Crystal structure of N'-[bis-(ethyl-sulfan-yl)methyl-idene]-2-hy-droxy-4-meth-oxy-benzohydrazide.

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 di-thio-ate groups are in an anti conformation [torsion angles = 173.68 (8) and -9.98 (10)°]. An intra-molecular 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].

Related literature

For S-alk­yl/aryl esters of di­thio­carbaza­tes that form n class="Chemical">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 ▸).

Experimental

Crystal data

C13H18N2O3S2

M = 314.41

Monoclinic,

a = 8.479 (2) Å

b = 12.894 (3) Å

c = 13.843 (3) Å

β = 104.156 (10)°

V = 1467.5 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.37 mm−1

T = 293 K

0.2 × 0.2 × 0.2 mm

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

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.077

S = 1.08

2685 reflections

192 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.27 e Å−3

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.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015021271/jj2195sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015021271/jj2195Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015021271/jj2195Isup3.cml

Click here for additional data file.

13 18 2 3 2 . DOI: 10.1107/S2056989015021271/jj2195fig1.tif

A reaction scheme showing the synthesis of the title compound, C13H18N2O3S2.

Click here for additional data file.

13 18 2 3 2 . DOI: 10.1107/S2056989015021271/jj2195fig2.tif

Mol­ecular structure of the title compound, C13H18N2O3S2, showing 50% probability displacement ellipsoids.

Click here for additional data file.

13 18 2 3 2 c H carbon­yl n class="Chemical">carbon­yl . DOI: 10.1107/S2056989015021271/jj2195fig3.tif

Mol­ecular packing of C13H18N2O3S2 viewed along the n class="Species">c-axis. Dashed lines indicate inter­molecular hydroxyl O—H⋯Ocarbon­ylhydrogen bonds and weak phenyl C—H⋯Ocarbon­yl inter­actions.

CCDC reference: 1431260

Additional supporting information: crystallographic information; 3D view; checkCIF report

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) Å3	Prism, colorless
Z = 4	0.2 × 0.2 × 0.2 mm

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 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)] = 0.029	Hydrogen site location: mixed
wR(F2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0391P)2 + 0.8434P] where P = (Fo2 + 2Fc2)/3
2685 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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. 1H 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.

	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*

	U11	U22	U33	U12	U13	U23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3i	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···O3i	0.93	2.52	3.1975 (18)	130

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O3i	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⋯O3i	0.93	2.52	3.1975 (18)	130

Symmetry code: (i) .