1,5-Bis(1-phenyl­ethyl­idene)thio­carbono­hydrazide

Feng, L.; Ji, H.; Wang, R.; Ge, H.; Li, L.

doi:10.1107/S1600536811018320

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1514

doi:10.1107/S1600536811018320

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1,5-Bis(1-phenylethylidene)thiocarbonohydrazide

Lei Feng,^a ^* Haiwei Ji,^b Renliang Wang,^b Haiyan Ge ^b and Li Li ^b

^aAtherosclerosis Institute, Taishan Medical University, 271000 Taian, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Taishan Medical University, 271016 Taian, People's Republic of China
^*Correspondence e-mail: jzpap@yahoo.com.cn

(Received 23 April 2011; accepted 14 May 2011; online 25 May 2011)

The title molecule, C₁₇H₁₈N₄S, is not planar, as indicated by the dihedral angle of 27.24 (9)° between the two benzene rings. In the crystal, intermolecular N—H⋯S hydrogen bonds link pairs of molecules into inversion dimers.

Related literature

For the biological activity and catalytic abilities of Schiff base derivatives and complexes, see: Loncle et al. (2004 ); Camp et al. (2010 ). For a related structure, see: Meyers et al. (1995 ).

Experimental

Crystal data

C₁₇H₁₈N₄S
M_r = 310.41
Triclinic, $[P \overline 1]$
a = 7.5947 (15) Å
b = 8.8202 (18) Å
c = 13.084 (3) Å
α = 76.62 (3)°
β = 76.39 (3)°
γ = 82.35 (3)°
V = 825.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 293 K
0.20 × 0.16 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.962, T_max = 0.977
4272 measured reflections
2876 independent reflections
2033 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.146
S = 1.02
2876 reflections
202 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯S1ⁱ	0.86	2.67	3.515 (2)	169
Symmetry code: (i) -x+2, -y+1, -z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018320/vm2088sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018320/vm2088Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811018320/vm2088Isup3.cml

checkCIF report

Comment top

Much interest has recently been paid to the design of schiff base derivatives and complexes, owing to their wide range of biological activities and catalytical abilities (Loncle et al., 2004; Camp et al., 2010). We have synthesized title compound, (I), and report here its crystal structure (Fig. 1). The bond lengths and angles are normal and correspond to those observed in bis(3-fluorophenylmethine)carbonohydrazide (Meyers et al., 1995). The planes of atoms N2/N1/C1 and benzene ring C4-C9 form a dihedral angle of 2.62 (23)°, indicating that this part of the molecule is nearly planar. However, benzene rings C4-C9 and C12-C17 form a dihedral angle of 27.24 (9)°. Intermolecular N—H···S hydrogen bonds link two molecules into one dimer (Table 1, Fig. 2).

Related literature top

For the biological activity and catalytical abilities of Schiff base derivatives and complexes, see: Loncle et al. (2004); Camp et al. (2010). For a related structure, see: Meyers et al. (1995).

Experimental top

Acetophenone (10.0 mmol) and thiocarbohydrazide (5.0 mmol) were mixed in 50 ml flash under sovlent-free condtions After stirring 3 h at 373 K, the resulting mixture was cooled to room temperature, and recrystalized from ethanol, and afforded the title compound as a crystalline solid.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of (I) showing the atomic numbering and 30% probability displacement ellipsoids.
	Fig. 2. View along a-axis of the packing of (I). N—H···S interactions are represented by dashed lines.

1,5-Bis(1-phenylethylidene)thiocarbonohydrazide top

Crystal data top

C₁₇H₁₈N₄S	Z = 2
M_r = 310.41	F(000) = 328
Triclinic, P1	D_x = 1.248 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5947 (15) Å	Cell parameters from 1351 reflections
b = 8.8202 (18) Å	θ = 2.6–25.1°
c = 13.084 (3) Å	µ = 0.20 mm⁻¹
α = 76.62 (3)°	T = 293 K
β = 76.39 (3)°	Block, colourless
γ = 82.35 (3)°	0.20 × 0.16 × 0.12 mm
V = 825.8 (3) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2876 independent reflections
Radiation source: fine-focus sealed tube	2033 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
T_min = 0.962, T_max = 0.977	k = −10→9
4272 measured reflections	l = −15→15

Refinement top

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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.0718P)² + 0.2086P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
2876 reflections	Δρ_max = 0.24 e Å⁻³
202 parameters	Δρ_min = −0.19 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (4)

Crystal data top

C₁₇H₁₈N₄S	γ = 82.35 (3)°
M_r = 310.41	V = 825.8 (3) Å³
Triclinic, P1	Z = 2
a = 7.5947 (15) Å	Mo Kα radiation
b = 8.8202 (18) Å	µ = 0.20 mm⁻¹
c = 13.084 (3) Å	T = 293 K
α = 76.62 (3)°	0.20 × 0.16 × 0.12 mm
β = 76.39 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2876 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2033 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.977	R_int = 0.022
4272 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	1 restraint
wR(F²) = 0.146	H-atom parameters constrained
S = 1.02	Δρ_max = 0.24 e Å⁻³
2876 reflections	Δρ_min = −0.19 e Å⁻³
202 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.91194 (11)	0.69768 (7)	−0.10817 (5)	0.0688 (3)
N1	0.7946 (3)	0.9200 (2)	0.00704 (14)	0.0560 (6)
H1	0.7779	0.9500	0.0669	0.067*
N2	0.7386 (3)	1.0205 (2)	−0.07909 (14)	0.0521 (5)
N3	0.9241 (3)	0.6971 (2)	0.09311 (14)	0.0566 (6)
H3	0.9787	0.6046	0.0982	0.068*
N4	0.8830 (3)	0.7712 (2)	0.17832 (15)	0.0520 (5)
C1	0.8745 (3)	0.7765 (3)	−0.00005 (18)	0.0524 (6)
C2	0.6582 (3)	1.1530 (3)	−0.06107 (18)	0.0498 (6)
C3	0.6205 (4)	1.2028 (3)	0.0448 (2)	0.0677 (8)
H3A	0.6098	1.1120	0.1022	0.102*
H3B	0.5091	1.2689	0.0525	0.102*
H3C	0.7185	1.2592	0.0474	0.102*
C4	0.6017 (3)	1.2612 (2)	−0.15566 (18)	0.0514 (6)
C5	0.6339 (4)	1.2169 (3)	−0.25393 (19)	0.0617 (7)
H5	0.6893	1.1180	−0.2604	0.074*
C6	0.5846 (4)	1.3179 (3)	−0.3422 (2)	0.0701 (8)
H6	0.6078	1.2867	−0.4076	0.084*
C7	0.5015 (4)	1.4645 (3)	−0.3343 (2)	0.0704 (8)
H7	0.4694	1.5324	−0.3942	0.085*
C8	0.4666 (4)	1.5095 (3)	−0.2381 (2)	0.0748 (8)
H8	0.4092	1.6080	−0.2321	0.090*
C9	0.5164 (4)	1.4089 (3)	−0.1491 (2)	0.0661 (8)
H9	0.4921	1.4411	−0.0839	0.079*
C10	0.9131 (3)	0.6990 (3)	0.27089 (18)	0.0516 (6)
C11	0.9913 (4)	0.5327 (3)	0.2956 (2)	0.0708 (8)
H11A	0.9160	0.4657	0.2797	0.106*
H11B	0.9961	0.5032	0.3703	0.106*
H11C	1.1118	0.5228	0.2525	0.106*
C12	0.8641 (3)	0.7926 (3)	0.35463 (18)	0.0528 (6)
C13	0.8581 (5)	0.9550 (3)	0.3268 (2)	0.0790 (9)
H13	0.8894	1.0049	0.2550	0.095*
C14	0.8063 (7)	1.0415 (4)	0.4049 (3)	0.1186 (16)
H14	0.8012	1.1501	0.3855	0.142*
C15	0.7621 (7)	0.9703 (4)	0.5109 (3)	0.1202 (16)
H15	0.7270	1.0304	0.5631	0.144*
C16	0.7691 (5)	0.8118 (4)	0.5402 (2)	0.0960 (12)
H16	0.7384	0.7633	0.6124	0.115*
C17	0.8217 (4)	0.7239 (3)	0.4628 (2)	0.0696 (8)
H17	0.8291	0.6154	0.4834	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.1111 (7)	0.0488 (4)	0.0460 (4)	0.0237 (4)	−0.0270 (4)	−0.0155 (3)
N1	0.0858 (16)	0.0416 (10)	0.0403 (10)	0.0161 (10)	−0.0229 (10)	−0.0105 (8)
N2	0.0758 (14)	0.0391 (10)	0.0407 (10)	0.0090 (9)	−0.0189 (9)	−0.0079 (8)
N3	0.0823 (15)	0.0436 (11)	0.0424 (11)	0.0156 (10)	−0.0214 (10)	−0.0092 (9)
N4	0.0683 (14)	0.0459 (11)	0.0418 (10)	0.0067 (9)	−0.0171 (9)	−0.0102 (8)
C1	0.0691 (17)	0.0430 (12)	0.0427 (13)	0.0073 (11)	−0.0156 (11)	−0.0071 (10)
C2	0.0654 (16)	0.0407 (12)	0.0446 (13)	0.0064 (11)	−0.0165 (11)	−0.0128 (10)
C3	0.097 (2)	0.0580 (15)	0.0537 (15)	0.0202 (14)	−0.0303 (15)	−0.0234 (12)
C4	0.0660 (16)	0.0410 (12)	0.0474 (13)	0.0063 (11)	−0.0176 (12)	−0.0103 (10)
C5	0.086 (2)	0.0492 (14)	0.0503 (14)	0.0137 (13)	−0.0234 (13)	−0.0130 (11)
C6	0.096 (2)	0.0658 (17)	0.0490 (14)	0.0156 (15)	−0.0264 (14)	−0.0144 (13)
C7	0.086 (2)	0.0609 (16)	0.0582 (17)	0.0102 (14)	−0.0271 (15)	0.0019 (13)
C8	0.103 (2)	0.0476 (14)	0.0700 (18)	0.0218 (15)	−0.0289 (16)	−0.0092 (13)
C9	0.094 (2)	0.0482 (14)	0.0533 (15)	0.0171 (13)	−0.0203 (14)	−0.0140 (12)
C10	0.0650 (16)	0.0453 (13)	0.0444 (13)	0.0039 (11)	−0.0194 (11)	−0.0058 (10)
C11	0.101 (2)	0.0559 (15)	0.0552 (15)	0.0207 (15)	−0.0320 (15)	−0.0116 (12)
C12	0.0649 (16)	0.0496 (13)	0.0446 (13)	0.0031 (11)	−0.0183 (11)	−0.0088 (11)
C13	0.132 (3)	0.0535 (16)	0.0543 (16)	0.0003 (16)	−0.0293 (17)	−0.0106 (13)
C14	0.230 (5)	0.0540 (18)	0.078 (2)	0.015 (2)	−0.049 (3)	−0.0248 (17)
C15	0.219 (5)	0.078 (2)	0.065 (2)	0.028 (3)	−0.036 (3)	−0.0342 (18)
C16	0.156 (3)	0.080 (2)	0.0468 (16)	0.014 (2)	−0.0207 (19)	−0.0171 (15)
C17	0.104 (2)	0.0558 (15)	0.0473 (15)	0.0050 (15)	−0.0223 (14)	−0.0075 (12)

Geometric parameters (Å, º) top

S1—C1	1.667 (2)	C7—H7	0.9300
N1—C1	1.343 (3)	C8—C9	1.388 (3)
N1—N2	1.378 (2)	C8—H8	0.9300
N1—H1	0.8600	C9—H9	0.9300
N2—C2	1.290 (3)	C10—C12	1.471 (3)
N3—C1	1.367 (3)	C10—C11	1.499 (3)
N3—N4	1.374 (3)	C11—H11A	0.9600
N3—H3	0.8600	C11—H11B	0.9600
N4—C10	1.288 (3)	C11—H11C	0.9600
C2—C4	1.490 (3)	C12—C17	1.383 (3)
C2—C3	1.502 (3)	C12—C13	1.392 (3)
C3—H3A	0.9600	C13—C14	1.368 (4)
C3—H3B	0.9600	C13—H13	0.9300
C3—H3C	0.9600	C14—C15	1.366 (5)
C4—C5	1.387 (3)	C14—H14	0.9300
C4—C9	1.388 (3)	C15—C16	1.358 (5)
C5—C6	1.380 (3)	C15—H15	0.9300
C5—H5	0.9300	C16—C17	1.370 (4)
C6—C7	1.376 (4)	C16—H16	0.9300
C6—H6	0.9300	C17—H17	0.9300
C7—C8	1.363 (4)

C1—N1—N2	121.73 (18)	C7—C8—H8	119.9
C1—N1—H1	119.1	C9—C8—H8	119.9
N2—N1—H1	119.1	C8—C9—C4	121.1 (2)
C2—N2—N1	115.81 (18)	C8—C9—H9	119.5
C1—N3—N4	117.21 (18)	C4—C9—H9	119.5
C1—N3—H3	121.4	N4—C10—C12	114.8 (2)
N4—N3—H3	121.4	N4—C10—C11	124.5 (2)
C10—N4—N3	120.56 (19)	C12—C10—C11	120.7 (2)
N1—C1—N3	112.62 (19)	C10—C11—H11A	109.5
N1—C1—S1	125.52 (17)	C10—C11—H11B	109.5
N3—C1—S1	121.86 (17)	H11A—C11—H11B	109.5
N2—C2—C4	114.99 (19)	C10—C11—H11C	109.5
N2—C2—C3	125.2 (2)	H11A—C11—H11C	109.5
C4—C2—C3	119.78 (19)	H11B—C11—H11C	109.5
C2—C3—H3A	109.5	C17—C12—C13	117.6 (2)
C2—C3—H3B	109.5	C17—C12—C10	121.9 (2)
H3A—C3—H3B	109.5	C13—C12—C10	120.5 (2)
C2—C3—H3C	109.5	C14—C13—C12	120.2 (3)
H3A—C3—H3C	109.5	C14—C13—H13	119.9
H3B—C3—H3C	109.5	C12—C13—H13	119.9
C5—C4—C9	117.8 (2)	C15—C14—C13	120.7 (3)
C5—C4—C2	120.7 (2)	C15—C14—H14	119.6
C9—C4—C2	121.6 (2)	C13—C14—H14	119.6
C6—C5—C4	120.8 (2)	C16—C15—C14	120.2 (3)
C6—C5—H5	119.6	C16—C15—H15	119.9
C4—C5—H5	119.6	C14—C15—H15	119.9
C7—C6—C5	120.6 (2)	C15—C16—C17	119.6 (3)
C7—C6—H6	119.7	C15—C16—H16	120.2
C5—C6—H6	119.7	C17—C16—H16	120.2
C8—C7—C6	119.5 (2)	C16—C17—C12	121.6 (3)
C8—C7—H7	120.2	C16—C17—H17	119.2
C6—C7—H7	120.2	C12—C17—H17	119.2
C7—C8—C9	120.2 (2)

C1—N1—N2—C2	177.7 (2)	C7—C8—C9—C4	−0.2 (5)
C1—N3—N4—C10	174.7 (2)	C5—C4—C9—C8	−0.6 (4)
N2—N1—C1—N3	178.3 (2)	C2—C4—C9—C8	179.1 (3)
N2—N1—C1—S1	−1.9 (4)	N3—N4—C10—C12	179.5 (2)
N4—N3—C1—N1	1.4 (3)	N3—N4—C10—C11	−0.6 (4)
N4—N3—C1—S1	−178.43 (18)	N4—C10—C12—C17	155.1 (3)
N1—N2—C2—C4	179.0 (2)	C11—C10—C12—C17	−24.8 (4)
N1—N2—C2—C3	−0.8 (4)	N4—C10—C12—C13	−24.6 (4)
N2—C2—C4—C5	0.8 (4)	C11—C10—C12—C13	155.6 (3)
C3—C2—C4—C5	−179.5 (2)	C17—C12—C13—C14	−1.9 (5)
N2—C2—C4—C9	−178.9 (3)	C10—C12—C13—C14	177.7 (3)
C3—C2—C4—C9	0.8 (4)	C12—C13—C14—C15	0.8 (6)
C9—C4—C5—C6	0.9 (4)	C13—C14—C15—C16	0.0 (7)
C2—C4—C5—C6	−178.8 (3)	C14—C15—C16—C17	0.3 (7)
C4—C5—C6—C7	−0.4 (5)	C15—C16—C17—C12	−1.5 (6)
C5—C6—C7—C8	−0.5 (5)	C13—C12—C17—C16	2.3 (5)
C6—C7—C8—C9	0.7 (5)	C10—C12—C17—C16	−177.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S1ⁱ	0.86	2.67	3.515 (2)	169

Symmetry code: (i) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₈N₄S
M_r	310.41
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5947 (15), 8.8202 (18), 13.084 (3)
α, β, γ (°)	76.62 (3), 76.39 (3), 82.35 (3)
V (Å³)	825.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.20 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.962, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	4272, 2876, 2033
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.146, 1.02
No. of reflections	2876
No. of parameters	202
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S1ⁱ	0.86	2.67	3.515 (2)	169

Symmetry code: (i) −x+2, −y+1, −z.

Acknowledgements

The authors acknowledge financial support by Taishan Medical University.

References

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