N'-[Bis(benzyl-sulfan-yl)methyl-idene]benzohydrazide.

In the title hydrazonodithio-ate, C(21)H(19)N(3)OS(2), the amide group is twisted out of the plane through the S(2)C=N atoms: the C-N-N-C torsion angle is 139.71 (13)°. The pyridine ring forms dihedral angles of 52.96 (8) and 86.46 (8)° with the phenyl rings, and the latter are approximately orthogonal [dihedral angle = 76.42 (9)°]. Supra-molecular chains sustained by N-H⋯O hydrogen bonds and propagated by glide symmetry along the c axis are found in the crystal structure. The chains are consolidated into a three-dimensional architecture by C-H⋯O and C-H⋯N inter-actions.

Related literature

For background to the coordination chemistry of dithio­carbazate derivatives, see: Tarafder et al. (2002 ▶); Ravoof et al. (2010 ▶). For related syntheses, see: Ali & Tarafder (1977 ▶); Ali et al. (2001 ▶); Manan et al. (2012 ▶). For related structures, see: Jasinski et al. (2010 ▶); Singh et al. (2007 ▶).

Experimental

Crystal data

C21H19N3OS2

M = 393.51

Monoclinic,

a = 11.2593 (4) Å

b = 21.2182 (7) Å

c = 8.6041 (3) Å

β = 103.678 (3)°

V = 1997.24 (12) Å3

Z = 4

Cu Kα radiation

μ = 2.54 mm−1

T = 150 K

0.50 × 0.36 × 0.16 mm

Data collection

Agilent Xcaliber Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.42, T max = 0.67

38338 measured reflections

3867 independent reflections

3715 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.097

S = 1.03

3867 reflections

247 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.32 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812019472/hb6755sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019472/hb6755Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812019472/hb6755Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H19N3OS2	F(000) = 824
Mr = 393.51	Dx = 1.309 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 17900 reflections
a = 11.2593 (4) Å	θ = 4–71°
b = 21.2182 (7) Å	µ = 2.54 mm−1
c = 8.6041 (3) Å	T = 150 K
β = 103.678 (3)°	Block, dark yellow
V = 1997.24 (12) Å3	0.50 × 0.36 × 0.16 mm
Z = 4

Agilent Xcaliber Eos Gemini diffractometer	3867 independent reflections
Radiation source: fine-focus sealed tube	3715 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 16.1952 pixels mm-1	θmax = 71.4°, θmin = 4.0°
ω/2θ scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −24→26
Tmin = 0.42, Tmax = 0.67	l = −10→10
38338 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0631P)2 + 0.6548P] where P = (Fo2 + 2Fc2)/3
3867 reflections	(Δ/σ)max = 0.001
247 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

	x	y	z	Uiso*/Ueq
S1	0.58342 (3)	0.395419 (15)	0.24637 (4)	0.02644 (11)
S2	0.37808 (3)	0.403747 (16)	0.41378 (4)	0.03091 (12)
O1	0.55367 (12)	0.19229 (5)	0.45894 (12)	0.0423 (3)
N1	0.45622 (11)	0.29676 (5)	0.32219 (13)	0.0266 (2)
N2	0.53822 (10)	0.26152 (5)	0.25652 (13)	0.0246 (2)
H2N	0.5455 (15)	0.2700 (8)	0.161 (2)	0.030*
N3	0.82288 (13)	0.08675 (8)	0.1580 (2)	0.0510 (4)
C1	0.47186 (11)	0.35652 (7)	0.32465 (14)	0.0240 (3)
C2	0.58359 (14)	0.47567 (7)	0.32153 (18)	0.0316 (3)
H2A	0.5016	0.4948	0.2845	0.038*
H2B	0.6056	0.4758	0.4399	0.038*
C3	0.67684 (13)	0.51237 (7)	0.25762 (17)	0.0288 (3)
C4	0.64021 (15)	0.55501 (9)	0.1339 (2)	0.0423 (4)
H4	0.5556	0.5605	0.0867	0.051*
C5	0.72615 (19)	0.58997 (10)	0.0779 (2)	0.0525 (5)
H5	0.7001	0.6193	−0.0068	0.063*
C6	0.84883 (17)	0.58206 (9)	0.1453 (2)	0.0465 (4)
H6	0.9076	0.6057	0.1069	0.056*
C7	0.88623 (15)	0.53955 (8)	0.2688 (2)	0.0421 (4)
H7	0.9709	0.5341	0.3155	0.051*
C8	0.80055 (14)	0.50489 (7)	0.32481 (19)	0.0351 (3)
H8	0.8269	0.4758	0.4099	0.042*
C9	0.27606 (13)	0.34592 (7)	0.47123 (17)	0.0297 (3)
H9A	0.3219	0.3063	0.5034	0.036*
H9B	0.2487	0.3620	0.5651	0.036*
C10	0.16574 (13)	0.33186 (7)	0.33872 (17)	0.0308 (3)
C11	0.15710 (15)	0.27626 (9)	0.2525 (2)	0.0469 (4)
H11	0.2216	0.2463	0.2766	0.056*
C12	0.05412 (18)	0.26418 (11)	0.1306 (3)	0.0620 (6)
H12	0.0489	0.2261	0.0712	0.074*
C13	−0.04034 (18)	0.30698 (12)	0.0955 (2)	0.0582 (5)
H13	−0.1102	0.2986	0.0116	0.070*
C14	−0.03337 (18)	0.36186 (10)	0.1820 (2)	0.0555 (5)
H14	−0.0989	0.3912	0.1591	0.067*
C15	0.06947 (16)	0.37429 (8)	0.3028 (2)	0.0441 (4)
H15	0.0741	0.4124	0.3618	0.053*
C16	0.57822 (13)	0.20778 (6)	0.33232 (15)	0.0262 (3)
C17	0.66171 (12)	0.16710 (7)	0.26297 (16)	0.0277 (3)
C18	0.72075 (14)	0.18668 (8)	0.14762 (18)	0.0352 (3)
H18	0.7077	0.2277	0.1026	0.042*
C19	0.79978 (15)	0.14459 (10)	0.0994 (2)	0.0475 (4)
H19	0.8397	0.1581	0.0195	0.057*
C20	0.76652 (16)	0.06886 (9)	0.2706 (2)	0.0489 (4)
H20	0.7824	0.0278	0.3144	0.059*
C21	0.68633 (15)	0.10680 (7)	0.3272 (2)	0.0381 (4)
H21	0.6487	0.0921	0.4082	0.046*

	U11	U22	U33	U12	U13	U23
S1	0.02696 (19)	0.02388 (19)	0.03094 (19)	−0.00467 (12)	0.01177 (14)	−0.00630 (12)
S2	0.0295 (2)	0.02387 (19)	0.0439 (2)	−0.00234 (12)	0.01763 (16)	−0.00832 (13)
O1	0.0760 (9)	0.0293 (6)	0.0282 (5)	0.0116 (5)	0.0256 (5)	0.0044 (4)
N1	0.0300 (6)	0.0239 (6)	0.0292 (6)	0.0011 (4)	0.0134 (5)	−0.0024 (4)
N2	0.0309 (6)	0.0230 (6)	0.0232 (5)	0.0012 (4)	0.0129 (4)	−0.0005 (4)
N3	0.0308 (7)	0.0560 (10)	0.0626 (10)	0.0119 (7)	0.0037 (7)	−0.0243 (8)
C1	0.0233 (6)	0.0253 (7)	0.0238 (6)	−0.0008 (5)	0.0067 (5)	−0.0035 (5)
C2	0.0332 (7)	0.0232 (7)	0.0420 (8)	−0.0061 (5)	0.0159 (6)	−0.0090 (6)
C3	0.0312 (7)	0.0242 (7)	0.0328 (7)	−0.0057 (5)	0.0115 (6)	−0.0065 (5)
C4	0.0343 (8)	0.0482 (10)	0.0408 (8)	−0.0068 (7)	0.0017 (6)	0.0066 (7)
C5	0.0559 (11)	0.0585 (12)	0.0407 (9)	−0.0109 (9)	0.0067 (8)	0.0181 (8)
C6	0.0450 (9)	0.0502 (10)	0.0493 (9)	−0.0164 (8)	0.0213 (8)	0.0037 (8)
C7	0.0292 (8)	0.0413 (9)	0.0567 (10)	−0.0062 (7)	0.0123 (7)	0.0017 (7)
C8	0.0325 (8)	0.0301 (8)	0.0432 (8)	−0.0020 (6)	0.0096 (6)	0.0034 (6)
C9	0.0297 (7)	0.0292 (7)	0.0340 (7)	−0.0023 (5)	0.0153 (6)	−0.0026 (6)
C10	0.0312 (7)	0.0316 (7)	0.0339 (7)	−0.0053 (6)	0.0166 (6)	−0.0028 (6)
C11	0.0328 (8)	0.0466 (10)	0.0657 (11)	−0.0076 (7)	0.0207 (8)	−0.0230 (9)
C12	0.0445 (10)	0.0750 (14)	0.0714 (13)	−0.0194 (10)	0.0237 (9)	−0.0421 (11)
C13	0.0388 (10)	0.0868 (15)	0.0471 (10)	−0.0165 (10)	0.0069 (8)	−0.0133 (10)
C14	0.0430 (10)	0.0600 (12)	0.0576 (11)	0.0036 (9)	0.0004 (8)	0.0024 (9)
C15	0.0433 (9)	0.0379 (9)	0.0487 (9)	0.0024 (7)	0.0058 (7)	−0.0035 (7)
C16	0.0341 (7)	0.0230 (7)	0.0217 (6)	−0.0012 (5)	0.0071 (5)	−0.0037 (5)
C17	0.0261 (7)	0.0296 (7)	0.0246 (6)	0.0005 (5)	0.0006 (5)	−0.0084 (5)
C18	0.0296 (7)	0.0448 (9)	0.0314 (7)	0.0052 (6)	0.0073 (6)	−0.0037 (6)
C19	0.0301 (8)	0.0687 (12)	0.0451 (9)	0.0065 (8)	0.0116 (7)	−0.0148 (9)
C20	0.0382 (9)	0.0370 (9)	0.0662 (11)	0.0098 (7)	0.0018 (8)	−0.0138 (8)
C21	0.0374 (8)	0.0283 (8)	0.0465 (9)	0.0024 (6)	0.0059 (7)	−0.0062 (6)

S1—C1	1.7643 (13)	C8—H8	0.9500
S1—C2	1.8213 (14)	C9—C10	1.504 (2)
S2—C1	1.7579 (13)	C9—H9A	0.9900
S2—C9	1.8270 (14)	C9—H9B	0.9900
O1—C16	1.2304 (17)	C10—C11	1.385 (2)
N1—C1	1.2795 (18)	C10—C15	1.387 (2)
N1—N2	1.4063 (15)	C11—C12	1.391 (3)
N2—C16	1.3376 (18)	C11—H11	0.9500
N2—H2N	0.867 (18)	C12—C13	1.377 (3)
N3—C20	1.333 (3)	C12—H12	0.9500
N3—C19	1.329 (3)	C13—C14	1.374 (3)
C2—C3	1.5113 (19)	C13—H13	0.9500
C2—H2A	0.9900	C14—C15	1.386 (3)
C2—H2B	0.9900	C14—H14	0.9500
C3—C8	1.385 (2)	C15—H15	0.9500
C3—C4	1.384 (2)	C16—C17	1.5001 (18)
C4—C5	1.392 (2)	C17—C18	1.383 (2)
C4—H4	0.9500	C17—C21	1.395 (2)
C5—C6	1.376 (3)	C18—C19	1.391 (2)
C5—H5	0.9500	C18—H18	0.9500
C6—C7	1.382 (3)	C19—H19	0.9500
C6—H6	0.9500	C20—C21	1.381 (2)
C7—C8	1.387 (2)	C20—H20	0.9500
C7—H7	0.9500	C21—H21	0.9500
C1—S1—C2	104.06 (6)	S2—C9—H9B	109.0
C1—S2—C9	102.48 (7)	H9A—C9—H9B	107.8
C1—N1—N2	115.64 (11)	C11—C10—C15	118.79 (15)
C16—N2—N1	115.76 (11)	C11—C10—C9	121.06 (14)
C16—N2—H2N	123.0 (12)	C15—C10—C9	120.14 (14)
N1—N2—H2N	119.4 (11)	C10—C11—C12	120.09 (18)
C20—N3—C19	117.05 (15)	C10—C11—H11	120.0
N1—C1—S2	118.53 (10)	C12—C11—H11	120.0
N1—C1—S1	124.39 (10)	C13—C12—C11	120.47 (18)
S2—C1—S1	117.07 (8)	C13—C12—H12	119.8
C3—C2—S1	107.16 (9)	C11—C12—H12	119.8
C3—C2—H2A	110.3	C12—C13—C14	119.84 (18)
S1—C2—H2A	110.3	C12—C13—H13	120.1
C3—C2—H2B	110.3	C14—C13—H13	120.1
S1—C2—H2B	110.3	C13—C14—C15	119.87 (19)
H2A—C2—H2B	108.5	C13—C14—H14	120.1
C8—C3—C4	118.91 (14)	C15—C14—H14	120.1
C8—C3—C2	120.38 (13)	C14—C15—C10	120.92 (17)
C4—C3—C2	120.69 (13)	C14—C15—H15	119.5
C3—C4—C5	120.62 (16)	C10—C15—H15	119.5
C3—C4—H4	119.7	O1—C16—N2	122.64 (13)
C5—C4—H4	119.7	O1—C16—C17	119.44 (12)
C6—C5—C4	119.99 (16)	N2—C16—C17	117.84 (12)
C6—C5—H5	120.0	C18—C17—C21	118.39 (14)
C4—C5—H5	120.0	C18—C17—C16	124.44 (13)
C5—C6—C7	119.77 (15)	C21—C17—C16	117.05 (13)
C5—C6—H6	120.1	C17—C18—C19	118.11 (16)
C7—C6—H6	120.1	C17—C18—H18	120.9
C6—C7—C8	120.20 (16)	C19—C18—H18	120.9
C6—C7—H7	119.9	N3—C19—C18	124.13 (17)
C8—C7—H7	119.9	N3—C19—H19	117.9
C3—C8—C7	120.51 (15)	C18—C19—H19	117.9
C3—C8—H8	119.7	N3—C20—C21	123.60 (18)
C7—C8—H8	119.7	N3—C20—H20	118.2
C10—C9—S2	112.79 (10)	C21—C20—H20	118.2
C10—C9—H9A	109.0	C20—C21—C17	118.70 (17)
S2—C9—H9A	109.0	C20—C21—H21	120.7
C10—C9—H9B	109.0	C17—C21—H21	120.6
C1—N1—N2—C16	139.71 (13)	C9—C10—C11—C12	179.87 (16)
N2—N1—C1—S2	−176.89 (9)	C10—C11—C12—C13	−0.5 (3)
N2—N1—C1—S1	2.25 (17)	C11—C12—C13—C14	−0.5 (3)
C9—S2—C1—N1	−2.38 (12)	C12—C13—C14—C15	0.9 (3)
C9—S2—C1—S1	178.42 (7)	C13—C14—C15—C10	−0.4 (3)
C2—S1—C1—N1	−168.24 (12)	C11—C10—C15—C14	−0.6 (3)
C2—S1—C1—S2	10.91 (9)	C9—C10—C15—C14	−179.43 (16)
C1—S1—C2—C3	−179.46 (10)	N1—N2—C16—O1	−5.9 (2)
S1—C2—C3—C8	−76.56 (15)	N1—N2—C16—C17	177.46 (11)
S1—C2—C3—C4	105.00 (15)	O1—C16—C17—C18	−162.44 (15)
C8—C3—C4—C5	−0.1 (3)	N2—C16—C17—C18	14.3 (2)
C2—C3—C4—C5	178.34 (16)	O1—C16—C17—C21	13.6 (2)
C3—C4—C5—C6	0.3 (3)	N2—C16—C17—C21	−169.68 (13)
C4—C5—C6—C7	−0.3 (3)	C21—C17—C18—C19	1.3 (2)
C5—C6—C7—C8	0.1 (3)	C16—C17—C18—C19	177.25 (13)
C4—C3—C8—C7	−0.1 (2)	C20—N3—C19—C18	−0.4 (3)
C2—C3—C8—C7	−178.54 (14)	C17—C18—C19—N3	−0.5 (2)
C6—C7—C8—C3	0.1 (3)	C19—N3—C20—C21	0.4 (3)
C1—S2—C9—C10	−86.57 (11)	N3—C20—C21—C17	0.4 (3)
S2—C9—C10—C11	104.40 (15)	C18—C17—C21—C20	−1.3 (2)
S2—C9—C10—C15	−76.77 (16)	C16—C17—C21—C20	−177.54 (14)
C15—C10—C11—C12	1.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1i	0.864 (17)	1.936 (17)	2.7852 (15)	167.4 (16)
C7—H7···N3ii	0.95	2.54	3.339 (2)	142
C8—H8···N3iii	0.95	2.52	3.424 (2)	158
C18—H18···O1i	0.95	2.53	3.365 (2)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O1i	0.864 (17)	1.936 (17)	2.7852 (15)	167.4 (16)
C7—H7⋯N3ii	0.95	2.54	3.339 (2)	142
C8—H8⋯N3iii	0.95	2.52	3.424 (2)	158
C18—H18⋯O1i	0.95	2.53	3.365 (2)	147

Symmetry codes: (i) ; (ii) ; (iii) .