Bis(glycinato-[kappa]²N,O)dinitro­sylmolybdenum(0) and bis­(2-amino­ethanethiol­ato-[kappa]²N,S)dinitro­syl­molybdenum(0) acetonitrile monosolvate

The title compounds, [Mo(C₂H₄NO₂)₂(NO)₂], (I), and [Mo(C₂H₆NS)₂(NO)₂]·CH₃CN, (II), contain distorted octa­hedral complexes in which the monoanionic N,S- and N,O-bidentate ligands coordinate the molybdenum centres in different modes. The anionic O atoms of the glycinate ligands in (I) are coordinated trans to the nitrosyl ligands and the amine N atoms are located trans to each other, whereas in (II) the anionic S atoms are coordinated trans to each other and the amine N atoms are located trans to the nitrosyl ligands. Each compound has a single complete complex in the asymmetric unit on a general position. Six N-H...O contacts with N...O distances of less than 3.2 Å are observed in (I) between the amine groups and the nitrosyl and carboxyl­ate O atoms. In the 1:1 solvate (II), the acetonitrile mol­ecule forms short N-H...N contacts (N...N < 3.2 Å) between the solvent N atoms and one of the amine H atoms. In addition, three weak inter­molecular N-H...S inter­actions (N...S > 3.3 Å) contribute to the stabilization of the structure of (II).

S1. Comment

With the aim of preparing water-soluble dinitrosyl–molybdenum complexes to study their ability to release NO in aqueous solution, the title compounds, Mo(NO)₂(H₂NCH₂COO)₂, (I), and Mo(NO)₂(H₂NCH₂CH₂S)₂·CH₃CN, (II), resulting from the reactions of the [Mo(NO)₂]²⁺ cation with bidentate monoanionic (N,X)-donor ligands (X = O and S), were prepared.

In compounds (I) and (II), the Mo atoms present distorted octahedral coordinations with nearly linear Mo—N—O bond angles and normal Mo—NO bond distances (Fig. 1 and 2). The amine N atoms of the glycinate ligand in (I) are bound to molybdenum in trans positions, showing a significantly closed N3—Mo1—N4 bond angle, whereas the anionic O atoms are located cis to each other and trans to the nitrosyl ligands, with nearly linear O—Mn—N angles (Table 1). The crystal structure of (II) reveals a different coordination mode in comparison with (I), since the monoanionic bidentate ligands coordinate to the metal center with the anionic S atoms in trans positions to each other with a significantly closed S1—Mo1—S2 bond angle and the amine N atoms located trans to the nitrosyl ligands with relatively undistorted N—Mn—N angles (Table 2). The known molybdenum dinitrosyl complexes of 2-picolinate and 2-pyrimidinethiolate, Mo(NO)₂(2-picolinate)₂ (Perpiñán et al., 1987) and Mo(NO)₂(2-pyrimidinethiolate)₂ (Yonemura et al., 2001) show the same systematic trend at least in the coordination manner of the N,S- and N,O-bidentate ligands.

In order to trace the electronic causes for this phenomenon on the molecular orbital level, simple density functional theory (DFT) calculations were carried out using the TURBOMOLE program package (Von Arnim & Ahlrichs, 1998; Treutler & Ahlrichs, 1995; Ahlrichs et al., 1989). Two different coordination geometries have been optimized for each complex, one with the amine N atoms trans to the nitrosyl ligands (a) and the other with the anionic chalcogen atoms [oxygen in (I), sulfur in (II)] trans to the nitrosyl ligands (b). The computed total energies confirm the solid-state structures of (I) and (II) as the global energetic minima. Indeed, the thermodynamically most favourable geometries show the amine N atoms [(Ib), 8.7 kcal mol^-1 below I(a)] and the anionic D atoms [(IIa), 5.1 kcal mol^-1 below (IIb)] trans to each other, respectively. From basic considerations, the van der Waals radius of the S atom is significantly larger than those of the O and N atoms (1.815 Å versus 1.060 and 1.050 Å, respectively), and consequently the trans-S,S geometry should be preferred over the cis-S,S one. The computed highest occupied molecular orbitals (HOMOs) of (I) and (II) indicate that the electron population of the sulfur lone pairs is expectedly larger than in the oxygen lone pairs, leading to a strong antibonding interaction between the in-plane sulfur lone pairs in the energetically high-lying HOMO of the trans-N,N geometry of (II). In the case of the trans-N,N geometry of (I), the HOMO exhibits a π-type antibonding character between the oxygen lone pairs and a d orbital of the metal, but with a less destabilizing effect than in (II).

Six N—H···O contacts (D < 3.2 Å) between the amine groups and the nitrosyl and carboxylate O atoms are observed in (I) (Fig. 3 and Table 1). Not surprisingly, the shortest and most linear of these interactions are with the non-coordinating carboxylate O atoms. Solvent molecules of acetonitrile cocrystallized with compound (II), forming short N—H···N contacts (D < 3.2 Å) between the solvent N atoms and one of the amine H atoms (Fig. 4 and Table 2). Three other weak N—H···S intermolecular interactions (D > 3.3 Å) contribute to the stabilization of the structure of (II).

Related literature

For related literature, see: Ahlrichs et al. (1989); Becke (1988); Perdew (1986, 1986); Perpiñán, Ballester, Santos, Monge, Ruiz-Valero & Puebla (1987); Treutler & Ahlrichs (1995); Von Arnim & Ahlrichs (1998); Vosko et al. (1980); Yonemura et al. (2001).

S2. Experimental

For the preparation of (I), a solution of H₂NCH₂COOLi (154 mg, 1.90 mmol) in methanol (5 ml) was added to a solution of the bromide polymer [Mo(NO)₂(Br)₂]_n (300 mg, 0.95 mmol) in the same solvent (5 ml), and the reaction mixture was stirred for 2 h. During that time, a colour change from green to dark green was observed. The reaction solution was filtered over Celite to remove insoluble materials, and the solvent was removed under vacuum leaving the product and LiBr. Adding some tetrahydrofuran and stirring the mixture for 10 min resulted in dissolution of LiBr. The green solid was filtered off over a frit, washed with cold tetrahydrofuran (243 K) and dried under vacuum. The obtained powder was redissolved in methanol, and green crystals of (I) were formed on slow evaporation at room temperature in a low yield of about 20%. Analysis calculated for C₄H₈MoN₄O₆ (304.06): C 15.80, H 2.65, N 18.42%; found: C 16.02, H 2.48, N 18.14%.

For the preparation of (II), a solution of H₂NCH₂CH₂SLi (130 mg, 0.156 mmol) in acetonitrile (4 ml) was added to a green solution of the bromide polymer [Mo(NO)₂(Br)₂]_n (247 mg, 0.78 mmol) in the same solvent (4 ml). During the course of addition, the colour of the solution changed from green to red-brown. After the addition was completed, the reaction mixture was stirred for 2 h and then filtered over Celite. Slow evaporation of acetonitrile at room temperature gave, after a few days, 90 mg of (II) as red–brown microcrystals. Analysis calculated for C₄H₁₂MoN₄O₂S₂ (308.24): C 15.59, H 3.92, N 18.18%; found: C 15.87, H 3.92, N 17.99% (the elemental analysis was carried out after desolvation of the crystals).

DFT calculations were performed with the TURBOMOLE program package (Version 5.5; Von Arnim & Ahlrichs, 1998; Treutler & Ahlrichs, 1995; Ahlrichs et al., 1989). The Vosko–Wilk–Nusair (Vosko et al., 1980) local density approximation (LDA) and the generalized gradient approximation (GGA) with corrections for exchange and correlation according to Becke (1988) and Perdew (1986a,b) (BP86) were used for all calculations. The TURBOMOLE approach to DFT GGA calculations is based on the use of Gaussian-type orbitals as basis functions. Geometries were optimized using accurate triple-ζ valence basis sets augmented by one polarization function TZV(P) (Schäfer et al., 1992, 1994) for all elements.

S3. Refinement

All H-atom positions were calculated after each cycle of refinement with SHELXL97 using a riding model in both structures with C—H distances in the range 0.97–0.99 Å and N—H distances in the range 0.90–0.92 Å. U_iso(H) values were set equal to 1.3U_eq of the parent C or N atoms in (I), and 1.2U_eq(C,N) in (II) [1.5U_eq(C) for the methyl H atoms]. Please check; text changed in accordance with data in CIF.

Computing details

For both compounds, data collection: IPDS Software (Stoe & Cie, 1999); cell refinement: IPDS Software (Stoe & Cie, 1999); data reduction: X-RED (Stoe & Cie, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. A view of the molecular structure of (I), showing the atomic labelling scheme and 30% probability displacement ellipsoids.
	Fig. 2. A view of the molecular structure of (II), showing the atomic labelling scheme and 30% probability displacement ellipsoids.
	Fig. 3. A projection of the structure of (I) normal to (010), showing the shortest hydrogen-bonding interactions, H3B···O5 and H4B···O6 (dashed lines), in the crystal structure.
	Fig. 4. A projection of the structure of (II) normal to (010), showing the short intermolecular interactions between (II) and the acetonitrile solvent molecules (dashed lines).

(I) Dinitrosylbis(glycinato-κ²N,O)molybdenum(IV)

Crystal data

[Mo(C2H4NO2)2(NO)2]	F(000) = 600
Mr = 304.08	Dx = 2.18 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8000 reflections
a = 12.9088 (15) Å	θ = 3.1–30.3°
b = 7.5727 (6) Å	µ = 1.44 mm^−1
c = 9.6922 (11) Å	T = 183 K
β = 102.051 (13)°	Large block, dark green
V = 926.58 (17) Å^3	0.43 × 0.41 × 0.39 mm
Z = 4

Data collection

Stoe IPDS diffractometer	2265 reflections with I > 2σ(I)
ϕ rotation scan	Rint = 0.045
Absorption correction: numerical (Coppens et al., 1965)	θmax = 30.3°, θmin = 3.1°
Tmin = 0.56, Tmax = 0.669	h = −18→17
17540 measured reflections	k = 0→10
2745 independent reflections	l = 0→13

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.021	w = 1/[σ^2(Fo^2) + (0.0362P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.051	(Δ/σ)max = 0.001
S = 0.93	Δρmax = 0.38 e Å^−3
2745 reflections	Δρmin = −0.68 e Å^−3
136 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mo1	0.743377 (9)	0.010475 (17)	0.739870 (12)	0.01311 (5)
N1	0.65454 (11)	0.11528 (19)	0.59101 (15)	0.0171 (3)
O1	0.59989 (11)	0.18088 (19)	0.49203 (13)	0.0267 (3)
N2	0.77398 (11)	0.23186 (19)	0.81326 (14)	0.0164 (3)
O2	0.78870 (10)	0.37614 (18)	0.85722 (14)	0.0250 (3)
N3	0.88320 (10)	−0.02513 (19)	0.64756 (14)	0.0150 (2)
H3A	0.8714	−0.1127	0.5834	0.02*
H3B	0.8959	0.0747	0.6035	0.02*
N4	0.62795 (11)	−0.0701 (2)	0.86340 (15)	0.0174 (3)
H4A	0.6588	−0.0695	0.9557	0.023*
H4B	0.5741	0.0077	0.8499	0.023*
O3	0.84757 (10)	−0.12713 (17)	0.89868 (12)	0.0183 (2)
O4	0.70123 (10)	−0.24220 (17)	0.65952 (13)	0.0194 (2)
O5	1.00834 (10)	−0.24170 (18)	0.97058 (13)	0.0221 (3)
O6	0.59528 (10)	−0.47367 (17)	0.65815 (14)	0.0234 (3)
C1	0.97608 (13)	−0.0690 (2)	0.76000 (17)	0.0172 (3)
H1A	1.0155	0.038	0.7905	0.022*
H1B	1.0223	−0.1485	0.7224	0.022*
C2	0.94366 (13)	−0.1552 (2)	0.88601 (16)	0.0148 (3)
C3	0.58652 (17)	−0.2466 (3)	0.8232 (2)	0.0289 (4)
H3C	0.51	−0.2395	0.7941	0.038*
H3D	0.6027	−0.3227	0.9054	0.038*
C4	0.62994 (13)	−0.3302 (2)	0.70586 (16)	0.0160 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01210 (7)	0.01532 (7)	0.01280 (7)	0.00059 (5)	0.00464 (4)	0.00046 (5)
N1	0.0168 (6)	0.0181 (6)	0.0170 (6)	0.0014 (5)	0.0049 (5)	−0.0005 (5)
O1	0.0263 (7)	0.0324 (7)	0.0198 (6)	0.0092 (5)	0.0012 (5)	0.0039 (5)
N2	0.0141 (6)	0.0193 (7)	0.0155 (6)	0.0012 (5)	0.0029 (5)	−0.0007 (5)
O2	0.0244 (6)	0.0205 (6)	0.0278 (6)	0.0007 (5)	0.0005 (5)	−0.0056 (5)
N3	0.0154 (6)	0.0170 (6)	0.0136 (5)	0.0000 (5)	0.0053 (5)	0.0019 (5)
N4	0.0164 (6)	0.0223 (7)	0.0153 (6)	0.0003 (5)	0.0075 (5)	−0.0009 (5)
O3	0.0163 (5)	0.0236 (6)	0.0165 (5)	0.0031 (5)	0.0070 (4)	0.0053 (5)
O4	0.0211 (6)	0.0197 (6)	0.0205 (6)	−0.0039 (5)	0.0112 (5)	−0.0041 (4)
O5	0.0240 (6)	0.0249 (6)	0.0173 (6)	0.0091 (5)	0.0040 (5)	0.0037 (5)
O6	0.0237 (6)	0.0226 (6)	0.0246 (6)	−0.0068 (5)	0.0064 (5)	−0.0046 (5)
C1	0.0155 (7)	0.0203 (8)	0.0167 (7)	0.0013 (6)	0.0055 (6)	0.0027 (6)
C2	0.0179 (7)	0.0132 (7)	0.0139 (6)	0.0008 (5)	0.0044 (5)	−0.0022 (5)
C3	0.0391 (11)	0.0253 (9)	0.0285 (9)	−0.0104 (8)	0.0214 (8)	−0.0050 (7)
C4	0.0147 (7)	0.0189 (7)	0.0140 (7)	0.0008 (6)	0.0018 (5)	0.0025 (5)

Geometric parameters (Å, º)

Mo1—N1	1.8264 (15)	N4—H4A	0.9
Mo1—N2	1.8318 (15)	N4—H4B	0.9
Mo1—O4	2.0945 (12)	O3—C2	1.289 (2)
Mo1—O3	2.0976 (12)	O4—C4	1.290 (2)
Mo1—N4	2.1843 (14)	O5—C2	1.230 (2)
Mo1—N3	2.1921 (14)	O6—C4	1.228 (2)
N1—O1	1.1756 (19)	C1—C2	1.519 (2)
N2—O2	1.1737 (19)	C1—H1A	0.97
N3—C1	1.480 (2)	C1—H1B	0.97
N3—H3A	0.9	C3—C4	1.508 (2)
N3—H3B	0.9	C3—H3C	0.97
N4—C3	1.462 (2)	C3—H3D	0.97
N1—Mo1—N2	87.59 (6)	Mo1—N4—H4A	109.4
N1—Mo1—O4	91.82 (6)	C3—N4—H4B	109.4
N2—Mo1—O4	177.12 (5)	Mo1—N4—H4B	109.4
N1—Mo1—O3	175.03 (5)	H4A—N4—H4B	108
N2—Mo1—O3	96.69 (6)	C2—O3—Mo1	119.62 (10)
O4—Mo1—O3	84.03 (5)	C4—O4—Mo1	119.40 (10)
N1—Mo1—N4	99.60 (6)	N3—C1—C2	111.83 (13)
N2—Mo1—N4	99.17 (6)	N3—C1—H1A	109.2
O4—Mo1—N4	78.14 (5)	C2—C1—H1A	109.2
O3—Mo1—N4	82.25 (5)	N3—C1—H1B	109.2
N1—Mo1—N3	99.54 (6)	C2—C1—H1B	109.2
N2—Mo1—N3	98.16 (6)	H1A—C1—H1B	107.9
O4—Mo1—N3	84.72 (5)	O5—C2—O3	123.86 (15)
O3—Mo1—N3	77.40 (5)	O5—C2—C1	120.15 (15)
N4—Mo1—N3	154.60 (6)	O3—C2—C1	115.96 (14)
O1—N1—Mo1	177.50 (13)	N4—C3—C4	114.31 (15)
O2—N2—Mo1	176.75 (13)	N4—C3—H3C	108.7
C1—N3—Mo1	109.67 (9)	C4—C3—H3C	108.7
C1—N3—H3A	109.7	N4—C3—H3D	108.7
Mo1—N3—H3A	109.7	C4—C3—H3D	108.7
C1—N3—H3B	109.7	H3C—C3—H3D	107.6
Mo1—N3—H3B	109.7	O6—C4—O4	123.77 (16)
H3A—N3—H3B	108.2	O6—C4—C3	119.45 (15)
C3—N4—Mo1	111.27 (11)	O4—C4—C3	116.77 (15)
C3—N4—H4A	109.4
N1—Mo1—N3—C1	166.27 (11)	N1—Mo1—O4—C4	−97.12 (13)
N2—Mo1—N3—C1	77.35 (11)	O3—Mo1—O4—C4	85.62 (12)
O4—Mo1—N3—C1	−102.77 (11)	N4—Mo1—O4—C4	2.31 (12)
O3—Mo1—N3—C1	−17.73 (10)	N3—Mo1—O4—C4	163.47 (13)
N4—Mo1—N3—C1	−55.28 (17)	Mo1—N3—C1—C2	25.47 (16)
N1—Mo1—N4—C3	89.48 (13)	Mo1—O3—C2—O5	−176.42 (13)
N2—Mo1—N4—C3	178.57 (13)	Mo1—O3—C2—C1	5.52 (18)
O4—Mo1—N4—C3	−0.37 (12)	N3—C1—C2—O5	160.50 (15)
O3—Mo1—N4—C3	−85.86 (13)	N3—C1—C2—O3	−21.4 (2)
N3—Mo1—N4—C3	−48.96 (18)	Mo1—N4—C3—C4	−1.2 (2)
N2—Mo1—O3—C2	−89.78 (12)	Mo1—O4—C4—O6	174.89 (12)
O4—Mo1—O3—C2	93.03 (12)	Mo1—O4—C4—C3	−3.7 (2)
N4—Mo1—O3—C2	171.82 (13)	N4—C3—C4—O6	−175.46 (16)
N3—Mo1—O3—C2	7.12 (12)	N4—C3—C4—O4	3.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O3^i	0.90	2.64	3.5357 (18)	177
N3—H3A···O5^i	0.90	2.52	3.1347 (19)	126
N3—H3B···O5^ii	0.90	2.08	2.9237 (19)	155
N3—H3B···O2^iii	0.90	2.52	3.0408 (19)	117
N4—H4A···O4^iv	0.90	2.41	3.1651 (19)	142
N4—H4A···O6^iv	0.90	2.30	2.9920 (19)	133
N4—H4B···O6^v	0.90	2.18	2.9377 (19)	142

Symmetry codes: (i) x, −y−1/2, z−1/2; (ii) −x+2, y+1/2, −z+3/2; (iii) x, −y+1/2, z−1/2; (iv) x, −y−1/2, z+1/2; (v) −x+1, y+1/2, −z+3/2.

(II) bis(2-aminoethanethiolato-κ²N,S)dinitrosylmolybdenum(IV) acetonitrile monosolvate

Crystal data

[Mo(C2H6NS)2(NO)2]·C2H3N	F(000) = 704
Mr = 349.29	Dx = 1.73 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7998 reflections
a = 8.8660 (7) Å	θ = 2.9–30.3°
b = 8.5980 (7) Å	µ = 1.28 mm^−1
c = 18.0218 (16) Å	T = 183 K
β = 102.487 (10)°	Block, dark-red
V = 1341.30 (19) Å^3	0.41 × 0.4 × 0.19 mm
Z = 4

Data collection

Stoe IPDS diffractometer	3459 reflections with I > 2σ(I)
ϕ rotation scan	Rint = 0.087
Absorption correction: numerical (Coppens et al., 1965)	θmax = 30.3°, θmin = 3.4°
Tmin = 0.621, Tmax = 0.793	h = −12→12
17511 measured reflections	k = −12→12
3976 independent reflections	l = 0→25

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.049	w = 1/[σ^2^(Fo^2^) + (0.1076P)^2^] where P = (Fo^2^ + 2Fc^2^)/3
wR(F^2) = 0.145	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 1.45 e Å^−3
3976 reflections	Δρmin = −1.35 e Å^−3
146 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mo1	0.10625 (2)	0.76357 (3)	0.399378 (12)	0.01589 (11)
S1	−0.05030 (8)	0.67138 (8)	0.27570 (4)	0.02511 (17)
S2	0.24934 (8)	0.94452 (8)	0.49479 (4)	0.02137 (16)
N1	−0.0030 (3)	0.6919 (3)	0.46758 (15)	0.0247 (5)
O1	−0.0620 (4)	0.6569 (3)	0.51757 (18)	0.0492 (8)
N2	0.2376 (3)	0.5962 (3)	0.41855 (13)	0.0215 (4)
O2	0.3207 (3)	0.4886 (3)	0.43120 (15)	0.0359 (5)
C1	−0.1838 (3)	0.8338 (4)	0.24984 (16)	0.0262 (6)
H1A	−0.1414	0.9077	0.2175	0.031*
H1B	−0.2838	0.7947	0.2202	0.031*
C2	−0.2096 (3)	0.9175 (3)	0.32035 (16)	0.0245 (5)
H2A	−0.2739	1.0113	0.3053	0.029*
H2B	−0.2650	0.8483	0.3494	0.029*
N3	−0.0583 (3)	0.9632 (3)	0.36852 (12)	0.0183 (4)
H3A	−0.0747	1.0081	0.4124	0.022*
H3B	−0.0136	1.0369	0.3431	0.022*
C3	0.3243 (3)	1.0742 (3)	0.43135 (16)	0.0235 (5)
H3C	0.2417	1.1458	0.4059	0.028*
H3D	0.4097	1.1375	0.4610	0.028*
C4	0.3822 (3)	0.9802 (4)	0.37256 (16)	0.0233 (5)
H4A	0.4195	1.0510	0.3371	0.028*
H4B	0.4699	0.9143	0.3979	0.028*
N4	0.2561 (3)	0.8803 (3)	0.32944 (12)	0.0192 (4)
H4C	0.2996	0.8045	0.3047	0.023*
H4D	0.1939	0.9403	0.2929	0.023*
N5	0.4991 (4)	0.6320 (4)	0.30213 (18)	0.0383 (6)
C5	0.5742 (4)	0.5346 (4)	0.33329 (19)	0.0337 (7)
C6	0.6686 (6)	0.4097 (6)	0.3723 (3)	0.0584 (12)
H6A	0.7765	0.4436	0.3861	0.088*
H6B	0.6603	0.3189	0.3387	0.088*
H6C	0.6329	0.3819	0.4183	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01591 (17)	0.01506 (15)	0.01653 (16)	0.00061 (6)	0.00312 (10)	0.00077 (6)
S1	0.0244 (3)	0.0228 (3)	0.0257 (3)	0.0011 (2)	0.0001 (2)	−0.0093 (2)
S2	0.0199 (3)	0.0274 (3)	0.0163 (3)	−0.0025 (2)	0.0029 (2)	−0.0030 (2)
N1	0.0251 (11)	0.0202 (11)	0.0319 (12)	0.0004 (9)	0.0127 (9)	0.0064 (9)
O1	0.0651 (18)	0.0372 (14)	0.0600 (17)	0.0085 (13)	0.0463 (15)	0.0170 (13)
N2	0.0226 (10)	0.0210 (10)	0.0215 (10)	0.0025 (8)	0.0064 (8)	0.0029 (8)
O2	0.0355 (12)	0.0309 (11)	0.0435 (13)	0.0150 (10)	0.0138 (10)	0.0122 (10)
C1	0.0261 (13)	0.0240 (13)	0.0240 (12)	0.0000 (10)	−0.0041 (10)	−0.0030 (10)
C2	0.0187 (11)	0.0234 (12)	0.0287 (13)	0.0015 (9)	−0.0007 (9)	−0.0038 (10)
N3	0.0188 (10)	0.0177 (9)	0.0177 (9)	0.0001 (8)	0.0026 (7)	−0.0029 (7)
C3	0.0227 (12)	0.0222 (12)	0.0251 (12)	−0.0029 (10)	0.0036 (9)	−0.0022 (10)
C4	0.0176 (11)	0.0284 (13)	0.0240 (11)	−0.0029 (10)	0.0049 (9)	0.0003 (10)
N4	0.0191 (9)	0.0218 (10)	0.0173 (9)	0.0005 (8)	0.0053 (7)	0.0004 (8)
N5	0.0350 (14)	0.0398 (16)	0.0412 (15)	−0.0020 (13)	0.0107 (12)	−0.0038 (13)
C5	0.0366 (16)	0.0362 (17)	0.0298 (14)	−0.0074 (13)	0.0102 (12)	−0.0060 (13)
C6	0.063 (3)	0.061 (3)	0.048 (2)	0.010 (2)	0.005 (2)	0.019 (2)

Geometric parameters (Å, º)

Mo1—N1	1.828 (2)	N3—H3A	0.9200
Mo1—N2	1.837 (2)	N3—H3B	0.9200
Mo1—N3	2.243 (2)	C3—C4	1.508 (4)
Mo1—N4	2.255 (2)	C3—H3C	0.9900
Mo1—S2	2.4584 (7)	C3—H3D	0.9900
Mo1—S1	2.4870 (7)	C4—N4	1.489 (4)
S1—C1	1.825 (3)	C4—H4A	0.9900
S2—C3	1.823 (3)	C4—H4B	0.9900
N1—O1	1.175 (3)	N4—H4C	0.9200
N2—O2	1.173 (3)	N4—H4D	0.9200
C1—C2	1.520 (4)	N5—C5	1.139 (5)
C1—H1A	0.9900	C5—C6	1.447 (6)
C1—H1B	0.9900	C6—H6A	0.9800
C2—N3	1.485 (3)	C6—H6B	0.9800
C2—H2A	0.9900	C6—H6C	0.9800
C2—H2B	0.9900
N1—Mo1—N2	90.91 (11)	C2—N3—Mo1	113.56 (16)
N1—Mo1—N3	90.80 (10)	C2—N3—H3A	108.9
N2—Mo1—N3	176.49 (9)	Mo1—N3—H3A	108.9
N1—Mo1—N4	170.91 (10)	C2—N3—H3B	108.9
N2—Mo1—N4	91.59 (9)	Mo1—N3—H3B	108.9
N3—Mo1—N4	87.20 (8)	H3A—N3—H3B	107.7
N1—Mo1—S2	90.65 (9)	C4—C3—S2	109.8 (2)
N2—Mo1—S2	98.86 (8)	C4—C3—H3C	109.7
N3—Mo1—S2	84.19 (6)	S2—C3—H3C	109.7
N4—Mo1—S2	80.33 (6)	C4—C3—H3D	109.7
N1—Mo1—S1	102.77 (9)	S2—C3—H3D	109.7
N2—Mo1—S1	97.30 (8)	H3C—C3—H3D	108.2
N3—Mo1—S1	79.32 (6)	N4—C4—C3	110.2 (2)
N4—Mo1—S1	85.58 (6)	N4—C4—H4A	109.6
S2—Mo1—S1	158.78 (3)	C3—C4—H4A	109.6
C1—S1—Mo1	100.97 (9)	N4—C4—H4B	109.6
C3—S2—Mo1	98.72 (9)	C3—C4—H4B	109.6
O1—N1—Mo1	172.1 (3)	H4A—C4—H4B	108.1
O2—N2—Mo1	179.4 (2)	C4—N4—Mo1	115.58 (16)
C2—C1—S1	110.83 (19)	C4—N4—H4C	108.4
C2—C1—H1A	109.5	Mo1—N4—H4C	108.4
S1—C1—H1A	109.5	C4—N4—H4D	108.4
C2—C1—H1B	109.5	Mo1—N4—H4D	108.4
S1—C1—H1B	109.5	H4C—N4—H4D	107.4
H1A—C1—H1B	108.1	N5—C5—C6	179.4 (4)
N3—C2—C1	109.5 (2)	C5—C6—H6A	109.5
N3—C2—H2A	109.8	C5—C6—H6B	109.5
C1—C2—H2A	109.8	H6A—C6—H6B	109.5
N3—C2—H2B	109.8	C5—C6—H6C	109.5
C1—C2—H2B	109.8	H6A—C6—H6C	109.5
H2A—C2—H2B	108.2	H6B—C6—H6C	109.5
N1—Mo1—S1—C1	88.74 (14)	C1—C2—N3—Mo1	−55.0 (3)
N2—Mo1—S1—C1	−178.66 (13)	N1—Mo1—N3—C2	−74.5 (2)
N3—Mo1—S1—C1	0.36 (12)	N4—Mo1—N3—C2	114.35 (19)
N4—Mo1—S1—C1	−87.62 (13)	S2—Mo1—N3—C2	−165.09 (18)
S2—Mo1—S1—C1	−39.26 (14)	S1—Mo1—N3—C2	28.32 (17)
N1—Mo1—S2—C3	−162.82 (13)	Mo1—S2—C3—C4	−43.09 (19)
N2—Mo1—S2—C3	106.16 (12)	S2—C3—C4—N4	57.3 (3)
N3—Mo1—S2—C3	−72.09 (11)	C3—C4—N4—Mo1	−41.5 (3)
N4—Mo1—S2—C3	16.05 (11)	N2—Mo1—N4—C4	−87.97 (19)
S1—Mo1—S2—C3	−33.05 (13)	N3—Mo1—N4—C4	95.33 (19)
Mo1—S1—C1—C2	−27.8 (2)	S2—Mo1—N4—C4	10.75 (17)
S1—C1—C2—N3	53.8 (3)	S1—Mo1—N4—C4	174.83 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···S2^i	0.92	2.55	3.372 (2)	150
N3—H3B···S1^ii	0.92	2.60	3.459 (2)	155
N4—H4C···N5	0.92	2.32	3.146 (4)	150
N4—H4D···S1^ii	0.92	2.53	3.419 (2)	162

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