(Z)-N,N-Dimethyl-2-[phen-yl(pyridin-2-yl)methyl-idene]hydrazinecarbothio-amide.

The title compound, C(15)H(16)N(4)S, exists in the Z conformation with the thionyl S atom lying cis to the azomethine N atom. The shortening of the N-N distance [1.3697 (17) Å] is due to extensive delocalization with the pyridine ring. The hydrazine-carbothio-amide unit is almost planar, with a maximum deviation of 0.013 (2) Å for the amide N atom. The stability of this conformation is favoured by the formation of an intra-molecular N-H⋯N hydrogen bond. The packing of the mol-ecules involves no classical inter-molecular hydrogen-bonding inter-actions; however, a C-H⋯π inter-action occurs.

Related literature

For abackground to hydrazinecarbothio­amide and its derivatives, see: Beraldo & Gambino (2004 ▶). For the synthesis, see: Joseph et al. (2006 ▶). For related structures of hydrazinecarbothio­amides, see: Philip et al. (2006 ▶); Arumugam et al. (2011 ▶). For related structures, see: Seena et al. (2008 ▶); Usman et al. (2002 ▶); Huheey et al. (1993 ▶); Joseph et al. (2004 ▶).

Experimental

Crystal data

C15H16N4S

M = 284.39

Monoclinic,

a = 10.011 (2) Å

b = 8.888 (2) Å

c = 16.256 (4) Å

β = 94.528 (3)°

V = 1441.9 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 153 K

0.32 × 0.28 × 0.22 mm

Data collection

Bruker P4 diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.932, T max = 0.953

14231 measured reflections

2828 independent reflections

2405 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.110

S = 1.06

2828 reflections

188 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811045739/fj2463sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045739/fj2463Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811045739/fj2463Isup3.cml

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

C15H16N4S	F(000) = 600.0
Mr = 284.39	Dx = 1.310 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8120 reflections
a = 10.011 (2) Å	θ = 2.0–26.0°
b = 8.888 (2) Å	µ = 0.22 mm−1
c = 16.256 (4) Å	T = 153 K
β = 94.528 (3)°	Block, yellow
V = 1441.9 (6) Å3	0.32 × 0.28 × 0.22 mm
Z = 4

Bruker P4 diffractometer	2828 independent reflections
Radiation source: fine-focus sealed tube	2405 reflections with I > 2σ(I)
graphite	Rint = 0.031
Detector resolution: 8.33 pixels mm-1	θmax = 26.0°, θmin = 2.0°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −10→10
Tmin = 0.932, Tmax = 0.953	l = −20→20
14231 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.0606P)2 + 0.2366P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.014
2828 reflections	Δρmax = 0.19 e Å−3
188 parameters	Δρmin = −0.20 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0104 (16)

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.

	x	y	z	Uiso*/Ueq
S1	0.75460 (4)	0.15132 (5)	0.31975 (3)	0.05808 (18)
N1	0.98755 (14)	0.68420 (14)	0.33757 (8)	0.0466 (3)
N2	0.99018 (12)	0.35758 (13)	0.36663 (7)	0.0413 (3)
N3	0.87523 (12)	0.42001 (16)	0.33015 (8)	0.0459 (3)
N4	0.68025 (13)	0.41370 (17)	0.25113 (9)	0.0552 (4)
C1	1.33165 (15)	0.42244 (19)	0.39734 (10)	0.0496 (4)
H1	1.3333	0.4983	0.3580	0.059*
C2	1.44999 (16)	0.3531 (2)	0.42682 (12)	0.0584 (5)
H2	1.5307	0.3820	0.4069	0.070*
C3	1.44848 (18)	0.2420 (2)	0.48527 (12)	0.0604 (5)
H3	1.5280	0.1956	0.5048	0.072*
C4	1.32983 (18)	0.1993 (2)	0.51494 (11)	0.0586 (5)
H4	1.3291	0.1248	0.5551	0.070*
C5	1.21090 (16)	0.26692 (18)	0.48536 (10)	0.0474 (4)
H5	1.1305	0.2368	0.5053	0.057*
C6	1.21111 (14)	0.37895 (16)	0.42634 (9)	0.0386 (3)
C7	1.08395 (14)	0.45037 (16)	0.39224 (8)	0.0383 (3)
C8	1.07742 (14)	0.61797 (16)	0.39196 (9)	0.0404 (3)
C9	1.15590 (16)	0.70179 (18)	0.44910 (10)	0.0499 (4)
H9	1.2173	0.6546	0.4865	0.060*
C10	1.14187 (19)	0.85641 (19)	0.44978 (13)	0.0600 (5)
H10	1.1928	0.9143	0.4882	0.072*
C11	1.05114 (18)	0.92430 (19)	0.39262 (12)	0.0574 (4)
H11	1.0408	1.0283	0.3912	0.069*
C12	0.97729 (18)	0.83393 (18)	0.33834 (11)	0.0527 (4)
H12	0.9165	0.8793	0.2998	0.063*
C13	0.77074 (15)	0.33429 (18)	0.29902 (9)	0.0442 (4)
C14	0.56134 (19)	0.3425 (3)	0.21167 (14)	0.0755 (6)
H14A	0.5778	0.3140	0.1564	0.113*
H14B	0.4877	0.4119	0.2101	0.113*
H14C	0.5400	0.2547	0.2424	0.113*
C15	0.6980 (2)	0.5728 (2)	0.23277 (14)	0.0770 (6)
H15A	0.6945	0.6306	0.2824	0.115*
H15B	0.6279	0.6051	0.1930	0.115*
H15C	0.7833	0.5874	0.2108	0.115*
H3'	0.8833 (15)	0.511 (2)	0.3188 (9)	0.043 (4)*

	U11	U22	U33	U12	U13	U23
S1	0.0506 (3)	0.0477 (3)	0.0740 (3)	−0.00580 (18)	−0.0075 (2)	−0.00052 (19)
N1	0.0516 (8)	0.0409 (7)	0.0469 (7)	0.0035 (6)	0.0016 (6)	0.0030 (5)
N2	0.0353 (6)	0.0410 (7)	0.0462 (7)	0.0030 (5)	−0.0045 (5)	0.0000 (5)
N3	0.0394 (7)	0.0388 (7)	0.0574 (8)	0.0035 (5)	−0.0087 (6)	0.0003 (6)
N4	0.0427 (7)	0.0588 (9)	0.0613 (8)	0.0069 (6)	−0.0143 (6)	−0.0006 (7)
C1	0.0441 (9)	0.0505 (9)	0.0542 (9)	0.0001 (7)	0.0042 (7)	0.0044 (7)
C2	0.0347 (8)	0.0697 (12)	0.0705 (11)	0.0005 (8)	0.0022 (8)	−0.0032 (9)
C3	0.0425 (9)	0.0639 (11)	0.0711 (11)	0.0098 (8)	−0.0182 (8)	−0.0052 (9)
C4	0.0562 (10)	0.0552 (10)	0.0611 (10)	0.0010 (8)	−0.0157 (8)	0.0113 (8)
C5	0.0418 (8)	0.0478 (9)	0.0513 (9)	−0.0055 (7)	−0.0045 (7)	0.0039 (7)
C6	0.0363 (7)	0.0361 (7)	0.0421 (8)	0.0002 (6)	−0.0042 (6)	−0.0050 (6)
C7	0.0372 (7)	0.0394 (7)	0.0380 (7)	0.0016 (6)	0.0014 (6)	−0.0007 (6)
C8	0.0373 (7)	0.0400 (8)	0.0442 (8)	0.0019 (6)	0.0058 (6)	0.0004 (6)
C9	0.0448 (9)	0.0463 (9)	0.0577 (9)	−0.0007 (7)	−0.0016 (7)	−0.0048 (7)
C10	0.0582 (11)	0.0457 (10)	0.0756 (12)	−0.0065 (8)	0.0024 (9)	−0.0123 (8)
C11	0.0634 (11)	0.0360 (8)	0.0745 (11)	−0.0007 (8)	0.0162 (9)	−0.0006 (8)
C12	0.0595 (10)	0.0438 (9)	0.0553 (9)	0.0074 (7)	0.0069 (8)	0.0092 (7)
C13	0.0373 (8)	0.0499 (9)	0.0444 (8)	0.0043 (6)	−0.0021 (6)	−0.0052 (6)
C14	0.0502 (11)	0.0935 (16)	0.0781 (13)	0.0042 (10)	−0.0250 (10)	−0.0092 (11)
C15	0.0699 (13)	0.0660 (13)	0.0902 (15)	0.0183 (10)	−0.0245 (11)	0.0121 (11)

S1—C13	1.6712 (17)	C5—C6	1.383 (2)
N1—C12	1.335 (2)	C5—H5	0.9300
N1—C8	1.3461 (19)	C6—C7	1.4898 (19)
N2—C7	1.2934 (18)	C7—C8	1.491 (2)
N2—N3	1.3697 (17)	C8—C9	1.386 (2)
N3—C13	1.3591 (19)	C9—C10	1.381 (2)
N3—H3'	0.837 (17)	C9—H9	0.9300
N4—C13	1.3466 (19)	C10—C11	1.385 (3)
N4—C14	1.452 (2)	C10—H10	0.9300
N4—C15	1.459 (3)	C11—C12	1.366 (2)
C1—C6	1.385 (2)	C11—H11	0.9300
C1—C2	1.387 (2)	C12—H12	0.9300
C1—H1	0.9300	C14—H14A	0.9600
C2—C3	1.371 (3)	C14—H14B	0.9600
C2—H2	0.9300	C14—H14C	0.9600
C3—C4	1.370 (3)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C5	1.385 (2)	C15—H15C	0.9600
C4—H4	0.9300
C12—N1—C8	118.54 (14)	N1—C8—C7	117.75 (13)
C7—N2—N3	116.40 (12)	C9—C8—C7	120.85 (13)
C13—N3—N2	121.99 (13)	C10—C9—C8	119.18 (16)
C13—N3—H3'	123.1 (11)	C10—C9—H9	120.4
N2—N3—H3'	113.3 (11)	C8—C9—H9	120.4
C13—N4—C14	121.18 (15)	C9—C10—C11	119.31 (16)
C13—N4—C15	122.61 (14)	C9—C10—H10	120.3
C14—N4—C15	116.16 (14)	C11—C10—H10	120.3
C6—C1—C2	120.13 (16)	C12—C11—C10	118.02 (15)
C6—C1—H1	119.9	C12—C11—H11	121.0
C2—C1—H1	119.9	C10—C11—H11	121.0
C3—C2—C1	120.23 (16)	N1—C12—C11	123.63 (16)
C3—C2—H2	119.9	N1—C12—H12	118.2
C1—C2—H2	119.9	C11—C12—H12	118.2
C4—C3—C2	120.04 (16)	N4—C13—N3	112.61 (14)
C4—C3—H3	120.0	N4—C13—S1	123.72 (12)
C2—C3—H3	120.0	N3—C13—S1	123.65 (11)
C3—C4—C5	120.19 (16)	N4—C14—H14A	109.5
C3—C4—H4	119.9	N4—C14—H14B	109.5
C5—C4—H4	119.9	H14A—C14—H14B	109.5
C6—C5—C4	120.31 (15)	N4—C14—H14C	109.5
C6—C5—H5	119.8	H14A—C14—H14C	109.5
C4—C5—H5	119.8	H14B—C14—H14C	109.5
C5—C6—C1	119.09 (14)	N4—C15—H15A	109.5
C5—C6—C7	121.12 (13)	N4—C15—H15B	109.5
C1—C6—C7	119.77 (13)	H15A—C15—H15B	109.5
N2—C7—C6	115.17 (12)	N4—C15—H15C	109.5
N2—C7—C8	127.26 (13)	H15A—C15—H15C	109.5
C6—C7—C8	117.56 (12)	H15B—C15—H15C	109.5
N1—C8—C9	121.30 (14)
C7—N2—N3—C13	178.44 (14)	N2—C7—C8—N1	−23.7 (2)
C6—C1—C2—C3	−0.5 (3)	C6—C7—C8—N1	157.05 (13)
C1—C2—C3—C4	−0.2 (3)	N2—C7—C8—C9	152.63 (15)
C2—C3—C4—C5	0.8 (3)	C6—C7—C8—C9	−26.6 (2)
C3—C4—C5—C6	−0.7 (3)	N1—C8—C9—C10	−0.4 (2)
C4—C5—C6—C1	0.0 (2)	C7—C8—C9—C10	−176.54 (16)
C4—C5—C6—C7	178.48 (14)	C8—C9—C10—C11	−0.9 (3)
C2—C1—C6—C5	0.6 (2)	C9—C10—C11—C12	1.0 (3)
C2—C1—C6—C7	−177.91 (14)	C8—N1—C12—C11	−1.5 (3)
N3—N2—C7—C6	−175.96 (12)	C10—C11—C12—N1	0.2 (3)
N3—N2—C7—C8	4.8 (2)	C14—N4—C13—N3	179.72 (16)
C5—C6—C7—N2	−50.15 (19)	C15—N4—C13—N3	2.5 (2)
C1—C6—C7—N2	128.32 (15)	C14—N4—C13—S1	−1.7 (2)
C5—C6—C7—C8	129.21 (15)	C15—N4—C13—S1	−178.84 (15)
C1—C6—C7—C8	−52.32 (19)	N2—N3—C13—N4	−166.98 (14)
C12—N1—C8—C9	1.5 (2)	N2—N3—C13—S1	14.4 (2)
C12—N1—C8—C7	177.81 (14)

Cg is the centroid of the N1/C8–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3'···N1	0.837 (17)	1.869 (17)	2.602 (2)	145.4 (15)
C14—H14C···S1	0.96	2.57	3.030 (2)	109.
C5—H5···Cgi	0.93	2.66	3.536 (2)	157

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N1/C8–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3′⋯N1	0.837 (17)	1.869 (17)	2.602 (2)	145.4 (15)
C5—H5⋯Cgi	0.93	2.66	3.536 (2)	157

Symmetry code: (i) .