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

Rizal, M.R.; Ali, H.M.; Ng, S.W.

doi:10.1107/S160053680801101X

organic compounds

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Volume 64| Part 5| May 2008| Page o918

doi:10.1107/S160053680801101X

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

Mohd. Razali Rizal,^a Hapipah Mohd. Ali ^a and Seik Weng Ng ^a ^*

^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 ). 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

Crystal data

C₁₀H₉BrN₄S
M_r = 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 ) T_min = 0.381, T_max = 0.516 (expected range = 0.344–0.467)
6176 measured reflections
2563 independent reflections
2281 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); 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/S160053680801101X/lh2609sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801101X/lh2609Isup2.hkl

checkCIF report

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.

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. 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

C₁₀H₉BrN₄S	Z = 2
M_r = 297.18	F(000) = 296
Triclinic, P1	D_x = 1.753 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7731 (2) Å	Cell parameters from 6604 reflections
b = 8.7551 (2) Å	θ = 4.0–28.3°
c = 10.6539 (2) Å	µ = 3.81 mm⁻¹
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 tube	2281 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→8
T_min = 0.381, T_max = 0.516	k = −11→11
6176 measured reflections	l = −13→13

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0383P)² + 0.1P] where P = (F_o² + 2F_c²)/3
2563 reflections	(Δ/σ)_max = 0.001
161 parameters	Δρ_max = 0.36 e Å⁻³
4 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₀H₉BrN₄S	γ = 72.886 (1)°
M_r = 297.18	V = 563.00 (2) Å³
Triclinic, P1	Z = 2
a = 6.7731 (2) Å	Mo Kα radiation
b = 8.7551 (2) Å	µ = 3.81 mm⁻¹
c = 10.6539 (2) Å	T = 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)
T_min = 0.381, T_max = 0.516	R_int = 0.025
6176 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	4 restraints
wR(F²) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.36 e Å⁻³
2563 reflections	Δρ_min = −0.40 e Å⁻³
161 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.51693 (4)	0.13022 (2)	0.31237 (2)	0.02102 (9)
S1	0.01187 (9)	0.22591 (6)	1.06142 (5)	0.01534 (12)
N1	0.2717 (3)	0.8577 (2)	0.27383 (17)	0.0153 (4)
N2	0.1383 (3)	0.4698 (2)	0.68281 (16)	0.0116 (3)
N3	0.0718 (3)	0.4342 (2)	0.81750 (16)	0.0118 (3)
N4	0.1492 (3)	0.1567 (2)	0.83268 (18)	0.0169 (4)
C1	0.1846 (3)	0.8475 (3)	0.4006 (2)	0.0151 (4)
H1	0.1266	0.9415	0.4320	0.018*
C2	0.3383 (3)	0.6981 (2)	0.2626 (2)	0.0122 (4)
C3	0.4355 (3)	0.6471 (3)	0.1529 (2)	0.0142 (4)
H3	0.4641	0.7265	0.0687	0.017*
C4	0.4889 (3)	0.4765 (3)	0.1711 (2)	0.0131 (4)
H4	0.5573	0.4359	0.0990	0.016*
C5	0.4422 (3)	0.3633 (2)	0.2960 (2)	0.0127 (4)
C6	0.3464 (3)	0.4108 (2)	0.40581 (19)	0.0118 (4)
H6	0.3184	0.3300	0.4893	0.014*
C7	0.2917 (3)	0.5832 (2)	0.38933 (19)	0.0109 (4)
C8	0.1921 (3)	0.6825 (2)	0.4770 (2)	0.0120 (4)
C9	0.1249 (3)	0.6266 (2)	0.6176 (2)	0.0127 (4)
H9	0.0693	0.7074	0.6633	0.015*
C10	0.0822 (3)	0.2737 (2)	0.8937 (2)	0.0123 (4)
H1N	0.254 (5)	0.953 (2)	0.207 (2)	0.028 (7)*
H3N	0.037 (4)	0.510 (2)	0.858 (2)	0.013 (6)*
H4N1	0.137 (4)	0.0533 (17)	0.876 (2)	0.023 (7)*
H4N2	0.173 (5)	0.190 (4)	0.7452 (11)	0.035 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02971 (15)	0.01243 (12)	0.02039 (12)	−0.00512 (9)	0.00410 (9)	−0.00765 (8)
S1	0.0217 (3)	0.0111 (2)	0.0101 (2)	−0.0029 (2)	0.00152 (19)	−0.00200 (18)
N1	0.0190 (10)	0.0104 (8)	0.0119 (8)	−0.0022 (7)	0.0015 (7)	−0.0005 (6)
N2	0.0105 (8)	0.0144 (8)	0.0100 (8)	−0.0056 (6)	0.0021 (6)	−0.0034 (6)
N3	0.0154 (9)	0.0112 (8)	0.0091 (7)	−0.0032 (7)	0.0020 (6)	−0.0051 (6)
N4	0.0239 (10)	0.0117 (8)	0.0144 (8)	−0.0050 (7)	0.0044 (7)	−0.0056 (7)
C1	0.0176 (11)	0.0133 (9)	0.0127 (9)	−0.0021 (8)	0.0005 (8)	−0.0045 (8)
C2	0.0120 (10)	0.0108 (9)	0.0134 (9)	−0.0032 (7)	−0.0023 (8)	−0.0025 (7)
C3	0.0121 (10)	0.0167 (10)	0.0119 (9)	−0.0036 (8)	−0.0015 (8)	−0.0022 (7)
C4	0.0109 (10)	0.0174 (10)	0.0111 (9)	−0.0028 (8)	−0.0020 (7)	−0.0049 (7)
C5	0.0113 (10)	0.0106 (9)	0.0165 (9)	−0.0031 (7)	−0.0014 (8)	−0.0042 (7)
C6	0.0102 (10)	0.0124 (9)	0.0117 (9)	−0.0030 (7)	−0.0017 (7)	−0.0021 (7)
C7	0.0090 (10)	0.0132 (9)	0.0103 (9)	−0.0028 (7)	−0.0012 (7)	−0.0032 (7)
C8	0.0114 (10)	0.0116 (9)	0.0131 (9)	−0.0035 (8)	−0.0011 (7)	−0.0037 (7)
C9	0.0107 (10)	0.0137 (9)	0.0133 (9)	−0.0024 (8)	−0.0003 (8)	−0.0049 (7)
C10	0.0103 (10)	0.0129 (9)	0.0130 (9)	−0.0029 (7)	0.0001 (7)	−0.0038 (7)

Geometric parameters (Å, º) top

Br1—C5	1.9032 (19)	C1—H1	0.9500
S1—C10	1.699 (2)	C2—C3	1.388 (3)
N1—C1	1.359 (3)	C2—C7	1.418 (3)
N1—C2	1.378 (3)	C3—C4	1.379 (3)
N1—H1N	0.878 (10)	C3—H3	0.9500
N2—C9	1.284 (3)	C4—C5	1.399 (3)
N2—N3	1.378 (2)	C4—H4	0.9500
N3—C10	1.339 (3)	C5—C6	1.372 (3)
N3—H3N	0.876 (10)	C6—C7	1.398 (3)
N4—C10	1.331 (3)	C6—H6	0.9500
N4—H4N1	0.880 (10)	C7—C8	1.447 (3)
N4—H4N2	0.873 (10)	C8—C9	1.437 (3)
C1—C8	1.376 (3)	C9—H9	0.9500

C1—N1—C2	109.25 (17)	C3—C4—H4	120.1
C1—N1—H1N	122.5 (19)	C5—C4—H4	120.1
C2—N1—H1N	126.2 (18)	C6—C5—C4	123.94 (18)
C9—N2—N3	115.12 (17)	C6—C5—Br1	118.76 (15)
C10—N3—N2	119.25 (16)	C4—C5—Br1	117.30 (15)
C10—N3—H3N	117.5 (16)	C5—C6—C7	117.04 (18)
N2—N3—H3N	122.8 (16)	C5—C6—H6	121.5
C10—N4—H4N1	119.9 (17)	C7—C6—H6	121.5
C10—N4—H4N2	118.1 (19)	C6—C7—C2	119.09 (17)
H4N1—N4—H4N2	120 (3)	C6—C7—C8	134.17 (18)
N1—C1—C8	110.69 (18)	C2—C7—C8	106.75 (17)
N1—C1—H1	124.7	C1—C8—C9	124.92 (18)
C8—C1—H1	124.7	C1—C8—C7	105.86 (17)
N1—C2—C3	129.70 (18)	C9—C8—C7	129.10 (18)
N1—C2—C7	107.45 (17)	N2—C9—C8	121.41 (18)
C3—C2—C7	122.85 (18)	N2—C9—H9	119.3
C4—C3—C2	117.27 (18)	C8—C9—H9	119.3
C4—C3—H3	121.4	N4—C10—N3	117.36 (18)
C2—C3—H3	121.4	N4—C10—S1	122.58 (16)
C3—C4—C5	119.81 (18)	N3—C10—S1	120.06 (15)

C9—N2—N3—C10	−179.30 (19)	C3—C2—C7—C6	0.3 (3)
C2—N1—C1—C8	0.5 (3)	N1—C2—C7—C8	0.4 (2)
C1—N1—C2—C3	180.0 (2)	C3—C2—C7—C8	179.9 (2)
C1—N1—C2—C7	−0.6 (2)	N1—C1—C8—C9	176.0 (2)
N1—C2—C3—C4	178.9 (2)	N1—C1—C8—C7	−0.2 (3)
C7—C2—C3—C4	−0.6 (3)	C6—C7—C8—C1	179.4 (2)
C2—C3—C4—C5	0.8 (3)	C2—C7—C8—C1	−0.2 (2)
C3—C4—C5—C6	−0.8 (3)	C6—C7—C8—C9	3.4 (4)
C3—C4—C5—Br1	179.01 (16)	C2—C7—C8—C9	−176.2 (2)
C4—C5—C6—C7	0.6 (3)	N3—N2—C9—C8	178.80 (19)
Br1—C5—C6—C7	−179.25 (15)	C1—C8—C9—N2	−179.4 (2)
C5—C6—C7—C2	−0.3 (3)	C7—C8—C9—N2	−4.0 (4)
C5—C6—C7—C8	−179.8 (2)	N2—N3—C10—N4	−2.8 (3)
N1—C2—C7—C6	−179.18 (18)	N2—N3—C10—S1	177.10 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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.

Experimental details

Crystal data
Chemical formula	C₁₀H₉BrN₄S
M_r	297.18
Crystal system, space group	Triclinic, 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)
V (Å³)	563.00 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.81
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.381, 0.516
No. of measured, independent and observed [I > 2σ(I)] reflections	6176, 2563, 2281
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.066, 1.06
No. of reflections	2563
No. of parameters	161
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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.

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.

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