N'-[(E)-3-Chloro-2-fluoro-benzyl-idene]-6-methyl-nicotinohydrazide monohydrate.

The title compound, C(14)H(11)ClFN(3)O·H(2)O, exists in an E conformation with respect to the N=C bond. The pyridine ring forms a dihedral angle of 5.00 (9)° with the benzene ring. In the crystal, the ketone O atom accepts one O-H⋯O and one C-H⋯O hydrogen bond, the water O atom accepts one N-H⋯O and two C-H⋯O hydrogen bonds and the pyridine N atom accepts one O-H⋯N hydrogen bond, forming layers parallel to the ab plane.

Related literature

For general background to and the biological properties of hydrazone derivatives, see: Rollas & Kucukguzel (2007 ▶); Sondhi et al. (2009 ▶); Belskaya et al. (2010 ▶); Vijesh et al. (2011 ▶); Galil & Amr (2000 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For related structures, see: Fun, Quah & Abdel-Aziz (2012 ▶); Fun, Quah, Shetty et al. (2012 ▶); Fun, Quah, Nitinchandra et al. (2012 ▶).

Experimental

Crystal data

C14H11ClFN3O·H2O

M = 309.72

Monoclinic,

a = 9.7898 (12) Å

b = 6.4440 (8) Å

c = 23.121 (3) Å

β = 106.614 (5)°

V = 1397.7 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.29 mm−1

T = 100 K

0.47 × 0.24 × 0.13 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.874, T max = 0.962

12000 measured reflections

3154 independent reflections

2625 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.137

S = 1.05

3154 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.63 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812026736/is5156sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026736/is5156Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812026736/is5156Isup3.cml

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

C14H11ClFN3O·H2O	F(000) = 640
Mr = 309.72	Dx = 1.472 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5275 reflections
a = 9.7898 (12) Å	θ = 3.2–30.0°
b = 6.4440 (8) Å	µ = 0.29 mm−1
c = 23.121 (3) Å	T = 100 K
β = 106.614 (5)°	Block, colourless
V = 1397.7 (3) Å3	0.47 × 0.24 × 0.13 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	3154 independent reflections
Radiation source: fine-focus sealed tube	2625 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
Tmin = 0.874, Tmax = 0.962	k = −8→8
12000 measured reflections	l = −30→30

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0777P)2 + 0.8539P] where P = (Fo2 + 2Fc2)/3
3154 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.63 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Cl1	0.13433 (5)	0.04401 (12)	−0.22498 (2)	0.0433 (2)
F1	0.41013 (12)	0.18849 (16)	−0.14979 (5)	0.0253 (3)
O1	0.90720 (13)	−0.28353 (18)	0.07189 (6)	0.0216 (3)
N1	0.69521 (15)	−0.1028 (2)	−0.01138 (6)	0.0147 (3)
N2	0.81273 (15)	0.0080 (2)	0.02094 (6)	0.0140 (3)
H3	0.8209	0.1329	0.0139	0.017*
N3	1.18040 (16)	0.3394 (2)	0.11873 (7)	0.0175 (3)
C1	1.1389 (2)	−0.0710 (3)	0.14649 (8)	0.0213 (4)
H1A	1.1260	−0.2118	0.1559	0.026*
C2	1.2558 (2)	0.0394 (3)	0.17998 (8)	0.0224 (4)
H2A	1.3235	−0.0246	0.2130	0.027*
C3	1.27378 (18)	0.2453 (3)	0.16504 (8)	0.0158 (3)
C4	1.06603 (18)	0.2327 (3)	0.08720 (8)	0.0164 (3)
H4A	0.9987	0.3015	0.0551	0.020*
C5	1.04020 (18)	0.0268 (2)	0.09874 (7)	0.0134 (3)
C6	0.91479 (18)	−0.0965 (2)	0.06299 (7)	0.0144 (3)
C7	0.60432 (18)	−0.0013 (2)	−0.05240 (7)	0.0145 (3)
H7A	0.6211	0.1397	−0.0602	0.017*
C8	0.47374 (17)	−0.1065 (3)	−0.08721 (7)	0.0146 (3)
C9	0.37845 (19)	−0.0051 (3)	−0.13481 (8)	0.0182 (4)
C10	0.25093 (19)	−0.0955 (3)	−0.16783 (8)	0.0243 (4)
C11	0.2185 (2)	−0.2941 (3)	−0.15368 (9)	0.0276 (4)
H11A	0.1321	−0.3580	−0.1760	0.033*
C12	0.3126 (2)	−0.3998 (3)	−0.10675 (9)	0.0254 (4)
H12A	0.2903	−0.5365	−0.0970	0.030*
C13	0.43891 (19)	−0.3077 (3)	−0.07395 (8)	0.0191 (4)
H13A	0.5027	−0.3824	−0.0420	0.023*
C14	1.4001 (2)	0.3715 (3)	0.19936 (8)	0.0216 (4)
H14A	1.3685	0.5111	0.2064	0.032*
H14B	1.4689	0.3811	0.1759	0.032*
H14C	1.4453	0.3046	0.2382	0.032*
O1W	0.78116 (14)	0.41994 (18)	−0.02068 (6)	0.0207 (3)
H2W1	0.8016	0.5100	0.0026	0.031*
H1W1	0.7882	0.4580	−0.0518	0.031*

	U11	U22	U33	U12	U13	U23
Cl1	0.0185 (3)	0.0809 (5)	0.0264 (3)	0.0020 (3)	−0.00018 (19)	0.0134 (3)
F1	0.0256 (6)	0.0188 (5)	0.0300 (6)	0.0021 (4)	0.0052 (4)	0.0078 (4)
O1	0.0211 (7)	0.0072 (6)	0.0320 (7)	−0.0027 (5)	0.0004 (5)	0.0036 (5)
N1	0.0146 (7)	0.0096 (6)	0.0195 (7)	−0.0031 (5)	0.0040 (5)	−0.0031 (5)
N2	0.0149 (7)	0.0062 (6)	0.0194 (7)	−0.0033 (5)	0.0025 (5)	−0.0010 (5)
N3	0.0166 (7)	0.0121 (7)	0.0221 (7)	−0.0031 (5)	0.0027 (6)	−0.0012 (5)
C1	0.0214 (9)	0.0125 (8)	0.0270 (9)	−0.0021 (7)	0.0024 (7)	0.0045 (7)
C2	0.0175 (9)	0.0190 (9)	0.0257 (9)	−0.0014 (7)	−0.0018 (7)	0.0053 (7)
C3	0.0149 (8)	0.0142 (8)	0.0186 (8)	−0.0015 (6)	0.0053 (6)	−0.0020 (6)
C4	0.0162 (8)	0.0109 (7)	0.0198 (8)	−0.0018 (6)	0.0018 (6)	0.0015 (6)
C5	0.0135 (8)	0.0094 (7)	0.0181 (8)	−0.0016 (6)	0.0057 (6)	−0.0014 (6)
C6	0.0149 (8)	0.0091 (7)	0.0197 (8)	−0.0022 (6)	0.0058 (6)	−0.0006 (6)
C7	0.0164 (8)	0.0088 (7)	0.0182 (8)	−0.0014 (6)	0.0050 (6)	−0.0011 (6)
C8	0.0142 (8)	0.0122 (7)	0.0185 (7)	−0.0025 (6)	0.0065 (6)	−0.0040 (6)
C9	0.0177 (8)	0.0181 (8)	0.0199 (8)	−0.0011 (7)	0.0070 (6)	−0.0010 (6)
C10	0.0139 (8)	0.0409 (11)	0.0181 (8)	−0.0028 (8)	0.0045 (6)	−0.0038 (8)
C11	0.0173 (9)	0.0395 (12)	0.0276 (10)	−0.0127 (8)	0.0090 (7)	−0.0136 (8)
C12	0.0251 (10)	0.0204 (9)	0.0348 (10)	−0.0109 (8)	0.0153 (8)	−0.0099 (8)
C13	0.0204 (9)	0.0130 (8)	0.0251 (9)	−0.0035 (7)	0.0088 (7)	−0.0024 (6)
C14	0.0182 (9)	0.0209 (9)	0.0235 (8)	−0.0044 (7)	0.0023 (7)	−0.0033 (7)
O1W	0.0282 (7)	0.0081 (5)	0.0244 (6)	−0.0042 (5)	0.0052 (5)	0.0019 (5)

Cl1—C10	1.731 (2)	C5—C6	1.497 (2)
F1—C9	1.354 (2)	C7—C8	1.467 (2)
O1—C6	1.228 (2)	C7—H7A	0.9500
N1—C7	1.279 (2)	C8—C9	1.386 (2)
N1—N2	1.3786 (18)	C8—C13	1.397 (2)
N2—C6	1.357 (2)	C9—C10	1.391 (2)
N2—H3	0.8295	C10—C11	1.380 (3)
N3—C3	1.338 (2)	C11—C12	1.385 (3)
N3—C4	1.338 (2)	C11—H11A	0.9500
C1—C2	1.381 (2)	C12—C13	1.386 (2)
C1—C5	1.393 (2)	C12—H12A	0.9500
C1—H1A	0.9500	C13—H13A	0.9500
C2—C3	1.395 (2)	C14—H14A	0.9800
C2—H2A	0.9500	C14—H14B	0.9800
C3—C14	1.503 (2)	C14—H14C	0.9800
C4—C5	1.391 (2)	O1W—H2W1	0.7778
C4—H4A	0.9500	O1W—H1W1	0.7815
C7—N1—N2	115.64 (14)	C9—C8—C13	117.44 (15)
C6—N2—N1	117.43 (13)	C9—C8—C7	120.04 (15)
C6—N2—H3	122.0	C13—C8—C7	122.51 (15)
N1—N2—H3	120.6	F1—C9—C8	119.08 (15)
C3—N3—C4	118.47 (15)	F1—C9—C10	118.73 (16)
C2—C1—C5	119.13 (16)	C8—C9—C10	122.19 (17)
C2—C1—H1A	120.4	C11—C10—C9	119.29 (18)
C5—C1—H1A	120.4	C11—C10—Cl1	121.11 (15)
C1—C2—C3	119.62 (16)	C9—C10—Cl1	119.59 (16)
C1—C2—H2A	120.2	C10—C11—C12	119.69 (17)
C3—C2—H2A	120.2	C10—C11—H11A	120.2
N3—C3—C2	121.56 (15)	C12—C11—H11A	120.2
N3—C3—C14	116.62 (15)	C11—C12—C13	120.50 (18)
C2—C3—C14	121.81 (16)	C11—C12—H12A	119.8
N3—C4—C5	123.74 (15)	C13—C12—H12A	119.8
N3—C4—H4A	118.1	C12—C13—C8	120.87 (17)
C5—C4—H4A	118.1	C12—C13—H13A	119.6
C4—C5—C1	117.45 (15)	C8—C13—H13A	119.6
C4—C5—C6	124.46 (15)	C3—C14—H14A	109.5
C1—C5—C6	118.08 (15)	C3—C14—H14B	109.5
O1—C6—N2	122.65 (15)	H14A—C14—H14B	109.5
O1—C6—C5	120.50 (15)	C3—C14—H14C	109.5
N2—C6—C5	116.85 (14)	H14A—C14—H14C	109.5
N1—C7—C8	118.86 (15)	H14B—C14—H14C	109.5
N1—C7—H7A	120.6	H2W1—O1W—H1W1	109.3
C8—C7—H7A	120.6
C7—N1—N2—C6	−177.06 (15)	N2—N1—C7—C8	−177.73 (13)
C5—C1—C2—C3	−0.7 (3)	N1—C7—C8—C9	−175.30 (16)
C4—N3—C3—C2	1.4 (3)	N1—C7—C8—C13	5.6 (3)
C4—N3—C3—C14	−179.66 (15)	C13—C8—C9—F1	−178.62 (15)
C1—C2—C3—N3	−0.1 (3)	C7—C8—C9—F1	2.2 (2)
C1—C2—C3—C14	−179.06 (18)	C13—C8—C9—C10	1.4 (3)
C3—N3—C4—C5	−1.8 (3)	C7—C8—C9—C10	−177.74 (16)
N3—C4—C5—C1	0.9 (3)	F1—C9—C10—C11	178.90 (16)
N3—C4—C5—C6	−178.41 (16)	C8—C9—C10—C11	−1.1 (3)
C2—C1—C5—C4	0.4 (3)	F1—C9—C10—Cl1	−2.2 (2)
C2—C1—C5—C6	179.74 (16)	C8—C9—C10—Cl1	177.77 (14)
N1—N2—C6—O1	1.7 (3)	C9—C10—C11—C12	0.4 (3)
N1—N2—C6—C5	−178.62 (13)	Cl1—C10—C11—C12	−178.47 (15)
C4—C5—C6—O1	172.25 (17)	C10—C11—C12—C13	0.0 (3)
C1—C5—C6—O1	−7.1 (3)	C11—C12—C13—C8	0.4 (3)
C4—C5—C6—N2	−7.4 (2)	C9—C8—C13—C12	−1.0 (3)
C1—C5—C6—N2	173.25 (15)	C7—C8—C13—C12	178.11 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W1···O1i	0.78	2.11	2.8713 (18)	166
O1W—H1W1···N3ii	0.78	2.11	2.859 (2)	160
N2—H3···O1W	0.83	2.01	2.8104 (18)	162
C4—H4A···O1W	0.95	2.46	3.388 (2)	165
C7—H7A···O1W	0.95	2.39	3.1902 (19)	141
C12—H12A···O1iii	0.95	2.46	3.230 (2)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W1⋯O1i	0.78	2.11	2.8713 (18)	166
O1W—H1W1⋯N3ii	0.78	2.11	2.859 (2)	160
N2—H3⋯O1W	0.83	2.01	2.8104 (18)	162
C4—H4A⋯O1W	0.95	2.46	3.388 (2)	165
C7—H7A⋯O1W	0.95	2.39	3.1902 (19)	141
C12—H12A⋯O1iii	0.95	2.46	3.230 (2)	138

Symmetry codes: (i) ; (ii) ; (iii) .