Crystal structure of N′-[bis­­(ethyl­sulfan­yl)methyl­­idene]-2-hy­dr­oxy-4-meth­­oxy­benzohydrazide

In the title compound, C₁₃H₁₈N₂O₃S₂, the amide group is in the plane of the ­benzoyl ring with a C—N—N—C torsion angle of 177.63 (12)°. The two di­thio­ate groups are in an anti conformation [torsion angles = 173.68 (8) and −9.98 (10)°]. An intra­molecular N—H⋯O hydrogen bond is observed. In the crystal, an O—H⋯O hydrogen bond and a weak C—H⋯O contact involving the same acceptor atom generate an S(6) ring motif and give rise to chains along [010].

1. Related literature

For S-alk­yl/aryl esters of di­thio­carbaza­tes that form metal complexes, see: Ali et al. (2008); Singh et al. (2010, 2012). For their biological properties, see: Bharti et al. (2000). For cyclization of potassium salts of N-(aro­yl)hydrazine carbodi­thio­ates, see: Singh et al. (2008, 2009); Bharty et al. (2012). For bidentate, tridentate and multidentate esters, see: Wang et al. (2002); Tarafder et al. (2000); Ali et al. (2001). For related structures, see: Jasinski et al. (2010); Butcher et al. (2007); Tayamon et al. (2012).

2. Experimental

2.1. Crystal data

• C₁₃H₁₈N₂O₃S₂

• M_r = 314.41

• Monoclinic, P 2₁ /n

• a = 8.479 (2) Å

• b = 12.894 (3) Å

• c = 13.843 (3) Å

• β = 104.156 (10)°

• V = 1467.5 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.37 mm⁻¹

• T = 293 K

• 0.2 × 0.2 × 0.2 mm

2.2. Data collection

• Rigaku Mercury 375R diffractometer

• Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) T_min = 0.938, T_max = 1.000

• 12952 measured reflections

• 2685 independent reflections

• 2530 reflections with I > 2σ(I)

• R_int = 0.027

2.3. Refinement

• R[F² > 2σ(F²)] = 0.029

• wR(F²) = 0.077

• S = 1.08

• 2685 reflections

• 192 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.28 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O3^i	0.82 (2)	1.80 (2)	2.6118 (15)	177 (2)
N1—H1A⋯O2	0.836 (19)	1.957 (19)	2.6384 (16)	137.9 (17)
C3—H3A⋯O3^i	0.93	2.52	3.1975 (18)	130
Symmetry code: (i) .

Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

S1. Comment

Nitro­gen-sulfur donor chelating agents such as di­thio­carbaza­tes and their S-alkyl/aryl esters have shown inter­esting biological properties (Bharti et al. (2000). They form large number of metal complexes with novel structural features (Ali et al., 2008; Singh et al., 2010; Singh et al., 2012). The S-alkyl/aryl esters derived from potassium salts of N-aroylhydrazine carbodi­thio­ates have been found to be more stable towardscyclization (Singh et al., 2008) and form 1,3,4-oxa­diazole-2-thio­nes in the presence of acid or base (Singh et al., 2009; Bharty et al., 2012). The above esters behave as bidentate, tridentate or multidentate chelating agents with hetero donor atoms (Wang et al., 2002; Tarafder et al., 2000; Ali et al., 2001). In view of the importance of the title compound, (I), herein we report its synthesis and crystal structure.

In the title compound, C₁₃H₁₈N₂O₃S₂, the sum of the angles around C9 (120.0°) and the S1/C9/S2 bond angle of 117.94 (8)° indicate a nearly planar sp² hybridized carbon atom (Fig. 2). The amide group is in plane to the benzoyl ring with a C8—N1—N2—C9 torsion angle of 177.63 (12)°, in contrast to the values in related structures (Jasinski et al. (2010); Butcher et al. (2007); Tayamon et al. (2012)). The two di­ethyl di­thio­ate groups are in an anti conformation with respect to each other, as reflected by torsion angles C10/S1/C9/S2 of 173.68 (8)° and S1/C9/S2/C12 of – 9.98 (10)°. The N2 atom in the amide linkage possesses distorted tetra­hedral geometry (C9/N2/N1 = 116.59 (12)° while the N1 atom is almost planar (sum of bond angles 359.6°). The C8—N1 and C9—N2 bond lengths (1.3448 (18) Å and 1.2837 (18) Å) lie between typical C–N and C═N values owing to the extensive delocalization of π electron density over the C9/N2/N1/C8 linkage.

In the crystal, an inter­molecular O2–H2A···O3 hydrogen bond and weak inter­molecular C3–H3A···O3 contact in bifurcated bonding arrangement (Fig. 3) generate an S(6) ring motif (Table 1). Intra­molecular N1–H1A···O2 hydrogen bonds are also observed.

S2. Experimental

Potassium 2-(2-hy­droxy-4-meth­oxy­benzoyl)­hydrazinecarbodi­thio­ate was prepared by adding carbon di­sulfide (20.0 mmol, 1.50 mL) to a solution of 4-meth­oxy­salicylic acid hydrazide (20.0 mmol, 3.65 g) and potassium hydroxide (20.0 mmol, 1.12 g) in ethanol (30 mL), then stirring the reaction mixture for 2 h (Fig. 1). The solid separated was filtered off, washed with ethanol and dried in vacuo. Ethyl iodide (20.0 mmol, 1.60 mL) was added drop-wise to a suspension of potassium 2-(2-hy­droxy-4-meth­oxy­benzoyl)­hydrazinecarbodi­thio­ate (10.0 mmol, 2.96 g) in ethanol (20 mL) and stirring the reaction mixture for a period of 3–4 h. The resulting yellow solution was concentrated and acidified with dilute CH₃COOH (20% v/v) which yielded a yellow precipitate, washed with water and dried in vacuo. Yellow crystals of (I) (m.p. 427–429 K), suitable for X-ray analysis were obtained by slow evaporation of the methanol solution over a period of 9–10 days (yield 60%): Anal. Calc. for C₁₃H₁₈N₂O₃S₂ (%): C, 49.61; H, 5.77; N, 8.91; S, 20.40. Found: C, 49.24; H, 5.85; N, 8.86; S, 20.12.

S3. Refinement

The H atoms bonded to N1 and O2 were located in a difference Fourier map and refined freely; N1–H1A = 0.836 (19) Å and O2–H2A = 0.82 (2)Å. Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.97 Å, and with U_iso(H) = 1.2–1.5U_eq(C).

Related literature

For S-alkyl/aryl esters of dithiocarbazates that form metal complexes, see: Ali et al. (2008); Singh et al. (2010, 2012). For their biological properties, see: Bharti et al. (2000). For cyclization of potassium salts of N-(aroyl)hydrazine carbodithioates, see: Singh et al. (2008, 2009); Bharty et al. (2012). For bidentate, tridentate and multidentate esters, see: Wang et al. (2002); Tarafder et al. (2000); Ali et al. (2001). For related structures, see: Jasinski et al. (2010); Butcher et al. (2007); Tayamon et al. (2012).

Structure description

Nitro­gen-sulfur donor chelating agents such as di­thio­carbaza­tes and their S-alkyl/aryl esters have shown inter­esting biological properties (Bharti et al. (2000). They form large number of metal complexes with novel structural features (Ali et al., 2008; Singh et al., 2010; Singh et al., 2012). The S-alkyl/aryl esters derived from potassium salts of N-aroylhydrazine carbodi­thio­ates have been found to be more stable towardscyclization (Singh et al., 2008) and form 1,3,4-oxa­diazole-2-thio­nes in the presence of acid or base (Singh et al., 2009; Bharty et al., 2012). The above esters behave as bidentate, tridentate or multidentate chelating agents with hetero donor atoms (Wang et al., 2002; Tarafder et al., 2000; Ali et al., 2001). In view of the importance of the title compound, (I), herein we report its synthesis and crystal structure.

In the title compound, C₁₃H₁₈N₂O₃S₂, the sum of the angles around C9 (120.0°) and the S1/C9/S2 bond angle of 117.94 (8)° indicate a nearly planar sp² hybridized carbon atom (Fig. 2). The amide group is in plane to the benzoyl ring with a C8—N1—N2—C9 torsion angle of 177.63 (12)°, in contrast to the values in related structures (Jasinski et al. (2010); Butcher et al. (2007); Tayamon et al. (2012)). The two di­ethyl di­thio­ate groups are in an anti conformation with respect to each other, as reflected by torsion angles C10/S1/C9/S2 of 173.68 (8)° and S1/C9/S2/C12 of – 9.98 (10)°. The N2 atom in the amide linkage possesses distorted tetra­hedral geometry (C9/N2/N1 = 116.59 (12)° while the N1 atom is almost planar (sum of bond angles 359.6°). The C8—N1 and C9—N2 bond lengths (1.3448 (18) Å and 1.2837 (18) Å) lie between typical C–N and C═N values owing to the extensive delocalization of π electron density over the C9/N2/N1/C8 linkage.

In the crystal, an inter­molecular O2–H2A···O3 hydrogen bond and weak inter­molecular C3–H3A···O3 contact in bifurcated bonding arrangement (Fig. 3) generate an S(6) ring motif (Table 1). Intra­molecular N1–H1A···O2 hydrogen bonds are also observed.

Potassium 2-(2-hy­droxy-4-meth­oxy­benzoyl)­hydrazinecarbodi­thio­ate was prepared by adding carbon di­sulfide (20.0 mmol, 1.50 mL) to a solution of 4-meth­oxy­salicylic acid hydrazide (20.0 mmol, 3.65 g) and potassium hydroxide (20.0 mmol, 1.12 g) in ethanol (30 mL), then stirring the reaction mixture for 2 h (Fig. 1). The solid separated was filtered off, washed with ethanol and dried in vacuo. Ethyl iodide (20.0 mmol, 1.60 mL) was added drop-wise to a suspension of potassium 2-(2-hy­droxy-4-meth­oxy­benzoyl)­hydrazinecarbodi­thio­ate (10.0 mmol, 2.96 g) in ethanol (20 mL) and stirring the reaction mixture for a period of 3–4 h. The resulting yellow solution was concentrated and acidified with dilute CH₃COOH (20% v/v) which yielded a yellow precipitate, washed with water and dried in vacuo. Yellow crystals of (I) (m.p. 427–429 K), suitable for X-ray analysis were obtained by slow evaporation of the methanol solution over a period of 9–10 days (yield 60%): Anal. Calc. for C₁₃H₁₈N₂O₃S₂ (%): C, 49.61; H, 5.77; N, 8.91; S, 20.40. Found: C, 49.24; H, 5.85; N, 8.86; S, 20.12.

For S-alkyl/aryl esters of dithiocarbazates that form metal complexes, see: Ali et al. (2008); Singh et al. (2010, 2012). For their biological properties, see: Bharti et al. (2000). For cyclization of potassium salts of N-(aroyl)hydrazine carbodithioates, see: Singh et al. (2008, 2009); Bharty et al. (2012). For bidentate, tridentate and multidentate esters, see: Wang et al. (2002); Tarafder et al. (2000); Ali et al. (2001). For related structures, see: Jasinski et al. (2010); Butcher et al. (2007); Tayamon et al. (2012).

Refinement details

The H atoms bonded to N1 and O2 were located in a difference Fourier map and refined freely; N1–H1A = 0.836 (19) Å and O2–H2A = 0.82 (2)Å. Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.97 Å, and with U_iso(H) = 1.2–1.5U_eq(C).

Computing details

Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert (Rigaku, 2011); data reduction: CrystalClear-SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A reaction scheme showing the synthesis of the title compound, C13H18N2O3S2.
	Fig. 2. Molecular structure of the title compound, C13H18N2O3S2, showing 50% probability displacement ellipsoids.
	Fig. 3. Molecular packing of C13H18N2O3S2 viewed along the c-axis. Dashed lines indicate intermolecular hydroxyl O—H···Ocarbonylhydrogen bonds and weak phenyl C—H···Ocarbonyl interactions.

N'-[Bis(ethylsulfanyl)methylidene]-2-hydroxy-4-methoxybenzohydrazide

Crystal data

C13H18N2O3S2	F(000) = 664
Mr = 314.41	Dx = 1.423 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.479 (2) Å	Cell parameters from 4529 reflections
b = 12.894 (3) Å	θ = 3.0–27.5°
c = 13.843 (3) Å	µ = 0.37 mm^−1
β = 104.156 (10)°	T = 293 K
V = 1467.5 (6) Å^3	Prism, colorless
Z = 4	0.2 × 0.2 × 0.2 mm

Data collection

Rigaku Mercury 375R diffractometer	2685 independent reflections
Radiation source: Sealed Tube	2530 reflections with I > 2σ(I)
Detector resolution: 13.6612 pixels mm^-1	Rint = 0.027
ω scans	θmax = 25.3°, θmin = 3.0°
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011)	h = −10→10
Tmin = 0.938, Tmax = 1.000	k = −15→15
12952 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: mixed
wR(F^2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0391P)^2 + 0.8434P] where P = (Fo^2 + 2Fc^2)/3
2685 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. IR (selected, KBr): 3320 [ν(O–H)], 3276 [ν(N–H)], 1634 [ν(C═ O)], 1094 [ν(N–N)], 876 [ν(C═S)] cm^{-1. 1}H NMR (DMSO-d₆); δ [p.p.m.] = 12.26 (s, 1H, OH), 9.77 (s, 1H, NH), 7.80–6.40 (m, 3H, C₆H₃, phenyl), 3.82 (s, 3H, –OCH₃), 3.06 (q, 4H, CH₂), 1.44 (t, 6H, CH₃). ¹³C NMR (DMSO-d₆) δ [p.p.m.] = 168.3 (C4), 163.3 (C8), 162.0 (C2), 157.9 (C9), 132.1 (C6), 128.2 (C5), 106.8 (C3), 55.2 (C7), 27.1 (C10, C12), 14.4 (C11, C13).

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 on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
S1	0.18898 (4)	0.33147 (3)	0.40368 (3)	0.01707 (12)
S2	0.36737 (4)	0.51413 (3)	0.34551 (3)	0.01997 (12)
O1	1.14563 (12)	0.43927 (8)	0.07886 (8)	0.0191 (2)
O2	0.73950 (13)	0.50561 (8)	0.24846 (8)	0.0175 (2)
H2A	0.775 (2)	0.5643 (17)	0.2477 (15)	0.034 (5)*
O3	0.63540 (13)	0.19012 (8)	0.25602 (8)	0.0211 (2)
N1	0.55185 (14)	0.35185 (9)	0.27860 (9)	0.0141 (2)
H1A	0.571 (2)	0.4154 (15)	0.2769 (13)	0.025 (5)*
N2	0.43294 (14)	0.31214 (9)	0.32068 (9)	0.0154 (3)
C1	0.78058 (16)	0.32991 (10)	0.20495 (10)	0.0127 (3)
C2	0.82146 (17)	0.43652 (10)	0.20485 (10)	0.0136 (3)
C3	0.94371 (17)	0.46929 (11)	0.16183 (10)	0.0147 (3)
H3A	0.9696	0.5394	0.1619	0.018*
C4	1.02795 (16)	0.39806 (11)	0.11852 (10)	0.0150 (3)
C5	0.98999 (17)	0.29255 (11)	0.11710 (10)	0.0157 (3)
H5A	1.0459	0.2447	0.0877	0.019*
C6	0.86766 (17)	0.26095 (11)	0.16032 (10)	0.0147 (3)
H6A	0.8423	0.1907	0.1596	0.018*
C7	1.23586 (18)	0.36914 (12)	0.03325 (12)	0.0214 (3)
H7A	1.3118	0.4074	0.0059	0.032*
H7B	1.1626	0.3318	−0.0190	0.032*
H7C	1.2938	0.3211	0.0822	0.032*
C8	0.65227 (16)	0.28531 (11)	0.24849 (10)	0.0139 (3)
C9	0.34330 (17)	0.37829 (11)	0.35163 (10)	0.0145 (3)
C10	0.19836 (17)	0.19372 (11)	0.37997 (11)	0.0173 (3)
H10A	0.1809	0.1812	0.3090	0.021*
H10B	0.3044	0.1666	0.4134	0.021*
C11	0.06688 (18)	0.14095 (12)	0.41920 (11)	0.0220 (3)
H11A	0.0628	0.0687	0.4021	0.033*
H11B	−0.0363	0.1725	0.3900	0.033*
H11C	0.0909	0.1483	0.4903	0.033*
C12	0.19060 (17)	0.56936 (11)	0.37838 (11)	0.0186 (3)
H12A	0.1653	0.6353	0.3444	0.022*
H12B	0.0985	0.5237	0.3543	0.022*
C13	0.2116 (2)	0.58643 (13)	0.48938 (12)	0.0253 (3)
H13A	0.1168	0.6202	0.5006	0.038*
H13B	0.3054	0.6291	0.5146	0.038*
H13C	0.2260	0.5208	0.5231	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0167 (2)	0.01427 (19)	0.0235 (2)	0.00006 (13)	0.01113 (15)	0.00050 (13)
S2	0.0224 (2)	0.01129 (19)	0.0307 (2)	0.00183 (14)	0.01520 (16)	0.00151 (14)
O1	0.0207 (5)	0.0153 (5)	0.0264 (6)	−0.0009 (4)	0.0156 (4)	−0.0009 (4)
O2	0.0195 (5)	0.0094 (5)	0.0276 (6)	−0.0009 (4)	0.0135 (4)	−0.0018 (4)
O3	0.0208 (5)	0.0106 (5)	0.0367 (6)	−0.0004 (4)	0.0161 (5)	0.0010 (4)
N1	0.0136 (6)	0.0098 (6)	0.0214 (6)	−0.0017 (5)	0.0091 (5)	0.0004 (5)
N2	0.0143 (6)	0.0147 (6)	0.0195 (6)	−0.0011 (5)	0.0085 (5)	0.0010 (5)
C1	0.0111 (6)	0.0128 (7)	0.0140 (6)	0.0004 (5)	0.0027 (5)	0.0004 (5)
C2	0.0143 (6)	0.0125 (7)	0.0135 (6)	0.0020 (5)	0.0026 (5)	−0.0002 (5)
C3	0.0171 (7)	0.0112 (6)	0.0160 (7)	−0.0008 (5)	0.0043 (5)	0.0001 (5)
C4	0.0140 (7)	0.0180 (7)	0.0137 (6)	−0.0007 (6)	0.0048 (5)	0.0023 (5)
C5	0.0163 (7)	0.0148 (7)	0.0174 (7)	0.0018 (5)	0.0069 (6)	−0.0019 (5)
C6	0.0167 (7)	0.0102 (6)	0.0173 (7)	0.0000 (5)	0.0044 (5)	−0.0005 (5)
C7	0.0212 (8)	0.0198 (7)	0.0284 (8)	0.0029 (6)	0.0162 (6)	−0.0001 (6)
C8	0.0125 (7)	0.0134 (7)	0.0154 (6)	−0.0001 (5)	0.0024 (5)	−0.0001 (5)
C9	0.0148 (7)	0.0124 (7)	0.0164 (6)	−0.0002 (5)	0.0043 (5)	0.0018 (5)
C10	0.0175 (7)	0.0136 (7)	0.0221 (7)	−0.0015 (6)	0.0073 (6)	−0.0003 (6)
C11	0.0207 (8)	0.0219 (8)	0.0242 (8)	−0.0059 (6)	0.0071 (6)	0.0020 (6)
C12	0.0170 (7)	0.0144 (7)	0.0242 (7)	0.0042 (6)	0.0048 (6)	−0.0018 (6)
C13	0.0302 (9)	0.0225 (8)	0.0259 (8)	−0.0003 (7)	0.0121 (7)	−0.0043 (6)

Geometric parameters (Å, º)

S1—C9	1.7485 (14)	C4—C5	1.397 (2)
S1—C10	1.8115 (15)	C5—C6	1.380 (2)
S2—C9	1.7678 (15)	C5—H5A	0.9300
S2—C12	1.8151 (15)	C6—H6A	0.9300
O1—C4	1.3591 (17)	C7—H7A	0.9600
O1—C7	1.4276 (17)	C7—H7B	0.9600
O2—C2	1.3588 (17)	C7—H7C	0.9600
O2—H2A	0.82 (2)	C10—C11	1.516 (2)
O3—C8	1.2430 (17)	C10—H10A	0.9700
N1—C8	1.3448 (18)	C10—H10B	0.9700
N1—N2	1.3804 (16)	C11—H11A	0.9600
N1—H1A	0.836 (19)	C11—H11B	0.9600
N2—C9	1.2837 (18)	C11—H11C	0.9600
C1—C6	1.3932 (19)	C12—C13	1.519 (2)
C1—C2	1.4176 (19)	C12—H12A	0.9700
C1—C8	1.4827 (19)	C12—H12B	0.9700
C2—C3	1.382 (2)	C13—H13A	0.9600
C3—C4	1.387 (2)	C13—H13B	0.9600
C3—H3A	0.9300	C13—H13C	0.9600
C9—S1—C10	101.15 (7)	H7B—C7—H7C	109.5
C9—S2—C12	105.35 (7)	O3—C8—N1	120.63 (13)
C4—O1—C7	117.17 (11)	O3—C8—C1	121.87 (12)
C2—O2—H2A	111.7 (14)	N1—C8—C1	117.49 (12)
C8—N1—N2	118.51 (12)	N2—C9—S1	118.17 (11)
C8—N1—H1A	118.4 (13)	N2—C9—S2	123.89 (11)
N2—N1—H1A	122.7 (13)	S1—C9—S2	117.94 (8)
C9—N2—N1	116.59 (12)	C11—C10—S1	107.85 (10)
C6—C1—C2	117.53 (12)	C11—C10—H10A	110.1
C6—C1—C8	116.99 (12)	S1—C10—H10A	110.1
C2—C1—C8	125.48 (12)	C11—C10—H10B	110.1
O2—C2—C3	120.66 (12)	S1—C10—H10B	110.1
O2—C2—C1	118.91 (12)	H10A—C10—H10B	108.4
C3—C2—C1	120.42 (13)	C10—C11—H11A	109.5
C2—C3—C4	120.25 (13)	C10—C11—H11B	109.5
C2—C3—H3A	119.9	H11A—C11—H11B	109.5
C4—C3—H3A	119.9	C10—C11—H11C	109.5
O1—C4—C3	114.98 (12)	H11A—C11—H11C	109.5
O1—C4—C5	124.37 (13)	H11B—C11—H11C	109.5
C3—C4—C5	120.65 (13)	C13—C12—S2	114.24 (11)
C6—C5—C4	118.46 (13)	C13—C12—H12A	108.7
C6—C5—H5A	120.8	S2—C12—H12A	108.7
C4—C5—H5A	120.8	C13—C12—H12B	108.7
C5—C6—C1	122.69 (13)	S2—C12—H12B	108.7
C5—C6—H6A	118.7	H12A—C12—H12B	107.6
C1—C6—H6A	118.7	C12—C13—H13A	109.5
O1—C7—H7A	109.5	C12—C13—H13B	109.5
O1—C7—H7B	109.5	H13A—C13—H13B	109.5
H7A—C7—H7B	109.5	C12—C13—H13C	109.5
O1—C7—H7C	109.5	H13A—C13—H13C	109.5
H7A—C7—H7C	109.5	H13B—C13—H13C	109.5
C8—N1—N2—C9	177.63 (12)	C8—C1—C6—C5	179.98 (12)
C6—C1—C2—O2	−179.53 (12)	N2—N1—C8—O3	1.9 (2)
C8—C1—C2—O2	0.6 (2)	N2—N1—C8—C1	−179.09 (11)
C6—C1—C2—C3	−0.1 (2)	C6—C1—C8—O3	8.5 (2)
C8—C1—C2—C3	−179.96 (12)	C2—C1—C8—O3	−171.64 (13)
O2—C2—C3—C4	179.25 (12)	C6—C1—C8—N1	−170.50 (12)
C1—C2—C3—C4	−0.2 (2)	C2—C1—C8—N1	9.4 (2)
C7—O1—C4—C3	−179.94 (12)	N1—N2—C9—S1	179.01 (9)
C7—O1—C4—C5	−0.2 (2)	N1—N2—C9—S2	−1.42 (18)
C2—C3—C4—O1	−179.83 (12)	C10—S1—C9—N2	−6.72 (13)
C2—C3—C4—C5	0.4 (2)	C10—S1—C9—S2	173.68 (8)
O1—C4—C5—C6	179.87 (12)	C12—S2—C9—N2	170.45 (12)
C3—C4—C5—C6	−0.4 (2)	C12—S2—C9—S1	−9.98 (10)
C4—C5—C6—C1	0.1 (2)	C9—S1—C10—C11	−178.68 (10)
C2—C1—C6—C5	0.1 (2)	C9—S2—C12—C13	88.23 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3^i	0.82 (2)	1.80 (2)	2.6118 (15)	177 (2)
N1—H1A···O2	0.836 (19)	1.957 (19)	2.6384 (16)	137.9 (17)
C3—H3A···O3^i	0.93	2.52	3.1975 (18)	130

Symmetry code: (i) −x+3/2, y+1/2, −z+1/2.