N′-[(5-Chloro-1H-indol-3-yl)methyl­ene]-3,4,5-trihydroxy­benzohydrazide

Khaledi, H.; Mohd Ali, H.; Ng, S.W.

doi:10.1107/S160053680804258X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o169

doi:10.1107/S160053680804258X

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N′-[(5-Chloro-1H-indol-3-yl)methylene]-3,4,5-trihydroxybenzohydrazide

Hamid Khaledi,^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 15 December 2008; accepted 15 December 2008; online 20 December 2008)

The two aromatic parts of the title compound, C₁₆H₁₃ClN₃O₄, are connected through a conjugated –CH=N–NH–C(O)– fragment, giving an almost planar molecule (r.m.s. deviation 0.08 Å). In the crystal structure, adjacent molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For the isostructural C₁₆H₁₃BrN₃O₄ analog, see: Khaledi et al. (2008 ).

Experimental

Crystal data

C₁₆H₁₂ClN₃O₄
M_r = 345.74
Monoclinic, P 2₁ /n
a = 9.6481 (2) Å
b = 15.1408 (3) Å
c = 10.2206 (2) Å
β = 98.232 (1)°
V = 1477.64 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 (2) K
0.32 × 0.22 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.914, T_max = 0.966
10185 measured reflections
3389 independent reflections
2907 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.093
S = 1.06
3389 reflections
220 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2o⋯O3	0.84	2.20	2.6726 (14)	116
O3—H3o⋯O1ⁱ	0.84	1.74	2.5818 (14)	175
O4—H4o⋯N2ⁱ	0.84	2.01	2.7668 (15)	149
N1—H1n⋯O2ⁱⁱ	0.88	2.23	3.0875 (16)	163
N3—H3n⋯O4ⁱⁱⁱ	0.88	2.15	2.9518 (15)	152
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680804258X/xu2471sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680804258X/xu2471Isup2.hkl

checkCIF report

Related literature top

For the isostructural C₁₆H₁₃BrN₃O₄ analog, see: Khaledi et al. (2008).

Experimental top

5-Chloroindole-3-carbaldehyde (0.27 g, 1.5 mmol) and 3,4,5-trihydroxybenzoylhydrazine (0.27 g, 1.5 mmol) were heated in ethanol (20 ml) for 3 h. About 1 ml of acetic acid also added. The solid that separated out was collected, washed with water and then recrystallized from DMSO.

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, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₆H₁₂ClN₃O₄ at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

N'-[(5-Chloro-1H-indol-3-yl)methylene]-3,4,5-trihydroxybenzohydrazide top

Crystal data top

C₁₆H₁₂ClN₃O₄	F(000) = 712
M_r = 345.74	D_x = 1.554 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4113 reflections
a = 9.6481 (2) Å	θ = 2.4–28.2°
b = 15.1408 (3) Å	µ = 0.29 mm⁻¹
c = 10.2206 (2) Å	T = 100 K
β = 98.232 (1)°	Prism, orange
V = 1477.64 (5) Å³	0.32 × 0.22 × 0.12 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3389 independent reflections
Radiation source: fine-focus sealed tube	2907 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
T_min = 0.914, T_max = 0.966	k = −19→19
10185 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0452P)² + 0.6635P] where P = (F_o² + 2F_c²)/3
3389 reflections	(Δ/σ)_max = 0.001
220 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₆H₁₂ClN₃O₄	V = 1477.64 (5) Å³
M_r = 345.74	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6481 (2) Å	µ = 0.29 mm⁻¹
b = 15.1408 (3) Å	T = 100 K
c = 10.2206 (2) Å	0.32 × 0.22 × 0.12 mm
β = 98.232 (1)°

Data collection top

Bruker SMART APEX diffractometer	3389 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2907 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.966	R_int = 0.025
10185 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.06	Δρ_max = 0.34 e Å⁻³
3389 reflections	Δρ_min = −0.33 e Å⁻³
220 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.99034 (4)	1.07558 (3)	0.24671 (4)	0.02606 (12)
O1	0.68592 (10)	0.82901 (7)	0.56884 (10)	0.0165 (2)
O2	0.64086 (10)	0.62519 (7)	0.94667 (10)	0.0172 (2)
H2O	0.5962	0.5961	0.9968	0.026*
O3	0.36728 (11)	0.59550 (6)	0.94304 (9)	0.0140 (2)
H3O	0.3047	0.6195	0.9801	0.021*
O4	0.16964 (10)	0.67781 (7)	0.73963 (10)	0.0149 (2)
H4O	0.1521	0.6414	0.7971	0.022*
N1	0.46397 (12)	0.86816 (8)	0.48430 (11)	0.0138 (2)
H1N	0.3740	0.8638	0.4895	0.017*
N2	0.51003 (13)	0.92205 (7)	0.38882 (11)	0.0137 (2)
N3	0.39990 (13)	1.10793 (8)	0.03144 (12)	0.0162 (3)
H3N	0.3544	1.1361	−0.0369	0.019*
C1	0.50119 (15)	0.76183 (9)	0.66318 (13)	0.0130 (3)
C2	0.59758 (15)	0.72084 (9)	0.75913 (13)	0.0141 (3)
H2	0.6952	0.7305	0.7616	0.017*
C3	0.54846 (15)	0.66576 (9)	0.85061 (13)	0.0131 (3)
C4	0.40551 (15)	0.65121 (9)	0.84928 (13)	0.0123 (3)
C5	0.31087 (14)	0.69082 (9)	0.75114 (13)	0.0125 (3)
C6	0.35827 (15)	0.74599 (9)	0.65851 (13)	0.0133 (3)
H6	0.2932	0.7730	0.5919	0.016*
C7	0.55811 (15)	0.82260 (9)	0.56894 (13)	0.0131 (3)
C8	0.41317 (15)	0.96681 (9)	0.31823 (13)	0.0142 (3)
H8	0.3195	0.9615	0.3358	0.017*
C9	0.44207 (15)	1.02444 (9)	0.21398 (13)	0.0142 (3)
C10	0.33977 (16)	1.05950 (9)	0.11972 (14)	0.0162 (3)
H10	0.2419	1.0509	0.1172	0.019*
C11	0.57451 (15)	1.05429 (9)	0.18016 (13)	0.0133 (3)
C12	0.71420 (15)	1.04422 (9)	0.23767 (13)	0.0147 (3)
H12	0.7386	1.0109	0.3164	0.018*
C13	0.81494 (16)	1.08455 (10)	0.17549 (14)	0.0169 (3)
C14	0.78385 (16)	1.13505 (10)	0.06023 (14)	0.0187 (3)
H14	0.8574	1.1609	0.0206	0.022*
C15	0.64682 (16)	1.14724 (9)	0.00445 (14)	0.0172 (3)
H15	0.6235	1.1823	−0.0727	0.021*
C16	0.54321 (16)	1.10616 (9)	0.06539 (13)	0.0146 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01421 (19)	0.0351 (2)	0.0286 (2)	−0.00330 (15)	0.00218 (15)	0.00450 (16)
O1	0.0125 (5)	0.0194 (5)	0.0187 (5)	−0.0004 (4)	0.0054 (4)	0.0023 (4)
O2	0.0113 (5)	0.0246 (6)	0.0156 (5)	0.0001 (4)	0.0013 (4)	0.0057 (4)
O3	0.0132 (5)	0.0167 (5)	0.0131 (5)	0.0012 (4)	0.0055 (4)	0.0018 (4)
O4	0.0101 (5)	0.0191 (5)	0.0155 (5)	−0.0022 (4)	0.0017 (4)	0.0035 (4)
N1	0.0124 (6)	0.0149 (6)	0.0152 (6)	−0.0011 (5)	0.0059 (4)	0.0021 (4)
N2	0.0159 (6)	0.0135 (6)	0.0129 (5)	−0.0014 (5)	0.0060 (4)	−0.0005 (4)
N3	0.0185 (6)	0.0160 (6)	0.0135 (5)	0.0028 (5)	0.0003 (5)	0.0009 (4)
C1	0.0145 (7)	0.0119 (6)	0.0134 (6)	−0.0007 (5)	0.0050 (5)	−0.0029 (5)
C2	0.0110 (7)	0.0166 (7)	0.0154 (6)	−0.0016 (5)	0.0039 (5)	−0.0022 (5)
C3	0.0122 (7)	0.0143 (6)	0.0125 (6)	0.0024 (5)	0.0009 (5)	−0.0020 (5)
C4	0.0140 (7)	0.0126 (6)	0.0110 (6)	−0.0013 (5)	0.0038 (5)	−0.0024 (5)
C5	0.0109 (6)	0.0137 (6)	0.0135 (6)	−0.0009 (5)	0.0034 (5)	−0.0038 (5)
C6	0.0134 (7)	0.0137 (6)	0.0125 (6)	0.0010 (5)	0.0014 (5)	−0.0007 (5)
C7	0.0151 (7)	0.0121 (6)	0.0131 (6)	−0.0004 (5)	0.0049 (5)	−0.0040 (5)
C8	0.0132 (7)	0.0149 (6)	0.0153 (6)	−0.0012 (5)	0.0046 (5)	−0.0039 (5)
C9	0.0153 (7)	0.0136 (6)	0.0139 (6)	0.0004 (5)	0.0029 (5)	−0.0029 (5)
C10	0.0164 (7)	0.0155 (7)	0.0167 (7)	0.0003 (6)	0.0020 (5)	−0.0032 (5)
C11	0.0173 (7)	0.0102 (6)	0.0130 (6)	−0.0005 (5)	0.0041 (5)	−0.0028 (5)
C12	0.0167 (7)	0.0134 (7)	0.0139 (6)	−0.0003 (5)	0.0024 (5)	−0.0005 (5)
C13	0.0143 (7)	0.0173 (7)	0.0193 (7)	−0.0007 (6)	0.0024 (6)	−0.0022 (5)
C14	0.0224 (8)	0.0159 (7)	0.0192 (7)	−0.0037 (6)	0.0082 (6)	−0.0005 (5)
C15	0.0255 (8)	0.0133 (6)	0.0137 (6)	−0.0004 (6)	0.0058 (6)	−0.0002 (5)
C16	0.0191 (7)	0.0122 (6)	0.0125 (6)	0.0003 (5)	0.0022 (5)	−0.0028 (5)

Geometric parameters (Å, º) top

Cl1—C13	1.7491 (15)	C2—H2	0.9500
O1—C7	1.2371 (17)	C3—C4	1.3948 (19)
O2—C3	1.3731 (16)	C4—C5	1.3919 (19)
O2—H2O	0.8400	C5—C6	1.3883 (19)
O3—C4	1.3664 (16)	C6—H6	0.9500
O3—H3O	0.8400	C8—C9	1.4350 (19)
O4—C5	1.3650 (16)	C8—H8	0.9500
O4—H4O	0.8400	C9—C10	1.383 (2)
N1—C7	1.3506 (18)	C9—C11	1.443 (2)
N1—N2	1.3927 (16)	C10—H10	0.9500
N1—H1N	0.8800	C11—C12	1.399 (2)
N2—C8	1.2884 (19)	C11—C16	1.4080 (19)
N3—C10	1.3558 (19)	C12—C13	1.378 (2)
N3—C16	1.3768 (19)	C12—H12	0.9500
N3—H3N	0.8800	C13—C14	1.400 (2)
C1—C6	1.3936 (19)	C14—C15	1.375 (2)
C1—C2	1.397 (2)	C14—H14	0.9500
C1—C7	1.4925 (19)	C15—C16	1.397 (2)
C2—C3	1.3860 (19)	C15—H15	0.9500

C3—O2—H2O	109.5	O1—C7—C1	120.52 (13)
C4—O3—H3O	109.5	N1—C7—C1	116.90 (12)
C5—O4—H4O	109.5	N2—C8—C9	122.22 (13)
C7—N1—N2	119.69 (12)	N2—C8—H8	118.9
C7—N1—H1N	120.2	C9—C8—H8	118.9
N2—N1—H1N	120.2	C10—C9—C8	123.75 (14)
C8—N2—N1	114.96 (12)	C10—C9—C11	106.32 (12)
C10—N3—C16	109.38 (12)	C8—C9—C11	129.87 (13)
C10—N3—H3N	125.3	N3—C10—C9	109.91 (13)
C16—N3—H3N	125.3	N3—C10—H10	125.0
C6—C1—C2	120.24 (13)	C9—C10—H10	125.0
C6—C1—C7	122.53 (13)	C12—C11—C16	119.31 (13)
C2—C1—C7	117.23 (13)	C12—C11—C9	134.24 (13)
C3—C2—C1	118.90 (13)	C16—C11—C9	106.41 (13)
C3—C2—H2	120.5	C13—C12—C11	117.29 (13)
C1—C2—H2	120.5	C13—C12—H12	121.4
O2—C3—C2	120.11 (12)	C11—C12—H12	121.4
O2—C3—C4	118.44 (12)	C12—C13—C14	123.35 (14)
C2—C3—C4	121.44 (13)	C12—C13—Cl1	118.55 (11)
O3—C4—C5	123.80 (13)	C14—C13—Cl1	118.07 (11)
O3—C4—C3	117.16 (12)	C15—C14—C13	119.96 (14)
C5—C4—C3	118.99 (12)	C15—C14—H14	120.0
O4—C5—C6	116.76 (12)	C13—C14—H14	120.0
O4—C5—C4	122.94 (12)	C14—C15—C16	117.53 (13)
C6—C5—C4	120.30 (13)	C14—C15—H15	121.2
C5—C6—C1	120.07 (13)	C16—C15—H15	121.2
C5—C6—H6	120.0	N3—C16—C15	129.48 (13)
C1—C6—H6	120.0	N3—C16—C11	107.98 (12)
O1—C7—N1	122.58 (13)	C15—C16—C11	122.54 (14)

C7—N1—N2—C8	−175.96 (12)	N2—C8—C9—C10	166.52 (13)
C6—C1—C2—C3	−1.2 (2)	N2—C8—C9—C11	−10.3 (2)
C7—C1—C2—C3	178.31 (12)	C16—N3—C10—C9	−0.12 (16)
C1—C2—C3—O2	−179.47 (12)	C8—C9—C10—N3	−177.25 (12)
C1—C2—C3—C4	−0.5 (2)	C11—C9—C10—N3	0.18 (15)
O2—C3—C4—O3	−1.36 (18)	C10—C9—C11—C12	177.59 (15)
C2—C3—C4—O3	179.69 (12)	C8—C9—C11—C12	−5.2 (3)
O2—C3—C4—C5	−178.98 (12)	C10—C9—C11—C16	−0.17 (15)
C2—C3—C4—C5	2.1 (2)	C8—C9—C11—C16	177.04 (14)
O3—C4—C5—O4	0.2 (2)	C16—C11—C12—C13	−1.65 (19)
C3—C4—C5—O4	177.70 (12)	C9—C11—C12—C13	−179.19 (14)
O3—C4—C5—C6	−179.32 (12)	C11—C12—C13—C14	0.7 (2)
C3—C4—C5—C6	−1.9 (2)	C11—C12—C13—Cl1	178.50 (10)
O4—C5—C6—C1	−179.44 (12)	C12—C13—C14—C15	0.8 (2)
C4—C5—C6—C1	0.2 (2)	Cl1—C13—C14—C15	−176.97 (11)
C2—C1—C6—C5	1.4 (2)	C13—C14—C15—C16	−1.3 (2)
C7—C1—C6—C5	−178.09 (12)	C10—N3—C16—C15	−179.12 (14)
N2—N1—C7—O1	2.73 (19)	C10—N3—C16—C11	0.00 (15)
N2—N1—C7—C1	−176.29 (11)	C14—C15—C16—N3	179.40 (14)
C6—C1—C7—O1	−173.65 (13)	C14—C15—C16—C11	0.4 (2)
C2—C1—C7—O1	6.83 (19)	C12—C11—C16—N3	−178.05 (12)
C6—C1—C7—N1	5.39 (19)	C9—C11—C16—N3	0.11 (15)
C2—C1—C7—N1	−174.13 (12)	C12—C11—C16—C15	1.1 (2)
N1—N2—C8—C9	−178.92 (12)	C9—C11—C16—C15	179.30 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···O3	0.84	2.20	2.6726 (14)	116
O3—H3o···O1ⁱ	0.84	1.74	2.5818 (14)	175
O4—H4o···N2ⁱ	0.84	2.01	2.7668 (15)	149
N1—H1n···O2ⁱⁱ	0.88	2.23	3.0875 (16)	163
N3—H3n···O4ⁱⁱⁱ	0.88	2.15	2.9518 (15)	152

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂ClN₃O₄
M_r	345.74
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.6481 (2), 15.1408 (3), 10.2206 (2)
β (°)	98.232 (1)
V (Å³)	1477.64 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.32 × 0.22 × 0.12

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.914, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	10185, 3389, 2907
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.093, 1.06
No. of reflections	3389
No. of parameters	220
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.33

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···O3	0.84	2.20	2.6726 (14)	116
O3—H3o···O1ⁱ	0.84	1.74	2.5818 (14)	175
O4—H4o···N2ⁱ	0.84	2.01	2.7668 (15)	149
N1—H1n···O2ⁱⁱ	0.88	2.23	3.0875 (16)	163
N3—H3n···O4ⁱⁱⁱ	0.88	2.15	2.9518 (15)	152

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

Acknowledgements

We thank the University of Malaya for funding this study (Science Fund grants 12–02-03–2031, 12–02-03–2051).

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