Benzaldehyde thio­semicarbazone

Kong, L.; Qiao, Y.; Zhang, J.-D.; Ju, X.-P.

doi:10.1107/S1600536808038270

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2412

doi:10.1107/S1600536808038270

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Benzaldehyde thiosemicarbazone

Lingqian Kong,^a ^* Yan Qiao,^a Ji-Dong Zhang ^a and Xiu-Ping Ju ^a

^aDongchang College, Liaocheng University, Liaocheng 250059, People's Republic of China
^*Correspondence e-mail: konglingqian08@163.com

(Received 5 October 2008; accepted 17 November 2008; online 22 November 2008)

The title compound, C₈H₉N₃S, contains two molecules in the asymmetric unit. One molecule is close to being planar (r.m.s. deviation from the mean plane = 0.06 Å for the non-H atoms), while the other exhibits a dihedral angle of 21.7 (1)° between the benzene ring and the mean plane of the thiosemicarbazone unit. Intermolecular N—H⋯S hydrogen bonds link the molecules into layers parallel to the (010) plane.

Related literature

For background literature concerning arylhydrazone compounds, see: Beraldo & Gambino (2004 ); Bondock et al. (2007 ). For the related 2,4-dichlorobenzylidene compound, see: Jing et al. (2006 ).

Experimental

Crystal data

C₈H₉N₃S
M_r = 179.24
Triclinic, $[P \overline 1]$
a = 5.8692 (13) Å
b = 12.513 (2) Å
c = 13.519 (2) Å
α = 112.735 (3)°
β = 95.384 (2)°
γ = 96.153 (2)°
V = 900.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 298 (2) K
0.24 × 0.13 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.930, T_max = 0.970
4740 measured reflections
3124 independent reflections
1846 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.162
S = 0.95
3124 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.31 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
N2—H2⋯S1ⁱ	0.86	2.64	3.443 (3)	155
N3—H3A⋯S1ⁱⁱ	0.86	2.98	3.488 (3)	120
N5—H5⋯S1ⁱⁱ	0.86	2.61	3.441 (3)	162
N6—H6B⋯S2ⁱⁱⁱ	0.86	2.51	3.368 (3)	173
Symmetry codes: (i) -x+3, -y+2, -z+2; (ii) x-1, y, z; (iii) -x+2, -y+2, -z+1.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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/S1600536808038270/bi2310sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038270/bi2310Isup2.hkl

checkCIF report

Comment top

Aryl-hydrazones, such as semicarbazones, thiosemicarbazones and guanyl hydrazones, often exhibit strong biological activity and are important compounds for drug design (Beraldo & Gambino, 2004), organocatalysis and the preparation of heterocyclic rings (Bondock et al., 2007).

Related literature top

For background literature concerning arylhydrazone compounds, see: Beraldo & Gambino (2004); Bondock et al. (2007). For the related 2,4-dichlorobenzylidene compound, see: Jing et al. (2006).

Experimental top

Benzaldehyde (0.3 mmol), thiosemicarbazide (0.3 mmol) and 10 ml water were mixed in a 50 ml flask. After stirring for 30 min at 373 K, the resulting mixture was recrystallized from ethanol, affording the title compound as colourless crystals. Elemental analysis: calculated C 53.61, H 5.06, N 23.44%; found: C 53.58, H 5.55, N 23.51%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. Two molecules in the asymmetric unit of the title compound with displacement ellipsoids shown at 30% probability for non-H atoms.

Benzaldehyde thiosemicarbazone top

Crystal data top

C₈H₉N₃S	Z = 4
M_r = 179.24	F(000) = 376
Triclinic, P1	D_x = 1.322 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8692 (13) Å	Cell parameters from 1310 reflections
b = 12.513 (2) Å	θ = 2.9–25.0°
c = 13.519 (2) Å	µ = 0.31 mm⁻¹
α = 112.735 (3)°	T = 298 K
β = 95.384 (2)°	Block, orange
γ = 96.153 (2)°	0.24 × 0.13 × 0.10 mm
V = 900.4 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3124 independent reflections
Radiation source: fine-focus sealed tube	1846 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
T_min = 0.930, T_max = 0.970	k = −12→14
4740 measured reflections	l = −16→14

Refinement top

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0856P)²] where P = (F_o² + 2F_c²)/3
3124 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₈H₉N₃S	γ = 96.153 (2)°
M_r = 179.24	V = 900.4 (3) Å³
Triclinic, P1	Z = 4
a = 5.8692 (13) Å	Mo Kα radiation
b = 12.513 (2) Å	µ = 0.31 mm⁻¹
c = 13.519 (2) Å	T = 298 K
α = 112.735 (3)°	0.24 × 0.13 × 0.10 mm
β = 95.384 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3124 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1846 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.970	R_int = 0.039
4740 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.162	H-atom parameters constrained
S = 0.95	Δρ_max = 0.31 e Å⁻³
3124 reflections	Δρ_min = −0.27 e Å⁻³
217 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
N1	0.9674 (5)	0.8260 (3)	0.9684 (2)	0.0484 (8)
N2	1.1667 (5)	0.8822 (3)	0.9512 (2)	0.0504 (8)
H2	1.2934	0.8999	0.9956	0.061*
N3	0.9536 (5)	0.8863 (3)	0.8034 (2)	0.0550 (9)
H3A	0.8331	0.8563	0.8208	0.066*
H3B	0.9414	0.9020	0.7467	0.066*
N4	0.3374 (5)	0.7659 (3)	0.4823 (2)	0.0486 (8)
N5	0.4649 (5)	0.8653 (3)	0.5625 (2)	0.0518 (8)
H5	0.4200	0.8950	0.6249	0.062*
N6	0.7036 (6)	0.8737 (3)	0.4423 (3)	0.0612 (10)
H6A	0.6092	0.8166	0.3930	0.073*
H6B	0.8262	0.9031	0.4259	0.073*
S1	1.40293 (17)	0.96409 (10)	0.83250 (8)	0.0561 (3)
S2	0.83277 (19)	1.02721 (9)	0.64490 (8)	0.0610 (4)
C1	0.9813 (7)	0.8063 (3)	1.0543 (3)	0.0500 (9)
H1	1.1169	0.8341	1.1040	0.060*
C2	0.7837 (7)	0.7398 (3)	1.0749 (3)	0.0493 (10)
C3	0.5747 (7)	0.7039 (3)	1.0076 (3)	0.0569 (10)
H3	0.5566	0.7229	0.9475	0.068*
C4	0.3920 (8)	0.6403 (4)	1.0277 (4)	0.0660 (12)
H4	0.2516	0.6167	0.9814	0.079*
C5	0.4178 (9)	0.6118 (4)	1.1169 (4)	0.0700 (13)
H5A	0.2950	0.5690	1.1309	0.084*
C6	0.6255 (9)	0.6472 (4)	1.1845 (4)	0.0675 (12)
H6	0.6431	0.6283	1.2447	0.081*
C7	0.8081 (8)	0.7104 (3)	1.1640 (3)	0.0584 (11)
H7	0.9486	0.7336	1.2100	0.070*
C8	1.1574 (6)	0.9084 (3)	0.8637 (3)	0.0438 (9)
C9	0.1484 (7)	0.7251 (3)	0.5034 (3)	0.0484 (9)
H9	0.0969	0.7658	0.5687	0.058*
C10	0.0129 (6)	0.6152 (3)	0.4263 (3)	0.0455 (9)
C11	−0.2018 (7)	0.5775 (4)	0.4462 (4)	0.0607 (11)
H11	−0.2622	0.6246	0.5065	0.073*
C12	−0.3267 (8)	0.4700 (4)	0.3766 (4)	0.0695 (13)
H12	−0.4716	0.4453	0.3898	0.083*
C13	−0.2378 (9)	0.4002 (4)	0.2889 (4)	0.0736 (13)
H13	−0.3205	0.3270	0.2435	0.088*
C14	−0.0287 (9)	0.4368 (4)	0.2671 (4)	0.0730 (13)
H14	0.0287	0.3893	0.2060	0.088*
C15	0.0981 (7)	0.5436 (3)	0.3350 (3)	0.0576 (11)
H15	0.2410	0.5680	0.3198	0.069*
C16	0.6604 (6)	0.9162 (3)	0.5434 (3)	0.0443 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0460 (19)	0.0479 (18)	0.0522 (19)	0.0088 (15)	0.0119 (15)	0.0195 (15)
N2	0.0434 (18)	0.056 (2)	0.0511 (19)	0.0056 (15)	0.0037 (15)	0.0225 (16)
N3	0.0415 (19)	0.072 (2)	0.0521 (19)	−0.0021 (16)	0.0018 (16)	0.0296 (17)
N4	0.0452 (19)	0.0479 (18)	0.0471 (18)	−0.0024 (15)	0.0008 (15)	0.0170 (15)
N5	0.048 (2)	0.0513 (19)	0.0488 (19)	−0.0080 (15)	0.0049 (15)	0.0170 (15)
N6	0.055 (2)	0.063 (2)	0.055 (2)	−0.0165 (17)	0.0107 (17)	0.0171 (17)
S1	0.0434 (6)	0.0700 (7)	0.0494 (6)	0.0008 (5)	0.0081 (5)	0.0196 (5)
S2	0.0595 (7)	0.0634 (7)	0.0504 (6)	−0.0189 (5)	−0.0037 (5)	0.0224 (5)
C1	0.054 (2)	0.046 (2)	0.049 (2)	0.0123 (19)	0.0080 (19)	0.0165 (18)
C2	0.060 (3)	0.039 (2)	0.047 (2)	0.0102 (19)	0.014 (2)	0.0133 (17)
C3	0.058 (3)	0.057 (3)	0.056 (2)	0.012 (2)	0.004 (2)	0.023 (2)
C4	0.054 (3)	0.060 (3)	0.082 (3)	0.013 (2)	0.011 (2)	0.024 (2)
C5	0.078 (3)	0.053 (3)	0.083 (3)	0.010 (2)	0.033 (3)	0.028 (2)
C6	0.088 (4)	0.058 (3)	0.060 (3)	0.011 (3)	0.021 (3)	0.026 (2)
C7	0.071 (3)	0.048 (2)	0.050 (2)	0.004 (2)	0.006 (2)	0.0163 (19)
C8	0.044 (2)	0.043 (2)	0.040 (2)	0.0094 (17)	0.0079 (18)	0.0112 (17)
C9	0.044 (2)	0.050 (2)	0.051 (2)	0.0031 (18)	0.0108 (18)	0.0215 (18)
C10	0.039 (2)	0.044 (2)	0.054 (2)	0.0005 (16)	0.0022 (17)	0.0224 (18)
C11	0.049 (2)	0.062 (3)	0.074 (3)	−0.001 (2)	0.013 (2)	0.032 (2)
C12	0.047 (3)	0.070 (3)	0.094 (4)	−0.012 (2)	−0.001 (2)	0.043 (3)
C13	0.078 (3)	0.048 (3)	0.081 (3)	−0.012 (2)	−0.015 (3)	0.022 (2)
C14	0.078 (3)	0.062 (3)	0.066 (3)	0.002 (3)	0.005 (3)	0.015 (2)
C15	0.052 (2)	0.053 (2)	0.063 (3)	0.000 (2)	0.007 (2)	0.020 (2)
C16	0.044 (2)	0.044 (2)	0.048 (2)	−0.0003 (17)	0.0004 (18)	0.0248 (18)

Geometric parameters (Å, º) top

N1—C1	1.274 (5)	C3—H3	0.930
N1—N2	1.385 (4)	C4—C5	1.384 (6)
N2—C8	1.342 (5)	C4—H4	0.930
N2—H2	0.860	C5—C6	1.371 (7)
N3—C8	1.320 (5)	C5—H5A	0.930
N3—H3A	0.860	C6—C7	1.377 (6)
N3—H3B	0.860	C6—H6	0.930
N4—C9	1.274 (5)	C7—H7	0.930
N4—N5	1.375 (4)	C9—C10	1.453 (5)
N5—C16	1.347 (4)	C9—H9	0.930
N5—H5	0.860	C10—C11	1.385 (5)
N6—C16	1.321 (4)	C10—C15	1.390 (5)
N6—H6A	0.860	C11—C12	1.383 (6)
N6—H6B	0.860	C11—H11	0.930
S1—C8	1.693 (4)	C12—C13	1.362 (6)
S2—C16	1.674 (4)	C12—H12	0.930
C1—C2	1.466 (5)	C13—C14	1.362 (6)
C1—H1	0.930	C13—H13	0.930
C2—C3	1.375 (5)	C14—C15	1.376 (6)
C2—C7	1.388 (5)	C14—H14	0.930
C3—C4	1.377 (6)	C15—H15	0.930

C1—N1—N2	116.5 (3)	C7—C6—H6	119.8
C8—N2—N1	118.4 (3)	C6—C7—C2	120.4 (4)
C8—N2—H2	120.8	C6—C7—H7	119.8
N1—N2—H2	120.8	C2—C7—H7	119.8
C8—N3—H3A	120.0	N3—C8—N2	117.6 (3)
C8—N3—H3B	120.0	N3—C8—S1	122.5 (3)
H3A—N3—H3B	120.0	N2—C8—S1	119.9 (3)
C9—N4—N5	117.1 (3)	N4—C9—C10	120.4 (4)
C16—N5—N4	120.0 (3)	N4—C9—H9	119.8
C16—N5—H5	120.0	C10—C9—H9	119.8
N4—N5—H5	120.0	C11—C10—C15	118.8 (4)
C16—N6—H6A	120.0	C11—C10—C9	119.6 (4)
C16—N6—H6B	120.0	C15—C10—C9	121.6 (3)
H6A—N6—H6B	120.0	C12—C11—C10	120.1 (4)
N1—C1—C2	120.0 (4)	C12—C11—H11	119.9
N1—C1—H1	120.0	C10—C11—H11	119.9
C2—C1—H1	120.0	C13—C12—C11	120.1 (4)
C3—C2—C7	118.8 (4)	C13—C12—H12	119.9
C3—C2—C1	121.9 (4)	C11—C12—H12	119.9
C7—C2—C1	119.3 (4)	C14—C13—C12	120.5 (4)
C2—C3—C4	121.0 (4)	C14—C13—H13	119.8
C2—C3—H3	119.5	C12—C13—H13	119.8
C4—C3—H3	119.5	C13—C14—C15	120.4 (5)
C3—C4—C5	119.8 (5)	C13—C14—H14	119.8
C3—C4—H4	120.1	C15—C14—H14	119.8
C5—C4—H4	120.1	C14—C15—C10	120.1 (4)
C6—C5—C4	119.7 (4)	C14—C15—H15	119.9
C6—C5—H5A	120.2	C10—C15—H15	119.9
C4—C5—H5A	120.2	N6—C16—N5	116.4 (3)
C5—C6—C7	120.4 (4)	N6—C16—S2	123.6 (3)
C5—C6—H6	119.8	N5—C16—S2	120.0 (3)

C1—N1—N2—C8	−177.7 (3)	N1—N2—C8—S1	−173.6 (2)
C9—N4—N5—C16	−176.7 (3)	N5—N4—C9—C10	−175.1 (3)
N2—N1—C1—C2	−175.6 (3)	N4—C9—C10—C11	−174.2 (4)
N1—C1—C2—C3	−4.5 (6)	N4—C9—C10—C15	8.9 (6)
N1—C1—C2—C7	174.5 (4)	C15—C10—C11—C12	0.6 (6)
C7—C2—C3—C4	0.2 (6)	C9—C10—C11—C12	−176.4 (4)
C1—C2—C3—C4	179.3 (4)	C10—C11—C12—C13	0.8 (7)
C2—C3—C4—C5	0.0 (6)	C11—C12—C13—C14	−1.9 (7)
C3—C4—C5—C6	0.0 (6)	C12—C13—C14—C15	1.7 (7)
C4—C5—C6—C7	−0.2 (7)	C13—C14—C15—C10	−0.2 (7)
C5—C6—C7—C2	0.4 (6)	C11—C10—C15—C14	−0.9 (6)
C3—C2—C7—C6	−0.4 (6)	C9—C10—C15—C14	176.0 (4)
C1—C2—C7—C6	−179.5 (3)	N4—N5—C16—N6	7.6 (5)
N1—N2—C8—N3	4.7 (5)	N4—N5—C16—S2	−172.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.86	2.64	3.443 (3)	155
N3—H3A···S1ⁱⁱ	0.86	2.98	3.488 (3)	120
N5—H5···S1ⁱⁱ	0.86	2.61	3.441 (3)	162
N6—H6B···S2ⁱⁱⁱ	0.86	2.51	3.368 (3)	173

Symmetry codes: (i) −x+3, −y+2, −z+2; (ii) x−1, y, z; (iii) −x+2, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₉N₃S
M_r	179.24
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.8692 (13), 12.513 (2), 13.519 (2)
α, β, γ (°)	112.735 (3), 95.384 (2), 96.153 (2)
V (Å³)	900.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.24 × 0.13 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.930, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	4740, 3124, 1846
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.162, 0.95
No. of reflections	3124
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.27

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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
N2—H2···S1ⁱ	0.86	2.64	3.443 (3)	155.1
N3—H3A···S1ⁱⁱ	0.86	2.98	3.488 (3)	120.1
N5—H5···S1ⁱⁱ	0.86	2.61	3.441 (3)	161.9
N6—H6B···S2ⁱⁱⁱ	0.86	2.51	3.368 (3)	173.3

Symmetry codes: (i) −x+3, −y+2, −z+2; (ii) x−1, y, z; (iii) −x+2, −y+2, −z+1.

Acknowledgements

This project was supported by the Foundation of Dongchang College, Liaocheng University (grant No. DCLG2008002).

References

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