Pyridine-2-carbaldehyde thio­semi­carbazone

Song, L.-H.; Zhang, X.; Jiang, K.; Yang, S.-X.

doi:10.1107/S1600536809001962

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o356

doi:10.1107/S1600536809001962

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Pyridine-2-carbaldehyde thiosemicarbazone

Li-Hua Song,^a Xiang Zhang,^b Kun Jiang ^a and Sheng-Xiang Yang ^a ^*

^aHuainan Union University, Huainan, Anhui 232038, People's Republic of China, and ^bAnhui Huainan Environmental Protection Agency, Huainan, Anhui 232038, People's Republic of China
^*Correspondence e-mail: yang_shengxiang@126.com

(Received 26 December 2008; accepted 15 January 2009; online 23 January 2009)

The asymmetric unit of the title compound, C₇H₈N₄S, contains two independent molecules with slightly different conformations; the dihedral angles between the pyridine ring and mean plane of the thiosemicarbazone unit in the two molecules are 2.88 (5) and 6.30 (5)°. Intermolecular N—H⋯N and N—H⋯S hydrogen bonds link the molecules into layers parallel to the ab plane.

Related literature

For the properties of thiosemicarbazones, see: Beraldo & Gambino (2004 ). For the crystal structure of a related compound, see: Gu et al. (2008 ).

Experimental

Crystal data

C₇H₈N₄S
M_r = 180.23
Orthorhombic, P n a 2₁
a = 20.725 (2) Å
b = 4.7857 (6) Å
c = 17.393 (2) Å
V = 1725.1 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 298 (2) K
0.45 × 0.20 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.868, T_max = 0.941
7296 measured reflections
2797 independent reflections
1951 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.165
S = 0.96
2797 reflections
218 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.96 e Å⁻³
Absolute structure: Flack (1983 ), 1218 Friedel pairs
Flack parameter: 0.02 (19)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N8ⁱ	0.86	2.18	3.032 (8)	169
N3—H3B⋯S2ⁱⁱ	0.86	2.57	3.417 (6)	168
N7—H7B⋯S1ⁱⁱⁱ	0.86	2.60	3.455 (7)	172
N5—H5⋯N4	0.86	2.36	3.199 (8)	164
Symmetry codes: (i) x, y+1, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, z]$ .

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/S1600536809001962/cv2504sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001962/cv2504Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones have been known for many years to show a broad spectrum of therapeutic properties against a range of diseases, with antibacterial, antimalarial, antiviral and antitumour activities (Beraldo & Gambino, 2004), In this paper, we present the crystal structure of the title compound, (I).

In (I) (Fig. 1), the bond lengths and angles are normal and comparable to those observed in the reported compound (Gu et al., 2008). The mean planes C10/C11/C12/C13/C14/N8 and C9/N6/N5 form a dihedral angle of 2.88 (5)°, while C3/C4/C5/C6/C7/N4 and C2/N2/N1 form a dihedral angle of 6.30 (5)°.

In the crystal, the intermolecular N—H···N and N—H···S hydrogen bonds (Table 1) link the molecules into layers parallel to ab plane.

Related literature top

For the properties of thiosemicarbazones, see: Beraldo & Gambino (2004). For the crystal structure of related compound, see: Gu et al. (2008).

Experimental top

Pyridine-2-carbaldehyde (0.5 mmol), thiosemicarbazide (0.5 mmol) and 20 ml ethanol were mixed in 50 ml flask. After stirring 30 min at 373 K, the resulting mixture was recrystalized from ethanol, affording the title compound as a orange crystalline solid. Elemental analysis: calculated for C₇H₈N₄S: C 46.65, H 4.47, N 31.09%; found: C46.58, H 4.56, N 31.11%.

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. The content of asymmetric unit of the title compound showing the atomic numbering scheme and 30% probability displacement ellipsoids. Dashed line denotes hydrogen bond.

Pyridine-2-carbaldehyde thiosemicarbazone top

Crystal data top

C₇H₈N₄S	D_x = 1.388 Mg m⁻³
M_r = 180.23	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 1607 reflections
a = 20.725 (2) Å	θ = 2.3–21.6°
b = 4.7857 (6) Å	µ = 0.32 mm⁻¹
c = 17.393 (2) Å	T = 298 K
V = 1725.1 (4) Å³	Block, orange
Z = 8	0.45 × 0.20 × 0.19 mm
F(000) = 752

Data collection top

Bruker SMART CCD area-detector diffractometer	2797 independent reflections
Radiation source: fine-focus sealed tube	1951 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→20
T_min = 0.868, T_max = 0.941	k = −5→5
7296 measured reflections	l = −20→17

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)] = 0.066	H-atom parameters constrained
wR(F²) = 0.165	w = 1/[σ²(F_o²) + (0.0511P)² + 6.2026P] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max = 0.001
2797 reflections	Δρ_max = 0.97 e Å⁻³
218 parameters	Δρ_min = −0.96 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1218 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (19)

Crystal data top

C₇H₈N₄S	V = 1725.1 (4) Å³
M_r = 180.23	Z = 8
Orthorhombic, Pna2₁	Mo Kα radiation
a = 20.725 (2) Å	µ = 0.32 mm⁻¹
b = 4.7857 (6) Å	T = 298 K
c = 17.393 (2) Å	0.45 × 0.20 × 0.19 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2797 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1951 reflections with I > 2σ(I)
T_min = 0.868, T_max = 0.941	R_int = 0.059
7296 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	H-atom parameters constrained
wR(F²) = 0.165	Δρ_max = 0.97 e Å⁻³
S = 0.96	Δρ_min = −0.96 e Å⁻³
2797 reflections	Absolute structure: Flack (1983), 1218 Friedel pairs
218 parameters	Absolute structure parameter: 0.02 (19)
1 restraint

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
N8	0.6201 (3)	−0.1518 (12)	0.5432 (3)	0.0387 (14)
N1	0.5188 (3)	0.9637 (13)	0.4216 (3)	0.0405 (15)
H1	0.5464	0.9533	0.4584	0.049*
N2	0.5264 (3)	0.8019 (12)	0.3566 (3)	0.0385 (14)
N3	0.4295 (3)	1.1564 (14)	0.3672 (3)	0.0514 (18)
H3A	0.4376	1.0591	0.3267	0.062*
H3B	0.3965	1.2651	0.3682	0.062*
N4	0.6451 (3)	0.3132 (13)	0.2989 (3)	0.0443 (15)
N5	0.7451 (3)	0.5151 (13)	0.4275 (3)	0.0411 (14)
H5	0.7213	0.4881	0.3877	0.049*
N6	0.7334 (3)	0.3664 (12)	0.4937 (3)	0.0371 (14)
N7	0.8267 (3)	0.7425 (15)	0.4879 (4)	0.0493 (17)
H7A	0.8170	0.6506	0.5288	0.059*
H7B	0.8580	0.8603	0.4885	0.059*
S1	0.45768 (9)	1.3182 (4)	0.50951 (10)	0.0483 (5)
S2	0.80649 (9)	0.8767 (4)	0.34251 (11)	0.0480 (5)
C1	0.4677 (3)	1.1390 (15)	0.4274 (4)	0.0352 (16)
C2	0.5761 (3)	0.6438 (14)	0.3561 (4)	0.0383 (17)
H2	0.6046	0.6495	0.3975	0.046*
C3	0.5892 (3)	0.4557 (14)	0.2926 (4)	0.0362 (16)
C4	0.5478 (3)	0.4143 (16)	0.2310 (4)	0.0438 (18)
H4	0.5097	0.5157	0.2272	0.053*
C5	0.5637 (4)	0.2228 (17)	0.1758 (5)	0.054 (2)
H5A	0.5367	0.1944	0.1338	0.064*
C6	0.6199 (4)	0.0727 (17)	0.1829 (5)	0.054 (2)
H6	0.6310	−0.0623	0.1468	0.065*
C7	0.6591 (4)	0.1270 (17)	0.2447 (4)	0.049 (2)
H7	0.6976	0.0283	0.2488	0.058*
C8	0.7935 (3)	0.7027 (15)	0.4244 (4)	0.0365 (17)
C9	0.6886 (3)	0.1868 (15)	0.4895 (4)	0.0383 (18)
H9	0.6667	0.1636	0.4432	0.046*
C10	0.6706 (3)	0.0160 (14)	0.5554 (4)	0.0351 (16)
C11	0.7028 (4)	0.0259 (17)	0.6248 (4)	0.049 (2)
H11	0.7375	0.1461	0.6317	0.058*
C12	0.6825 (4)	−0.1454 (17)	0.6836 (5)	0.053 (2)
H12	0.7030	−0.1408	0.7311	0.063*
C13	0.6313 (3)	−0.3245 (16)	0.6709 (4)	0.0471 (19)
H13	0.6166	−0.4438	0.7093	0.057*
C14	0.6029 (3)	−0.3205 (17)	0.6003 (5)	0.047 (2)
H14	0.5691	−0.4445	0.5914	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N8	0.044 (3)	0.040 (3)	0.033 (3)	0.004 (3)	−0.004 (3)	0.003 (3)
N1	0.044 (3)	0.044 (4)	0.033 (3)	0.003 (3)	−0.006 (3)	−0.004 (3)
N2	0.043 (3)	0.039 (3)	0.034 (4)	−0.002 (3)	−0.003 (3)	−0.001 (3)
N3	0.049 (4)	0.064 (4)	0.041 (4)	0.013 (3)	−0.013 (3)	−0.018 (3)
N4	0.043 (3)	0.050 (4)	0.040 (4)	0.002 (3)	−0.005 (3)	−0.002 (3)
N5	0.048 (4)	0.047 (4)	0.029 (3)	0.001 (3)	−0.002 (3)	−0.003 (3)
N6	0.042 (3)	0.037 (3)	0.032 (4)	−0.001 (3)	−0.003 (2)	−0.007 (3)
N7	0.053 (3)	0.057 (4)	0.038 (4)	0.014 (3)	−0.003 (3)	−0.013 (3)
S1	0.0529 (10)	0.0535 (11)	0.0384 (11)	0.0042 (10)	−0.0040 (9)	−0.0095 (10)
S2	0.0506 (10)	0.0558 (11)	0.0377 (10)	0.0049 (10)	−0.0046 (9)	−0.0140 (10)
C1	0.035 (4)	0.034 (4)	0.037 (4)	−0.006 (3)	0.003 (3)	0.001 (3)
C2	0.040 (4)	0.040 (4)	0.034 (4)	0.000 (3)	−0.003 (3)	0.001 (3)
C3	0.043 (4)	0.033 (4)	0.033 (4)	0.001 (3)	0.003 (3)	−0.001 (3)
C4	0.040 (4)	0.050 (5)	0.041 (4)	0.010 (4)	−0.010 (3)	−0.003 (4)
C5	0.058 (5)	0.061 (5)	0.042 (5)	0.000 (5)	−0.014 (4)	−0.004 (4)
C6	0.070 (5)	0.056 (5)	0.038 (5)	0.003 (4)	0.002 (4)	−0.008 (4)
C7	0.044 (4)	0.058 (5)	0.044 (5)	0.008 (4)	0.005 (4)	−0.002 (4)
C8	0.034 (4)	0.037 (4)	0.038 (4)	−0.010 (3)	0.000 (3)	−0.004 (3)
C9	0.043 (4)	0.039 (4)	0.033 (4)	0.001 (3)	−0.003 (3)	−0.002 (3)
C10	0.039 (4)	0.034 (4)	0.033 (4)	0.000 (3)	−0.005 (3)	0.001 (3)
C11	0.050 (4)	0.056 (5)	0.040 (5)	0.008 (4)	−0.011 (3)	−0.006 (4)
C12	0.060 (5)	0.067 (6)	0.031 (4)	−0.006 (4)	−0.011 (4)	−0.006 (4)
C13	0.048 (4)	0.052 (5)	0.042 (5)	0.001 (4)	0.000 (3)	−0.013 (4)
C14	0.041 (4)	0.050 (5)	0.050 (5)	0.003 (4)	−0.002 (3)	0.003 (4)

Geometric parameters (Å, º) top

N8—C14	1.328 (9)	C2—C3	1.450 (9)
N8—C10	1.336 (8)	C2—H2	0.9300
N1—C1	1.354 (8)	C3—C4	1.388 (9)
N1—N2	1.380 (8)	C4—C5	1.367 (10)
N1—H1	0.8600	C4—H4	0.9300
N2—C2	1.278 (8)	C5—C6	1.373 (10)
N3—C1	1.316 (9)	C5—H5A	0.9300
N3—H3A	0.8600	C6—C7	1.372 (10)
N3—H3B	0.8600	C6—H6	0.9300
N4—C7	1.330 (9)	C7—H7	0.9300
N4—C3	1.348 (8)	C9—C10	1.458 (10)
N5—C8	1.347 (8)	C9—H9	0.9300
N5—N6	1.375 (8)	C10—C11	1.379 (9)
N5—H5	0.8600	C11—C12	1.376 (11)
N6—C9	1.267 (9)	C11—H11	0.9300
N7—C8	1.314 (9)	C12—C13	1.382 (10)
N7—H7A	0.8600	C12—H12	0.9300
N7—H7B	0.8600	C13—C14	1.362 (10)
S1—C1	1.679 (7)	C13—H13	0.9300
S2—C8	1.671 (8)	C14—H14	0.9300

C14—N8—C10	117.2 (6)	C4—C5—H5A	120.3
C1—N1—N2	119.9 (6)	C6—C5—H5A	120.3
C1—N1—H1	120.1	C7—C6—C5	118.3 (7)
N2—N1—H1	120.1	C7—C6—H6	120.8
C2—N2—N1	115.5 (6)	C5—C6—H6	120.8
C1—N3—H3A	120.0	N4—C7—C6	123.5 (7)
C1—N3—H3B	120.0	N4—C7—H7	118.2
H3A—N3—H3B	120.0	C6—C7—H7	118.2
C7—N4—C3	118.0 (6)	N7—C8—N5	116.9 (7)
C8—N5—N6	120.7 (6)	N7—C8—S2	124.0 (6)
C8—N5—H5	119.7	N5—C8—S2	119.1 (5)
N6—N5—H5	119.7	N6—C9—C10	121.4 (7)
C9—N6—N5	115.6 (6)	N6—C9—H9	119.3
C8—N7—H7A	120.0	C10—C9—H9	119.3
C8—N7—H7B	120.0	N8—C10—C11	122.6 (7)
H7A—N7—H7B	120.0	N8—C10—C9	114.3 (6)
N3—C1—N1	116.8 (6)	C11—C10—C9	123.1 (7)
N3—C1—S1	124.8 (6)	C12—C11—C10	118.8 (7)
N1—C1—S1	118.5 (5)	C12—C11—H11	120.6
N2—C2—C3	121.5 (6)	C10—C11—H11	120.6
N2—C2—H2	119.2	C11—C12—C13	119.0 (7)
C3—C2—H2	119.2	C11—C12—H12	120.5
N4—C3—C4	121.4 (6)	C13—C12—H12	120.5
N4—C3—C2	114.4 (6)	C14—C13—C12	117.8 (8)
C4—C3—C2	124.2 (6)	C14—C13—H13	121.1
C5—C4—C3	119.3 (7)	C12—C13—H13	121.1
C5—C4—H4	120.4	N8—C14—C13	124.5 (8)
C3—C4—H4	120.4	N8—C14—H14	117.8
C4—C5—C6	119.5 (7)	C13—C14—H14	117.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N8ⁱ	0.86	2.18	3.032 (8)	169
N3—H3B···S2ⁱⁱ	0.86	2.57	3.417 (6)	168
N7—H7B···S1ⁱⁱⁱ	0.86	2.60	3.455 (7)	172
N5—H5···N4	0.86	2.36	3.199 (8)	164

Symmetry codes: (i) x, y+1, z; (ii) x−1/2, −y+5/2, z; (iii) x+1/2, −y+5/2, z.

Experimental details

Crystal data
Chemical formula	C₇H₈N₄S
M_r	180.23
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	298
a, b, c (Å)	20.725 (2), 4.7857 (6), 17.393 (2)
V (Å³)	1725.1 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.45 × 0.20 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.868, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	7296, 2797, 1951
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.165, 0.96
No. of reflections	2797
No. of parameters	218
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.97, −0.96
Absolute structure	Flack (1983), 1218 Friedel pairs
Absolute structure parameter	0.02 (19)

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
N1—H1···N8ⁱ	0.86	2.18	3.032 (8)	169.2
N3—H3B···S2ⁱⁱ	0.86	2.57	3.417 (6)	167.5
N7—H7B···S1ⁱⁱⁱ	0.86	2.60	3.455 (7)	171.5
N5—H5···N4	0.86	2.36	3.199 (8)	164.4

Symmetry codes: (i) x, y+1, z; (ii) x−1/2, −y+5/2, z; (iii) x+1/2, −y+5/2, z.

Acknowledgements

This project was supported by the Foundation of Huainan Union University (grant No. HNU0801).

References

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