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

Abstract

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,

• a = 9.6481 (2) Å

• b = 15.1408 (3) Å

• c = 10.2206 (2) Å

• β = 98.232 (1)°

• V = 1477.64 (5) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) ; (ii) ; (iii) .

supplementary crystallographic information

Experimental

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.

Refinement

Hydrogen atoms were placed at calculated positions (C–H 0.95, N–H 0.88, O–H 0.84 Å) and were treated as riding on their parent carbon atoms, with U(H) set to 1.2–1.5 times U_eq(C,N,O). The hydroxy groups were rotated to fit the electron density.

Figures

Fig. 1.

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

Crystal data

C16H12ClN3O4	F(000) = 712
Mr = 345.74	Dx = 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

Bruker SMART APEX diffractometer	3389 independent reflections
Radiation source: fine-focus sealed tube	2907 reflections with I > 2σ(I)
graphite	Rint = 0.025
ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
Tmin = 0.914, Tmax = 0.966	k = −19→19
10185 measured reflections	l = −13→13

Refinement

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(Fo2) + (0.0452P)2 + 0.6635P] where P = (Fo2 + 2Fc2)/3
3389 reflections	(Δ/σ)max = 0.001
220 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.