Redetermination of di-μ-sulfido-bis­{[(2R)-2-acet­oxy-2-amino­ethane-1-thiol­ato-κ2N,S]oxidomolybdenum(V)}

Akashi, H.; Shiraga, Y.; Shibahara, T.

doi:10.1107/S1600536810014625

metal-organic compounds

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Volume 66| Part 5| May 2010| Page m573

https://doi.org/10.1107/S1600536810014625

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Redetermination of di-μ-sulfido-bis{[(2R)-2-acetoxy-2-aminoethane-1-thiolato-κ²N,S]oxidomolybdenum(V)}

Haruo Akashi,^a ^* Yuji Shiraga ^b and Takashi Shibahara ^b

^aResearch Institute of Natural Sciences, Okayama University of Science, Ridai-cho, kita-ku, Okayama 700-0005, Japan, and ^bDepartment of Chemistry, Okayama University of Science, Ridai-cho, Kita-ku, Okayama 700-0005, Japan
^*Correspondence e-mail: akashi@high.ous.ac.jp

(Received 12 April 2010; accepted 21 April 2010; online 24 April 2010)

The structure of the title compound, [Mo₂(C₄H₈NO₂S)₂O₂S₂], has been redetermined. Besides obvious differences between the original [Drew & Kay (1971 ). J. Chem. Soc. A, pp. 1851–1854] and the current unit-cell parameters, some packing features of the structure are also different; these findings are the result of significant improvements in the precision and accuracy of the present structure analysis. The two Mo atoms in the dimeric complex have very similar distorted trigonal–bipyramidal environments. Each Mo atom is bonded to an S atom and to an N atom of an L-cysteine ester ligand, to a terminal O atom and to two S atoms which bridge to the adjacent Mo atom [Mo⋯Mo separation = 2.8191 (2) Å]. N—H⋯O_carbonyl and N—H⋯O_terminal hydrogen-bonding interactions consolidate the crystal packing. During the synthesis, the originally employed L-cysteinate ligand has been converted to the L-cysteinate methyl ester ligand. Since this reaction does not take place without tin(IV) chloride, it is clear that tin(IV) chloride acts as a catalyst for the reaction.

Related literature

For the properties of molybdenum complexes with sulfur ligands, see: Newton & Otsuka (1980 ); Ueyama et al. (1982 ). For syntheses of related compounds, see: Shibahara & Akashi (1992 ); Kay & Mitchell (1970 ). For related structures, see: Shibahara et al. (1983 ); Drew & Kay (1971).

Experimental

Crystal data

[Mo₂(C₄H₈NO₂S)₂O₂S₂]
M_r = 556.34
Monoclinic, P 2₁
a = 9.195 (5) Å
b = 5.622 (3) Å
c = 17.437 (9) Å
β = 91.6763 (15)°
V = 901.0 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.88 mm⁻¹
T = 93 K
0.32 × 0.23 × 0.15 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.680, T_max = 0.759
10030 measured reflections
5007 independent reflections
4966 reflections with F² > 2σ(F²)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.067
S = 1.12
5007 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 1.23 e Å⁻³
Δρ_min = −0.63 e Å⁻³
Absolute structure: Flack (1983 ), 2185 Friedel pairs
Flack parameter: −0.08 (3)

Data collection: CrystalClear (Rigaku, 1999 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku Americas and Rigaku, 2007 ); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick et al., 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810014625/wm2325sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810014625/wm2325Isup2.hkl

checkCIF report

Comment top

Molybdenum complexes with sulfur ligands including L-cysteine or L-cysteine ethers are of interest in relation to redox-active molybdo-enzymes (Newton et al., 1980). Doubly sulfur-bridged molybdenum(V) compounds are prepared and examined as catalysts for redox reactions (Ueyama et al., 1982). The formation of the title compound, C₈H₁₆Mo₂N₂O₆S₈, (I), has been reported previously in the reaction of sodium molybdate with hydrogen sulphide and L-cysteine methyl ester (Kay & Mitchell, 1970). However, the direct formation of (I) from Na₂[Mo₂O₂S₂(L-cys)₂] (Shibahara & Akashi, 1992) has not been reported previously. In this reaction in methanol, the L-cysteinato ligand has changed to the L-cysteinato methyl ester ligand.

The structure of (I) has been reported previously by Drew & Kay (1971), but there are significant differences between the original and the current unit cell parameters which, in part, may be ascribed to the different measurement temperatures: Drew & Kay (1971), room temperature measurement: monoclinic, P2₁, with a = 9.348 (9), b = 5.640 (7), c = 19.440 (16) Å, β = 116.66 (10)°. This work: monoclinic, P2₁, with a = 9.195 (5), b = 5.622 (3), c = 17.437, β = 91.6763 (15)°. In the present work, the structure of (I) (Fig. 1) was determined with sufficient accuracy (R-factor = 0.024) and all hydrogen atoms in the structure were refined. The Mo - Mo distance is 2.8191 (2) Å. The Mo-S_bridge distances are 3.079 (7) and 3.3941 (7) Å. The range of these distances is within the range of values observed previously in doubly sulfur-bridged molybdenum(V) compounds, see, for example: Shibahara et al. (1983). The packing of the structure of (I) (Fig. 2) is also obviously different from that reported by Drew & Kay (1971). It is clear that N—H···O_carbonyl and N—H···O_terminal intermolecular hydrogen bonds exist in the structure of (I) (Fig. 3).

Related literature top

For the properties of molybdenum complexes with sulfur ligands, see: Newton et al. (1980); Ueyama et al. (1982). For syntheses of related compounds, see: Shibahara & Akashi (1992); Kay & Mitchell (1970). For related structures, see: Shibahara et al. (1983); Drew et al. (1971).

Experimental top

Tin(IV) chloride pentahydrate (108.8 mg, 0.155 mmol) was added to Na₂[Mo₂O₂S₂(L-cys)₂] (100 mg, 0.155 mmol) in methanol (40 ml). Single crystals suitable for X-ray diffraction were grown from the solution through slow evaporation of the solvent.

Structure description top

Computing details top

Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear (Rigaku, 1999); data reduction: CrystalStructure (Rigaku Americas and Rigaku, 2007); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick et al., 2008); molecular graphics: ORTEPIII (Burnett et al., 1996); software used to prepare material for publication: CrystalStructure (Rigaku Americas and Rigaku, 2007).

Figures top

	Fig. 1. Molecular configuration and atom-numbering scheme for compound (I) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A view of the molecular packing of the structutre of compound (I) along the b axis. H atoms have been omitted for clarity.
	Fig. 3. Scheme of intermolecular N—H···O interactions of (I). Symmetry codes: (i) -x+1, y+1/2, -z, (ii) x, y+1, z, (iii) -x+2, y-1/2, -z+1.

di-µ-sulfido-bis{[(2R)-2-acetoxy-2-aminoethane-1-thiolato- κ²N,S]oxidomolybdenum(V)} top

Crystal data top

[Mo₂(C₄H₈NO₂S)₂O₂S₂]	F(000) = 548.00
M_r = 556.34	D_x = 2.051 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2yb	Cell parameters from 3110 reflections
a = 9.195 (5) Å	θ = 5.5–30.0°
b = 5.622 (3) Å	µ = 1.88 mm⁻¹
c = 17.437 (9) Å	T = 93 K
β = 91.6763 (15)°	Platelet, orange
V = 901.0 (8) Å³	0.32 × 0.23 × 0.15 mm
Z = 2

Data collection top

Rigaku Mercury diffractometer	4966 reflections with F² > 2σ(F²)
Detector resolution: 7.31 pixels mm^-1	R_int = 0.024
ω scans	θ_max = 30.0°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −12→12
T_min = 0.680, T_max = 0.759	k = −7→7
10030 measured reflections	l = −24→24
5007 independent reflections

Refinement top

Refinement on F²	w = 1/[σ²(F_o²) + (0.0278P)² + 0.6607P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.024	(Δ/σ)_max = 0.007
wR(F²) = 0.067	Δρ_max = 1.23 e Å⁻³
S = 1.12	Δρ_min = −0.63 e Å⁻³
5007 reflections	Absolute structure: Flack (1983), 2185 Friedel pairs
200 parameters	Absolute structure parameter: −0.08 (3)
H-atom parameters constrained

Crystal data top

[Mo₂(C₄H₈NO₂S)₂O₂S₂]	V = 901.0 (8) Å³
M_r = 556.34	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.195 (5) Å	µ = 1.88 mm⁻¹
b = 5.622 (3) Å	T = 93 K
c = 17.437 (9) Å	0.32 × 0.23 × 0.15 mm
β = 91.6763 (15)°

Data collection top

Rigaku Mercury diffractometer	5007 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	4966 reflections with F² > 2σ(F²)
T_min = 0.680, T_max = 0.759	R_int = 0.024
10030 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.067	Δρ_max = 1.23 e Å⁻³
S = 1.12	Δρ_min = −0.63 e Å⁻³
5007 reflections	Absolute structure: Flack (1983), 2185 Friedel pairs
200 parameters	Absolute structure parameter: −0.08 (3)

Special details top

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mo(1)	0.56160 (2)	0.35614 (4)	0.237407 (11)	0.01531 (5)
Mo(2)	0.83145 (2)	0.39138 (4)	0.317580 (11)	0.01609 (5)
S(1)	0.77619 (7)	0.16995 (14)	0.20725 (4)	0.02024 (13)
S(2)	0.64491 (7)	0.66478 (13)	0.31650 (4)	0.01814 (13)
S(3)	0.42535 (7)	0.67618 (13)	0.18011 (4)	0.01799 (12)
S(4)	1.05984 (8)	0.40575 (19)	0.25678 (4)	0.02909 (17)
O(1)	0.4563 (2)	0.1814 (4)	0.29126 (11)	0.0214 (4)
O(2)	0.8209 (2)	0.1968 (4)	0.39132 (12)	0.0229 (4)
O(3)	0.1638 (2)	0.2314 (5)	0.00266 (13)	0.0307 (5)
O(4)	0.3678 (2)	0.0163 (4)	−0.00768 (12)	0.0238 (4)
O(5)	1.3237 (2)	0.8121 (4)	0.44041 (12)	0.0255 (4)
O(6)	1.1181 (2)	1.0185 (4)	0.45859 (12)	0.0235 (4)
N(1)	0.4930 (2)	0.2095 (4)	0.12429 (12)	0.0163 (4)
N(2)	0.9461 (2)	0.6727 (4)	0.38715 (13)	0.0187 (4)
C(1)	0.3251 (3)	0.5388 (5)	0.09977 (16)	0.0199 (5)
C(2)	0.3400 (2)	0.2688 (5)	0.10319 (14)	0.0169 (4)
C(3)	0.2942 (2)	0.1557 (5)	0.02689 (15)	0.0202 (5)
C(4)	0.1122 (3)	0.1453 (7)	−0.0722 (2)	0.0348 (7)
C(5)	1.1683 (3)	0.6098 (7)	0.31658 (16)	0.0275 (6)
C(6)	1.1053 (2)	0.6353 (5)	0.39573 (15)	0.0196 (5)
C(7)	1.1797 (2)	0.8438 (5)	0.43657 (13)	0.0194 (5)
C(8)	1.4106 (3)	1.0111 (7)	0.46876 (18)	0.0307 (7)
H(1)	0.5035	0.0467	0.1253	0.020*
H(2)	0.5528	0.2685	0.0875	0.020*
H(3)	0.9294	0.8180	0.3643	0.022*
H(4)	0.9071	0.6773	0.4351	0.022*
H(5)	0.2210	0.5831	0.1017	0.024*
H(6)	0.3632	0.5982	0.0508	0.024*
H(7)	0.2758	0.2067	0.1439	0.020*
H(8)	0.0229	0.2301	−0.0876	0.042*
H(9)	0.1869	0.1739	−0.1100	0.042*
H(10)	0.0921	−0.0254	−0.0691	0.042*
H(11)	1.2694	0.5498	0.3217	0.033*
H(12)	1.1712	0.7678	0.2915	0.033*
H(13)	1.1244	0.4864	0.4257	0.024*
H(14)	1.5112	0.9920	0.4528	0.037*
H(15)	1.3707	1.1598	0.4477	0.037*
H(16)	1.4085	1.0157	0.5249	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo(1)	0.01791 (9)	0.01641 (12)	0.01172 (9)	0.00422 (8)	0.00248 (6)	0.00076 (7)
Mo(2)	0.01801 (10)	0.01769 (12)	0.01263 (9)	0.00569 (8)	0.00168 (6)	0.00010 (7)
S(1)	0.0209 (2)	0.0222 (3)	0.0177 (2)	0.0068 (2)	0.0019 (2)	−0.0043 (2)
S(2)	0.0213 (2)	0.0178 (3)	0.0153 (2)	0.0066 (2)	−0.0001 (2)	−0.0009 (2)
S(3)	0.0215 (2)	0.0160 (3)	0.0164 (2)	0.0027 (2)	−0.0001 (2)	0.0015 (2)
S(4)	0.0215 (2)	0.0456 (5)	0.0204 (2)	0.0023 (3)	0.0050 (2)	−0.0127 (3)
O(1)	0.0243 (9)	0.0227 (11)	0.0174 (8)	0.0032 (8)	0.0043 (7)	0.0019 (7)
O(2)	0.0259 (9)	0.0216 (10)	0.0210 (8)	0.0082 (8)	−0.0017 (7)	0.0028 (7)
O(3)	0.0192 (9)	0.0432 (15)	0.0296 (10)	0.0050 (9)	−0.0040 (7)	−0.0126 (10)
O(4)	0.0265 (9)	0.0281 (12)	0.0171 (8)	0.0035 (8)	0.0029 (7)	−0.0019 (8)
O(5)	0.0188 (8)	0.0347 (13)	0.0230 (9)	0.0061 (8)	−0.0006 (6)	−0.0066 (8)
O(6)	0.0245 (9)	0.0282 (12)	0.0175 (8)	0.0080 (8)	−0.0031 (7)	−0.0018 (8)
N(1)	0.0169 (9)	0.0182 (11)	0.0138 (8)	0.0026 (8)	0.0022 (7)	0.0017 (8)
N(2)	0.0194 (9)	0.0199 (11)	0.0168 (9)	0.0038 (8)	0.0004 (7)	0.0023 (8)
C(1)	0.0177 (11)	0.0198 (13)	0.0222 (12)	0.0027 (9)	−0.0016 (9)	0.0005 (9)
C(2)	0.0157 (10)	0.0189 (13)	0.0161 (10)	0.0017 (9)	0.0016 (8)	0.0001 (9)
C(3)	0.0189 (10)	0.0223 (14)	0.0196 (11)	−0.0022 (10)	0.0025 (8)	0.0015 (9)
C(4)	0.0306 (15)	0.042 (2)	0.0316 (14)	−0.0012 (14)	−0.0089 (12)	−0.0107 (14)
C(5)	0.0210 (11)	0.044 (2)	0.0180 (11)	0.0007 (13)	0.0033 (9)	−0.0086 (12)
C(6)	0.0190 (10)	0.0223 (14)	0.0175 (10)	0.0064 (10)	0.0004 (8)	−0.0008 (9)
C(7)	0.0203 (10)	0.0273 (14)	0.0106 (8)	0.0049 (11)	0.0012 (7)	0.0037 (9)
C(8)	0.0270 (14)	0.041 (2)	0.0244 (13)	−0.0002 (13)	−0.0024 (11)	−0.0038 (13)

Geometric parameters (Å, º) top

Mo(1)—Mo(2)	2.8191 (2)	C(1)—C(2)	1.525 (4)
Mo(1)—S(1)	2.3079 (7)	C(2)—C(3)	1.523 (3)
Mo(1)—S(2)	2.3319 (7)	C(5)—C(6)	1.519 (3)
Mo(1)—S(3)	2.3941 (7)	C(6)—C(7)	1.524 (4)
Mo(1)—O(1)	1.685 (2)	N(1)—H(1)	0.920
Mo(1)—N(1)	2.213 (2)	N(1)—H(2)	0.920
Mo(2)—S(1)	2.3349 (7)	N(2)—H(3)	0.920
Mo(2)—S(2)	2.3028 (7)	N(2)—H(4)	0.920
Mo(2)—S(4)	2.3814 (7)	C(1)—H(5)	0.990
Mo(2)—O(2)	1.693 (2)	C(1)—H(6)	0.990
Mo(2)—N(2)	2.238 (2)	C(2)—H(7)	1.000
S(3)—C(1)	1.826 (2)	C(4)—H(8)	0.980
S(4)—C(5)	1.827 (3)	C(4)—H(9)	0.979
O(3)—C(3)	1.330 (3)	C(4)—H(10)	0.979
O(3)—C(4)	1.458 (4)	C(5)—H(11)	0.990
O(4)—C(3)	1.208 (3)	C(5)—H(12)	0.991
O(5)—C(7)	1.336 (3)	C(6)—H(13)	1.000
O(5)—C(8)	1.453 (4)	C(8)—H(14)	0.980
O(6)—C(7)	1.202 (3)	C(8)—H(15)	0.980
N(1)—C(2)	1.482 (3)	C(8)—H(16)	0.980
N(2)—C(6)	1.482 (3)

S(2)···O(1)ⁱ	3.405 (2)	H(1)···C(1)ⁱⁱⁱ	3.317
S(3)···O(1)ⁱ	3.445 (2)	H(1)···H(6)ⁱⁱⁱ	3.100
S(3)···N(1)ⁱ	3.218 (2)	H(1)···H(6)^vi	3.352
S(3)···C(5)ⁱⁱ	3.423 (2)	H(1)···H(9)^vi	3.552
O(1)···S(2)ⁱⁱⁱ	3.405 (2)	H(2)···O(4)^x	2.114
O(1)···S(3)ⁱⁱⁱ	3.445 (2)	H(2)···C(3)^x	3.295
O(1)···O(5)^iv	3.570 (3)	H(2)···H(6)^vi	2.727
O(1)···C(8)^iv	3.278 (3)	H(2)···H(9)^x	3.320
O(2)···O(5)^v	3.321 (3)	H(2)···H(10)^x	3.488
O(2)···O(6)ⁱⁱⁱ	3.108 (3)	H(3)···Mo(2)ⁱ	3.438
O(2)···O(6)^v	3.217 (3)	H(3)···O(2)ⁱ	2.404
O(2)···N(2)ⁱⁱⁱ	3.165 (3)	H(3)···O(6)^v	3.556
O(2)···C(7)^v	3.113 (3)	H(4)···O(2)ⁱ	3.115
O(4)···N(1)^vi	2.984 (3)	H(4)···O(6)^v	2.077
O(4)···C(1)ⁱⁱⁱ	3.304 (3)	H(4)···C(7)^v	3.044
O(4)···C(1)^vi	3.292 (3)	H(4)···C(8)^v	3.536
O(4)···C(2)^vi	3.492 (3)	H(4)···H(13)^viii	3.006
O(5)···O(1)^vii	3.570 (3)	H(4)···H(15)^v	3.319
O(5)···O(2)^viii	3.321 (3)	H(4)···H(16)^v	3.139
O(5)···C(8)^ix	3.334 (4)	H(5)···S(4)ⁱⁱ	3.277
O(6)···O(2)ⁱ	3.108 (3)	H(5)···O(4)ⁱ	3.397
O(6)···O(2)^viii	3.217 (3)	H(5)···C(3)ⁱ	3.545
O(6)···N(2)^viii	2.903 (3)	H(5)···C(4)^xiii	3.112
O(6)···C(6)^viii	3.377 (3)	H(5)···H(8)^xiii	2.396
N(1)···S(3)ⁱⁱⁱ	3.218 (2)	H(5)···H(10)^xiii	2.982
N(1)···O(4)^x	2.984 (3)	H(5)···H(12)ⁱⁱ	3.512
N(2)···O(2)ⁱ	3.165 (3)	H(6)···O(4)ⁱ	2.563
N(2)···O(6)^v	2.903 (3)	H(6)···O(4)^x	2.647
C(1)···O(4)ⁱ	3.304 (3)	H(6)···N(1)^x	3.421
C(1)···O(4)^x	3.292 (3)	H(6)···C(3)ⁱ	3.223
C(2)···O(4)^x	3.492 (3)	H(6)···C(3)^x	3.481
C(5)···S(3)^xi	3.423 (2)	H(6)···H(1)ⁱ	3.100
C(6)···O(6)^v	3.377 (3)	H(6)···H(1)^x	3.352
C(7)···O(2)^viii	3.113 (3)	H(6)···H(2)^x	2.727
C(8)···O(1)^vii	3.278 (3)	H(7)···S(3)ⁱⁱⁱ	3.337
C(8)···O(5)^xii	3.334 (4)	H(7)···S(4)ⁱⁱ	3.049
C(8)···C(8)^ix	3.419 (5)	H(8)···S(4)^vi	3.533
C(8)···C(8)^xii	3.419 (5)	H(8)···C(1)^xiv	3.376
Mo(1)···H(11)ⁱⁱ	3.286	H(8)···H(5)^xiv	2.396
Mo(2)···H(3)ⁱⁱⁱ	3.438	H(8)···H(10)^xiii	3.261
S(1)···H(9)^vi	3.286	H(9)···S(1)^vi	3.324
S(1)···H(9)^x	3.324	H(9)···S(1)^x	3.286
S(1)···H(10)^x	3.221	H(9)···H(1)^x	3.552
S(2)···H(11)ⁱⁱ	3.517	H(9)···H(2)^vi	3.320
S(2)···H(14)ⁱⁱ	3.273	H(10)···S(1)^vi	3.221
S(2)···H(16)^v	2.945	H(10)···S(4)^vi	3.543
S(3)···H(1)ⁱ	2.410	H(10)···O(3)^xiv	2.985
S(3)···H(7)ⁱ	3.337	H(10)···H(2)^vi	3.488
S(3)···H(11)ⁱⁱ	2.977	H(10)···H(5)^xiv	2.982
S(3)···H(12)ⁱⁱ	3.125	H(10)···H(8)^xiv	3.261
S(4)···H(5)^xi	3.277	H(11)···Mo(1)^xi	3.286
S(4)···H(7)^xi	3.049	H(11)···S(2)^xi	3.517
S(4)···H(8)^x	3.533	H(11)···S(3)^xi	2.977
S(4)···H(10)^x	3.543	H(11)···O(1)^xi	2.753
O(1)···H(11)ⁱⁱ	2.753	H(11)···H(15)ⁱⁱⁱ	3.222
O(1)···H(12)^iv	3.504	H(12)···S(3)^xi	3.125
O(1)···H(14)^iv	3.039	H(12)···O(1)^vii	3.504
O(1)···H(15)^iv	2.864	H(12)···H(5)^xi	3.512
O(2)···H(3)ⁱⁱⁱ	2.404	H(13)···O(2)^viii	3.426
O(2)···H(4)ⁱⁱⁱ	3.115	H(13)···O(6)ⁱⁱⁱ	2.693
O(2)···H(13)^v	3.426	H(13)···O(6)^v	3.056
O(2)···H(14)^iv	3.280	H(13)···H(4)^v	3.006
O(2)···H(16)^v	3.158	H(13)···H(15)ⁱⁱⁱ	2.932
O(3)···H(10)^xiii	2.985	H(14)···S(2)^xi	3.273
O(4)···H(1)^vi	3.566	H(14)···O(1)^vii	3.039
O(4)···H(2)^vi	2.114	H(14)···O(2)^vii	3.280
O(4)···H(5)ⁱⁱⁱ	3.397	H(14)···O(5)^xii	2.974
O(4)···H(6)ⁱⁱⁱ	2.563	H(14)···C(8)^ix	3.105
O(4)···H(6)^vi	2.647	H(14)···C(8)^xii	3.294
O(5)···H(14)^ix	2.974	H(14)···H(14)^ix	3.267
O(5)···H(15)^ix	3.480	H(14)···H(14)^xii	3.267
O(5)···H(16)^ix	3.020	H(14)···H(15)^ix	2.751
O(6)···H(3)^viii	3.556	H(14)···H(16)^ix	2.802
O(6)···H(4)^viii	2.077	H(14)···H(16)^xii	3.057
O(6)···H(13)ⁱ	2.693	H(15)···O(1)^vii	2.864
O(6)···H(13)^viii	3.056	H(15)···O(5)^xii	3.480
N(1)···H(6)^vi	3.421	H(15)···C(8)^xii	3.146
C(1)···H(1)ⁱ	3.317	H(15)···H(4)^viii	3.319
C(1)···H(8)^xiii	3.376	H(15)···H(11)ⁱ	3.222
C(3)···H(2)^vi	3.295	H(15)···H(13)ⁱ	2.932
C(3)···H(5)ⁱⁱⁱ	3.545	H(15)···H(14)^xii	2.751
C(3)···H(6)ⁱⁱⁱ	3.223	H(15)···H(16)^xii	2.881
C(3)···H(6)^vi	3.481	H(16)···S(2)^viii	2.945
C(4)···H(5)^xiv	3.112	H(16)···O(2)^viii	3.158
C(7)···H(4)^viii	3.044	H(16)···O(5)^xii	3.020
C(8)···H(4)^viii	3.536	H(16)···C(8)^ix	3.289
C(8)···H(14)^ix	3.294	H(16)···C(8)^xii	3.245
C(8)···H(14)^xii	3.105	H(16)···H(4)^viii	3.139
C(8)···H(15)^ix	3.146	H(16)···H(14)^ix	3.057
C(8)···H(16)^ix	3.245	H(16)···H(14)^xii	2.802
C(8)···H(16)^xii	3.289	H(16)···H(15)^ix	2.881
H(1)···S(3)ⁱⁱⁱ	2.410	H(16)···H(16)^ix	3.402
H(1)···O(4)^x	3.566	H(16)···H(16)^xii	3.402

Mo(2)—Mo(1)—S(1)	53.049 (18)	S(4)—C(5)—C(6)	111.2 (2)
Mo(2)—Mo(1)—S(2)	52.068 (17)	N(2)—C(6)—C(5)	108.9 (2)
Mo(2)—Mo(1)—S(3)	126.612 (19)	N(2)—C(6)—C(7)	111.5 (2)
Mo(2)—Mo(1)—O(1)	106.05 (6)	C(5)—C(6)—C(7)	108.6 (2)
Mo(2)—Mo(1)—N(1)	133.81 (5)	O(5)—C(7)—O(6)	124.7 (2)
S(1)—Mo(1)—S(2)	101.77 (2)	O(5)—C(7)—C(6)	110.6 (2)
S(1)—Mo(1)—S(3)	133.33 (2)	O(6)—C(7)—C(6)	124.6 (2)
S(1)—Mo(1)—O(1)	111.82 (7)	Mo(1)—N(1)—H(1)	109.1
S(1)—Mo(1)—N(1)	81.45 (6)	Mo(1)—N(1)—H(2)	109.1
S(2)—Mo(1)—S(3)	81.17 (2)	C(2)—N(1)—H(1)	109.1
S(2)—Mo(1)—O(1)	106.77 (7)	C(2)—N(1)—H(2)	109.2
S(2)—Mo(1)—N(1)	152.22 (6)	H(1)—N(1)—H(2)	107.9
S(3)—Mo(1)—O(1)	111.63 (7)	Mo(2)—N(2)—H(3)	108.8
S(3)—Mo(1)—N(1)	77.05 (6)	Mo(2)—N(2)—H(4)	108.8
O(1)—Mo(1)—N(1)	97.23 (9)	C(6)—N(2)—H(3)	108.8
Mo(1)—Mo(2)—S(1)	52.177 (17)	C(6)—N(2)—H(4)	108.8
Mo(1)—Mo(2)—S(2)	53.005 (18)	H(3)—N(2)—H(4)	107.7
Mo(1)—Mo(2)—S(4)	123.814 (18)	S(3)—C(1)—H(5)	109.6
Mo(1)—Mo(2)—O(2)	105.19 (7)	S(3)—C(1)—H(6)	109.6
Mo(1)—Mo(2)—N(2)	135.42 (6)	C(2)—C(1)—H(5)	109.6
S(1)—Mo(2)—S(2)	101.83 (2)	C(2)—C(1)—H(6)	109.6
S(1)—Mo(2)—S(4)	79.91 (2)	H(5)—C(1)—H(6)	108.1
S(1)—Mo(2)—O(2)	105.39 (7)	N(1)—C(2)—H(7)	108.7
S(1)—Mo(2)—N(2)	155.64 (6)	C(1)—C(2)—H(7)	108.7
S(2)—Mo(2)—S(4)	129.80 (3)	C(3)—C(2)—H(7)	108.7
S(2)—Mo(2)—O(2)	112.22 (7)	O(3)—C(4)—H(8)	109.4
S(2)—Mo(2)—N(2)	82.64 (6)	O(3)—C(4)—H(9)	109.4
S(4)—Mo(2)—O(2)	115.52 (7)	O(3)—C(4)—H(10)	109.4
S(4)—Mo(2)—N(2)	79.03 (6)	H(8)—C(4)—H(9)	109.5
O(2)—Mo(2)—N(2)	94.67 (9)	H(8)—C(4)—H(10)	109.5
Mo(1)—S(1)—Mo(2)	74.77 (2)	H(9)—C(4)—H(10)	109.6
Mo(1)—S(2)—Mo(2)	74.93 (2)	S(4)—C(5)—H(11)	109.4
Mo(1)—S(3)—C(1)	104.40 (10)	S(4)—C(5)—H(12)	109.4
Mo(2)—S(4)—C(5)	103.96 (9)	C(6)—C(5)—H(11)	109.4
C(3)—O(3)—C(4)	116.4 (2)	C(6)—C(5)—H(12)	109.4
C(7)—O(5)—C(8)	116.6 (2)	H(11)—C(5)—H(12)	108.0
Mo(1)—N(1)—C(2)	112.43 (15)	N(2)—C(6)—H(13)	109.3
Mo(2)—N(2)—C(6)	113.75 (18)	C(5)—C(6)—H(13)	109.2
S(3)—C(1)—C(2)	110.37 (18)	C(7)—C(6)—H(13)	109.3
N(1)—C(2)—C(1)	108.5 (2)	O(5)—C(8)—H(14)	109.4
N(1)—C(2)—C(3)	111.0 (2)	O(5)—C(8)—H(15)	109.5
C(1)—C(2)—C(3)	111.0 (2)	O(5)—C(8)—H(16)	109.5
O(3)—C(3)—O(4)	124.2 (2)	H(14)—C(8)—H(15)	109.5
O(3)—C(3)—C(2)	111.6 (2)	H(14)—C(8)—H(16)	109.4
O(4)—C(3)—C(2)	124.2 (2)	H(15)—C(8)—H(16)	109.5

Symmetry codes: (i) x, y+1, z; (ii) x−1, y, z; (iii) x, y−1, z; (iv) x−1, y−1, z; (v) −x+2, y−1/2, −z+1; (vi) −x+1, y−1/2, −z; (vii) x+1, y+1, z; (viii) −x+2, y+1/2, −z+1; (ix) −x+3, y−1/2, −z+1; (x) −x+1, y+1/2, −z; (xi) x+1, y, z; (xii) −x+3, y+1/2, −z+1; (xiii) −x, y+1/2, −z; (xiv) −x, y−1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N(1)—H(2)···O(4)^x	0.92	2.11	2.984 (3)	157
N(2)—H(3)···O(2)ⁱ	0.92	2.40	3.165 (3)	140
N(2)—H(4)···O(6)^v	0.92	2.08	2.903 (3)	149

Symmetry codes: (i) x, y+1, z; (v) −x+2, y−1/2, −z+1; (x) −x+1, y+1/2, −z.

Experimental details

Crystal data
Chemical formula	[Mo₂(C₄H₈NO₂S)₂O₂S₂]
M_r	556.34
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	93
a, b, c (Å)	9.195 (5), 5.622 (3), 17.437 (9)
β (°)	91.6763 (15)
V (Å³)	901.0 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.88
Crystal size (mm)	0.32 × 0.23 × 0.15

Data collection
Diffractometer	Rigaku Mercury
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.680, 0.759
No. of measured, independent and observed [F² > 2σ(F²)] reflections	10030, 5007, 4966
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.067, 1.12
No. of reflections	5007
No. of parameters	200
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.23, −0.63
Absolute structure	Flack (1983), 2185 Friedel pairs
Absolute structure parameter	−0.08 (3)

Computer programs: CrystalClear (Rigaku, 1999), CrystalStructure (Rigaku Americas and Rigaku, 2007), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick et al., 2008), ORTEPIII (Burnett et al., 1996).

Acknowledgements

This work was supported by KAKENHI (18550063).

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Burnett, M. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Drew, M. G. B. & Kay, A. (1971). J. Chem. Soc. A, pp. 1851–1854. CSD CrossRef Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jacobson, R. (1998). REQAB. Private communication to the Rigaku Corporation, Tokyo, Japan. Google Scholar
Kay, A. & Mitchell, P. C. H. (1970). J. Chem. Soc. A, pp. 2421–2428. CrossRef Google Scholar
Newton, W. E. & Otsuka, S. (1980). In Molybdenum Chemistry of Biological Significance. New York and London: Plenum Press. Google Scholar
Rigaku (1999). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku Americas and Rigaku (2007). CrystalStructure. Rigaku Americas, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shibahara, T. & Akashi, H. (1992). Inorg. Synth. 29, 254–260. CrossRef CAS Google Scholar
Shibahara, T., Kuroya, H., Matumoto, K. & Ooi, S. (1983). Bull. Chem. Soc. Jpn, 56, 2945–2948. CrossRef CAS Web of Science Google Scholar
Ueyama, N., Nakata, M. & Nakamura, A. (1982). J. Mol. Catal. 14, 341–350. CrossRef CAS Google Scholar

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