N′-(3-Fluoro­benzyl­idene)-4-hy­droxy-3-meth­oxy­benzohydrazide methanol monosolvate

Zong, Q.-S.

doi:10.1107/S1600536812012196

organic compounds

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doi:10.1107/S1600536812012196

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N′-(3-Fluorobenzylidene)-4-hydroxy-3-methoxybenzohydrazide methanol monosolvate

Qian-Shou Zong ^a ^*

^aCollege of Biology and Chemical Engineering, Jiaxing University, Jiaxing Zhejiang 314001, People's Republic of China, and School of Pharmaceutical Sciences, Zhejiang University, Hangzhou Zhejiang 310058, People's Republic of China
^*Correspondence e-mail: zongqs@iccas.ac.cn

(Received 20 March 2012; accepted 21 March 2012; online 6 April 2012)

In the title compound, C₁₅H₁₃FN₂O₃·CH₃OH, the dihedral angle between the benzene rings of the benzohydrazone molecule is 5.3 (3)°. The C atom of the methoxy group is almost coplanar with its attached ring [deviation = 0.017 (2) Å]. The r.m.s. deviation of the 21 non-H atoms of the hydrazone molecule is 0.106 Å. In the crystal, the components are linked by O_m—H⋯O_h, N_h—H⋯O_m and O_h—H⋯O_h (m = methanol and h = hydrazone) hydrogen bonds, forming (001) layers.

Related literature

For related structures, see: Horkaew et al. (2012); Fun et al. (2011 ); Zhang (2011 ).

Experimental

Crystal data

C₁₅H₁₃FN₂O₃·CH₄O
M_r = 320.32
Orthorhombic, P b c a
a = 14.9566 (18) Å
b = 11.1123 (16) Å
c = 19.351 (2) Å
V = 3216.1 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.20 × 0.18 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.980, T_max = 0.983
22845 measured reflections
3270 independent reflections
2588 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.161
S = 1.12
3270 reflections
215 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.91 (1)	2.03 (1)	2.916 (2)	164 (2)
O4—H4⋯O3	0.82	1.95	2.772 (2)	176
O1—H1A⋯O3ⁱⁱ	0.82	1.94	2.7504 (17)	168
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812012196/hb6695sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012196/hb6695Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812012196/hb6695Isup3.cml

checkCIF report

Comment top

In this paper, the title new benzohydrazide compound, (I), which crystallised as a methanol solvate, is reported.

The dihedral angle between the benzene rings C1–C6 and C9–C14 of the benzohydrazone molecule is 5.3 (3)°. The bond lengths in the benzohydrazone molecule are comparable to those in similar benzohydrazone compounds (Horkaew et al., 2012; Fun et al., 2011; Zhang, 2011). In the crystal, the benzohydrazone molecules are linked by methanol molecules through hydrogen bonds (Table 1), to form layers parallel to the ab plane (Fig. 2).

Related literature top

For related structures, see: Horkaew et al. (2012); Fun et al. (2011); Zhang (2011).

Experimental top

3-Fluorobenzaldehyde (0.124 g, 1 mmol) and 4-hydroxy-3-methoxybenzohydrazide (0.182 g, 1 mmol) were mixed in methanol. The mixture was stirred at room temperature for 1 h to give a colorless solution. Colourless blocks were obtained by slow evaporation from the solution in air.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecule of the title compound with displacement ellipsoids drawn at the 30% probability level. Hydrogen bond is shown as a dashed line.
	Fig. 2. The crystal structure of the title compound, viewed along a axis. Hydrogen bonds are shown as dashed lines.

N'-(3-Fluorobenzylidene)-4-hydroxy-3-methoxybenzohydrazide methanol monosolvate top

Crystal data top

C₁₅H₁₃FN₂O₃·CH₄O	D_x = 1.323 Mg m⁻³
M_r = 320.32	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 8503 reflections
a = 14.9566 (18) Å	θ = 2.5–26.0°
b = 11.1123 (16) Å	µ = 0.10 mm⁻¹
c = 19.351 (2) Å	T = 298 K
V = 3216.1 (7) Å³	Block, colorless
Z = 8	0.20 × 0.18 × 0.17 mm
F(000) = 1344

Data collection top

Bruker APEXII CCD diffractometer	3270 independent reflections
Radiation source: fine-focus sealed tube	2588 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 26.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −18→17
T_min = 0.980, T_max = 0.983	k = −13→13
22845 measured reflections	l = −24→24

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0956P)² + 0.5869P] where P = (F_o² + 2F_c²)/3
3270 reflections	(Δ/σ)_max < 0.001
215 parameters	Δρ_max = 0.28 e Å⁻³
1 restraint	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₅H₁₃FN₂O₃·CH₄O	V = 3216.1 (7) Å³
M_r = 320.32	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 14.9566 (18) Å	µ = 0.10 mm⁻¹
b = 11.1123 (16) Å	T = 298 K
c = 19.351 (2) Å	0.20 × 0.18 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	3270 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2588 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.983	R_int = 0.030
22845 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.28 e Å⁻³
3270 reflections	Δρ_min = −0.34 e Å⁻³
215 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
F1	0.62214 (8)	1.20264 (15)	0.71230 (10)	0.0899 (5)
N1	0.27077 (9)	0.93828 (13)	0.59540 (8)	0.0396 (4)
N2	0.33902 (9)	1.00033 (12)	0.62766 (8)	0.0390 (3)
O1	0.02644 (7)	0.56459 (11)	0.42821 (6)	0.0430 (3)
H1A	−0.0236	0.5933	0.4332	0.064*
O2	0.19271 (8)	0.52220 (13)	0.40048 (7)	0.0540 (4)
O3	0.37143 (7)	0.80593 (11)	0.55390 (8)	0.0497 (4)
O4	0.39737 (10)	0.57101 (14)	0.59772 (13)	0.0833 (6)
H4	0.3917	0.6416	0.5862	0.125*
C1	0.38310 (11)	1.16625 (15)	0.69775 (9)	0.0397 (4)
C2	0.35539 (13)	1.26065 (17)	0.73975 (10)	0.0500 (5)
H2	0.2946	1.2747	0.7460	0.060*
C3	0.41710 (15)	1.33379 (19)	0.77229 (11)	0.0585 (5)
H3	0.3976	1.3964	0.8004	0.070*
C4	0.50739 (14)	1.31446 (19)	0.76342 (12)	0.0601 (6)
H4A	0.5494	1.3629	0.7854	0.072*
C5	0.53336 (13)	1.22155 (18)	0.72118 (11)	0.0533 (5)
C6	0.47444 (12)	1.14675 (16)	0.68772 (10)	0.0449 (4)
H6	0.4947	1.0851	0.6593	0.054*
C7	0.31604 (11)	1.09122 (16)	0.66320 (9)	0.0419 (4)
H7	0.2558	1.1105	0.6674	0.050*
C8	0.29236 (10)	0.84020 (15)	0.55851 (9)	0.0361 (4)
C9	0.21891 (10)	0.77204 (14)	0.52525 (9)	0.0351 (4)
C10	0.24240 (10)	0.68253 (15)	0.47763 (9)	0.0383 (4)
H10	0.3023	0.6698	0.4670	0.046*
C11	0.17751 (10)	0.61309 (15)	0.44635 (9)	0.0371 (4)
C12	0.08669 (10)	0.63371 (14)	0.46134 (8)	0.0341 (4)
C13	0.06435 (10)	0.72117 (16)	0.50909 (9)	0.0381 (4)
H13	0.0046	0.7337	0.5201	0.046*
C14	0.12929 (10)	0.79028 (15)	0.54072 (9)	0.0379 (4)
H14	0.1129	0.8492	0.5724	0.046*
C15	0.28296 (14)	0.4987 (2)	0.38116 (13)	0.0658 (6)
H15A	0.3077	0.5685	0.3591	0.099*
H15B	0.2847	0.4318	0.3498	0.099*
H15C	0.3173	0.4798	0.4216	0.099*
C16	0.48620 (15)	0.5484 (2)	0.61393 (16)	0.0715 (7)
H16A	0.5145	0.6218	0.6283	0.107*
H16B	0.5164	0.5171	0.5740	0.107*
H16C	0.4892	0.4906	0.6507	0.107*
H1	0.2134 (9)	0.965 (2)	0.5972 (14)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0391 (7)	0.0999 (11)	0.1307 (13)	−0.0092 (7)	−0.0109 (7)	−0.0398 (10)
N1	0.0252 (6)	0.0355 (8)	0.0580 (9)	−0.0004 (5)	−0.0071 (6)	−0.0071 (6)
N2	0.0296 (7)	0.0345 (7)	0.0529 (8)	−0.0032 (5)	−0.0072 (6)	−0.0026 (6)
O1	0.0290 (6)	0.0475 (7)	0.0524 (7)	−0.0020 (5)	−0.0040 (5)	−0.0134 (6)
O2	0.0345 (7)	0.0598 (9)	0.0676 (8)	0.0074 (6)	−0.0031 (6)	−0.0287 (7)
O3	0.0231 (6)	0.0446 (7)	0.0815 (9)	0.0013 (5)	−0.0042 (5)	−0.0166 (6)
O4	0.0364 (8)	0.0443 (9)	0.169 (2)	−0.0031 (6)	−0.0031 (9)	0.0085 (10)
C1	0.0402 (9)	0.0368 (9)	0.0422 (9)	−0.0020 (7)	−0.0044 (7)	−0.0019 (7)
C2	0.0479 (10)	0.0492 (10)	0.0528 (11)	−0.0004 (8)	0.0039 (8)	−0.0106 (9)
C3	0.0659 (13)	0.0514 (12)	0.0583 (12)	−0.0030 (10)	−0.0009 (10)	−0.0193 (9)
C4	0.0610 (13)	0.0533 (12)	0.0659 (13)	−0.0158 (10)	−0.0114 (10)	−0.0157 (10)
C5	0.0407 (10)	0.0546 (12)	0.0646 (12)	−0.0063 (8)	−0.0064 (9)	−0.0086 (10)
C6	0.0410 (9)	0.0414 (9)	0.0524 (10)	−0.0009 (7)	−0.0061 (8)	−0.0082 (8)
C7	0.0318 (8)	0.0421 (9)	0.0519 (10)	0.0004 (7)	−0.0022 (7)	−0.0057 (8)
C8	0.0257 (7)	0.0332 (8)	0.0494 (9)	0.0012 (6)	−0.0016 (6)	0.0000 (7)
C9	0.0266 (7)	0.0331 (8)	0.0456 (9)	−0.0006 (6)	−0.0026 (6)	−0.0007 (7)
C10	0.0241 (7)	0.0397 (9)	0.0511 (9)	0.0034 (6)	−0.0009 (7)	−0.0044 (7)
C11	0.0301 (8)	0.0390 (9)	0.0421 (9)	0.0038 (6)	−0.0014 (6)	−0.0065 (7)
C12	0.0263 (7)	0.0354 (8)	0.0407 (8)	−0.0018 (6)	−0.0038 (6)	−0.0006 (7)
C13	0.0233 (7)	0.0430 (10)	0.0480 (9)	0.0009 (6)	0.0005 (6)	−0.0063 (7)
C14	0.0281 (8)	0.0375 (9)	0.0482 (9)	0.0011 (6)	−0.0001 (6)	−0.0074 (7)
C15	0.0436 (11)	0.0745 (15)	0.0794 (14)	0.0136 (10)	0.0079 (10)	−0.0270 (12)
C16	0.0519 (13)	0.0620 (14)	0.1007 (19)	−0.0047 (10)	−0.0152 (12)	0.0040 (13)

Geometric parameters (Å, º) top

F1—C5	1.355 (2)	C4—H4A	0.9300
N1—C8	1.342 (2)	C5—C6	1.374 (3)
N1—N2	1.3809 (19)	C6—H6	0.9300
N1—H1	0.910 (10)	C7—H7	0.9300
N2—C7	1.269 (2)	C8—C9	1.481 (2)
O1—C12	1.3465 (19)	C9—C14	1.388 (2)
O1—H1A	0.8200	C9—C10	1.401 (2)
O2—C11	1.364 (2)	C10—C11	1.380 (2)
O2—C15	1.425 (2)	C10—H10	0.9300
O3—C8	1.2456 (19)	C11—C12	1.408 (2)
O4—C16	1.388 (3)	C12—C13	1.382 (2)
O4—H4	0.8200	C13—C14	1.381 (2)
C1—C2	1.390 (3)	C13—H13	0.9300
C1—C6	1.397 (2)	C14—H14	0.9300
C1—C7	1.466 (2)	C15—H15A	0.9600
C2—C3	1.382 (3)	C15—H15B	0.9600
C2—H2	0.9300	C15—H15C	0.9600
C3—C4	1.378 (3)	C16—H16A	0.9600
C3—H3	0.9300	C16—H16B	0.9600
C4—C5	1.373 (3)	C16—H16C	0.9600

C8—N1—N2	117.91 (13)	C14—C9—C10	119.18 (14)
C8—N1—H1	121.0 (17)	C14—C9—C8	123.21 (15)
N2—N1—H1	121.0 (17)	C10—C9—C8	117.57 (14)
C7—N2—N1	116.24 (14)	C11—C10—C9	120.62 (14)
C12—O1—H1A	109.5	C11—C10—H10	119.7
C11—O2—C15	117.69 (14)	C9—C10—H10	119.7
C16—O4—H4	109.5	O2—C11—C10	125.62 (14)
C2—C1—C6	119.33 (16)	O2—C11—C12	114.55 (14)
C2—C1—C7	119.46 (16)	C10—C11—C12	119.83 (15)
C6—C1—C7	121.18 (16)	O1—C12—C13	123.90 (14)
C3—C2—C1	120.74 (18)	O1—C12—C11	117.05 (14)
C3—C2—H2	119.6	C13—C12—C11	119.04 (14)
C1—C2—H2	119.6	C14—C13—C12	121.15 (14)
C4—C3—C2	120.40 (19)	C14—C13—H13	119.4
C4—C3—H3	119.8	C12—C13—H13	119.4
C2—C3—H3	119.8	C13—C14—C9	120.15 (15)
C5—C4—C3	117.95 (18)	C13—C14—H14	119.9
C5—C4—H4A	121.0	C9—C14—H14	119.9
C3—C4—H4A	121.0	O2—C15—H15A	109.5
F1—C5—C4	117.99 (17)	O2—C15—H15B	109.5
F1—C5—C6	118.35 (18)	H15A—C15—H15B	109.5
C4—C5—C6	123.66 (19)	O2—C15—H15C	109.5
C5—C6—C1	117.91 (17)	H15A—C15—H15C	109.5
C5—C6—H6	121.0	H15B—C15—H15C	109.5
C1—C6—H6	121.0	O4—C16—H16A	109.5
N2—C7—C1	120.97 (15)	O4—C16—H16B	109.5
N2—C7—H7	119.5	H16A—C16—H16B	109.5
C1—C7—H7	119.5	O4—C16—H16C	109.5
O3—C8—N1	120.98 (15)	H16A—C16—H16C	109.5
O3—C8—C9	121.10 (15)	H16B—C16—H16C	109.5
N1—C8—C9	117.89 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.91 (1)	2.03 (1)	2.916 (2)	164 (2)
O4—H4···O3	0.82	1.95	2.772 (2)	176
O1—H1A···O3ⁱⁱ	0.82	1.94	2.7504 (17)	168

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃FN₂O₃·CH₄O
M_r	320.32
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	14.9566 (18), 11.1123 (16), 19.351 (2)
V (Å³)	3216.1 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.18 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.980, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	22845, 3270, 2588
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.161, 1.12
No. of reflections	3270
No. of parameters	215
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.34

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.910 (10)	2.031 (12)	2.916 (2)	164 (2)
O4—H4···O3	0.82	1.95	2.772 (2)	176
O1—H1A···O3ⁱⁱ	0.82	1.94	2.7504 (17)	168

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

Acknowledgements

The author thanks the Excellent Yong Teachers Program (No. 00511024) and the China Postdoctoral Science Foundation (No. 2011M500989) for financial support.

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fun, H.-K., Horkaew, J. & Chantrapromma, S. (2011). Acta Cryst. E67, o2644–o2645. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Horkaew, J., Chantrapromma, S., Anantapong, T., Kanjana-Opas, A. & Fun, H.-K. (2012). Acta Cryst. E68, o1069–o1070. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, Z. (2011). Acta Cryst. E67, o1630. Web of Science CSD CrossRef IUCr Journals Google Scholar

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N′-(3-Fluoro­benzyl­­idene)-4-hy­dr­oxy-3-meth­­oxy­benzohydrazide methanol monosolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

N′-(3-Fluorobenzylidene)-4-hydroxy-3-methoxybenzohydrazide methanol monosolvate