N′-(Di-2-pyridylmethyl­ene)benzo­hydrazide

Warad, I.; Al-Nuri, M.; Al-Resayes, S.; Al-Farhan, K.; Ghazzali, M.

doi:10.1107/S1600536809022090

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1597

doi:10.1107/S1600536809022090

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N′-(Di-2-pyridylmethylene)benzohydrazide

Ismail Warad,^a ^* Mohammed Al-Nuri,^b Saud Al-Resayes,^a Khalid Al-Farhan ^a and Mohamed Ghazzali ^a

^aDepartment of Chemistry, King Saud University, PO 2455, Riyadh 11451, Saudi Arabia, and ^bDepartment of Chemistry, An-Najah National University, PO 7, Nablus, West Bank, Palestinian Territories
^*Correspondence e-mail: warad@ksu.edu.sa

(Received 9 June 2009; accepted 10 June 2009; online 17 June 2009)

In the title Schiff base, C₁₈H₁₄N₄O, the amido –NH– unit is connected to one of the two pyridyl N atoms at an N(—H)⋯N distance of 2.624 (2) Å. The molecular packing features an intermolecular C—H⋯N R₂²(6) hydrogen-bonding ring motif.

Related literature

For medicinal applications of benzohydrazides, see: Raparti et al. (2009 ); Zhong et al. (2007 ). For a previous study on the synthesis of benzohyrazide derivatives, see: Abu-El-Halawa et al. (2007 ). For ring-motif analysis; see: Bernstein et al. (1995 ); Grell et al. (1999 ).

Experimental

Crystal data

C₁₈H₁₄N₄O
M_r = 302.33
Monoclinic, P 2₁ /c
a = 8.2741 (5) Å
b = 22.1436 (14) Å
c = 8.8006 (5) Å
β = 108.974 (2)°
V = 1524.82 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.50 × 0.30 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2007 ) T_min = 0.968, T_max = 0.989
33115 measured reflections
3491 independent reflections
2329 reflections with I > 2δ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.169
S = 0.99
3491 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H7⋯N3	0.86	1.94	2.624 (2)	136
C9—H9⋯N4	0.93	2.45	2.973 (2)	115

Data collection: CrystalClear (Rigaku/MSC, 2007); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ) and PLUTO (Motherwell et al., 1999 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022090/ng2595sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022090/ng2595Isup2.hkl

checkCIF report

Comment top

Benzohydrazide derivatives were known as good antitumor and antimycobacterial agent (Raparti et al. 2009; Zhong et al. 2007). The molecular packing of the title compound is supported by C— H···N intermolecular hydrogen bondings at D···A distance of 2.956 (1) and D— H···A angle of 128.92 (1)° that is recognized by R₂²(6) second order ring motif, as earlier defined (Bernstein et al. 1995; Grell et al. 1999) and calculated with Pluto (Motherwell et al., 1999), see Figure 2.

Related literature top

For medicinal applications of benzohydrazides, see: Raparti et al. (2009); Zhong et al. (2007). For a previous study, see: Abu-El-Halawa et al. (2007). For ring-motif analysis; see: Bernstein et al. (1995); Grell et al. (1999).

Experimental top

Equimolar amounts of di-2-pyridyl ketone and benzohydrazide were mixed in ethanol.(Abu-El-Halawa et al. 2007) Five drops of conc. HCl were added and the mixture was refluxed for 8–10 h. After cooling, distilled water was added up to 1:3 volume ratio followed by addition of several drops of sodium hydroxide solution. The product was re-crystallized twice by water. IR, cm^-1 (CHCl₃): 3280, 3210, 3100, 3020, 1660, 1620, 1600, 1580, 1480, 1450, 1350, 1160, 1040, 770, 660. ¹H NMR (p.p.m.): 10.70 (bs, 1H exchangeable with D₂O), 8.83 (cp, 2H of two pyridine rings), 8.02 (cp, 2H of two pyridine rings), 7.99 (cp, 2H of two pyridine rings), 7.95 (cp, 2H of benzene ring), 7.62 (cp, 2H of two pyridine rings), 7.44 (cp, 2H of benzene ring) p.p.m.; ¹³C NMR (p.p.m.): 163.0, 155.6, 152.6, 149.2, 136.1, 134.2, 132.2, 128.9, 127.5, 126.2, 123.9.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2007); cell refinement: CrystalClear (Rigaku/MSC, 2007); data reduction: CrystalClear (Rigaku/MSC, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006) and PLUTO (Motherwell et al., 1999); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. Perspective drawings of the title compound showing the atom-numbering scheme. The atomic displacement ellipsoids are shown at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. C— H···N intermolecular hydrogen bonding pattern of the title compound with hydrogen bonding shown as broken lines. For symmetry codes; i: 1 + x, y, z and ii: 1 - x, 1 - y, 2 - z.

N'-(Di-2-pyridylmethylene)benzohydrazide top

Crystal data top

C₁₈H₁₄N₄O	F(000) = 632
M_r = 302.33	D_x = 1.317 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 880 reflections
a = 8.2741 (5) Å	θ = 3.0–27.4°
b = 22.1436 (14) Å	µ = 0.09 mm⁻¹
c = 8.8006 (5) Å	T = 295 K
β = 108.974 (2)°	Block, colourless
V = 1524.82 (15) Å³	0.50 × 0.30 × 0.10 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3491 independent reflections
Radiation source: fine-focus sealed tube	2329 reflections with I > 2δ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2007)	h = −10→10
T_min = 0.968, T_max = 0.989	k = −28→28
33115 measured reflections	l = −11→11

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.1092P)² + 0.076P] where P = (F_o² + 2F_c²)/3
3491 reflections	(Δ/σ)_max < 0.001
208 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₈H₁₄N₄O	V = 1524.82 (15) Å³
M_r = 302.33	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2741 (5) Å	µ = 0.09 mm⁻¹
b = 22.1436 (14) Å	T = 295 K
c = 8.8006 (5) Å	0.50 × 0.30 × 0.10 mm
β = 108.974 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3491 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2007)	2329 reflections with I > 2δ(I)
T_min = 0.968, T_max = 0.989	R_int = 0.050
33115 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.169	H-atom parameters constrained
S = 0.99	Δρ_max = 0.15 e Å⁻³
3491 reflections	Δρ_min = −0.24 e Å⁻³
208 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
O1	0.17708 (18)	0.55123 (6)	0.48480 (14)	0.0649 (4)
N1	0.21198 (18)	0.51374 (6)	0.73562 (16)	0.0485 (4)
H7	0.1902	0.5186	0.8240	0.058*
C1	0.1073 (2)	0.62760 (7)	0.8228 (2)	0.0513 (4)
H1	0.1787	0.6045	0.9058	0.062*
N2	0.29967 (18)	0.46379 (6)	0.71474 (16)	0.0472 (3)
C2	0.0312 (2)	0.67909 (8)	0.8581 (2)	0.0598 (5)
H2	0.0526	0.6907	0.9644	0.072*
N3	0.22378 (18)	0.47159 (6)	1.01763 (16)	0.0509 (4)
C3	−0.0768 (2)	0.71315 (8)	0.7347 (2)	0.0604 (5)
H3	−0.1280	0.7477	0.7583	0.072*
N4	0.4144 (2)	0.31839 (6)	0.84066 (19)	0.0550 (4)
C4	−0.1087 (2)	0.69618 (8)	0.5779 (2)	0.0590 (5)
H4	−0.1829	0.7189	0.4956	0.071*
C5	−0.0308 (2)	0.64538 (8)	0.5414 (2)	0.0524 (4)
H5	−0.0509	0.6346	0.4346	0.063*
C6	0.0777 (2)	0.61027 (7)	0.66396 (19)	0.0455 (4)
C7	0.1590 (2)	0.55591 (7)	0.61664 (19)	0.0485 (4)
C8	0.3333 (2)	0.42967 (7)	0.99547 (18)	0.0432 (4)
C9	0.4310 (2)	0.39466 (8)	1.1233 (2)	0.0527 (4)
H9	0.5048	0.3655	1.1072	0.063*
C10	0.4182 (3)	0.40325 (8)	1.2745 (2)	0.0572 (5)
H10	0.4845	0.3804	1.3609	0.069*
C11	0.3068 (2)	0.44583 (8)	1.2965 (2)	0.0533 (4)
H11	0.2958	0.4523	1.3971	0.064*
C12	0.2125 (2)	0.47854 (8)	1.1649 (2)	0.0551 (4)
H12	0.1363	0.5072	1.1789	0.066*
C13	0.3515 (2)	0.42534 (7)	0.83260 (18)	0.0433 (4)
C14	0.4492 (2)	0.37362 (7)	0.79543 (18)	0.0444 (4)
C15	0.5690 (2)	0.38299 (8)	0.71803 (19)	0.0514 (4)
H15	0.5880	0.4216	0.6856	0.062*
C16	0.6594 (2)	0.33445 (9)	0.6899 (2)	0.0611 (5)
H16	0.7415	0.3399	0.6399	0.073*
C17	0.6260 (3)	0.27757 (9)	0.7371 (2)	0.0645 (5)
H17	0.6853	0.2440	0.7199	0.077*
C18	0.5033 (3)	0.27192 (8)	0.8099 (2)	0.0617 (5)
H18	0.4802	0.2334	0.8399	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0939 (10)	0.0613 (8)	0.0480 (7)	0.0160 (7)	0.0345 (7)	0.0053 (6)
N1	0.0645 (9)	0.0402 (7)	0.0455 (8)	0.0074 (6)	0.0244 (7)	0.0017 (5)
C1	0.0561 (10)	0.0503 (9)	0.0458 (9)	0.0045 (7)	0.0141 (8)	0.0005 (7)
N2	0.0561 (8)	0.0404 (7)	0.0474 (8)	0.0030 (6)	0.0197 (6)	−0.0015 (6)
C2	0.0679 (12)	0.0604 (11)	0.0519 (10)	0.0054 (9)	0.0209 (9)	−0.0086 (8)
N3	0.0565 (9)	0.0531 (8)	0.0476 (8)	0.0065 (6)	0.0230 (6)	0.0016 (6)
C3	0.0657 (12)	0.0517 (10)	0.0663 (12)	0.0110 (8)	0.0251 (10)	−0.0015 (8)
N4	0.0674 (10)	0.0388 (7)	0.0649 (9)	−0.0004 (6)	0.0300 (8)	−0.0024 (6)
C4	0.0631 (11)	0.0563 (10)	0.0579 (11)	0.0115 (8)	0.0204 (9)	0.0128 (8)
C5	0.0606 (10)	0.0517 (9)	0.0463 (9)	0.0027 (8)	0.0192 (8)	0.0053 (7)
C6	0.0506 (9)	0.0430 (8)	0.0454 (9)	−0.0013 (7)	0.0192 (7)	0.0018 (6)
C7	0.0570 (10)	0.0464 (9)	0.0444 (9)	0.0018 (7)	0.0197 (7)	0.0023 (7)
C8	0.0476 (9)	0.0383 (8)	0.0456 (9)	−0.0028 (6)	0.0176 (7)	−0.0025 (6)
C9	0.0607 (10)	0.0493 (9)	0.0488 (9)	0.0084 (8)	0.0188 (8)	0.0000 (7)
C10	0.0720 (12)	0.0539 (10)	0.0439 (9)	0.0034 (8)	0.0165 (8)	0.0025 (7)
C11	0.0668 (11)	0.0527 (10)	0.0452 (9)	−0.0066 (8)	0.0249 (8)	−0.0041 (7)
C12	0.0623 (11)	0.0565 (10)	0.0538 (10)	0.0040 (8)	0.0289 (9)	−0.0021 (8)
C13	0.0477 (9)	0.0407 (8)	0.0427 (8)	−0.0021 (6)	0.0165 (7)	−0.0027 (6)
C14	0.0495 (9)	0.0417 (8)	0.0409 (8)	−0.0002 (6)	0.0132 (7)	−0.0025 (6)
C15	0.0564 (10)	0.0511 (9)	0.0487 (9)	−0.0005 (7)	0.0197 (8)	0.0007 (7)
C16	0.0597 (11)	0.0703 (12)	0.0584 (11)	0.0085 (9)	0.0264 (9)	−0.0030 (9)
C17	0.0699 (12)	0.0594 (11)	0.0622 (12)	0.0174 (9)	0.0189 (10)	−0.0082 (9)
C18	0.0770 (13)	0.0423 (9)	0.0672 (12)	0.0041 (8)	0.0255 (10)	−0.0031 (8)

Geometric parameters (Å, º) top

O1—C7	1.2217 (18)	C6—C7	1.502 (2)
N1—C7	1.365 (2)	C8—C9	1.389 (2)
N1—N2	1.3677 (17)	C8—C13	1.492 (2)
N1—H7	0.8600	C9—C10	1.382 (2)
C1—C2	1.386 (2)	C9—H9	0.9300
C1—C6	1.392 (2)	C10—C11	1.375 (2)
C1—H1	0.9300	C10—H10	0.9300
N2—C13	1.302 (2)	C11—C12	1.374 (2)
C2—C3	1.384 (3)	C11—H11	0.9300
C2—H2	0.9300	C12—H12	0.9300
N3—C12	1.338 (2)	C13—C14	1.498 (2)
N3—C8	1.355 (2)	C14—C15	1.389 (2)
C3—C4	1.371 (3)	C15—C16	1.377 (2)
C3—H3	0.9300	C15—H15	0.9300
N4—C18	1.343 (2)	C16—C17	1.382 (3)
N4—C14	1.3458 (19)	C16—H16	0.9300
C4—C5	1.385 (2)	C17—C18	1.371 (3)
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.394 (2)	C18—H18	0.9300
C5—H5	0.9300

C7—N1—N2	120.17 (13)	C10—C9—C8	119.78 (15)
C7—N1—H7	119.9	C10—C9—H9	120.1
N2—N1—H7	119.9	C8—C9—H9	120.1
C2—C1—C6	120.52 (16)	C11—C10—C9	119.62 (16)
C2—C1—H1	119.7	C11—C10—H10	120.2
C6—C1—H1	119.7	C9—C10—H10	120.2
C13—N2—N1	118.27 (12)	C12—C11—C10	117.75 (15)
C3—C2—C1	119.78 (16)	C12—C11—H11	121.1
C3—C2—H2	120.1	C10—C11—H11	121.1
C1—C2—H2	120.1	N3—C12—C11	123.82 (16)
C12—N3—C8	118.61 (14)	N3—C12—H12	118.1
C4—C3—C2	120.29 (16)	C11—C12—H12	118.1
C4—C3—H3	119.9	N2—C13—C8	127.81 (14)
C2—C3—H3	119.9	N2—C13—C14	112.79 (13)
C18—N4—C14	116.92 (15)	C8—C13—C14	119.29 (13)
C3—C4—C5	120.30 (16)	N4—C14—C15	122.42 (15)
C3—C4—H4	119.8	N4—C14—C13	116.60 (14)
C5—C4—H4	119.8	C15—C14—C13	120.98 (14)
C4—C5—C6	120.28 (16)	C16—C15—C14	119.18 (16)
C4—C5—H5	119.9	C16—C15—H15	120.4
C6—C5—H5	119.9	C14—C15—H15	120.4
C1—C6—C5	118.80 (15)	C15—C16—C17	118.97 (17)
C1—C6—C7	123.43 (14)	C15—C16—H16	120.5
C5—C6—C7	117.76 (14)	C17—C16—H16	120.5
O1—C7—N1	124.24 (15)	C18—C17—C16	118.30 (17)
O1—C7—C6	122.38 (14)	C18—C17—H17	120.8
N1—C7—C6	113.37 (13)	C16—C17—H17	120.9
N3—C8—C9	120.41 (14)	N4—C18—C17	124.18 (17)
N3—C8—C13	117.62 (13)	N4—C18—H18	117.9
C9—C8—C13	121.88 (14)	C17—C18—H18	117.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H7···N3	0.86	1.94	2.624 (2)	136
C9—H9···N4	0.93	2.45	2.973 (2)	115

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄N₄O
M_r	302.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	8.2741 (5), 22.1436 (14), 8.8006 (5)
β (°)	108.974 (2)
V (Å³)	1524.82 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.30 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2007)
T_min, T_max	0.968, 0.989
No. of measured, independent and observed [I > 2δ(I)] reflections	33115, 3491, 2329
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.169, 0.99
No. of reflections	3491
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.24

Computer programs: CrystalClear (Rigaku/MSC, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006) and PLUTO (Motherwell et al., 1999), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H7···N3	0.86	1.94	2.624 (2)	135.7
C9—H9···N4	0.93	2.45	2.973 (2)	115

Acknowledgements

IW and SAR thank SABIC for financial support.

References

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