PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2999.
Published online 2010 October 31. doi:  10.1107/S1600536810043357
PMCID: PMC3009273

5-Bromo-2-hy­droxy­benzaldehyde thio­semicarbazone

Abstract

The mol­ecule of the title compound, C8H8BrN3OS, is close to being planar, with maximum deviations of −0.127 (3) and 0.135 (5) Å for the N atoms of the –NH– and NH2– groups, respectively. Intra­molecular N—H(...)N and O—H(...)N hydrogen bonds to the same acceptor N atom generate S(5) and S(6) ring motifs. In the crystal structure, mol­ecules are connected into [010] chains by pairs of N—H(...)S hydrogen bonds with R 2 2(8) graph-set motifs. The crystal used for data collection was found to be an inversion twin.

Related literature

For background on the biological activities and pharmaceutical properties of thio­semicarbazones and their derivatives, see: Casas et al. (2000 [triangle]); Ferrari et al. (2000 [triangle]); Maccioni et al. (2003 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2999-scheme1.jpg

Experimental

Crystal data

  • C8H8BrN3OS
  • M r = 274.14
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2999-efi1.jpg
  • a = 4.4564 (2) Å
  • b = 8.3515 (3) Å
  • c = 27.7153 (14) Å
  • V = 1031.50 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 4.16 mm−1
  • T = 296 K
  • 0.13 × 0.09 × 0.05 mm

Data collection

  • Stoe IPDS II diffractometer
  • Absorption correction: integration (X-RED32; Stoe & Cie, 2002 [triangle]) T min = 0.614, T max = 0.819
  • 9532 measured reflections
  • 1934 independent reflections
  • 1782 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.063
  • S = 1.04
  • 1934 reflections
  • 144 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.54 e Å−3
  • Δρmin = −0.29 e Å−3
  • Absolute structure: Flack (1983 [triangle]), with 744 Freidel pairs
  • Flack parameter: 0.477 (11)

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 [triangle]); program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043357/hb5704sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043357/hb5704Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant F.279 of the University Research Fund). HK thanks Payame Noor University (PNU) for financial support of this work. RK thanks the Science and Research Branch of Islamic Azad University of Tehran.

supplementary crystallographic information

Comment

Thiosemicarbazones constitute an important class of N,S donor ligands due to their propensity to react with a wide range of metals (Casas et al., 2000). Thiosemicarbazones exhibit various biological activities and have therefore attracted considerable pharmaceutical interest (Maccioni et al., 2003; Ferrari et al., 2000). We here report the crystal structure of the title compound (I).

The title molecule (I) shown in Fig. 1 is almost planar with the maximum deviations of -0.127 (3) Å for N2 and 0.135 (5) Å for N3. All bond lengths and angles are normal (Allen et al., 1987). In each independent molecule, there are intramolecular N—H···N and O—H···N hydrogen bonds, generating the S(5) and S(6) ring motifs, respectively (Table 1, Fig. 2).

In the crystal structure, adjacent molecules are linked by N—H···S hydrogen bonds, forming R22(8) dimers (Bernstein et al., 1995) (Table 1, Fig. 2).

Experimental

A mixture of 5-bromosalicylalehyde (0.01 mol) and hydrazinecarbothioamide (0.01 mol) in 20 ml of ethanol was refluxed for about 2 h. On cooling, the solid separated was filtered and recrystallized from ethanol to yield colourless prisms of (I).

Refinement

The H atoms of the O—H, N—H and NH2 groups were found from a difference Fourier map and their positional parameters were constrained [O1—H1 = 0.81 (3) and N2—HN1 = 0.84 (3), N3—HN2 = 0.86 (3) and N3—HN3 = 0.87 (4) Å]. Their isotropic displacement parameters were refined with Uiso(H) = 1.2Ueq(N) for the NH and NH2 groups and Uiso(H) = 1.5Ueq(O) for hydroxyl group. The remaining H atoms were placed in idealized positions and allowed to ride on their parent atoms, with C—H = 0.93 Å, and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
View of the title molecule, showing displacement ellipsoids for non-H atoms drawn at the 50% probability level.
Fig. 2.
View of the hydrogen bonding interactions of (I), showing dimer formation by R22(8) ring motif within chains.

Crystal data

C8H8BrN3OSF(000) = 544
Mr = 274.14Dx = 1.765 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 17874 reflections
a = 4.4564 (2) Åθ = 1.5–26.1°
b = 8.3515 (3) ŵ = 4.16 mm1
c = 27.7153 (14) ÅT = 296 K
V = 1031.50 (8) Å3Prism, colourless
Z = 40.13 × 0.09 × 0.05 mm

Data collection

Stoe IPDS II diffractometer1934 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus1782 reflections with I > 2σ(I)
plane graphiteRint = 0.037
Detector resolution: 6.67 pixels mm-1θmax = 25.6°, θmin = 2.6°
ω scansh = −5→5
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)k = −10→10
Tmin = 0.614, Tmax = 0.819l = −33→33
9532 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.063w = 1/[σ2(Fo2) + (0.0281P)2 + 0.5533P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1934 reflectionsΔρmax = 0.54 e Å3
144 parametersΔρmin = −0.29 e Å3
4 restraintsAbsolute structure: Flack (1983), with 744 Freidel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.477 (11)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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)

xyzUiso*/Ueq
Br10.80875 (10)−0.32853 (5)0.06313 (1)0.0606 (1)
S1−0.5577 (2)0.35791 (11)0.26412 (3)0.0517 (3)
O10.2883 (6)0.3331 (3)0.08454 (10)0.0596 (9)
N1−0.0227 (7)0.2201 (3)0.16022 (10)0.0407 (9)
N2−0.2226 (8)0.2237 (3)0.19824 (9)0.0408 (9)
N3−0.2703 (13)0.4940 (4)0.19194 (14)0.0786 (16)
C10.4380 (8)−0.0920 (4)0.10693 (12)0.0416 (10)
C20.6401 (7)−0.1207 (4)0.07038 (11)0.0420 (10)
C30.7260 (8)0.0001 (5)0.03956 (13)0.0486 (11)
C40.6033 (8)0.1505 (5)0.04464 (12)0.0485 (11)
C50.3981 (7)0.1819 (5)0.08111 (11)0.0418 (10)
C60.3119 (8)0.0589 (4)0.11293 (11)0.0382 (9)
C70.0966 (8)0.0836 (4)0.15148 (11)0.0389 (10)
C8−0.3365 (8)0.3610 (4)0.21496 (11)0.0416 (10)
H10.38530−0.174500.127800.0500*
HN2−0.323 (12)0.587 (3)0.2025 (16)0.089 (16)*
HN1−0.260 (9)0.135 (3)0.2114 (12)0.050 (11)*
H30.86620−0.019800.015400.0580*
HO10.169 (8)0.334 (6)0.1064 (12)0.071 (14)*
H40.658400.231800.023500.0580*
HN3−0.144 (9)0.486 (5)0.1681 (12)0.071 (14)*
H70.04290−0.003200.170600.0470*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0606 (2)0.0575 (2)0.0638 (2)0.0057 (2)0.0074 (2)−0.0153 (2)
S10.0657 (6)0.0400 (5)0.0495 (5)−0.0007 (5)0.0199 (4)−0.0055 (4)
O10.0646 (16)0.0493 (14)0.0649 (15)0.007 (2)0.0180 (14)0.0102 (14)
N10.0400 (16)0.0458 (16)0.0364 (13)−0.0052 (13)0.0067 (12)−0.0039 (11)
N20.0436 (18)0.0372 (14)0.0415 (14)−0.0028 (13)0.0117 (13)−0.0030 (11)
N30.122 (4)0.0397 (17)0.074 (2)0.011 (2)0.051 (3)0.0063 (17)
C10.0408 (17)0.0454 (19)0.0387 (17)−0.0065 (16)0.0004 (15)−0.0037 (15)
C20.0341 (18)0.0532 (19)0.0386 (16)−0.0029 (14)0.0002 (13)−0.0098 (14)
C30.038 (2)0.065 (2)0.0428 (17)−0.0032 (18)0.0111 (15)0.0010 (16)
C40.0427 (19)0.062 (2)0.0407 (16)−0.0058 (19)0.0012 (13)0.0095 (17)
C50.0368 (17)0.0475 (19)0.0411 (15)−0.0069 (17)0.0005 (12)0.0020 (15)
C60.0320 (14)0.0477 (18)0.0350 (15)−0.0045 (17)−0.0008 (15)−0.0019 (13)
C70.0374 (19)0.0462 (18)0.0332 (15)−0.0033 (15)0.0027 (13)−0.0010 (14)
C80.0465 (18)0.0381 (18)0.0402 (15)−0.0006 (17)0.0002 (15)−0.0030 (13)

Geometric parameters (Å, °)

Br1—C21.902 (3)C1—C21.377 (5)
S1—C81.682 (3)C1—C61.390 (5)
O1—C51.358 (5)C2—C31.376 (5)
O1—HO10.81 (3)C3—C41.377 (6)
N1—N21.380 (4)C4—C51.388 (5)
N1—C71.281 (4)C5—C61.407 (5)
N2—C81.337 (4)C6—C71.451 (5)
N3—C81.315 (5)C1—H10.9300
N2—HN10.84 (3)C3—H30.9300
N3—HN20.86 (3)C4—H40.9300
N3—HN30.87 (4)C7—H70.9300
C5—O1—HO1107 (4)O1—C5—C4117.7 (3)
N2—N1—C7115.6 (3)C5—C6—C7122.6 (3)
N1—N2—C8121.9 (3)C1—C6—C5118.5 (3)
C8—N2—HN1122 (2)C1—C6—C7119.0 (3)
N1—N2—HN1116 (2)N1—C7—C6122.7 (3)
HN2—N3—HN3120 (4)N2—C8—N3118.1 (3)
C8—N3—HN2122 (3)S1—C8—N2119.4 (3)
C8—N3—HN3117 (3)S1—C8—N3122.5 (3)
C2—C1—C6120.7 (3)C2—C1—H1120.00
Br1—C2—C3119.6 (3)C6—C1—H1120.00
C1—C2—C3120.7 (3)C2—C3—H3120.00
Br1—C2—C1119.7 (2)C4—C3—H3120.00
C2—C3—C4119.7 (3)C3—C4—H4120.00
C3—C4—C5120.6 (4)C5—C4—H4120.00
C4—C5—C6119.9 (4)N1—C7—H7119.00
O1—C5—C6122.5 (3)C6—C7—H7119.00
C7—N1—N2—C8172.0 (3)C2—C3—C4—C51.2 (5)
N2—N1—C7—C6−179.8 (3)C3—C4—C5—O1179.2 (3)
N1—N2—C8—S1−175.2 (3)C3—C4—C5—C6−0.6 (5)
N1—N2—C8—N34.9 (5)C4—C5—C6—C10.4 (5)
C2—C1—C6—C7179.1 (3)O1—C5—C6—C1−179.5 (3)
C2—C1—C6—C5−0.7 (5)O1—C5—C6—C70.7 (5)
C6—C1—C2—Br1180.0 (3)C4—C5—C6—C7−179.4 (3)
C6—C1—C2—C31.2 (5)C1—C6—C7—N1177.9 (3)
Br1—C2—C3—C4179.8 (3)C5—C6—C7—N1−2.3 (5)
C1—C2—C3—C4−1.5 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—HO1···N10.81 (3)1.97 (4)2.685 (4)149 (5)
N3—HN3···N10.87 (4)2.30 (4)2.688 (5)107 (3)
N2—HN1···S1i0.84 (3)2.55 (3)3.373 (3)168 (3)
N3—HN2···S1ii0.86 (3)2.50 (3)3.363 (4)176 (6)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5704).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Casas, J. S., Garcia-Tasende, M. S. & Sordo, J. (2000). Coord. Chem. Rev.209, 197–261.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Ferrari, M. B., Capacchi, S., Reffo, G., Pelosi, G., Tarasconi, P., Albertini, R., Pinelli, S. & Lunghi, P. (2000). J. Inorg. Biochem.81, 89–97. [PubMed]
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Maccioni, E., Cardia, M. C., Distinto, S., Bonsignore, L. & De Logu, A. (2003). Il Farmaco, 58, 951–959. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2002). X-AREA and X-RED32 Stoe & Cie, Darmstadt, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography