(E)-2-(Isonicotinoylhydrazonometh­yl)benzoic acid methanol monosolvate

Li, W.; Yin, H.; Wen, L.; Cui, J.; Wang, D.

doi:10.1107/S1600536809038902

organic compounds

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Volume 65| Part 10| October 2009| Page o2578

doi:10.1107/S1600536809038902

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(E)-2-(Isonicotinoylhydrazonomethyl)benzoic acid methanol monosolvate

Wenkuan Li,^a Handong Yin,^a ^* Liyuan Wen,^a Jichun Cui ^a and Daqi Wang ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: handongyin@163.com

(Received 14 September 2009; accepted 25 September 2009; online 30 September 2009)

The title compound, C₁₄H₁₁N₃O₃·CH₄O, was synthesized by the condensation reaction of isonicotinohydrazide with an equimolar quantity of 2-formylbenzoic acid in methanol. The hydrazone molecule displays an E configuration about the C=N bond. The dihedral angel between the pyridine and the benzene rings is 12.04 (5)°. In the crystal structure, molecules are linked by O—H⋯N, O—H⋯O and N—H⋯O hydrogen-bonding interactions.

Related literature

For general background to hydrazones, see: Dhande et al. (2007 ). For a related structure, see: Zhang et al. (2009 ).

Experimental

Crystal data

C₁₄H₁₁N₃O₃·CH₄O
M_r = 301.30
Monoclinic, P 2₁ /n
a = 6.9768 (11) Å
b = 12.2103 (13) Å
c = 17.2650 (19) Å
β = 95.497 (1)°
V = 1464.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.43 × 0.19 × 0.15 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.958, T_max = 0.985
7290 measured reflections
2508 independent reflections
1233 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.141
S = 0.99
2508 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.86	2.13	2.891 (3)	148
O4—H4⋯O1	0.82	2.14	2.864 (4)	148
O2—H2⋯N3ⁱⁱ	0.82	1.76	2.565 (3)	165
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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 I, global. DOI: 10.1107/S1600536809038902/bq2160sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809038902/bq2160Isup2.hkl

checkCIF report

Comment top

Hydrazones have been attracted significant attention because of their physiological activity, coordinative capability, and applications in analytical chemistry (Dhande et al. 2007). Recently, a large number of hydrazone compounds have been reported (Zhang et al. 2009). As a contribution to the chemistry of hydrazone, we report here the synthesis and crystal structure of the title compound (I).

The crystal structure of (I) is built up of hydrazone and methanol molecules (Fig.1). The dihedral angel between the pyridine and the benzene rings is 12.04 (5) °. The hydrazone molecule crystallizes in E conformation. In the crystal structure, three kinds of intermolecular O—H···N, O—H···O and N—H···O hydrogen bonding interactions are observed and the crystal packing is stabilized by these intermolecular interactions. (Table 1. and Fig. 2).

Related literature top

For general background to hydrazones, see: Dhande et al. (2007). For a related structure, see: Zhang et al. (2009).

Experimental top

Isonicotinohydrazide (10 mmol) was dissolved in ethanol (40 ml), then 2-formylbenzoic acid (10 mmol) was added into the solution. The reaction mixture was heated under reflux for 2 h. After the solution had cooled to room white sediment appeared. The product was crystallized from methanol. Anal. Calcd (%) for [(C₁₄H₁₁N₃O₃).(C₁H₄O₁)] (Mr = 301.30): C, 59.79; H, 5.02; N, 13.95; O, 21.24 Found (%): C, 59.83; H, 5.00; N, 13.92; O, 21.25

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. The molecular structure (I) with 50% probability displacement ellipsoids. O—H···O hydrogen bond is shown in dashed line.
	Fig. 2. The molecular packing of the title compound. Hydrogen bonding is shown in dashed lines.

(E)-2-(Isonicotinoylhydrazonomethyl)benzoic acid methanol monosolvate top

Crystal data top

C₁₄H₁₁N₃O₃·CH₄O	F(000) = 632
M_r = 301.30	D_x = 1.367 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1170 reflections
a = 6.9768 (11) Å	θ = 2.4–21.5°
b = 12.2103 (13) Å	µ = 0.10 mm⁻¹
c = 17.2650 (19) Å	T = 298 K
β = 95.497 (1)°	Block, yellow
V = 1464.0 (3) Å³	0.43 × 0.19 × 0.15 mm
Z = 4

Data collection top

Siemens SMART CCD area-detector diffractometer	2508 independent reflections
Radiation source: fine-focus sealed tube	1233 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.958, T_max = 0.985	k = −12→14
7290 measured reflections	l = −19→20

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0559P)²] where P = (F_o² + 2F_c²)/3
2508 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₄H₁₁N₃O₃·CH₄O	V = 1464.0 (3) Å³
M_r = 301.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.9768 (11) Å	µ = 0.10 mm⁻¹
b = 12.2103 (13) Å	T = 298 K
c = 17.2650 (19) Å	0.43 × 0.19 × 0.15 mm
β = 95.497 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2508 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1233 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.985	R_int = 0.076
7290 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 0.99	Δρ_max = 0.34 e Å⁻³
2508 reflections	Δρ_min = −0.19 e Å⁻³
199 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.2762 (4)	0.52906 (18)	0.52873 (12)	0.0371 (7)
H1	0.3076	0.5854	0.5570	0.045*
N2	0.2993 (4)	0.42528 (18)	0.55868 (14)	0.0390 (7)
N3	0.1111 (4)	0.8638 (2)	0.36585 (14)	0.0438 (7)
O1	0.1643 (3)	0.46359 (16)	0.41058 (12)	0.0537 (7)
O2	0.5588 (3)	0.46550 (16)	0.77984 (11)	0.0523 (7)
H2	0.5752	0.5125	0.8137	0.078*
O3	0.4040 (4)	0.38081 (18)	0.86917 (13)	0.0654 (8)
O4	0.4701 (4)	0.3132 (2)	0.38940 (15)	0.0876 (10)
H4	0.3697	0.3467	0.3775	0.131*
C1	0.2034 (5)	0.5407 (2)	0.45415 (17)	0.0361 (8)
C2	0.1221 (5)	0.8462 (3)	0.44169 (18)	0.0474 (9)
H2A	0.1103	0.9057	0.4745	0.057*
C3	0.1501 (5)	0.7440 (2)	0.47459 (17)	0.0406 (9)
H3	0.1551	0.7347	0.5282	0.049*
C4	0.1704 (4)	0.6558 (2)	0.42630 (15)	0.0312 (7)
C5	0.1561 (5)	0.6736 (2)	0.34726 (16)	0.0380 (8)
H5	0.1660	0.6155	0.3131	0.046*
C6	0.1271 (5)	0.7785 (3)	0.31942 (18)	0.0429 (9)
H6	0.1183	0.7900	0.2659	0.052*
C7	0.3532 (4)	0.4180 (2)	0.63048 (16)	0.0347 (8)
H7	0.3768	0.4809	0.6602	0.042*
C8	0.3783 (4)	0.3093 (2)	0.66650 (17)	0.0322 (8)
C9	0.4202 (5)	0.2943 (2)	0.74724 (17)	0.0353 (8)
C10	0.4338 (5)	0.1888 (2)	0.77718 (19)	0.0456 (9)
H10	0.4572	0.1786	0.8306	0.055*
C11	0.4133 (5)	0.0993 (3)	0.7289 (2)	0.0548 (10)
H11	0.4255	0.0290	0.7496	0.066*
C12	0.3750 (5)	0.1135 (3)	0.6503 (2)	0.0551 (10)
H12	0.3624	0.0530	0.6175	0.066*
C13	0.3551 (5)	0.2177 (2)	0.61980 (18)	0.0434 (9)
H13	0.3254	0.2264	0.5665	0.052*
C14	0.4585 (5)	0.3846 (3)	0.80510 (18)	0.0416 (9)
C15	0.4316 (6)	0.2034 (3)	0.3937 (2)	0.0742 (13)
H15A	0.4264	0.1828	0.4471	0.111*
H15B	0.5314	0.1626	0.3720	0.111*
H15C	0.3101	0.1879	0.3648	0.111*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0488 (19)	0.0284 (14)	0.0325 (15)	0.0004 (13)	−0.0045 (13)	0.0009 (11)
N2	0.0479 (19)	0.0308 (14)	0.0365 (15)	−0.0022 (13)	−0.0049 (13)	0.0049 (12)
N3	0.046 (2)	0.0452 (16)	0.0389 (16)	0.0059 (14)	−0.0003 (13)	0.0045 (13)
O1	0.076 (2)	0.0369 (12)	0.0436 (13)	0.0013 (12)	−0.0172 (12)	−0.0072 (11)
O2	0.078 (2)	0.0419 (13)	0.0375 (13)	−0.0119 (13)	0.0066 (12)	−0.0091 (10)
O3	0.099 (2)	0.0622 (16)	0.0371 (14)	0.0029 (15)	0.0188 (14)	0.0043 (12)
O4	0.091 (3)	0.0691 (19)	0.096 (2)	−0.0088 (17)	−0.0259 (17)	−0.0136 (15)
C1	0.041 (2)	0.0362 (18)	0.0302 (17)	0.0006 (16)	−0.0025 (15)	−0.0011 (14)
C2	0.063 (3)	0.045 (2)	0.0339 (19)	0.0114 (18)	0.0027 (16)	−0.0026 (15)
C3	0.055 (3)	0.0425 (19)	0.0232 (17)	0.0076 (17)	0.0002 (16)	0.0029 (14)
C4	0.030 (2)	0.0366 (17)	0.0266 (16)	0.0033 (14)	0.0013 (13)	−0.0005 (13)
C5	0.041 (2)	0.0438 (19)	0.0284 (17)	0.0048 (16)	0.0018 (15)	−0.0019 (14)
C6	0.046 (2)	0.054 (2)	0.0286 (18)	0.0026 (18)	−0.0005 (16)	0.0094 (16)
C7	0.041 (2)	0.0315 (17)	0.0309 (17)	−0.0005 (15)	−0.0007 (14)	0.0031 (13)
C8	0.028 (2)	0.0290 (17)	0.0388 (18)	−0.0009 (14)	0.0007 (14)	0.0024 (14)
C9	0.034 (2)	0.0332 (17)	0.0374 (18)	0.0021 (15)	−0.0006 (15)	0.0079 (14)
C10	0.051 (2)	0.041 (2)	0.044 (2)	0.0005 (17)	0.0033 (17)	0.0115 (16)
C11	0.061 (3)	0.0333 (19)	0.069 (3)	−0.0039 (18)	0.001 (2)	0.0131 (18)
C12	0.067 (3)	0.032 (2)	0.066 (2)	−0.0038 (18)	0.001 (2)	−0.0039 (18)
C13	0.048 (3)	0.0372 (19)	0.0430 (19)	−0.0029 (17)	−0.0059 (17)	−0.0002 (15)
C14	0.050 (2)	0.0410 (19)	0.0329 (18)	0.0089 (18)	0.0001 (16)	0.0054 (15)
C15	0.085 (4)	0.058 (3)	0.077 (3)	−0.005 (2)	−0.004 (2)	−0.007 (2)

Geometric parameters (Å, º) top

N1—C1	1.346 (3)	C5—C6	1.376 (4)
N1—N2	1.372 (3)	C5—H5	0.9300
N1—H1	0.8600	C6—H6	0.9300
N2—C7	1.264 (3)	C7—C8	1.469 (4)
N3—C2	1.322 (4)	C7—H7	0.9300
N3—C6	1.325 (4)	C8—C13	1.380 (4)
O1—C1	1.219 (3)	C8—C9	1.409 (4)
O2—C14	1.309 (4)	C9—C10	1.388 (4)
O2—H2	0.8200	C9—C14	1.495 (4)
O3—C14	1.205 (3)	C10—C11	1.374 (4)
O4—C15	1.371 (4)	C10—H10	0.9300
O4—H4	0.8200	C11—C12	1.369 (4)
C1—O1	1.219 (3)	C11—H11	0.9300
C1—C4	1.496 (4)	C12—C13	1.378 (4)
C2—C3	1.377 (4)	C12—H12	0.9300
C2—H2A	0.9300	C13—H13	0.9300
C3—C4	1.377 (4)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C5	1.376 (4)	C15—H15C	0.9600

C1—N1—N2	118.6 (2)	C8—C7—H7	120.3
C1—N1—H1	120.7	C13—C8—C9	118.3 (3)
N2—N1—H1	120.7	C13—C8—C7	118.9 (3)
C7—N2—N1	116.6 (2)	C9—C8—C7	122.8 (3)
C2—N3—C6	118.1 (3)	C10—C9—C8	119.3 (3)
C14—O2—H2	109.5	C10—C9—C14	115.7 (3)
C15—O4—H4	109.5	C8—C9—C14	124.9 (3)
O1—C1—N1	123.4 (3)	C11—C10—C9	120.9 (3)
O1—C1—N1	123.4 (3)	C11—C10—H10	119.6
O1—C1—C4	120.6 (3)	C9—C10—H10	119.6
O1—C1—C4	120.6 (3)	C12—C11—C10	120.0 (3)
N1—C1—C4	116.0 (3)	C12—C11—H11	120.0
N3—C2—C3	123.3 (3)	C10—C11—H11	120.0
N3—C2—H2A	118.4	C11—C12—C13	119.9 (3)
C3—C2—H2A	118.4	C11—C12—H12	120.0
C2—C3—C4	118.5 (3)	C13—C12—H12	120.0
C2—C3—H3	120.7	C12—C13—C8	121.6 (3)
C4—C3—H3	120.7	C12—C13—H13	119.2
C5—C4—C3	118.3 (3)	C8—C13—H13	119.2
C5—C4—C1	117.5 (2)	O3—C14—O2	124.1 (3)
C3—C4—C1	124.2 (2)	O3—C14—C9	122.2 (3)
C6—C5—C4	119.2 (3)	O2—C14—C9	113.7 (3)
C6—C5—H5	120.4	O4—C15—H15A	109.5
C4—C5—H5	120.4	O4—C15—H15B	109.5
N3—C6—C5	122.5 (3)	H15A—C15—H15B	109.5
N3—C6—H6	118.7	O4—C15—H15C	109.5
C5—C6—H6	118.7	H15A—C15—H15C	109.5
N2—C7—C8	119.4 (3)	H15B—C15—H15C	109.5
N2—C7—H7	120.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.86	2.13	2.891 (3)	148
O4—H4···O1	0.82	2.14	2.864 (4)	148
O2—H2···N3ⁱⁱ	0.82	1.76	2.565 (3)	165

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁N₃O₃·CH₄O
M_r	301.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	6.9768 (11), 12.2103 (13), 17.2650 (19)
β (°)	95.497 (1)
V (Å³)	1464.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.43 × 0.19 × 0.15

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.958, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	7290, 2508, 1233
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.141, 0.99
No. of reflections	2508
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.19

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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	0.86	2.13	2.891 (3)	148.1
O4—H4···O1	0.82	2.14	2.864 (4)	147.6
O2—H2···N3ⁱⁱ	0.82	1.76	2.565 (3)	165.2

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

Acknowledgements

We acknowledge the financial support of the Natural Science Foundation of China (No. 20771053) and the Natural Science Foundation of Shandong Province (Y2008B48). This work was also supported by the `Shangdong Tai-Shan Scholar Research Fund'.

References

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