2005 ).

Experimental

Crystal data

[Cr₂Mn₂(C₅H₁₁NO₂)₂(C₅H₁₂NO₂)₂(NCS)₄]·4C₃H₇NO
M_r = 1208.64
Monoclinic, P 2₁ /n
a = 11.5207 (2) Å
b = 13.5261 (2) Å
c = 18.5825 (4) Å
β = 106.123 (2)°
V = 2781.81 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 100 K
0.3 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.6, T_max = 0.8
14864 measured reflections
8065 independent reflections
5070 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.048
S = 0.98
8065 reflections
313 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O5	0.82	1.78	2.5985 (18)	176

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811049336/zk2033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049336/zk2033Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811049336/zk2033Isup3.cdx

checkCIF report

Comment top

Great interest in the synthesis and investigation of polynuclear chromium- and manganese-containing compounds dates from the late 90 s mostly due to the works R.E.P. Winpenny and coworkers devoted to magnetic studies of high-nuclear cages and wheels (McInnes et al., 2005; Affronte et al., 2005). At the same time, the potential of alcohols and amino alcohols in generating such metal clusters was widely explored (Saalfrank et al., 2001; Langley et al., 2009; Ferguson et al., 2008).The polydentate alkoxo ligands possessing versatile bridging modes were recognized as promising reagents for synthesis of new heterometallic complexes. Previously we have demonstrated that amino alcohols represent a powerful tool for assembling polynuclear metal complexes in conditions of the synthetic approach named "direct synthesis of coordination compounds". This strategy employs metal powders or metal oxides as starting materials and eliminates the separate step of building block construction, proving to be an efficient route to obtain new heterometallic complexes (Kokozay & Shevchenko, 2005). Novel heterometallic compound [Mn₂Cr₂(NCS)₄(HMeDea)₂(MeDea)₂]^.4dmf have been prepared in one-step self-assembly reaction of zerovalent manganese, Reineckes salt, ammonium thiocyanate and dymethylformamide (dmf) solution of N-methyldiethanolamine (H₂MeDea) in air using molar ratio Mn⁰:NH₄[Cr(NCS)₄(NH₃)₂]^.H₂O = 4: 1. X-ray diffraction studies reveal that the centrosymmetric molecular structure of the complex is based on a tetranuclear {Mn₂Cr₂(µ-O)₆} core with the metal atoms arranged in a planar rhombic array. In the present complex MeDea and HMeDea ligands adopt a chelating-bridging mode forming five-membered rings. Both manganese(II) ions are five coordinated and have N₂O₃ donor sets (Fig. 1) formed by three oxygen and one nitrogen atom of N-methyldiethanolamine ligands and one nitrogen atom of terminal thiocyanate group. The Mn–O(N) bond lengths vary in the range 2.0651 (10)–2.3004 (13) Å, while cis and trans O(N)–Mn–O(N) bond angles range from 65.28 (6)° to 124.35 (14)° and from 140.06 (9)° to 173.0 (3)°, respectively. Each chromium(III) atom has distorted octahedral environment comprised by four oxygen and one nitrogen atoms from N-methyldiethanolamine ligands and one nitrogen atom from terminal thiocyanate group. The Cr–O(N) distances are in the range of 1.9391 (10)–2.0974 (14) Å. The cis and trans O(N)–Cr–O(N) bond angles vary from 80.70 (5)° to 101.65 (5)° and from 158.59 (5)° to 177.32 (5)°, respectively. Tetranuclear molecule of the complex and two dmf molecules are linked together by O–H···O hydrogen bonds [O(3)–H(3)···O(5): D–A = 2.598 Å, D–H···A = 175.99°], two other uncoordinated molecules of dmf are not involved in hydrogen bonding.

Related literature top

For background to polynuclear chromium-containing complexes, see: McInnes et al. (2005); Affronte et al. (2005). For the use of aminoalcohols having versatile bridging modes in generating such metal clusters, see: Langley et al. (2009); Ferguson et al. (2008); Saalfrank et al. (2001). For background to direct synthesis, see: Kokozay & Shevchenko (2005).

Experimental top

Manganese powder (0.137 g, 2.5 mmol), NH₄[Cr(NCS)₄(NH₃)₂]^.H₂O (0.221 g, 0.625 mmol), NH₄NCS (0.333 g, 4.375 mmol), dmf (20 mL) and N-methyldiethanolamine (0.80 cm³) were heated to 50–60° and stirred magnetically during 2 h. Dark blue crystals suitable for the X-ray crystallographic study were deposited after several months after addition of diethyl ether and PrⁱOH into the resulting blue solution. The crystals were filtered off, washed with dry PrⁱOH, and finally dried at room temperature. Yield: 0.09 g, 24% (per chromium). Anal. Calc. for C₃₆H₇₄Mn₂Cr₂N₁₂O₁₂S₄ (M = 1208.64): Mn, 9.09; Cr, 8.60; C, 35.78; H, 6.12; N, 13.91; S, 10.61. Found: Mn, 9.1; Cr, 8.8; C, 35.8; H, 6.2; N, 13.8; S, 10.7. IR: 2889(m), 2867(sh), 2818(sh), 2080(vs), 1660(s), 1458(w), 1449(sh), 1410(sh), 1383(m), 1355(w), 1308(w), 1260(sh), 1253(w), 1207(sh), 1171(sh), 1143(sh), 1075(s), 1032(sh), 1002(sh), 980(sh), 913(m), 764(sh), 744(m), 676(m), 643(sh), 545(m), 517(m), 474(w), 419(sh), 412(w). The compound is sparingly soluble in dmso and dmf, insoluble in water and it is indefinitely stable in air.

Structure description top

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: ABSPACK in CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: CrysAlis PRO (Oxford Diffraction, 2010); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Molecular structure of the complex, showing the atom numbering, with 50% probability displacement ellipsoids

Bis{µ₂-2-[(2-hydroxyethyl)(methyl)amino]ethanolato}bis(µ₃-N- methyl-2,2'-azanediyldiethanolato)tetrakis(thiocyanatato- κN)dichromium(III)dimanganese(II) dimethylformamide tetrasolvate top

Crystal data top

[Cr₂Mn₂(C₅H₁₁NO₂)₂(C₅H₁₂NO₂)₂(NCS)₄]·4C₃H₇NO	Z = 2
M_r = 1208.64	F(000) = 1264
Monoclinic, P2₁/n	D_x = 1.443 Mg m⁻³
a = 11.5207 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.5261 (2) Å	µ = 1.04 mm⁻¹
c = 18.5825 (4) Å	T = 100 K
β = 106.123 (2)°	Block, dark blue
V = 2781.81 (9) Å³	0.3 × 0.2 × 0.1 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	5070 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 30°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	h = −12→16
T_min = 0.6, T_max = 0.8	k = −16→19
14864 measured reflections	l = −26→12
8065 independent 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.048	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.010P)²] where P = (F_o² + 2F_c²)/3
8065 reflections	(Δ/σ)_max = 0.002
313 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Cr₂Mn₂(C₅H₁₁NO₂)₂(C₅H₁₂NO₂)₂(NCS)₄]·4C₃H₇NO	V = 2781.81 (9) Å³
M_r = 1208.64	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.5207 (2) Å	µ = 1.04 mm⁻¹
b = 13.5261 (2) Å	T = 100 K
c = 18.5825 (4) Å	0.3 × 0.2 × 0.1 mm
β = 106.123 (2)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	8065 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	5070 reflections with I > 2σ(I)
T_min = 0.6, T_max = 0.8	R_int = 0.025
14864 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.048	H-atom parameters constrained
S = 0.98	Δρ_max = 0.43 e Å⁻³
8065 reflections	Δρ_min = −0.38 e Å⁻³
313 parameters

Special details top

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET) (compiled Apr 21 2008,18:23:10) 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
Mn1	0.50236 (2)	0.224755 (17)	0.513287 (14)	0.01778 (6)
Cr1	0.38351 (2)	−0.005009 (19)	0.523254 (14)	0.01505 (6)
S1	0.16877 (4)	−0.10240 (4)	0.69652 (3)	0.04214 (14)
S2	0.25156 (4)	0.38492 (3)	0.28877 (2)	0.02974 (11)
O1	0.44591 (9)	0.05372 (7)	0.44303 (6)	0.0156 (2)
O2	0.41428 (9)	0.12490 (7)	0.56870 (6)	0.0181 (2)
O3	0.62650 (11)	0.35388 (8)	0.52249 (7)	0.0325 (3)
H3	0.6726	0.3704	0.4981	0.049*
O4	0.34983 (9)	−0.13296 (7)	0.47288 (6)	0.0181 (2)
O5	0.77327 (11)	0.41465 (9)	0.44798 (7)	0.0340 (3)
O6	0.56001 (11)	0.24649 (9)	0.10559 (7)	0.0342 (3)
N1	0.48650 (11)	0.31521 (9)	0.61496 (7)	0.0197 (3)
N2	0.21359 (11)	0.02768 (9)	0.45005 (7)	0.0189 (3)
N3	0.31690 (12)	−0.05439 (10)	0.60560 (8)	0.0218 (3)
N4	0.38177 (13)	0.28738 (10)	0.41875 (8)	0.0270 (3)
N5	0.95472 (13)	0.40818 (10)	0.42324 (8)	0.0271 (4)
N6	0.55036 (12)	0.27485 (11)	0.22479 (8)	0.0262 (3)
C1	0.38489 (15)	0.16079 (12)	0.63305 (9)	0.0242 (4)
H1A	0.3877	0.1059	0.6688	0.029*
H1B	0.302	0.1882	0.6186	0.029*
C2	0.47414 (15)	0.24061 (12)	0.66996 (9)	0.0234 (4)
H2A	0.4462	0.2729	0.7099	0.028*
H2B	0.5539	0.2102	0.6933	0.028*
C3	0.59968 (16)	0.37190 (14)	0.64366 (10)	0.0316 (4)
H3A	0.6658	0.3265	0.6689	0.038*
H3B	0.5894	0.421	0.6809	0.038*
C4	0.63246 (17)	0.42432 (13)	0.58016 (10)	0.0333 (5)
H4A	0.5753	0.4792	0.5611	0.04*
H4B	0.715	0.4521	0.5978	0.04*
C5	0.38177 (16)	0.38211 (13)	0.59616 (10)	0.0347 (5)
H5A	0.38	0.4204	0.6406	0.052*
H5B	0.3074	0.3433	0.5792	0.052*
H5C	0.3882	0.4272	0.5562	0.052*
C6	0.23263 (14)	−0.14850 (12)	0.42388 (9)	0.0212 (4)
H6A	0.2025	−0.2145	0.4331	0.025*
H6B	0.2358	−0.146	0.3712	0.025*
C7	0.14866 (14)	−0.06917 (11)	0.43730 (10)	0.0226 (4)
H7A	0.0769	−0.0642	0.3934	0.027*
H7B	0.1209	−0.0865	0.4816	0.027*
C8	0.23655 (14)	0.06676 (12)	0.37959 (9)	0.0227 (4)
H8A	0.2299	0.1397	0.3791	0.027*
H8B	0.1737	0.041	0.3358	0.027*
C9	0.35990 (13)	0.03810 (12)	0.37239 (9)	0.0200 (4)
H9A	0.36	−0.0322	0.3577	0.024*
H9B	0.3806	0.079	0.3335	0.024*
C10	0.14028 (14)	0.09998 (13)	0.47868 (10)	0.0282 (4)
H10A	0.0638	0.1119	0.4403	0.042*
H10B	0.1849	0.1623	0.4907	0.042*
H10C	0.1237	0.0736	0.5239	0.042*
C11	0.25484 (15)	−0.07453 (12)	0.64353 (9)	0.0217 (4)
C12	0.32760 (15)	0.32850 (12)	0.36446 (9)	0.0208 (4)
C13	0.87761 (16)	0.38143 (13)	0.46022 (10)	0.0280 (4)
H13A	0.9033	0.3336	0.4988	0.034*
C14	1.07644 (16)	0.36743 (15)	0.44205 (12)	0.0428 (5)
H14A	1.0877	0.3222	0.4846	0.064*
H14B	1.1354	0.4213	0.4554	0.064*
H14C	1.0881	0.3314	0.3988	0.064*
C15	0.92280 (18)	0.48139 (15)	0.36406 (12)	0.0452 (6)
H15A	0.8354	0.4931	0.3504	0.068*
H15B	0.9458	0.4573	0.3202	0.068*
H15C	0.9656	0.5433	0.3816	0.068*
C16	0.59011 (15)	0.29153 (13)	0.16508 (10)	0.0283 (4)
H16A	0.6473	0.3433	0.169	0.034*
C17	0.46767 (16)	0.19439 (13)	0.22546 (10)	0.0310 (4)
H17A	0.4335	0.1699	0.1743	0.047*
H17B	0.4024	0.2181	0.2454	0.047*
H17C	0.5112	0.1408	0.2572	0.047*
C18	0.59935 (17)	0.32815 (15)	0.29436 (11)	0.0434 (5)
H18A	0.6562	0.3785	0.2872	0.065*
H18B	0.6415	0.2818	0.3335	0.065*
H18C	0.5334	0.3601	0.3094	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.02102 (13)	0.01665 (12)	0.01768 (13)	−0.00053 (12)	0.00874 (10)	−0.00076 (11)
Cr1	0.01441 (12)	0.01699 (13)	0.01527 (13)	−0.00159 (12)	0.00662 (10)	−0.00100 (11)
S1	0.0342 (3)	0.0666 (4)	0.0332 (3)	−0.0060 (3)	0.0221 (2)	0.0104 (3)
S2	0.0363 (3)	0.0302 (3)	0.0181 (2)	−0.0017 (2)	−0.00015 (19)	0.0021 (2)
O1	0.0148 (6)	0.0195 (6)	0.0124 (6)	−0.0011 (5)	0.0040 (4)	0.0002 (5)
O2	0.0213 (6)	0.0202 (6)	0.0160 (6)	−0.0023 (5)	0.0106 (5)	−0.0040 (5)
O3	0.0441 (8)	0.0250 (7)	0.0377 (8)	−0.0126 (6)	0.0269 (7)	−0.0112 (6)
O4	0.0160 (6)	0.0192 (6)	0.0191 (6)	−0.0028 (5)	0.0049 (5)	−0.0033 (5)
O5	0.0265 (7)	0.0378 (8)	0.0414 (8)	0.0010 (6)	0.0158 (6)	0.0019 (7)
O6	0.0396 (8)	0.0382 (8)	0.0284 (7)	0.0000 (6)	0.0153 (6)	−0.0026 (6)
N1	0.0210 (8)	0.0180 (7)	0.0205 (7)	0.0010 (6)	0.0065 (6)	−0.0007 (6)
N2	0.0151 (7)	0.0205 (7)	0.0218 (8)	−0.0003 (6)	0.0066 (6)	−0.0022 (6)
N3	0.0243 (8)	0.0235 (8)	0.0202 (8)	−0.0041 (7)	0.0108 (6)	−0.0015 (6)
N4	0.0353 (9)	0.0211 (8)	0.0254 (8)	0.0013 (7)	0.0098 (7)	0.0021 (7)
N5	0.0265 (8)	0.0276 (8)	0.0304 (9)	0.0025 (7)	0.0131 (7)	0.0070 (7)
N6	0.0246 (8)	0.0296 (8)	0.0253 (8)	0.0001 (7)	0.0086 (6)	−0.0018 (7)
C1	0.0336 (10)	0.0234 (9)	0.0217 (9)	−0.0031 (8)	0.0176 (8)	−0.0055 (8)
C2	0.0302 (10)	0.0244 (9)	0.0167 (9)	0.0027 (8)	0.0086 (7)	−0.0029 (7)
C3	0.0352 (11)	0.0326 (10)	0.0270 (10)	−0.0097 (9)	0.0087 (8)	−0.0085 (9)
C4	0.0452 (12)	0.0240 (10)	0.0362 (12)	−0.0136 (9)	0.0204 (10)	−0.0102 (9)
C5	0.0431 (12)	0.0319 (11)	0.0299 (11)	0.0153 (10)	0.0117 (9)	0.0025 (9)
C6	0.0199 (9)	0.0221 (9)	0.0213 (9)	−0.0064 (8)	0.0050 (7)	−0.0028 (8)
C7	0.0160 (9)	0.0265 (9)	0.0254 (10)	−0.0052 (8)	0.0059 (7)	−0.0030 (8)
C8	0.0206 (9)	0.0239 (9)	0.0206 (9)	−0.0017 (8)	0.0006 (7)	0.0026 (8)
C9	0.0202 (9)	0.0249 (9)	0.0139 (8)	−0.0039 (7)	0.0031 (7)	0.0016 (7)
C10	0.0190 (9)	0.0316 (10)	0.0338 (11)	0.0051 (8)	0.0066 (8)	−0.0047 (9)
C11	0.0222 (9)	0.0235 (9)	0.0182 (9)	−0.0029 (8)	0.0038 (7)	0.0016 (7)
C12	0.0257 (10)	0.0178 (9)	0.0213 (9)	−0.0037 (8)	0.0105 (8)	−0.0031 (8)
C13	0.0320 (11)	0.0252 (10)	0.0284 (10)	−0.0016 (9)	0.0108 (8)	−0.0002 (8)
C14	0.0319 (12)	0.0445 (13)	0.0566 (15)	0.0105 (10)	0.0198 (10)	0.0128 (11)
C15	0.0407 (12)	0.0525 (14)	0.0455 (14)	0.0039 (11)	0.0173 (10)	0.0217 (11)
C16	0.0232 (10)	0.0303 (11)	0.0354 (11)	0.0013 (8)	0.0151 (8)	0.0000 (9)
C17	0.0341 (11)	0.0305 (10)	0.0316 (11)	0.0012 (9)	0.0143 (9)	0.0048 (9)
C18	0.0436 (13)	0.0519 (14)	0.0351 (12)	−0.0069 (11)	0.0119 (10)	−0.0138 (11)

Geometric parameters (Å, º) top

Mn1—O4ⁱ	2.0651 (10)	C1—H1B	0.99
Mn1—N4	2.0923 (15)	C2—H2A	0.99
Mn1—O2	2.1199 (10)	C2—H2B	0.99
Mn1—O3	2.2337 (11)	C3—C4	1.512 (2)
Mn1—N1	2.3004 (13)	C3—H3A	0.99
Cr1—O2	1.9391 (10)	C3—H3B	0.99
Cr1—O4	1.9546 (10)	C4—H4A	0.99
Cr1—O1	1.9914 (10)	C4—H4B	0.99
Cr1—O1ⁱ	2.0013 (10)	C5—H5A	0.98
Cr1—N3	2.0071 (13)	C5—H5B	0.98
Cr1—N2	2.0974 (14)	C5—H5C	0.98
Cr1—Cr1ⁱ	3.0428 (4)	C6—C7	1.511 (2)
S1—C11	1.6240 (16)	C6—H6A	0.99
S2—C12	1.6260 (18)	C6—H6B	0.99
O1—C9	1.4238 (18)	C7—H7A	0.99
O1—Cr1ⁱ	2.0013 (10)	C7—H7B	0.99
O2—C1	1.4161 (16)	C8—C9	1.514 (2)
O3—C4	1.4212 (19)	C8—H8A	0.99
O3—H3	0.8197	C8—H8B	0.99
O4—C6	1.4189 (18)	C9—H9A	0.99
O4—Mn1ⁱ	2.0651 (10)	C9—H9B	0.99
O5—C13	1.2437 (18)	C10—H10A	0.98
O6—C16	1.225 (2)	C10—H10B	0.98
N1—C5	1.470 (2)	C10—H10C	0.98
N1—C2	1.4710 (19)	C13—H13A	0.95
N1—C3	1.479 (2)	C14—H14A	0.98
N2—C10	1.4841 (18)	C14—H14B	0.98
N2—C7	1.4944 (19)	C14—H14C	0.98
N2—C8	1.5021 (19)	C15—H15A	0.98
N3—C11	1.1671 (17)	C15—H15B	0.98
N4—C12	1.169 (2)	C15—H15C	0.98
N5—C13	1.3159 (19)	C16—H16A	0.95
N5—C15	1.449 (2)	C17—H17A	0.98
N5—C14	1.456 (2)	C17—H17B	0.98
N6—C16	1.332 (2)	C17—H17C	0.98
N6—C17	1.449 (2)	C18—H18A	0.98
N6—C18	1.451 (2)	C18—H18B	0.98
C1—C2	1.517 (2)	C18—H18C	0.98
C1—H1A	0.99

O4ⁱ—Mn1—N4	132.86 (5)	N1—C3—H3B	109.6
O4ⁱ—Mn1—O2	92.63 (4)	C4—C3—H3B	109.6
N4—Mn1—O2	111.71 (5)	H3A—C3—H3B	108.1
O4ⁱ—Mn1—O3	88.41 (4)	O3—C4—C3	107.69 (13)
N4—Mn1—O3	90.54 (5)	O3—C4—H4A	110.2
O2—Mn1—O3	147.52 (4)	C3—C4—H4A	110.2
O4ⁱ—Mn1—N1	117.93 (5)	O3—C4—H4B	110.2
N4—Mn1—N1	106.77 (5)	C3—C4—H4B	110.2
O2—Mn1—N1	77.41 (4)	H4A—C4—H4B	108.5
O3—Mn1—N1	73.53 (4)	N1—C5—H5A	109.5
O2—Cr1—O4	177.32 (5)	N1—C5—H5B	109.5
O2—Cr1—O1	84.50 (4)	H5A—C5—H5B	109.5
O4—Cr1—O1	93.42 (4)	N1—C5—H5C	109.5
O2—Cr1—O1ⁱ	96.72 (4)	H5A—C5—H5C	109.5
O4—Cr1—O1ⁱ	84.58 (4)	H5B—C5—H5C	109.5
O1—Cr1—O1ⁱ	80.70 (5)	O4—C6—C7	109.13 (13)
O2—Cr1—N3	91.83 (5)	O4—C6—H6A	109.9
O4—Cr1—N3	90.19 (5)	C7—C6—H6A	109.9
O1—Cr1—N3	175.88 (5)	O4—C6—H6B	109.9
O1ⁱ—Cr1—N3	101.65 (5)	C7—C6—H6B	109.9
O2—Cr1—N2	96.68 (5)	H6A—C6—H6B	108.3
O4—Cr1—N2	81.41 (5)	N2—C7—C6	109.47 (12)
O1—Cr1—N2	84.05 (4)	N2—C7—H7A	109.8
O1ⁱ—Cr1—N2	158.59 (5)	C6—C7—H7A	109.8
N3—Cr1—N2	94.53 (5)	N2—C7—H7B	109.8
O2—Cr1—Cr1ⁱ	90.82 (3)	C6—C7—H7B	109.8
O4—Cr1—Cr1ⁱ	88.67 (3)	H7A—C7—H7B	108.2
O1—Cr1—Cr1ⁱ	40.47 (3)	N2—C8—C9	112.56 (13)
O1ⁱ—Cr1—Cr1ⁱ	40.23 (3)	N2—C8—H8A	109.1
N3—Cr1—Cr1ⁱ	141.77 (4)	C9—C8—H8A	109.1
N2—Cr1—Cr1ⁱ	122.99 (4)	N2—C8—H8B	109.1
C9—O1—Cr1	109.12 (8)	C9—C8—H8B	109.1
C9—O1—Cr1ⁱ	127.69 (9)	H8A—C8—H8B	107.8
Cr1—O1—Cr1ⁱ	99.30 (5)	O1—C9—C8	108.09 (12)
C1—O2—Cr1	128.37 (9)	O1—C9—H9A	110.1
C1—O2—Mn1	116.79 (9)	C8—C9—H9A	110.1
Cr1—O2—Mn1	114.84 (4)	O1—C9—H9B	110.1
C4—O3—Mn1	118.54 (9)	C8—C9—H9B	110.1
C4—O3—H3	109.4	H9A—C9—H9B	108.4
Mn1—O3—H3	132.1	N2—C10—H10A	109.5
C6—O4—Cr1	117.74 (9)	N2—C10—H10B	109.5
C6—O4—Mn1ⁱ	126.56 (9)	H10A—C10—H10B	109.5
Cr1—O4—Mn1ⁱ	115.19 (5)	N2—C10—H10C	109.5
C5—N1—C2	110.85 (12)	H10A—C10—H10C	109.5
C5—N1—C3	110.47 (13)	H10B—C10—H10C	109.5
C2—N1—C3	110.54 (13)	N3—C11—S1	179.83 (19)
C5—N1—Mn1	112.29 (10)	N4—C12—S2	179.54 (18)
C2—N1—Mn1	104.53 (9)	O5—C13—N5	124.30 (17)
C3—N1—Mn1	107.99 (9)	O5—C13—H13A	117.9
C10—N2—C7	108.96 (12)	N5—C13—H13A	117.9
C10—N2—C8	109.64 (12)	N5—C14—H14A	109.5
C7—N2—C8	111.83 (12)	N5—C14—H14B	109.5
C10—N2—Cr1	115.34 (10)	H14A—C14—H14B	109.5
C7—N2—Cr1	104.72 (9)	N5—C14—H14C	109.5
C8—N2—Cr1	106.32 (9)	H14A—C14—H14C	109.5
C11—N3—Cr1	165.05 (14)	H14B—C14—H14C	109.5
C12—N4—Mn1	171.08 (13)	N5—C15—H15A	109.5
C13—N5—C15	121.22 (15)	N5—C15—H15B	109.5
C13—N5—C14	121.02 (15)	H15A—C15—H15B	109.5
C15—N5—C14	117.73 (14)	N5—C15—H15C	109.5
C16—N6—C17	120.90 (15)	H15A—C15—H15C	109.5
C16—N6—C18	121.30 (15)	H15B—C15—H15C	109.5
C17—N6—C18	117.37 (14)	O6—C16—N6	126.22 (17)
O2—C1—C2	109.56 (12)	O6—C16—H16A	116.9
O2—C1—H1A	109.8	N6—C16—H16A	116.9
C2—C1—H1A	109.8	N6—C17—H17A	109.5
O2—C1—H1B	109.8	N6—C17—H17B	109.5
C2—C1—H1B	109.8	H17A—C17—H17B	109.5
H1A—C1—H1B	108.2	N6—C17—H17C	109.5
N1—C2—C1	110.99 (13)	H17A—C17—H17C	109.5
N1—C2—H2A	109.4	H17B—C17—H17C	109.5
C1—C2—H2A	109.4	N6—C18—H18A	109.5
N1—C2—H2B	109.4	N6—C18—H18B	109.5
C1—C2—H2B	109.4	H18A—C18—H18B	109.5
H2A—C2—H2B	108	N6—C18—H18C	109.5
N1—C3—C4	110.37 (15)	H18A—C18—H18C	109.5
N1—C3—H3A	109.6	H18B—C18—H18C	109.5
C4—C3—H3A	109.6

O2—Cr1—O1—C9	−126.82 (9)	O3—Mn1—N1—C3	−24.90 (10)
O4—Cr1—O1—C9	51.49 (9)	O2—Cr1—N2—C10	−33.38 (11)
O1ⁱ—Cr1—O1—C9	135.43 (11)	O4—Cr1—N2—C10	148.52 (11)
N2—Cr1—O1—C9	−29.49 (9)	O1—Cr1—N2—C10	−117.11 (10)
Cr1ⁱ—Cr1—O1—C9	135.43 (11)	O1ⁱ—Cr1—N2—C10	−161.80 (12)
O2—Cr1—O1—Cr1ⁱ	97.75 (5)	N3—Cr1—N2—C10	59.00 (11)
O4—Cr1—O1—Cr1ⁱ	−83.93 (5)	Cr1ⁱ—Cr1—N2—C10	−128.72 (9)
O1ⁱ—Cr1—O1—Cr1ⁱ	0	O2—Cr1—N2—C7	−153.11 (9)
N2—Cr1—O1—Cr1ⁱ	−164.92 (5)	O4—Cr1—N2—C7	28.78 (9)
O1—Cr1—O2—C1	173.65 (13)	O1—Cr1—N2—C7	123.16 (9)
O1ⁱ—Cr1—O2—C1	−106.42 (13)	O1ⁱ—Cr1—N2—C7	78.47 (15)
N3—Cr1—O2—C1	−4.47 (13)	N3—Cr1—N2—C7	−60.73 (9)
N2—Cr1—O2—C1	90.32 (13)	Cr1ⁱ—Cr1—N2—C7	111.54 (8)
Cr1ⁱ—Cr1—O2—C1	−146.32 (12)	O2—Cr1—N2—C8	88.37 (10)
O1—Cr1—O2—Mn1	−5.92 (5)	O4—Cr1—N2—C8	−89.74 (9)
O1ⁱ—Cr1—O2—Mn1	74.01 (6)	O1—Cr1—N2—C8	4.64 (9)
N3—Cr1—O2—Mn1	175.97 (6)	O1ⁱ—Cr1—N2—C8	−40.06 (18)
N2—Cr1—O2—Mn1	−89.25 (6)	N3—Cr1—N2—C8	−179.25 (10)
Cr1ⁱ—Cr1—O2—Mn1	34.11 (5)	Cr1ⁱ—Cr1—N2—C8	−6.98 (11)
O4ⁱ—Mn1—O2—C1	121.25 (11)	O2—Cr1—N3—C11	87.0 (5)
N4—Mn1—O2—C1	−100.05 (11)	O4—Cr1—N3—C11	−91.3 (5)
O3—Mn1—O2—C1	30.08 (14)	O1ⁱ—Cr1—N3—C11	−175.8 (5)
N1—Mn1—O2—C1	3.21 (11)	N2—Cr1—N3—C11	−9.9 (5)
O4ⁱ—Mn1—O2—Cr1	−59.13 (6)	Cr1ⁱ—Cr1—N3—C11	−179.4 (5)
N4—Mn1—O2—Cr1	79.57 (6)	Cr1—O2—C1—C2	152.10 (10)
O3—Mn1—O2—Cr1	−150.30 (6)	Mn1—O2—C1—C2	−28.33 (16)
N1—Mn1—O2—Cr1	−177.17 (6)	C5—N1—C2—C1	76.39 (16)
O4ⁱ—Mn1—O3—C4	−121.36 (13)	C3—N1—C2—C1	−160.77 (13)
N4—Mn1—O3—C4	105.78 (13)	Mn1—N1—C2—C1	−44.81 (14)
O2—Mn1—O3—C4	−28.96 (16)	O2—C1—C2—N1	50.17 (17)
N1—Mn1—O3—C4	−1.57 (12)	C5—N1—C3—C4	−74.85 (17)
O1—Cr1—O4—C6	−91.82 (10)	C2—N1—C3—C4	162.08 (13)
O1ⁱ—Cr1—O4—C6	−172.13 (10)	Mn1—N1—C3—C4	48.29 (15)
N3—Cr1—O4—C6	86.19 (10)	Mn1—O3—C4—C3	27.02 (18)
N2—Cr1—O4—C6	−8.37 (10)	N1—C3—C4—O3	−49.63 (19)
Cr1ⁱ—Cr1—O4—C6	−132.03 (10)	Cr1—O4—C6—C7	−14.59 (15)
O1—Cr1—O4—Mn1ⁱ	80.51 (5)	Mn1ⁱ—O4—C6—C7	174.07 (9)
O1ⁱ—Cr1—O4—Mn1ⁱ	0.19 (5)	C10—N2—C7—C6	−168.24 (14)
N3—Cr1—O4—Mn1ⁱ	−101.49 (6)	C8—N2—C7—C6	70.40 (16)
N2—Cr1—O4—Mn1ⁱ	163.96 (6)	Cr1—N2—C7—C6	−44.32 (14)
Cr1ⁱ—Cr1—O4—Mn1ⁱ	40.29 (5)	O4—C6—C7—N2	39.62 (17)
O4ⁱ—Mn1—N1—C5	176.21 (10)	C10—N2—C8—C9	145.05 (14)
N4—Mn1—N1—C5	11.66 (11)	C7—N2—C8—C9	−93.99 (15)
O2—Mn1—N1—C5	−97.53 (11)	Cr1—N2—C8—C9	19.74 (15)
O3—Mn1—N1—C5	97.14 (11)	Cr1—O1—C9—C8	47.36 (14)
O4ⁱ—Mn1—N1—C2	−63.56 (10)	Cr1ⁱ—O1—C9—C8	166.30 (9)
N4—Mn1—N1—C2	131.89 (10)	N2—C8—C9—O1	−44.64 (17)
O2—Mn1—N1—C2	22.71 (9)	C15—N5—C13—O5	0.6 (3)
O3—Mn1—N1—C2	−142.63 (10)	C14—N5—C13—O5	178.61 (17)
O4ⁱ—Mn1—N1—C3	54.17 (11)	C17—N6—C16—O6	3.1 (3)
N4—Mn1—N1—C3	−110.38 (11)	C18—N6—C16—O6	175.29 (18)
O2—Mn1—N1—C3	140.44 (11)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5	0.82	1.78	2.5985 (18)	176

Experimental details

Crystal data
Chemical formula	[Cr₂Mn₂(C₅H₁₁NO₂)₂(C₅H₁₂NO₂)₂(NCS)₄]·4C₃H₇NO
M_r	1208.64
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	11.5207 (2), 13.5261 (2), 18.5825 (4)
β (°)	106.123 (2)
V (Å³)	2781.81 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.6, 0.8
No. of measured, independent and observed [I > 2σ(I)] reflections	14864, 8065, 5070
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.048, 0.98
No. of reflections	8065
No. of parameters	313
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.38

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), ABSPACK in CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5	0.82	1.78	2.5985 (18)	176

References

Affronte, M., Casson, I., Evangelisti, M., Candini, A., Carretta, S., Muryn, C. A., Teat, S. J., Timco, G. A., Wernsdorfer, W. & Winpenny, R. E. P. (2005). Angew. Chem. Int. Ed. 44, 6496–6500. Web of Science CSD CrossRef CAS Google Scholar
Ferguson, A., Lawrence, J., Parkin, A., Sanchez-Benitez, J., Kamenev, K. V., Brechin, E. K., Wernsdorfer, W., Hill, S. & Murrie, M. (2008). Dalton Trans. pp. 6409–6414. Web of Science CSD CrossRef Google Scholar
Kokozay, V. N. & Shevchenko, D. V. (2005). Mater. Sci. Poland, 23, 287–312. CAS Google Scholar
Langley, S. K., Berry, K.J., Moubaraki, B. & Murray, K. S. (2009). Dalton Trans. pp. 973–982. Web of Science CSD CrossRef Google Scholar
McInnes, E. J. L., Piligkos, S., Timco, G. A. & Winpenny, R. E. P. (2005). Coord. Chem. Rev. 249, 2577–2590. Web of Science CrossRef CAS Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Saalfrank, R. W., Bernt, I., Chowdhry, M. M., Hampel, F. & Vaughan, G. B. M. (2001). Chem. Eur. J. 7, 2765–2769. CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 67| Part 12| December 2011| Pages m1864-m1865

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