1,3-Propane­di­ammonium tetra­thio­tungstate and N,N,N',N'-tetra­methyl­ethyl­enedi­ammonium tetra­thio­tungstate

The title complexes, (C₃H₁₂N₂)[WS₄] and (C₆H₁₈N₂)[WS₄], contain tetrahedral [WS₄]^2- dianions, which accept a complex series of hydrogen bonds from the organic dications. The strength and number of these hydrogen bonds affect the W-S distances.

S1. Comment

The sulfur complexes of the group VI metals Mo (Coucouvanis, 1998) and W (Shibahara, 1993) are a unique class of compounds, encompassing an unusually wide range of metal:sulfur stoichiometries, metal oxidation states, coordination geometries and bonding modes of the sulfide ligands. The tetrahedral [MS₄]²⁻ (M = Mo or W) complexes are routinely used as the starting material for the preparation of a variety of structurally diverse di-, tri- and tetra-nuclear M/S complexes. The flexibility of the [MS₄]²⁻ unit is evidenced by its occurrence in different structural environments, as seen in the complexes [Ni(en)₃][MoS₄] (en is 1,2-diaminoethane) (Ellermeier et al., 1999a), [Co₂(tren)₃][MoS₄]₂ (tren is tris(2-aminoethyl)amine) (Ellermeier & Bensch, 2001a), [Mn(dien)₂][MoS₄] (dien is diethylenetriamine) (Ellermeier & Bensch, 2002), [Ni(tren)₂][WS₄] (Ellermeier et al., 2002), [W(WS₄)₂]²⁻ (Bhaduri & Ibers 1986), [SW(WS₄)₂]²⁻, (Müller et al., 1981 and references therein), [(W₂S₄)(WS₄)₂]²⁻ (Secheresse et al., 1982) and [Ni(WS₄)₂]²⁻ (Müller & Diemann, 1971). The reactivity of [MS₄]²⁻ towards several organic substrates, such as dibenzyl trisulfide (Simhon et al., 1981), diphenyl disulfide (Pan et al., 1984), 1,1-dithiolate disulfide (McConnachie & Stiefel, 1999) and alkyl halides (Dhar & Chandrasekaran, 1989), has been investigated. However, the reactions of [MS₄]²⁻ with organic amines have not been studied in detail (Srinivasan et al., 2001). These investigations are especially important in view of the accessibility of novel metal sulfide complexes under mild solvothermal conditions using organic amines (Ellermeier et al., 1999b, 2002; Ellermeier & Bensch, 2001b, 2002). In addition, it was reported that piperidinium tetrathiotungstate (Dhar & Chandrasekaran, 1989) and benzyltriethylammonium tetrathiomolybdate can be used as sulfur transfer reagents in organic synthesis for the formation of novel organo-sulfur compounds under mild reaction conditions (Prabhu et al., 2000). In continuation of our recent report on the structure determination of (enH₂)[WS₄] (Srinivasan et al., 2002), we have structurally characterized two new [WS₄]²⁻ complexes by reacting (NH₄)₂[WS₄] with two different diamines. The two amines, 1,3-propanediamine (1,3-pn) and N,N,N',N'-tetramethylethylenediamine (tmen), have different steric bulk and different numbers of potential H-bonding donors. Both diamines readily afford the corresponding organic diammonium salts of [WS₄]²⁻, (I) and (II), respectively, in good yields.

Compound (I) contains discrete (1,3-pnH₂)²⁺ dications and [WS₄]²⁻ anions (Fig. 1). The WS₄ tetrahedron is very slightly distorted with S—W—S angles between 108.04 (5) and 110.37 (5)°. The W—S bond lengths range from 2.1798 (12) to 2.1946 (10) Å (Table 1). All structural parameters of (I) are in good agreement with those reported for (enH₂)[WS₄]. Taking into account the estimated standard deviations, the W—S bond distances in (I) are in the range reported for (NH₄)₂[WS₄] (Lapasset et al.,1976). The cation and the anion are connected via hydrogen bonding. The differing W—S bond distances may be due to the different number and strengths of hydrogen-bonding contacts between the H atoms attached to the N atoms of the cation and the S atoms. Seven short intermolecular S···H contacts are observed with N···S distances ranging from 3.277 (4) to 3.458 (4) Å and N—H···S angles ranging from 124 to 169° (Fig. 1, Table 2). The atom S3 has one short contact, while the other S atoms have two short contacts each. The W—S bond length tends to be longer when the S···H contacts are shorter and the N—H···S angles are more linear (Table 2).

Compound (II) is composed of discrete [WS₄]²⁻ anions and (tmenH₂)²⁺ cations (Fig. 2). The S—W—S bond angles are nearly identical, with values ranging from 109.13 (5) to 109.85 (6)°, while the W—S bond lengths vary from 2.1772 (13) to 2.1995 (13) Å (Table 3). These structural parameters are in good agreement with those reported for the above-mentioned complexes and those observed in (I). Considering the estimated standard deviations, the W—S3 distance of 2.1995 (13) Å is in the range of the longest W—S distance of 2.1946 (10) Å found in (I). In view of the lower number of donor H atoms in (II) compared with (I), only four short intermolecular N—H···S contacts are observed (Table 4). The S3 atom is involved in two short contacts, while the S1 and S4 atoms have only one such contact. This feature is responsible for the presence of the short bond distance of 2.1771 (13) Å (W—S2) and the long distance of 2.1995 (13) Å (W—S3). Note that for [Ni(tren)₂][WS₄] (Ellermeier et al., 2002), which has an extended hydrogen-bond network, a very short W—S bond of 2.1580 (10) Å and a long bond of 2.212 (9) Å were reported. The N—H···S angles in (II) range from 131 to 143° (Table 4, Fig. 2). Because (I) and (II) contain different numbers of hydrogen bonds, different structures are generated, viz. a three-dimensional network in (I) and isolated groups consisting of two cations and two anions in (II) (compare Figs. 1 and 2). Further studies employing differently substituted amines are in progress in order to understand the influence of the alkyl groups attached to the N atom of the amine on the W—S bond distances.

S2. Experimental

(NH₄)₂[WS₄] (348 mg, 1 mmol) was dissolved in distilled water (10 ml) and the solution was filtered. The organic diamine 1,3-pn (0.3 ml) was added to the clear yellow filtrate, and the reaction mixture was left undisturbed in a 100 ml glass beaker in the refrigerator. After a day, well formed crystals of (I) separated. The crystals were filtered off, washed with cold water (5 ml) followed by 2-propanol (5 ml) and diethylether (99 ml), and air-dried. The yield was 65%. The use of tmen (0.4 ml) instead of 1,3-pn in the above reaction resulted in the formation of (II), with 60% yield. Both complexes are stable in air.

S3. Refinement

The H atoms bound to C atoms in each structure, as well as the H atoms bound to N atoms in (II), were positioned with idealized geometry (C—H = 0.96–0.97 Å; N—H = 0.91 Å) and constrained to ride on their parent atoms with U_iso(H) = 1.5U_eq(C) for the methyl H atoms and 1.2U_eq(parent atom) for the other H atoms. The positions of the N—H H atoms for (I) were idealized with N—H = 0.89 Å, then refined as rigid groups allowed to rotate but not tip with U_iso(H) = 1.5U_eq(N). The largest peak in the residual electron- density map for (I) (1.540 e Å⁻³) is located 0.84 Å from W1.

Computing details

For both compounds, data collection: DIF4 (STOE & Cie, 1998a); cell refinement: DIF4; data reduction: REDU4 (STOE & Cie, 1998b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL (Bruker, 1998).

Figures

	Fig. 1. (Top) A view of (I) showing the atom labelling and displacement ellipsoids drawn at the 50% probability level. (Bottom) the crystal packing viewed along the a axis. Dashed lines indicate hydrogen bonding.
	Fig. 2. : (Top) A view of (II) showing the atom labelling and displacement ellipsoids drawn at the 50% probability level. (Bottom) The crystal packing viewed along the crystallographic b axis. Dashed lines indicate hydrogen bonding.

(I) 1,3-propanediammonium tetrathiotungstate

Crystal data

(C3H12N2)[WS4]	F(000) = 728
Mr = 388.24	Dx = 2.402 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 94 reflections
a = 10.801 (2) Å	θ = 15.5–19°
b = 10.609 (2) Å	µ = 11.48 mm^−1
c = 10.774 (2) Å	T = 293 K
β = 119.60 (3)°	Block, yellow
V = 1073.5 (5) Å^3	0.11 × 0.10 × 0.08 mm
Z = 4

Data collection

STOE AED-II 4-circle diffractometer	2663 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
Graphite monochromator	θmax = 30.0°, θmin = 2.2°
ω–θ scans	h = −15→13
Absorption correction: numerical X-SHAPE (STOE & CIE, 1998)	k = −2→14
Tmin = 0.291, Tmax = 0.401	l = −1→15
4124 measured reflections	4 standard reflections every 120 min
3126 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.061	w = 1/[σ^2(Fo^2) + (0.0336P)^2 + 0.5352P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3126 reflections	Δρmax = 1.54 e Å^−3
94 parameters	Δρmin = −1.84 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0024 (2)

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
W1	0.256264 (14)	0.144131 (14)	0.514337 (14)	0.02592 (6)
S1	0.38411 (11)	0.31407 (10)	0.54493 (11)	0.0333 (2)
S2	0.26467 (12)	0.02225 (11)	0.35419 (11)	0.0372 (2)
S3	0.34737 (13)	0.04433 (10)	0.71747 (11)	0.0394 (2)
S4	0.03576 (11)	0.19875 (12)	0.44510 (15)	0.0471 (3)
N1	0.4379 (4)	0.7960 (3)	0.6059 (4)	0.0349 (7)
H1N1	0.4958	0.7514	0.5860	0.052*
H2N1	0.4858	0.8231	0.6957	0.052*
H3N1	0.4044	0.8618	0.5472	0.052*
C1	0.3169 (5)	0.7150 (5)	0.5871 (5)	0.0391 (9)
H1A	0.2436	0.7671	0.5879	0.047*
H1B	0.3499	0.6558	0.6657	0.047*
C2	0.2556 (5)	0.6437 (4)	0.4480 (5)	0.0386 (9)
H2A	0.3300	0.5940	0.4460	0.046*
H2B	0.2200	0.7032	0.3694	0.046*
C3	0.1355 (5)	0.5575 (4)	0.4293 (5)	0.0422 (9)
H3A	0.1665	0.5076	0.5151	0.051*
H3B	0.0546	0.6079	0.4152	0.051*
N2	0.0918 (4)	0.4723 (3)	0.3052 (4)	0.0407 (8)
H1N2	0.0256	0.5100	0.2264	0.061*
H2N2	0.0565	0.4013	0.3193	0.061*
H3N2	0.1670	0.4544	0.2954	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.02503 (8)	0.02638 (9)	0.02849 (8)	0.00060 (5)	0.01486 (6)	−0.00099 (5)
S1	0.0337 (5)	0.0317 (5)	0.0357 (4)	−0.0038 (4)	0.0181 (4)	0.0016 (4)
S2	0.0386 (5)	0.0418 (5)	0.0327 (4)	0.0037 (4)	0.0187 (4)	−0.0057 (4)
S3	0.0556 (6)	0.0333 (5)	0.0353 (5)	0.0005 (4)	0.0270 (5)	0.0030 (4)
S4	0.0271 (5)	0.0481 (7)	0.0673 (7)	0.0011 (5)	0.0244 (5)	−0.0126 (6)
N1	0.0333 (16)	0.0349 (17)	0.0370 (17)	0.0037 (14)	0.0179 (13)	−0.0012 (14)
C1	0.036 (2)	0.043 (2)	0.047 (2)	−0.0040 (18)	0.0270 (18)	−0.0049 (18)
C2	0.041 (2)	0.035 (2)	0.042 (2)	−0.0068 (17)	0.0216 (18)	−0.0039 (17)
C3	0.037 (2)	0.040 (2)	0.052 (2)	−0.0003 (19)	0.0238 (19)	−0.0028 (19)
N2	0.0312 (17)	0.0330 (18)	0.050 (2)	0.0008 (14)	0.0144 (15)	0.0031 (15)

Geometric parameters (Å, º)

W1—S3	2.1798 (12)	C1—H1B	0.9700
W1—S4	2.1931 (12)	C2—C3	1.517 (6)
W1—S2	2.1936 (10)	C2—H2A	0.9700
W1—S1	2.1946 (10)	C2—H2B	0.9700
N1—C1	1.492 (5)	C3—N2	1.485 (6)
N1—H1N1	0.8900	C3—H3A	0.9700
N1—H2N1	0.8900	C3—H3B	0.9700
N1—H3N1	0.8900	N2—H1N2	0.8900
C1—C2	1.508 (6)	N2—H2N2	0.8900
C1—H1A	0.9700	N2—H3N2	0.8900
S3—W1—S4	110.22 (6)	C1—C2—C3	111.2 (4)
S3—W1—S2	109.26 (4)	C1—C2—H2A	109.4
S4—W1—S2	110.37 (5)	C3—C2—H2A	109.4
S3—W1—S1	108.04 (5)	C1—C2—H2B	109.4
S4—W1—S1	109.33 (5)	C3—C2—H2B	109.4
S2—W1—S1	109.57 (4)	H2A—C2—H2B	108.0
C1—N1—H1N1	109.5	N2—C3—C2	111.0 (4)
C1—N1—H2N1	109.5	N2—C3—H3A	109.4
H1N1—N1—H2N1	109.5	C2—C3—H3A	109.4
C1—N1—H3N1	109.5	N2—C3—H3B	109.4
H1N1—N1—H3N1	109.5	C2—C3—H3B	109.4
H2N1—N1—H3N1	109.5	H3A—C3—H3B	108.0
N1—C1—C2	110.4 (3)	C3—N2—H1N2	109.5
N1—C1—H1A	109.6	C3—N2—H2N2	109.5
C2—C1—H1A	109.6	H1N2—N2—H2N2	109.5
N1—C1—H1B	109.6	C3—N2—H3N2	109.5
C2—C1—H1B	109.6	H1N2—N2—H3N2	109.5
H1A—C1—H1B	108.1	H2N2—N2—H3N2	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1^i	0.89	2.44	3.284 (3)	158
N1—H2N1···S1^ii	0.89	2.43	3.277 (4)	159
N1—H3N1···S2^iii	0.89	2.53	3.407 (4)	169
N2—H1N2···S4^iv	0.89	2.58	3.357 (4)	146
N2—H1N2···S2^iv	0.89	2.81	3.394 (4)	124
N2—H2N2···S4	0.89	2.61	3.458 (4)	160
N2—H3N2···S3^v	0.89	2.47	3.335 (4)	163

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

(II) N,N,N',N'-tetramethylethylenediammonium tetrathiotungstate

Crystal data

(C6H18N2)[WS4]	F(000) = 824
Mr = 430.31	Dx = 2.054 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 116 reflections
a = 8.5916 (11) Å	θ = 15–18.5°
b = 12.3365 (10) Å	µ = 8.87 mm^−1
c = 13.3799 (9) Å	T = 293 K
β = 101.113 (8)°	Block, orange
V = 1391.5 (2) Å^3	0.14 × 0.09 × 0.07 mm
Z = 4

Data collection

Phillips PW-1100 4-circle diffractometer	2725 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 28.0°, θmin = 2.6°
ω–θ scans	h = −1→11
Absorption correction: numerical X-SHAPE (STOE & CIE, 1998)	k = −16→3
Tmin = 0.390, Tmax = 0.541	l = −17→17
4851 measured reflections	4 standard reflections every 120 min
3363 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.069	w = 1/[σ^2(Fo^2) + (0.0323P)^2 + 1.5856P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
3363 reflections	Δρmax = 0.99 e Å^−3
119 parameters	Δρmin = −2.09 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0064 (3)

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
W1	0.72870 (2)	0.739699 (14)	0.523771 (13)	0.02625 (8)
S1	0.54564 (16)	0.80789 (12)	0.59831 (11)	0.0406 (3)
S2	0.94375 (16)	0.83676 (12)	0.56076 (11)	0.0429 (3)
S3	0.77895 (17)	0.57189 (11)	0.57564 (12)	0.0419 (3)
S4	0.64288 (17)	0.74008 (10)	0.35840 (10)	0.0366 (3)
C1	0.7826 (7)	0.5689 (5)	0.8550 (6)	0.0559 (17)
H1A	0.7638	0.5041	0.8147	0.084*
H1B	0.7669	0.5541	0.9228	0.084*
H1C	0.8895	0.5929	0.8574	0.084*
C2	0.6967 (8)	0.7567 (4)	0.8691 (6)	0.0501 (15)
H2A	0.6235	0.8111	0.8375	0.075*
H2B	0.8033	0.7814	0.8719	0.075*
H2C	0.6801	0.7432	0.9369	0.075*
N1	0.6704 (5)	0.6547 (3)	0.8085 (3)	0.0316 (8)
H1N1	0.6907	0.6691	0.7456	0.038*
C3	0.4999 (6)	0.6205 (4)	0.7953 (4)	0.0356 (11)
H3A	0.4318	0.6819	0.7726	0.043*
H3B	0.4780	0.5964	0.8602	0.043*
C4	0.4635 (5)	0.5295 (4)	0.7181 (4)	0.0301 (9)
H4A	0.5140	0.5449	0.6608	0.036*
H4B	0.5076	0.4624	0.7490	0.036*
N2	0.2894 (5)	0.5155 (3)	0.6805 (3)	0.0306 (9)
H1N2	0.2788	0.4602	0.6347	0.037*
C5	0.2041 (7)	0.4804 (5)	0.7622 (5)	0.0466 (14)
H5A	0.2564	0.4184	0.7967	0.070*
H5B	0.0966	0.4619	0.7324	0.070*
H5C	0.2044	0.5385	0.8100	0.070*
C6	0.2125 (7)	0.6114 (5)	0.6241 (4)	0.0433 (13)
H6A	0.1012	0.5976	0.6021	0.065*
H6B	0.2597	0.6247	0.5658	0.065*
H6C	0.2270	0.6737	0.6679	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.02458 (11)	0.03050 (11)	0.02479 (11)	−0.00126 (7)	0.00754 (7)	−0.00037 (7)
S1	0.0360 (7)	0.0468 (7)	0.0434 (8)	0.0044 (5)	0.0188 (6)	−0.0037 (6)
S2	0.0326 (7)	0.0505 (8)	0.0456 (8)	−0.0117 (6)	0.0078 (6)	−0.0103 (6)
S3	0.0421 (7)	0.0372 (7)	0.0492 (8)	0.0078 (5)	0.0157 (6)	0.0125 (6)
S4	0.0449 (7)	0.0378 (6)	0.0262 (6)	−0.0028 (5)	0.0045 (5)	−0.0013 (5)
C1	0.038 (3)	0.048 (3)	0.074 (5)	0.001 (3)	−0.008 (3)	0.008 (3)
C2	0.043 (3)	0.045 (3)	0.059 (4)	−0.012 (2)	0.002 (3)	−0.015 (3)
N1	0.026 (2)	0.038 (2)	0.029 (2)	−0.0035 (16)	0.0032 (16)	0.0000 (17)
C3	0.027 (2)	0.047 (3)	0.034 (3)	−0.003 (2)	0.007 (2)	−0.010 (2)
C4	0.023 (2)	0.033 (2)	0.034 (3)	−0.0006 (17)	0.0052 (18)	−0.0028 (19)
N2	0.023 (2)	0.0307 (19)	0.037 (2)	−0.0040 (15)	0.0035 (16)	−0.0082 (16)
C5	0.038 (3)	0.042 (3)	0.066 (4)	−0.005 (2)	0.023 (3)	0.001 (3)
C6	0.038 (3)	0.048 (3)	0.038 (3)	0.002 (2)	−0.008 (2)	0.003 (2)

Geometric parameters (Å, º)

W1—S2	2.1772 (13)	C3—H3A	0.9700
W1—S1	2.1864 (13)	C3—H3B	0.9700
W1—S4	2.1932 (13)	C4—N2	1.493 (6)
W1—S3	2.1995 (13)	C4—H4A	0.9700
C1—N1	1.485 (7)	C4—H4B	0.9700
C1—H1A	0.9600	N2—C6	1.487 (6)
C1—H1B	0.9600	N2—C5	1.492 (7)
C1—H1C	0.9600	N2—H1N2	0.9100
C2—N1	1.490 (6)	C5—H5A	0.9600
C2—H2A	0.9600	C5—H5B	0.9600
C2—H2B	0.9600	C5—H5C	0.9600
C2—H2C	0.9600	C6—H6A	0.9600
N1—C3	1.502 (6)	C6—H6B	0.9600
N1—H1N1	0.9100	C6—H6C	0.9600
C3—C4	1.516 (6)
S2—W1—S1	109.77 (5)	N1—C3—H3B	109.5
S2—W1—S4	109.49 (5)	C4—C3—H3B	109.5
S1—W1—S4	109.14 (5)	H3A—C3—H3B	108.0
S2—W1—S3	109.85 (6)	N2—C4—C3	112.1 (4)
S1—W1—S3	109.45 (5)	N2—C4—H4A	109.2
S4—W1—S3	109.13 (5)	C3—C4—H4A	109.2
N1—C1—H1A	109.5	N2—C4—H4B	109.2
N1—C1—H1B	109.5	C3—C4—H4B	109.2
H1A—C1—H1B	109.5	H4A—C4—H4B	107.9
N1—C1—H1C	109.5	C6—N2—C5	111.7 (4)
H1A—C1—H1C	109.5	C6—N2—C4	113.4 (4)
H1B—C1—H1C	109.5	C5—N2—C4	112.9 (4)
N1—C2—H2A	109.5	C6—N2—H1N2	106.1
N1—C2—H2B	109.5	C5—N2—H1N2	106.1
H2A—C2—H2B	109.5	C4—N2—H1N2	106.1
N1—C2—H2C	109.5	N2—C5—H5A	109.5
H2A—C2—H2C	109.5	N2—C5—H5B	109.5
H2B—C2—H2C	109.5	H5A—C5—H5B	109.5
C1—N1—C2	110.9 (5)	N2—C5—H5C	109.5
C1—N1—C3	112.9 (4)	H5A—C5—H5C	109.5
C2—N1—C3	110.1 (4)	H5B—C5—H5C	109.5
C1—N1—H1N1	107.6	N2—C6—H6A	109.5
C2—N1—H1N1	107.6	N2—C6—H6B	109.5
C3—N1—H1N1	107.6	H6A—C6—H6B	109.5
N1—C3—C4	110.9 (4)	N2—C6—H6C	109.5
N1—C3—H3A	109.5	H6A—C6—H6C	109.5
C4—C3—H3A	109.5	H6B—C6—H6C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1	0.91	2.72	3.387 (4)	131
N1—H1N1···S3	0.91	2.80	3.570 (4)	143
N2—H1N2···S4^i	0.91	2.56	3.266 (4)	135
N2—H1N2···S3^i	0.91	2.79	3.533 (4)	140

Symmetry code: (i) −x+1, −y+1, −z+1.