organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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5-Bromo-1H-indole-3-carbaldehyde thio­semicarbazone

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

(Received 27 March 2008; accepted 20 April 2008; online 26 April 2008)

In the essentially planar title mol­ecule, C10H9BrN4S, the C=N double bond is in a trans configuration. In the crystal structure, the S atom acts as a hydrogen-bond acceptor for the aromatic NH, aliphatic NH and terminal NH2 groups of three symmetry-related mol­ecules, forming a weak hydrogen-bonded layer structure.

Related literature

For a previous synthesis of the title compound, see: Dubey & Babu (2006[Dubey, P. K. & Babu, B. (2006). Ind. J. Heterocycl. Chem. 15, 209-219.]). For related literature, see: Doyle et al. (1956[Doyle, F. P., Ferrier, W., Holland, D. O., Mehta, M. D. & Nayler, J. H. C. (1956). J. Chem. Soc. pp. 2853-2857.]); French & Blanz (1966[French, F. A. & Blanz, E. J. (1966). J. Med. Chem. 9, 585-589.]); Fukukawa et al. (1966[Fukukawa, F., Isao, Y., Seno, T., Sasaki, M., Naito, M. & Shunji, T. (1966). Yakaguka Zasshi, 86, 801-804.]); Libermann et al. (1953[Libermann, D., Moyeux, M., Rouaix, A., Maillard, J., Hengl, L., Himbert, J. & Theraplix, M. (1953). Bull. Soc. Chim. Fr. pp. 957-962.]); Usi (1968[Usi, Y. (1968). Ann. Rep. Takeda Res. Lab. 27, 144-158.]); Weller et al. (1954[Weller, L. E., Sell, H. M. & Gotshall, R. Y. (1954). J. Am. Chem. Soc. 76, 1959.]).

[Scheme 1]

Experimental

Crystal data
  • C10H9BrN4S

  • Mr = 297.18

  • Triclinic, [P \overline 1]

  • a = 6.7731 (2) Å

  • b = 8.7551 (2) Å

  • c = 10.6539 (2) Å

  • α = 69.280 (1)°

  • β = 79.969 (1)°

  • γ = 72.886 (1)°

  • V = 563.00 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 3.81 mm−1

  • T = 100 (2) K

  • 0.30 × 0.20 × 0.20 mm

Data collection
  • Bruker SMART APEX diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.381, Tmax = 0.516 (expected range = 0.344–0.467)

  • 6176 measured reflections

  • 2563 independent reflections

  • 2281 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.024

  • wR(F2) = 0.066

  • S = 1.06

  • 2563 reflections

  • 161 parameters

  • 4 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.36 e Å−3

  • Δρmin = −0.40 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1n⋯S1i 0.88 (1) 2.60 (2) 3.390 (2) 150 (3)
N3—H3n⋯S1ii 0.88 (1) 2.65 (1) 3.508 (2) 167 (2)
N4—H4n1⋯S1iii 0.88 (1) 2.74 (1) 3.569 (2) 158 (2)
Symmetry codes: (i) x, y+1, z-1; (ii) -x, -y+1, -z+2; (iii) -x, -y, -z+2.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2008[Westrip, S. P. (2008). publCIF. In preparation.]).

Supporting information


Comment top

Indole-3-carboxaldehyde thiosemicarbazone and its substituted analogs possess useful medicinal properties; such activity has been known for a long time (Doyle et al., 1956; French & Blanz, 1966; Fukukawa et al., 1966; Libermann et al., 1953; Usi, 1968; Weller et al., 1954). The compounds, in the form of their metal derivatives, have been assesses for similar activity.

In the title compound (I) (Fig. 1), the double-bonded sulfur atom is a hydrogen-bond acceptor for the aromatic -N-H, aliphatic -N-H and terminal -NH2 groups of three adjacent molecules, forming a weak hydrogen-bonded layer structure.

Related literature top

For a previous synthesis of the title compound, see: Dubey & Babu (2006). For related literature, see: Doyle et al. (1956); French & Blanz (1966); Fukukawa et al. (1966); Libermann et al. (1953); Usi (1968); Weller et al. (1954).

Experimental top

5-Bromoindole-3-carboxaldehyde (0.3 g, 1.3 mmol) and thiosemicarbazide (0.12 g, 1.3 mmol) were heated in ethanol (50 ml) for an hour. The solvent was removed and the product and recrystallized from ethanol.

Refinement top

Carbon-bound H atoms were placed in calculated positions, and were included in the refinement in the riding model approximation. The nitrogen-bound H atoms were located in a difference Fourier map, and were refined with a distance restraint of N–H 0.88±0.01 Å; their temperature factors were freely refined.

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
[Figure 1] Fig. 1. The title molecule drawn using 70% probabilty ellipsoids. Hydrogen atoms are drawn as spheres of arbitrary radius.
5-Bromo-1H-indole-3-carboxaldehyde thiosemicarbazone top
Crystal data top
C10H9BrN4SZ = 2
Mr = 297.18F(000) = 296
Triclinic, P1Dx = 1.753 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7731 (2) ÅCell parameters from 6604 reflections
b = 8.7551 (2) Åθ = 4.0–28.3°
c = 10.6539 (2) ŵ = 3.81 mm1
α = 69.280 (1)°T = 100 K
β = 79.969 (1)°Block, yellow
γ = 72.886 (1)°0.30 × 0.20 × 0.20 mm
V = 563.00 (2) Å3
Data collection top
Bruker SMART APEX
diffractometer
2563 independent reflections
Radiation source: fine-focus sealed tube2281 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 68
Tmin = 0.381, Tmax = 0.516k = 1111
6176 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0383P)2 + 0.1P]
where P = (Fo2 + 2Fc2)/3
2563 reflections(Δ/σ)max = 0.001
161 parametersΔρmax = 0.36 e Å3
4 restraintsΔρmin = 0.40 e Å3
Crystal data top
C10H9BrN4Sγ = 72.886 (1)°
Mr = 297.18V = 563.00 (2) Å3
Triclinic, P1Z = 2
a = 6.7731 (2) ÅMo Kα radiation
b = 8.7551 (2) ŵ = 3.81 mm1
c = 10.6539 (2) ÅT = 100 K
α = 69.280 (1)°0.30 × 0.20 × 0.20 mm
β = 79.969 (1)°
Data collection top
Bruker SMART APEX
diffractometer
2563 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2281 reflections with I > 2σ(I)
Tmin = 0.381, Tmax = 0.516Rint = 0.025
6176 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0244 restraints
wR(F2) = 0.066H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.36 e Å3
2563 reflectionsΔρmin = 0.40 e Å3
161 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.51693 (4)0.13022 (2)0.31237 (2)0.02102 (9)
S10.01187 (9)0.22591 (6)1.06142 (5)0.01534 (12)
N10.2717 (3)0.8577 (2)0.27383 (17)0.0153 (4)
N20.1383 (3)0.4698 (2)0.68281 (16)0.0116 (3)
N30.0718 (3)0.4342 (2)0.81750 (16)0.0118 (3)
N40.1492 (3)0.1567 (2)0.83268 (18)0.0169 (4)
C10.1846 (3)0.8475 (3)0.4006 (2)0.0151 (4)
H10.12660.94150.43200.018*
C20.3383 (3)0.6981 (2)0.2626 (2)0.0122 (4)
C30.4355 (3)0.6471 (3)0.1529 (2)0.0142 (4)
H30.46410.72650.06870.017*
C40.4889 (3)0.4765 (3)0.1711 (2)0.0131 (4)
H40.55730.43590.09900.016*
C50.4422 (3)0.3633 (2)0.2960 (2)0.0127 (4)
C60.3464 (3)0.4108 (2)0.40581 (19)0.0118 (4)
H60.31840.33000.48930.014*
C70.2917 (3)0.5832 (2)0.38933 (19)0.0109 (4)
C80.1921 (3)0.6825 (2)0.4770 (2)0.0120 (4)
C90.1249 (3)0.6266 (2)0.6176 (2)0.0127 (4)
H90.06930.70740.66330.015*
C100.0822 (3)0.2737 (2)0.8937 (2)0.0123 (4)
H1N0.254 (5)0.953 (2)0.207 (2)0.028 (7)*
H3N0.037 (4)0.510 (2)0.858 (2)0.013 (6)*
H4N10.137 (4)0.0533 (17)0.876 (2)0.023 (7)*
H4N20.173 (5)0.190 (4)0.7452 (11)0.035 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02971 (15)0.01243 (12)0.02039 (12)0.00512 (9)0.00410 (9)0.00765 (8)
S10.0217 (3)0.0111 (2)0.0101 (2)0.0029 (2)0.00152 (19)0.00200 (18)
N10.0190 (10)0.0104 (8)0.0119 (8)0.0022 (7)0.0015 (7)0.0005 (6)
N20.0105 (8)0.0144 (8)0.0100 (8)0.0056 (6)0.0021 (6)0.0034 (6)
N30.0154 (9)0.0112 (8)0.0091 (7)0.0032 (7)0.0020 (6)0.0051 (6)
N40.0239 (10)0.0117 (8)0.0144 (8)0.0050 (7)0.0044 (7)0.0056 (7)
C10.0176 (11)0.0133 (9)0.0127 (9)0.0021 (8)0.0005 (8)0.0045 (8)
C20.0120 (10)0.0108 (9)0.0134 (9)0.0032 (7)0.0023 (8)0.0025 (7)
C30.0121 (10)0.0167 (10)0.0119 (9)0.0036 (8)0.0015 (8)0.0022 (7)
C40.0109 (10)0.0174 (10)0.0111 (9)0.0028 (8)0.0020 (7)0.0049 (7)
C50.0113 (10)0.0106 (9)0.0165 (9)0.0031 (7)0.0014 (8)0.0042 (7)
C60.0102 (10)0.0124 (9)0.0117 (9)0.0030 (7)0.0017 (7)0.0021 (7)
C70.0090 (10)0.0132 (9)0.0103 (9)0.0028 (7)0.0012 (7)0.0032 (7)
C80.0114 (10)0.0116 (9)0.0131 (9)0.0035 (8)0.0011 (7)0.0037 (7)
C90.0107 (10)0.0137 (9)0.0133 (9)0.0024 (8)0.0003 (8)0.0049 (7)
C100.0103 (10)0.0129 (9)0.0130 (9)0.0029 (7)0.0001 (7)0.0038 (7)
Geometric parameters (Å, º) top
Br1—C51.9032 (19)C1—H10.9500
S1—C101.699 (2)C2—C31.388 (3)
N1—C11.359 (3)C2—C71.418 (3)
N1—C21.378 (3)C3—C41.379 (3)
N1—H1N0.878 (10)C3—H30.9500
N2—C91.284 (3)C4—C51.399 (3)
N2—N31.378 (2)C4—H40.9500
N3—C101.339 (3)C5—C61.372 (3)
N3—H3N0.876 (10)C6—C71.398 (3)
N4—C101.331 (3)C6—H60.9500
N4—H4N10.880 (10)C7—C81.447 (3)
N4—H4N20.873 (10)C8—C91.437 (3)
C1—C81.376 (3)C9—H90.9500
C1—N1—C2109.25 (17)C3—C4—H4120.1
C1—N1—H1N122.5 (19)C5—C4—H4120.1
C2—N1—H1N126.2 (18)C6—C5—C4123.94 (18)
C9—N2—N3115.12 (17)C6—C5—Br1118.76 (15)
C10—N3—N2119.25 (16)C4—C5—Br1117.30 (15)
C10—N3—H3N117.5 (16)C5—C6—C7117.04 (18)
N2—N3—H3N122.8 (16)C5—C6—H6121.5
C10—N4—H4N1119.9 (17)C7—C6—H6121.5
C10—N4—H4N2118.1 (19)C6—C7—C2119.09 (17)
H4N1—N4—H4N2120 (3)C6—C7—C8134.17 (18)
N1—C1—C8110.69 (18)C2—C7—C8106.75 (17)
N1—C1—H1124.7C1—C8—C9124.92 (18)
C8—C1—H1124.7C1—C8—C7105.86 (17)
N1—C2—C3129.70 (18)C9—C8—C7129.10 (18)
N1—C2—C7107.45 (17)N2—C9—C8121.41 (18)
C3—C2—C7122.85 (18)N2—C9—H9119.3
C4—C3—C2117.27 (18)C8—C9—H9119.3
C4—C3—H3121.4N4—C10—N3117.36 (18)
C2—C3—H3121.4N4—C10—S1122.58 (16)
C3—C4—C5119.81 (18)N3—C10—S1120.06 (15)
C9—N2—N3—C10179.30 (19)C3—C2—C7—C60.3 (3)
C2—N1—C1—C80.5 (3)N1—C2—C7—C80.4 (2)
C1—N1—C2—C3180.0 (2)C3—C2—C7—C8179.9 (2)
C1—N1—C2—C70.6 (2)N1—C1—C8—C9176.0 (2)
N1—C2—C3—C4178.9 (2)N1—C1—C8—C70.2 (3)
C7—C2—C3—C40.6 (3)C6—C7—C8—C1179.4 (2)
C2—C3—C4—C50.8 (3)C2—C7—C8—C10.2 (2)
C3—C4—C5—C60.8 (3)C6—C7—C8—C93.4 (4)
C3—C4—C5—Br1179.01 (16)C2—C7—C8—C9176.2 (2)
C4—C5—C6—C70.6 (3)N3—N2—C9—C8178.80 (19)
Br1—C5—C6—C7179.25 (15)C1—C8—C9—N2179.4 (2)
C5—C6—C7—C20.3 (3)C7—C8—C9—N24.0 (4)
C5—C6—C7—C8179.8 (2)N2—N3—C10—N42.8 (3)
N1—C2—C7—C6179.18 (18)N2—N3—C10—S1177.10 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···S1i0.88 (1)2.60 (2)3.390 (2)150 (3)
N3—H3n···S1ii0.88 (1)2.65 (1)3.508 (2)167 (2)
N4—H4n1···S1iii0.88 (1)2.74 (1)3.569 (2)158 (2)
Symmetry codes: (i) x, y+1, z1; (ii) x, y+1, z+2; (iii) x, y, z+2.

Experimental details

Crystal data
Chemical formulaC10H9BrN4S
Mr297.18
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)6.7731 (2), 8.7551 (2), 10.6539 (2)
α, β, γ (°)69.280 (1), 79.969 (1), 72.886 (1)
V3)563.00 (2)
Z2
Radiation typeMo Kα
µ (mm1)3.81
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.381, 0.516
No. of measured, independent and
observed [I > 2σ(I)] reflections
6176, 2563, 2281
Rint0.025
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.066, 1.06
No. of reflections2563
No. of parameters161
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.36, 0.40

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···AD—HH···AD···AD—H···A
N1—H1n···S1i0.88 (1)2.60 (2)3.390 (2)150 (3)
N3—H3n···S1ii0.88 (1)2.65 (1)3.508 (2)167 (2)
N4—H4n1···S1iii0.88 (1)2.74 (1)3.569 (2)158 (2)
Symmetry codes: (i) x, y+1, z1; (ii) x, y+1, z+2; (iii) x, y, z+2.
 

Acknowledgements

We thank the Science Fund (12–02-03–2031) for supporting this study, and the University of Malaya for the purchase of the diffractometer.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDoyle, F. P., Ferrier, W., Holland, D. O., Mehta, M. D. & Nayler, J. H. C. (1956). J. Chem. Soc. pp. 2853–2857.  CrossRef Web of Science Google Scholar
First citationDubey, P. K. & Babu, B. (2006). Ind. J. Heterocycl. Chem. 15, 209–219.  CAS Google Scholar
First citationFrench, F. A. & Blanz, E. J. (1966). J. Med. Chem. 9, 585–589.  CrossRef CAS PubMed Web of Science Google Scholar
First citationFukukawa, F., Isao, Y., Seno, T., Sasaki, M., Naito, M. & Shunji, T. (1966). Yakaguka Zasshi, 86, 801–804.  Google Scholar
First citationLibermann, D., Moyeux, M., Rouaix, A., Maillard, J., Hengl, L., Himbert, J. & Theraplix, M. (1953). Bull. Soc. Chim. Fr. pp. 957–962.  Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationUsi, Y. (1968). Ann. Rep. Takeda Res. Lab. 27, 144–158.  Google Scholar
First citationWeller, L. E., Sell, H. M. & Gotshall, R. Y. (1954). J. Am. Chem. Soc. 76, 1959.  CrossRef Web of Science Google Scholar
First citationWestrip, S. P. (2008). publCIF. In preparation.  Google Scholar

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