2-[(4-Chloro­benzo­yl)­hydrazono]­propionic acid monohydrate

Abstract

In the title compound, C₁₀H₉ClN₂O₃·H₂O, the water mol­ecule is a hydrogen-bond donor to the amide and carbonyl O atoms of two acid mol­ecules; it is also a hydrogen-bond acceptor to the acid OH group and the amide H atom. The hydrogen-bonding inter­actions give rise to a two-dimensional array.

Related literature

For the structure of 2-[(4-methyl­benzo­yl)hydrazono]propionic acid monohydrate, see: Wong et al. (2009 ▶).

Experimental

Crystal data

• C₁₀H₉ClN₂O₃·H₂O

• M _r = 258.66

• Triclinic,

• a = 6.6516 (1) Å

• b = 6.9345 (1) Å

• c = 7.0988 (1) Å

• α = 73.833 (1)°

• β = 80.182 (1)°

• γ = 61.613 (1)°

• V = 276.39 (1) ų

• Z = 1

• Mo Kα radiation

• μ = 0.35 mm⁻¹

• T = 118 K

• 0.45 × 0.35 × 0.15 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.858, T _max = 0.949

• 2247 measured reflections

• 1965 independent reflections

• 1952 reflections with I > 2σ(I)

• R _int = 0.011

Refinement

• R[F ² > 2σ(F ²)] = 0.026

• wR(F ²) = 0.070

• S = 1.00

• 1965 reflections

• 171 parameters

• 7 restraints

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

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.33 e Å⁻³

• Absolute structure: Flack (1983 ▶), 733 Friedel pairs

• Flack parameter: 0.02 (3)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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: pubCIF (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
O1—H1O⋯O1W	0.83 (1)	1.92 (3)	2.659 (2)	147 (4)
O1W—H11⋯O2i	0.84 (1)	1.96 (1)	2.784 (2)	165 (2)
O1W—H12⋯O3	0.84 (1)	1.98 (1)	2.809 (2)	172 (2)
N1—H1N⋯O1Wii	0.88 (1)	2.48 (2)	3.3596 (18)	177 (2)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Experimental

4-Chlorobenzoylhydrazide (0.85 g, 0.005 mol) and pyruvic acid (0.43 g, 0.005 mol) were dissolved in methanol (30 ml). The solution was heated for 3 h; slow evaporation of the solvent gave colorless crystals.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95-0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2-1.5U(C). The methyl H-atoms were rotated to fit the electron density.

The oxygen- and nitrogen-bound H-atoms were located in a difference Fourier map, and were refined with distance restraints [N–H 0.88±0.01 and O–H 0.84±0.01 Å]; their U_iso values were freely refined.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of C10H9N2O3.H2O at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C10H9ClN2O3·H2O	Z = 1
Mr = 258.66	F(000) = 134
Triclinic, P1	Dx = 1.554 Mg m−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6516 (1) Å	Cell parameters from 2199 reflections
b = 6.9345 (1) Å	θ = 3.0–28.2°
c = 7.0988 (1) Å	µ = 0.35 mm−1
α = 73.833 (1)°	T = 118 K
β = 80.182 (1)°	Irregular block, colorless
γ = 61.613 (1)°	0.45 × 0.35 × 0.15 mm
V = 276.39 (1) Å3

Data collection

Bruker SMART APEX diffractometer	1965 independent reflections
Radiation source: fine-focus sealed tube	1952 reflections with I > 2σ(I)
graphite	Rint = 0.011
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.858, Tmax = 0.949	k = −8→8
2247 measured reflections	l = −9→9

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070	w = 1/[σ2(Fo2) + (0.0628P)2 + 0.0013P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
1965 reflections	Δρmax = 0.20 e Å−3
171 parameters	Δρmin = −0.33 e Å−3
7 restraints	Absolute structure: Flack (1983), 733 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.02 (3)

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

	x	y	z	Uiso*/Ueq
Cl1	0.50015 (5)	0.49992 (5)	0.49993 (4)	0.02415 (12)
O1	2.0776 (2)	0.41172 (18)	−0.23906 (16)	0.0184 (2)
O2	1.9975 (2)	0.76916 (19)	−0.31287 (18)	0.0221 (3)
O3	1.5700 (2)	0.18182 (19)	0.11932 (19)	0.0228 (3)
O1W	1.9830 (2)	0.06405 (18)	−0.10712 (18)	0.0216 (2)
N1	1.4403 (2)	0.5584 (2)	−0.0003 (2)	0.0168 (3)
N2	1.6543 (2)	0.5201 (2)	−0.07703 (19)	0.0154 (3)
C1	1.9322 (3)	0.6250 (3)	−0.2491 (2)	0.0161 (3)
C2	1.6887 (3)	0.6861 (2)	−0.1806 (2)	0.0165 (3)
C3	1.5134 (3)	0.9273 (3)	−0.2314 (3)	0.0279 (4)
H3A	1.3862	0.9390	−0.2937	0.042*
H3B	1.5830	1.0164	−0.3222	0.042*
H3C	1.4562	0.9845	−0.1115	0.042*
C4	1.4131 (3)	0.3718 (3)	0.1048 (2)	0.0169 (3)
C5	1.1830 (3)	0.4130 (3)	0.2013 (2)	0.0158 (3)
C6	1.1356 (3)	0.2284 (3)	0.2676 (2)	0.0197 (3)
H6	1.2483	0.0845	0.2492	0.024*
C7	0.9270 (3)	0.2526 (3)	0.3596 (2)	0.0200 (3)
H7	0.8955	0.1268	0.4045	0.024*
C8	0.7637 (3)	0.4649 (3)	0.3852 (2)	0.0187 (3)
C9	0.8072 (3)	0.6496 (3)	0.3209 (2)	0.0194 (3)
H9	0.6934	0.7934	0.3385	0.023*
C10	1.0168 (3)	0.6238 (2)	0.2310 (2)	0.0184 (3)
H10	1.0483	0.7497	0.1891	0.022*
H1O	2.032 (8)	0.321 (6)	−0.244 (7)	0.115 (18)*
H11	1.970 (4)	−0.004 (3)	−0.182 (3)	0.029 (5)*
H12	1.855 (2)	0.111 (4)	−0.048 (3)	0.028 (6)*
H1N	1.318 (3)	0.689 (2)	−0.024 (3)	0.013 (4)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0181 (2)	0.0375 (2)	0.02137 (18)	−0.01711 (17)	0.00484 (13)	−0.00835 (14)
O1	0.0136 (6)	0.0172 (5)	0.0225 (6)	−0.0068 (4)	0.0026 (4)	−0.0041 (4)
O2	0.0191 (6)	0.0202 (5)	0.0283 (6)	−0.0120 (5)	0.0068 (5)	−0.0066 (4)
O3	0.0183 (6)	0.0153 (5)	0.0309 (6)	−0.0077 (4)	0.0049 (5)	−0.0028 (4)
O1W	0.0183 (6)	0.0182 (5)	0.0274 (6)	−0.0087 (5)	0.0051 (5)	−0.0067 (4)
N1	0.0140 (7)	0.0163 (6)	0.0188 (6)	−0.0074 (5)	0.0021 (5)	−0.0027 (5)
N2	0.0120 (7)	0.0196 (6)	0.0160 (6)	−0.0082 (5)	0.0032 (5)	−0.0064 (5)
C1	0.0167 (8)	0.0171 (6)	0.0156 (6)	−0.0087 (6)	0.0011 (6)	−0.0044 (5)
C2	0.0165 (8)	0.0158 (7)	0.0176 (7)	−0.0080 (6)	0.0008 (6)	−0.0038 (5)
C3	0.0177 (8)	0.0165 (7)	0.0415 (10)	−0.0060 (6)	0.0068 (7)	−0.0028 (6)
C4	0.0154 (8)	0.0191 (7)	0.0173 (7)	−0.0093 (6)	0.0014 (6)	−0.0044 (5)
C5	0.0137 (8)	0.0178 (7)	0.0153 (7)	−0.0081 (6)	0.0014 (6)	−0.0026 (5)
C6	0.0197 (8)	0.0195 (7)	0.0206 (7)	−0.0105 (6)	0.0010 (6)	−0.0036 (5)
C7	0.0213 (9)	0.0222 (7)	0.0212 (7)	−0.0147 (7)	0.0018 (6)	−0.0044 (6)
C8	0.0143 (8)	0.0279 (8)	0.0151 (7)	−0.0123 (7)	0.0019 (6)	−0.0030 (6)
C9	0.0168 (8)	0.0191 (7)	0.0182 (7)	−0.0064 (6)	−0.0003 (6)	−0.0016 (5)
C10	0.0176 (8)	0.0187 (7)	0.0185 (7)	−0.0098 (6)	0.0018 (6)	−0.0023 (5)

Geometric parameters (Å, °)

Cl1—C8	1.7363 (18)	C3—H3B	0.9800
O1—C1	1.3161 (19)	C3—H3C	0.9800
O1—H1O	0.829 (10)	C4—C5	1.493 (2)
O2—C1	1.219 (2)	C5—C6	1.399 (2)
O3—C4	1.220 (2)	C5—C10	1.400 (2)
O1W—H11	0.842 (9)	C6—C7	1.382 (2)
O1W—H12	0.836 (10)	C6—H6	0.9500
N1—N2	1.360 (2)	C7—C8	1.393 (2)
N1—C4	1.379 (2)	C7—H7	0.9500
N1—H1N	0.878 (9)	C8—C9	1.383 (2)
N2—C2	1.281 (2)	C9—C10	1.380 (3)
C1—C2	1.495 (2)	C9—H9	0.9500
C2—C3	1.497 (2)	C10—H10	0.9500
C3—H3A	0.9800
C1—O1—H1O	120 (3)	N1—C4—C5	116.93 (13)
H11—O1W—H12	103 (2)	C6—C5—C10	119.14 (15)
N2—N1—C4	116.41 (12)	C6—C5—C4	117.42 (14)
N2—N1—H1N	124.6 (14)	C10—C5—C4	123.44 (14)
C4—N1—H1N	118.6 (14)	C7—C6—C5	120.85 (14)
C2—N2—N1	119.24 (13)	C7—C6—H6	119.6
O2—C1—O1	119.90 (16)	C5—C6—H6	119.6
O2—C1—C2	121.04 (14)	C6—C7—C8	118.77 (14)
O1—C1—C2	119.06 (13)	C6—C7—H7	120.6
N2—C2—C1	114.38 (13)	C8—C7—H7	120.6
N2—C2—C3	126.56 (16)	C9—C8—C7	121.30 (17)
C1—C2—C3	119.03 (14)	C9—C8—Cl1	119.04 (13)
C2—C3—H3A	109.5	C7—C8—Cl1	119.67 (13)
C2—C3—H3B	109.5	C10—C9—C8	119.64 (15)
H3A—C3—H3B	109.5	C10—C9—H9	120.2
C2—C3—H3C	109.5	C8—C9—H9	120.2
H3A—C3—H3C	109.5	C9—C10—C5	120.28 (14)
H3B—C3—H3C	109.5	C9—C10—H10	119.9
O3—C4—N1	121.63 (16)	C5—C10—H10	119.9
O3—C4—C5	121.44 (15)
C4—N1—N2—C2	178.11 (13)	N1—C4—C5—C10	−16.0 (2)
N1—N2—C2—C1	177.31 (11)	C10—C5—C6—C7	0.7 (2)
N1—N2—C2—C3	−0.7 (2)	C4—C5—C6—C7	179.58 (13)
O2—C1—C2—N2	−164.68 (14)	C5—C6—C7—C8	0.0 (2)
O1—C1—C2—N2	15.00 (19)	C6—C7—C8—C9	−0.1 (2)
O2—C1—C2—C3	13.5 (2)	C6—C7—C8—Cl1	179.90 (11)
O1—C1—C2—C3	−166.78 (14)	C7—C8—C9—C10	−0.6 (2)
N2—N1—C4—O3	−3.7 (2)	Cl1—C8—C9—C10	179.43 (11)
N2—N1—C4—C5	175.94 (11)	C8—C9—C10—C5	1.3 (2)
O3—C4—C5—C6	−15.2 (2)	C6—C5—C10—C9	−1.3 (2)
N1—C4—C5—C6	165.12 (13)	C4—C5—C10—C9	179.82 (13)
O3—C4—C5—C10	163.61 (15)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O1W	0.83 (1)	1.92 (3)	2.659 (2)	147 (4)
O1W—H11···O2i	0.84 (1)	1.96 (1)	2.784 (2)	165 (2)
O1W—H12···O3	0.84 (1)	1.98 (1)	2.809 (2)	172 (2)
N1—H1N···O1Wii	0.88 (1)	2.48 (2)	3.3596 (18)	177 (2)

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