2-Hydr­oxy-5-nitro­benzaldehyde thio­semicarbazone

Alhadi, A.A.; Ali, H.M.; Puvaneswary, S.; Robinson, W.T.; Ng, S.W.

doi:10.1107/S1600536808022976

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1606

doi:10.1107/S1600536808022976

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2-Hydroxy-5-nitrobenzaldehyde thiosemicarbazone

Abeer A. Alhadi,^a Hapipah M. Ali,^a Subramaniam Puvaneswary,^a Ward T. Robinson ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 10 July 2008; accepted 22 July 2008; online 26 July 2008)

The molecule of the title compound, C₈H₈N₄O₃S, is planar. Adjacent molecules are linked through O—H⋯S, N—H⋯S and N—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For the structure of 2-hydroxybenzaldehyde thiosemicarbazone, see: Chattopadhyay et al. (1988 ).

Experimental

Crystal data

C₈H₈N₄O₃S
M_r = 240.24
Monoclinic, P 2₁ /n
a = 12.6157 (3) Å
b = 5.4815 (2) Å
c = 14.2397 (2) Å
β = 94.039 (2)°
V = 982.27 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 (2) K
0.49 × 0.01 × 0.01 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.856, T_max = 0.997
9462 measured reflections
2247 independent reflections
1725 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.111
S = 1.04
2247 reflections
161 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯S1ⁱ	0.84 (1)	2.34 (1)	3.175 (2)	170 (3)
N3—H31⋯S1ⁱⁱ	0.85 (1)	2.50 (1)	3.337 (2)	167 (2)
N4—H41⋯O2ⁱⁱⁱ	0.85 (1)	2.14 (1)	2.987 (2)	172 (3)
N4—H42⋯O3^iv	0.85 (1)	2.31 (2)	3.044 (2)	144 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+3, -z+1; (iii) $[-x+{\script{3\over 2}}, y+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022976/rk2102sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808022976/rk2102Isup2.hkl

checkCIF report

Comment top

Salicylaldehyde thiosemicarbazone uses its 2-hydroxy group to form an intramolecular hydrogen bond (Chattopadhyay et al., 1988). In the present compound, the electron-withdrawing nitro group that is para to the hydroxy group renders the hydroxy group much more acidic, so that the compound (Scheme) is able to use the hydroxy group to form a hydrogen bond to an adjacent molecule instead (Fig. 1).

Related literature top

For the structure of 2-hydroxybenzaldehyde thiosemicarbazone, see: Chattopadhyay et al. (1988).

Experimental top

The Schiff base was prepared by refluxing thiosemicarbazide (0.30 g, 3.3 mmol) and 5-nitro-2-hydroxybenzaldehyde (0.55 g, 3.3 mmol) in ethanol for 2 h. The product was recrystallized from ethanol.

Computing details top

Data collection: APEX2 (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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Molecular structure of title compound with the atom numbering scheme (Barbour, 2001). Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

2-Hydroxy-5-nitrobenzaldehyde thiosemicarbazone top

Crystal data top

C₈H₈N₄O₃S	F(000) = 496
M_r = 240.24	D_x = 1.625 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2540 reflections
a = 12.6157 (3) Å	θ = 2.2–29.5°
b = 5.4815 (2) Å	µ = 0.33 mm⁻¹
c = 14.2397 (2) Å	T = 100 K
β = 94.039 (2)°	Block, yellow
V = 982.27 (5) Å³	0.49 × 0.01 × 0.01 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2247 independent reflections
Radiation source: fine-focus sealed tube	1725 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→15
T_min = 0.856, T_max = 0.997	k = −5→7
9462 measured reflections	l = −18→18

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0616P)² + 0.4126P] where P = (F_o² + 2F_c²)/3
2247 reflections	(Δ/σ)_max = 0.001
161 parameters	Δρ_max = 0.47 e Å⁻³
8 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₈H₈N₄O₃S	V = 982.27 (5) Å³
M_r = 240.24	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.6157 (3) Å	µ = 0.33 mm⁻¹
b = 5.4815 (2) Å	T = 100 K
c = 14.2397 (2) Å	0.49 × 0.01 × 0.01 mm
β = 94.039 (2)°

Data collection top

Bruker SMART APEX diffractometer	2247 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1725 reflections with I > 2σ(I)
T_min = 0.856, T_max = 0.997	R_int = 0.037
9462 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	8 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.47 e Å⁻³
2247 reflections	Δρ_min = −0.23 e Å⁻³
161 parameters

Special details top

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 >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	0.45571 (4)	1.58779 (11)	0.35227 (3)	0.02368 (17)
O1	0.78686 (12)	0.8925 (3)	0.67628 (10)	0.0271 (4)
O2	0.92212 (11)	0.0797 (3)	0.40282 (10)	0.0258 (3)
O3	0.82499 (11)	0.3034 (3)	0.30592 (9)	0.0243 (3)
N1	0.86480 (13)	0.2593 (3)	0.38518 (11)	0.0200 (4)
N2	0.64392 (12)	1.0445 (3)	0.42660 (11)	0.0179 (4)
N3	0.56870 (13)	1.2266 (3)	0.42711 (11)	0.0199 (4)
N4	0.57458 (14)	1.2637 (4)	0.26788 (12)	0.0222 (4)
C1	0.80683 (15)	0.7307 (4)	0.60870 (13)	0.0201 (4)
C2	0.87612 (16)	0.5353 (4)	0.62369 (13)	0.0215 (4)
H2	0.9106	0.5093	0.6843	0.026*
C3	0.89488 (15)	0.3793 (4)	0.55093 (13)	0.0211 (4)
H3	0.9414	0.2440	0.5609	0.025*
C4	0.84439 (15)	0.4236 (4)	0.46231 (13)	0.0185 (4)
C5	0.77372 (15)	0.6132 (4)	0.44565 (13)	0.0180 (4)
H5	0.7398	0.6378	0.3847	0.022*
C6	0.75301 (14)	0.7676 (4)	0.51947 (13)	0.0179 (4)
C7	0.67610 (15)	0.9650 (4)	0.50831 (13)	0.0197 (4)
H7	0.6492	1.0363	0.5626	0.024*
C8	0.53819 (15)	1.3452 (4)	0.34732 (13)	0.0195 (4)
H1	0.8337 (17)	0.880 (5)	0.7212 (14)	0.044 (8)*
H31	0.5515 (19)	1.281 (5)	0.4800 (11)	0.036 (7)*
H41	0.570 (2)	1.360 (4)	0.2208 (13)	0.038 (7)*
H42	0.6185 (16)	1.145 (3)	0.2711 (17)	0.030 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0247 (3)	0.0265 (3)	0.0193 (2)	0.0085 (2)	−0.00213 (18)	−0.0004 (2)
O1	0.0303 (8)	0.0290 (9)	0.0209 (7)	0.0072 (7)	−0.0059 (6)	−0.0041 (6)
O2	0.0268 (8)	0.0220 (8)	0.0287 (7)	0.0074 (7)	0.0022 (6)	−0.0008 (6)
O3	0.0268 (8)	0.0259 (9)	0.0200 (7)	0.0004 (7)	0.0016 (6)	0.0007 (6)
N1	0.0181 (8)	0.0185 (9)	0.0239 (8)	−0.0036 (7)	0.0047 (6)	0.0002 (7)
N2	0.0152 (8)	0.0175 (9)	0.0210 (7)	0.0005 (7)	0.0014 (6)	0.0008 (6)
N3	0.0201 (8)	0.0220 (10)	0.0174 (8)	0.0051 (7)	0.0008 (6)	0.0007 (7)
N4	0.0249 (9)	0.0228 (10)	0.0191 (8)	0.0049 (8)	0.0019 (7)	0.0015 (7)
C1	0.0201 (10)	0.0204 (11)	0.0200 (9)	−0.0020 (9)	0.0024 (7)	−0.0005 (8)
C2	0.0197 (10)	0.0242 (12)	0.0200 (9)	0.0011 (9)	−0.0029 (7)	0.0025 (8)
C3	0.0178 (10)	0.0198 (11)	0.0254 (10)	0.0022 (8)	−0.0001 (7)	0.0037 (8)
C4	0.0158 (9)	0.0175 (10)	0.0224 (9)	−0.0035 (8)	0.0029 (7)	−0.0005 (8)
C5	0.0155 (9)	0.0187 (11)	0.0198 (9)	−0.0028 (8)	0.0012 (7)	0.0043 (7)
C6	0.0149 (9)	0.0189 (11)	0.0199 (9)	−0.0013 (8)	0.0012 (7)	0.0023 (8)
C7	0.0188 (10)	0.0205 (11)	0.0198 (9)	0.0007 (8)	0.0015 (7)	−0.0010 (8)
C8	0.0166 (9)	0.0208 (11)	0.0207 (9)	−0.0024 (8)	−0.0016 (7)	0.0009 (8)

Geometric parameters (Å, º) top

S1—C8	1.693 (2)	N4—H42	0.852 (10)
O1—C1	1.345 (2)	C1—C2	1.390 (3)
O1—H1	0.842 (10)	C1—C6	1.412 (2)
O2—N1	1.237 (2)	C2—C3	1.377 (3)
O3—N1	1.227 (2)	C2—H2	0.9500
N1—C4	1.457 (3)	C3—C4	1.394 (3)
N2—C7	1.281 (2)	C3—H3	0.9500
N2—N3	1.378 (2)	C4—C5	1.379 (3)
N3—C8	1.342 (2)	C5—C6	1.389 (3)
N3—H31	0.852 (10)	C5—H5	0.9500
N4—C8	1.328 (3)	C6—C7	1.455 (3)
N4—H41	0.853 (10)	C7—H7	0.9500

C1—O1—H1	109 (2)	C2—C3—H3	120.6
O3—N1—O2	122.64 (17)	C4—C3—H3	120.6
O3—N1—C4	119.27 (17)	C5—C4—C3	122.38 (19)
O2—N1—C4	118.09 (16)	C5—C4—N1	118.87 (17)
C7—N2—N3	114.57 (16)	C3—C4—N1	118.73 (18)
C8—N3—N2	120.22 (16)	C4—C5—C6	118.88 (17)
C8—N3—H31	120.1 (18)	C4—C5—H5	120.6
N2—N3—H31	118.6 (18)	C6—C5—H5	120.6
C8—N4—H41	116.8 (18)	C5—C6—C1	119.31 (18)
C8—N4—H42	118.3 (17)	C5—C6—C7	122.03 (17)
H41—N4—H42	122 (2)	C1—C6—C7	118.65 (18)
O1—C1—C2	123.07 (17)	N2—C7—C6	121.22 (18)
O1—C1—C6	116.53 (18)	N2—C7—H7	119.4
C2—C1—C6	120.40 (18)	C6—C7—H7	119.4
C3—C2—C1	120.18 (18)	N4—C8—N3	117.54 (19)
C3—C2—H2	119.9	N4—C8—S1	123.38 (15)
C1—C2—H2	119.9	N3—C8—S1	119.07 (15)
C2—C3—C4	118.77 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···S1ⁱ	0.84 (1)	2.34 (1)	3.175 (2)	170 (3)
N3—H31···S1ⁱⁱ	0.85 (1)	2.50 (1)	3.337 (2)	167 (2)
N4—H41···O2ⁱⁱⁱ	0.85 (1)	2.14 (1)	2.987 (2)	172 (3)
N4—H42···O3^iv	0.85 (1)	2.31 (2)	3.044 (2)	144 (2)

Symmetry codes: (i) x+1/2, −y+5/2, z+1/2; (ii) −x+1, −y+3, −z+1; (iii) −x+3/2, y+3/2, −z+1/2; (iv) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₈N₄O₃S
M_r	240.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	12.6157 (3), 5.4815 (2), 14.2397 (2)
β (°)	94.039 (2)
V (Å³)	982.27 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.49 × 0.01 × 0.01

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.856, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	9462, 2247, 1725
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.111, 1.04
No. of reflections	2247
No. of parameters	161
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.23

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···S1ⁱ	0.84 (1)	2.34 (1)	3.175 (2)	170 (3)
N3—H31···S1ⁱⁱ	0.85 (1)	2.50 (1)	3.337 (2)	167 (2)
N4—H41···O2ⁱⁱⁱ	0.85 (1)	2.14 (1)	2.987 (2)	172 (3)
N4—H42···O3^iv	0.85 (1)	2.31 (2)	3.044 (2)	144 (2)

Symmetry codes: (i) x+1/2, −y+5/2, z+1/2; (ii) −x+1, −y+3, −z+1; (iii) −x+3/2, y+3/2, −z+1/2; (iv) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

The authors thank the Science Fund (grant Nos. 12-02-03-2031 and 12-02-03-2051) and the University of Malaya (PJP) for supporting this study. We are grateful to the University of Malaya for the purchase of the diffractometer.

References

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