Literature DB >> 25249898

5-Hy-droxy-2-nitro-benzaldehyde thio-semicarbazone (HNBATSC).

M Sivasankar Reddy1, Y Sarala2, M Jagadeesh1, Samar K Das3, Varada Reddy Ammireddy1.   

Abstract

The asymmetric unit of the title compound, C8H8N4O3S, consists of two independent mol-ecules. Each mol-ecule is approximately planar with dihedral angles of 8.71 (3) and 1.50 (2)° between the aromatic ring and the thio-semicarbazide moiety while the NO2 group makes dihedral angles of 29.27 (3) and 17.78 (3)° with the benzene ring. In the crystal, the molecules are linked by N-H⋯S, O-H⋯O and N-H⋯O hydrogen bonds, forming two-dimensional networks parallel to (100).

Entities:  

Keywords:  Crystallographic studies; Evolution of mol­ecular structure; Thio­semicarbazone; Triclinic symmetry; crystal structure

Year:  2014        PMID： 25249898      PMCID： PMC4158534          DOI： 10.1107/S1600536814015098

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the crystal structures of similar Schiff base compounds see: Chattopadhyay et al. (1988 ▶). For the structure of 2-hy­droxy-5-nitro­benzaldehyde thio­semicarbazone, see: Alhadi et al. (2008 ▶). For general background to the biological activity and anti-tumour activity of benzaldehyde thiosemicarbazone derivatives, see: Hamre et al. (1950 ▶); Brockman et al. (1956 ▶).

Experimental

Crystal data

C8H8N4O3S M = 240.24 Triclinic, a = 7.1328 (13) Å b = 8.0738 (15) Å c = 17.868 (3) Å α = 102.142 (16)° β = 94.325 (15)° γ = 95.212 (15)° V = 997.1 (3) Å3 Z = 4 Mo Kα radiation μ = 0.32 mm−1 T = 298 K 0.30 × 0.20 × 0.14 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T min = 0.796, T max = 1.000 7083 measured reflections 4063 independent reflections 1973 reflections with I > 2σ(I) R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.065 wR(F 2) = 0.137 S = 0.99 4063 reflections 321 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.28 e Å−3 Δρmin = −0.33 e Å−3 Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: publCIF (Westrip, 2010 ▶). Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814015098/ds2241sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015098/ds2241Isup2.hkl Click here for additional data file. Supporting information file. DOI: 10.1107/S1600536814015098/ds2241Isup3.cml CCDC reference: 1010403 Additional supporting information: crystallographic information; 3D view; checkCIF report
C8H8N4O3SZ = 4
Mr = 240.24F(000) = 496
Triclinic, P1Dx = 1.600 Mg m−3
Hall symbol: -P 1Melting point: 538 K
a = 7.1328 (13) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.0738 (15) ÅCell parameters from 858 reflections
c = 17.868 (3) Åθ = 2.9–23.0°
α = 102.142 (16)°µ = 0.32 mm−1
β = 94.325 (15)°T = 298 K
γ = 95.212 (15)°Block, colorless
V = 997.1 (3) Å30.30 × 0.20 × 0.14 mm
Agilent Xcalibur (Eos, Gemini) diffractometer1973 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.063
Graphite monochromatorθmax = 26.4°, θmin = 2.9°
ω scansh = −8→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)k = −10→9
Tmin = 0.796, Tmax = 1.000l = −22→21
7083 measured reflections3904 standard reflections every 0 reflections
4063 independent reflections intensity decay: none
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H atoms treated by a mixture of independent and constrained refinement
S = 0.99w = 1/[σ2(Fo2) + (0.0237P)2] where P = (Fo2 + 2Fc2)/3
4063 reflections(Δ/σ)max < 0.001
321 parametersΔρmax = 0.28 e Å−3
0 restraintsΔρmin = −0.33 e Å−3
Experimental. Absorption correction: (CrysAlisPro, Agilent Technologies, 2013) Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
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.
xyzUiso*/Ueq
S10.47754 (18)−0.25982 (13)0.26463 (6)0.0460 (3)
S20.46264 (19)1.26534 (13)0.31459 (7)0.0502 (4)
N30.6268 (5)−0.0428 (4)0.3896 (2)0.0412 (10)
N20.7076 (5)−0.0018 (4)0.46366 (19)0.0392 (9)
N60.6606 (5)1.0485 (4)0.1259 (2)0.0437 (9)
N80.6172 (7)1.3598 (5)0.1978 (3)0.0520 (12)
N40.6096 (6)−0.3229 (5)0.3963 (3)0.0483 (11)
C70.7530 (6)0.1563 (5)0.4924 (2)0.0413 (11)
H70.73020.23760.46390.050*
N70.5833 (5)1.0750 (4)0.1944 (2)0.0451 (10)
C10.9021 (6)0.3740 (5)0.6117 (2)0.0381 (11)
C60.8416 (6)0.2067 (5)0.5711 (2)0.0388 (11)
C80.5768 (6)−0.2103 (5)0.3549 (2)0.0363 (10)
C160.5603 (6)1.2346 (5)0.2306 (2)0.0405 (11)
O40.9804 (6)−0.0116 (5)0.7225 (2)0.0636 (12)
C50.8744 (6)0.0787 (5)0.6102 (2)0.0426 (11)
H50.8391−0.03440.58530.051*
C90.7661 (6)0.6841 (5)−0.0180 (2)0.0405 (11)
N10.8718 (6)0.5229 (5)0.5792 (2)0.0501 (11)
O50.9645 (5)0.6588 (4)0.6107 (2)0.0773 (12)
C130.7647 (6)0.9729 (5)−0.0234 (2)0.0428 (11)
H130.74241.0838−0.00200.051*
C40.9566 (7)0.1144 (6)0.6837 (2)0.0455 (12)
O60.8570 (5)1.0706 (4)−0.1298 (2)0.0665 (11)
C140.7334 (6)0.8488 (5)0.0184 (2)0.0397 (11)
C20.9894 (6)0.4091 (6)0.6850 (3)0.0505 (12)
H21.03050.52130.70960.061*
C100.8258 (7)0.6471 (6)−0.0898 (3)0.0521 (13)
H100.84360.5355−0.11230.063*
O70.7578 (6)0.5092 (4)0.5244 (2)0.0791 (13)
C120.8277 (7)0.9384 (6)−0.0954 (3)0.0484 (12)
C110.8594 (7)0.7740 (6)−0.1289 (3)0.0533 (13)
H110.90310.7499−0.17730.064*
C150.6601 (7)0.8923 (5)0.0926 (2)0.0474 (12)
H150.61290.80670.11590.057*
C31.0168 (6)0.2796 (6)0.7225 (3)0.0500 (12)
H31.07440.30270.77260.060*
O100.7007 (7)0.4005 (4)−0.0180 (2)0.0960 (15)
N50.7434 (6)0.5429 (5)0.0211 (3)0.0558 (12)
O90.7659 (6)0.5702 (4)0.0907 (2)0.0748 (12)
H4B0.572 (6)−0.428 (5)0.376 (2)0.054 (15)*
H3N0.598 (6)0.035 (5)0.358 (2)0.069 (15)*
H7N0.534 (6)0.983 (5)0.226 (2)0.081 (15)*
H8A0.667 (7)1.338 (6)0.147 (3)0.080 (18)*
H4A0.659 (6)−0.292 (5)0.444 (2)0.048 (15)*
H8B0.617 (9)1.453 (7)0.224 (4)0.13 (3)*
H6O0.891 (7)1.030 (6)−0.184 (3)0.082 (18)*
H4O0.939 (9)−0.096 (7)0.697 (3)0.10 (3)*
U11U22U33U12U13U23
S10.0546 (9)0.0391 (6)0.0446 (8)0.0091 (6)0.0054 (6)0.0076 (5)
S20.0669 (10)0.0391 (6)0.0465 (8)0.0115 (6)0.0140 (7)0.0084 (5)
N30.050 (3)0.035 (2)0.039 (2)0.0082 (19)0.0018 (19)0.0072 (18)
N20.042 (2)0.039 (2)0.036 (2)0.0052 (18)0.0036 (18)0.0061 (17)
N60.048 (3)0.043 (2)0.040 (2)0.0083 (19)0.0091 (19)0.0047 (18)
N80.074 (3)0.034 (2)0.048 (3)0.004 (2)0.016 (2)0.006 (2)
N40.064 (3)0.034 (2)0.046 (3)0.010 (2)−0.002 (2)0.007 (2)
C70.043 (3)0.037 (2)0.047 (3)0.005 (2)0.008 (2)0.012 (2)
N70.057 (3)0.0358 (19)0.045 (2)0.007 (2)0.014 (2)0.0111 (19)
C10.037 (3)0.034 (2)0.042 (3)0.002 (2)0.008 (2)0.007 (2)
C60.032 (3)0.041 (2)0.043 (3)0.003 (2)0.007 (2)0.008 (2)
C80.030 (3)0.038 (2)0.045 (3)0.007 (2)0.009 (2)0.015 (2)
C160.047 (3)0.038 (2)0.038 (3)0.005 (2)0.001 (2)0.012 (2)
O40.092 (3)0.053 (2)0.043 (2)0.009 (2)−0.010 (2)0.0098 (19)
C50.048 (3)0.035 (2)0.044 (3)0.005 (2)0.006 (2)0.006 (2)
C90.044 (3)0.040 (2)0.039 (3)0.008 (2)0.004 (2)0.010 (2)
N10.062 (3)0.036 (2)0.054 (3)0.009 (2)0.024 (2)0.008 (2)
O50.079 (3)0.0408 (19)0.109 (3)−0.005 (2)0.014 (2)0.012 (2)
C130.043 (3)0.039 (2)0.048 (3)0.007 (2)0.005 (2)0.012 (2)
C40.053 (3)0.051 (3)0.034 (3)0.009 (3)0.004 (2)0.011 (2)
O60.085 (3)0.067 (2)0.052 (2)0.003 (2)0.018 (2)0.023 (2)
C140.044 (3)0.037 (2)0.038 (3)0.004 (2)0.002 (2)0.009 (2)
C20.044 (3)0.044 (3)0.057 (3)−0.002 (2)0.011 (3)−0.004 (2)
C100.063 (4)0.049 (3)0.042 (3)0.018 (3)0.004 (3)0.000 (2)
O70.122 (4)0.056 (2)0.059 (3)0.019 (2)−0.011 (2)0.015 (2)
C120.043 (3)0.060 (3)0.045 (3)0.006 (3)0.006 (2)0.018 (3)
C110.059 (4)0.063 (3)0.041 (3)0.018 (3)0.016 (3)0.008 (2)
C150.061 (4)0.038 (2)0.044 (3)0.004 (2)0.007 (3)0.011 (2)
C30.042 (3)0.055 (3)0.050 (3)0.000 (3)0.001 (2)0.008 (3)
O100.147 (4)0.0392 (19)0.097 (3)0.009 (2)0.014 (3)0.005 (2)
N50.073 (3)0.038 (2)0.055 (3)0.011 (2)0.007 (2)0.005 (2)
O90.113 (4)0.063 (2)0.056 (2)0.020 (2)0.019 (2)0.023 (2)
S1—C81.664 (4)C4—C31.381 (6)
S2—C161.682 (4)O6—C121.347 (5)
N3—N21.364 (4)C14—C151.448 (6)
N3—C81.366 (5)C2—C31.376 (5)
N2—C71.274 (5)C10—C111.370 (5)
N6—C151.276 (5)C12—C111.382 (6)
N6—N71.365 (5)O10—N51.212 (4)
N8—C161.321 (5)N5—O91.212 (4)
N4—C81.312 (5)N3—H3N0.96 (4)
C7—C61.457 (5)N8—H8A0.98 (5)
N7—C161.345 (5)N8—H8B0.80 (6)
C1—C21.368 (5)N4—H4B0.86 (4)
C1—C61.403 (5)N4—H4A0.87 (4)
C1—N11.467 (5)C7—H70.9300
C6—C51.390 (5)N7—H7N1.07 (4)
O4—C41.362 (5)O4—H4O0.76 (5)
C5—C41.359 (5)C5—H50.9300
C9—C101.363 (5)C13—H130.9300
C9—C141.401 (5)O6—H6O1.00 (5)
C9—N51.461 (5)C2—H20.9300
N1—O71.204 (4)C10—H100.9300
N1—O51.229 (4)C11—H110.9300
C13—C121.377 (5)C15—H150.9300
C13—C141.381 (5)C3—H30.9300
N2—N3—C8119.2 (3)C13—C12—C11119.9 (4)
C7—N2—N3116.2 (3)C10—C11—C12119.2 (4)
C15—N6—N7114.8 (4)N6—C15—C14119.7 (4)
N2—C7—C6118.4 (4)C2—C3—C4118.1 (4)
C16—N7—N6119.7 (3)O9—N5—O10122.0 (4)
C2—C1—C6122.1 (4)O9—N5—C9120.0 (4)
C2—C1—N1115.5 (4)O10—N5—C9118.0 (4)
C6—C1—N1122.3 (4)N2—N3—H3N127 (3)
C5—C6—C1116.0 (4)C8—N3—H3N114 (3)
C5—C6—C7117.9 (4)C16—N8—H8A122 (3)
C1—C6—C7126.2 (4)C16—N8—H8B114 (4)
N4—C8—N3116.9 (4)H8A—N8—H8B124 (5)
N4—C8—S1124.0 (4)C8—N4—H4B117 (3)
N3—C8—S1119.0 (3)C8—N4—H4A122 (3)
N8—C16—N7117.4 (4)H4B—N4—H4A121 (4)
N8—C16—S2123.4 (3)N2—C7—H7120.8
N7—C16—S2119.2 (3)C6—C7—H7120.8
C4—C5—C6121.7 (4)C16—N7—H7N112 (2)
C10—C9—C14122.7 (4)N6—N7—H7N129 (2)
C10—C9—N5116.5 (4)C4—O4—H4O108 (4)
C14—C9—N5120.8 (4)C4—C5—H5119.1
O7—N1—O5122.7 (4)C6—C5—H5119.1
O7—N1—C1119.9 (4)C12—C13—H13118.8
O5—N1—C1117.4 (4)C14—C13—H13118.8
C12—C13—C14122.5 (4)C12—O6—H6O110 (2)
C5—C4—O4121.2 (4)C1—C2—H2119.8
C5—C4—C3121.5 (4)C3—C2—H2119.8
O4—C4—C3117.3 (4)C9—C10—H10120.0
C13—C14—C9115.6 (4)C11—C10—H10120.0
C13—C14—C15119.6 (4)C10—C11—H11120.4
C9—C14—C15124.6 (4)C12—C11—H11120.4
C1—C2—C3120.5 (4)N6—C15—H15120.1
C9—C10—C11120.1 (4)C14—C15—H15120.1
O6—C12—C13117.0 (4)C2—C3—H3120.9
O6—C12—C11123.1 (5)C4—C3—H3120.9
C8—N3—N2—C7179.2 (4)C10—C9—C14—C130.2 (7)
N3—N2—C7—C6−179.4 (4)N5—C9—C14—C13178.2 (4)
C15—N6—N7—C16−173.7 (4)C10—C9—C14—C15176.4 (4)
C2—C1—C6—C50.5 (6)N5—C9—C14—C15−5.7 (7)
N1—C1—C6—C5−177.9 (4)C6—C1—C2—C3−1.6 (7)
C2—C1—C6—C7−178.0 (4)N1—C1—C2—C3176.9 (4)
N1—C1—C6—C73.6 (7)C14—C9—C10—C111.2 (8)
N2—C7—C6—C51.0 (6)N5—C9—C10—C11−176.8 (4)
N2—C7—C6—C1179.4 (4)C14—C13—C12—O6−178.6 (4)
N2—N3—C8—N40.4 (6)C14—C13—C12—C110.9 (7)
N2—N3—C8—S1179.8 (3)C9—C10—C11—C12−1.6 (7)
N6—N7—C16—N8−0.8 (7)O6—C12—C11—C10−180.0 (4)
N6—N7—C16—S2179.3 (3)C13—C12—C11—C100.6 (8)
C1—C6—C5—C41.3 (6)N7—N6—C15—C14178.1 (4)
C7—C6—C5—C4179.9 (4)C13—C14—C15—N6−14.0 (7)
C2—C1—N1—O7−161.7 (4)C9—C14—C15—N6170.0 (4)
C6—C1—N1—O716.8 (7)C1—C2—C3—C41.0 (7)
C2—C1—N1—O517.3 (6)C5—C4—C3—C20.8 (7)
C6—C1—N1—O5−164.2 (4)O4—C4—C3—C2−178.3 (4)
C6—C5—C4—O4177.1 (4)C10—C9—N5—O9150.5 (5)
C6—C5—C4—C3−2.0 (7)C14—C9—N5—O9−27.6 (7)
C12—C13—C14—C9−1.3 (7)C10—C9—N5—O10−30.0 (7)
C12—C13—C14—C15−177.6 (4)C14—C9—N5—O10152.0 (5)
D—H···AD—HH···AD···AD—H···A
N8—H8B···S1i0.80 (6)2.59 (6)3.323 (5)153 (6)
N7—H7N···S1ii1.07 (4)2.22 (4)3.264 (4)162 (3)
N3—H3N···S2iii0.95 (4)2.41 (4)3.324 (4)160 (4)
N4—H4B···S2iv0.86 (4)2.51 (4)3.373 (4)180 (4)
O4—H4O···O5iii0.76 (5)2.27 (6)2.960 (5)153 (7)
C3—H3···O9v0.932.573.491 (6)168
C7—H7···O5v0.932.793.295 (5)115
N4—H4A···O7iii0.87 (4)2.48 (4)3.066 (5)125 (3)
O6—H6O···O4vi1.01 (5)1.81 (5)2.810 (5)170 (4)
N8—H8A···O9ii0.98 (5)2.39 (4)3.002 (5)120 (3)
C13—H13···O10ii0.932.673.506 (5)150
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A D—HH⋯A D⋯A D—H⋯A
N8—H8B⋯S1i 0.80 (6)2.59 (6)3.323 (5)153 (6)
N7—H7N⋯S1ii 1.07 (4)2.22 (4)3.264 (4)162 (3)
N3—H3N⋯S2iii 0.95 (4)2.41 (4)3.324 (4)160 (4)
N4—H4B⋯S2iv 0.86 (4)2.51 (4)3.373 (4)180 (4)
O4—H4O⋯O5iii 0.76 (5)2.27 (6)2.960 (5)153 (7)
C3—H3⋯O9v 0.932.573.491 (6)168
C7—H7⋯O5v 0.932.793.295 (5)115
N4—H4A⋯O7iii 0.87 (4)2.48 (4)3.066 (5)125 (3)
O6—H6O⋯O4vi 1.01 (5)1.81 (5)2.810 (5)170 (4)
N8—H8A⋯O9ii 0.98 (5)2.39 (4)3.002 (5)120 (3)
C13—H13⋯O10ii 0.932.673.506 (5)150

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

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