organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

N′-(Di-2-pyridylmethyl­ene)benzo­hydrazide

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[Raparti, V., Chitre, T., Bothara, K., Kumar, V., Dangre, S., Khachane, C., Gore, S. & Deshmane, B. (2009). Eur. J. Med. Chem. In the press.]); Zhong et al. (2007[Zhong, X., Wei, H.-L., Liu, W.-S., Wang, D. K. & Wang, X. (2007). Bioorg. Med. Chem. Lett. 17, 3774-3777.]). For a previous study on the synthesis of benzohyrazide derivatives, see: Abu-El-Halawa et al. (2007[Abu-El-Halawa, R., Al-Nuri, M. & Mahmoud, F. (2007). Asian J. Chem. 19, 1658-1666.]). For ring-motif analysis; see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]); Grell et al. (1999[Grell, J., Bernstein, J. & Tinhofer, G. (1999). Acta Cryst. B55, 1030-1043.]).

[Scheme 1]

Experimental

Crystal data
  • C18H14N4O

  • Mr = 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[Rigaku/MSC (2007). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA.]) Tmin = 0.968, Tmax = 0.989

  • 33115 measured reflections

  • 3491 independent reflections

  • 2329 reflections with I > 2δ(I)

  • Rint = 0.050

Refinement
  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 0.169

  • S = 0.99

  • 3491 reflections

  • 208 parameters

  • H-atom parameters constrained

  • Δρmax = 0.15 e Å−3

  • Δρmin = −0.24 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku/MSC (2007). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2006[K. Brandenburg (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and PLUTO (Motherwell et al., 1999[Motherwell, W. D. S., Shields, G. P. & Allen, F. H. (1999). Acta Cryst. B55, 1044-1056.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


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.

Refinement top

Hydrogen atoms were refined isotropically and were constrained to the ideal geometry using an appropriate riding model with Uiso(H) fixed at 1.2 times Ueq of the pivot atom.

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
[Figure 1] 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.
[Figure 2] 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
C18H14N4OF(000) = 632
Mr = 302.33Dx = 1.317 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybcCell parameters from 880 reflections
a = 8.2741 (5) Åθ = 3.0–27.4°
b = 22.1436 (14) ŵ = 0.09 mm1
c = 8.8006 (5) ÅT = 295 K
β = 108.974 (2)°Block, colourless
V = 1524.82 (15) Å30.50 × 0.30 × 0.10 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
3491 independent reflections
Radiation source: fine-focus sealed tube2329 reflections with I > 2δ(I)
Graphite monochromatorRint = 0.050
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2007)
h = 1010
Tmin = 0.968, Tmax = 0.989k = 2828
33115 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.1092P)2 + 0.076P]
where P = (Fo2 + 2Fc2)/3
3491 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C18H14N4OV = 1524.82 (15) Å3
Mr = 302.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.2741 (5) ŵ = 0.09 mm1
b = 22.1436 (14) ÅT = 295 K
c = 8.8006 (5) Å0.50 × 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)
Tmin = 0.968, Tmax = 0.989Rint = 0.050
33115 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.169H-atom parameters constrained
S = 0.99Δρmax = 0.15 e Å3
3491 reflectionsΔρmin = 0.24 e Å3
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
xyzUiso*/Ueq
O10.17708 (18)0.55123 (6)0.48480 (14)0.0649 (4)
N10.21198 (18)0.51374 (6)0.73562 (16)0.0485 (4)
H70.19020.51860.82400.058*
C10.1073 (2)0.62760 (7)0.8228 (2)0.0513 (4)
H10.17870.60450.90580.062*
N20.29967 (18)0.46379 (6)0.71474 (16)0.0472 (3)
C20.0312 (2)0.67909 (8)0.8581 (2)0.0598 (5)
H20.05260.69070.96440.072*
N30.22378 (18)0.47159 (6)1.01763 (16)0.0509 (4)
C30.0768 (2)0.71315 (8)0.7347 (2)0.0604 (5)
H30.12800.74770.75830.072*
N40.4144 (2)0.31839 (6)0.84066 (19)0.0550 (4)
C40.1087 (2)0.69618 (8)0.5779 (2)0.0590 (5)
H40.18290.71890.49560.071*
C50.0308 (2)0.64538 (8)0.5414 (2)0.0524 (4)
H50.05090.63460.43460.063*
C60.0777 (2)0.61027 (7)0.66396 (19)0.0455 (4)
C70.1590 (2)0.55591 (7)0.61664 (19)0.0485 (4)
C80.3333 (2)0.42967 (7)0.99547 (18)0.0432 (4)
C90.4310 (2)0.39466 (8)1.1233 (2)0.0527 (4)
H90.50480.36551.10720.063*
C100.4182 (3)0.40325 (8)1.2745 (2)0.0572 (5)
H100.48450.38041.36090.069*
C110.3068 (2)0.44583 (8)1.2965 (2)0.0533 (4)
H110.29580.45231.39710.064*
C120.2125 (2)0.47854 (8)1.1649 (2)0.0551 (4)
H120.13630.50721.17890.066*
C130.3515 (2)0.42534 (7)0.83260 (18)0.0433 (4)
C140.4492 (2)0.37362 (7)0.79543 (18)0.0444 (4)
C150.5690 (2)0.38299 (8)0.71803 (19)0.0514 (4)
H150.58800.42160.68560.062*
C160.6594 (2)0.33445 (9)0.6899 (2)0.0611 (5)
H160.74150.33990.63990.073*
C170.6260 (3)0.27757 (9)0.7371 (2)0.0645 (5)
H170.68530.24400.71990.077*
C180.5033 (3)0.27192 (8)0.8099 (2)0.0617 (5)
H180.48020.23340.83990.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0939 (10)0.0613 (8)0.0480 (7)0.0160 (7)0.0345 (7)0.0053 (6)
N10.0645 (9)0.0402 (7)0.0455 (8)0.0074 (6)0.0244 (7)0.0017 (5)
C10.0561 (10)0.0503 (9)0.0458 (9)0.0045 (7)0.0141 (8)0.0005 (7)
N20.0561 (8)0.0404 (7)0.0474 (8)0.0030 (6)0.0197 (6)0.0015 (6)
C20.0679 (12)0.0604 (11)0.0519 (10)0.0054 (9)0.0209 (9)0.0086 (8)
N30.0565 (9)0.0531 (8)0.0476 (8)0.0065 (6)0.0230 (6)0.0016 (6)
C30.0657 (12)0.0517 (10)0.0663 (12)0.0110 (8)0.0251 (10)0.0015 (8)
N40.0674 (10)0.0388 (7)0.0649 (9)0.0004 (6)0.0300 (8)0.0024 (6)
C40.0631 (11)0.0563 (10)0.0579 (11)0.0115 (8)0.0204 (9)0.0128 (8)
C50.0606 (10)0.0517 (9)0.0463 (9)0.0027 (8)0.0192 (8)0.0053 (7)
C60.0506 (9)0.0430 (8)0.0454 (9)0.0013 (7)0.0192 (7)0.0018 (6)
C70.0570 (10)0.0464 (9)0.0444 (9)0.0018 (7)0.0197 (7)0.0023 (7)
C80.0476 (9)0.0383 (8)0.0456 (9)0.0028 (6)0.0176 (7)0.0025 (6)
C90.0607 (10)0.0493 (9)0.0488 (9)0.0084 (8)0.0188 (8)0.0000 (7)
C100.0720 (12)0.0539 (10)0.0439 (9)0.0034 (8)0.0165 (8)0.0025 (7)
C110.0668 (11)0.0527 (10)0.0452 (9)0.0066 (8)0.0249 (8)0.0041 (7)
C120.0623 (11)0.0565 (10)0.0538 (10)0.0040 (8)0.0289 (9)0.0021 (8)
C130.0477 (9)0.0407 (8)0.0427 (8)0.0021 (6)0.0165 (7)0.0027 (6)
C140.0495 (9)0.0417 (8)0.0409 (8)0.0002 (6)0.0132 (7)0.0025 (6)
C150.0564 (10)0.0511 (9)0.0487 (9)0.0005 (7)0.0197 (8)0.0007 (7)
C160.0597 (11)0.0703 (12)0.0584 (11)0.0085 (9)0.0264 (9)0.0030 (9)
C170.0699 (12)0.0594 (11)0.0622 (12)0.0174 (9)0.0189 (10)0.0082 (9)
C180.0770 (13)0.0423 (9)0.0672 (12)0.0041 (8)0.0255 (10)0.0031 (8)
Geometric parameters (Å, º) top
O1—C71.2217 (18)C6—C71.502 (2)
N1—C71.365 (2)C8—C91.389 (2)
N1—N21.3677 (17)C8—C131.492 (2)
N1—H70.8600C9—C101.382 (2)
C1—C21.386 (2)C9—H90.9300
C1—C61.392 (2)C10—C111.375 (2)
C1—H10.9300C10—H100.9300
N2—C131.302 (2)C11—C121.374 (2)
C2—C31.384 (3)C11—H110.9300
C2—H20.9300C12—H120.9300
N3—C121.338 (2)C13—C141.498 (2)
N3—C81.355 (2)C14—C151.389 (2)
C3—C41.371 (3)C15—C161.377 (2)
C3—H30.9300C15—H150.9300
N4—C181.343 (2)C16—C171.382 (3)
N4—C141.3458 (19)C16—H160.9300
C4—C51.385 (2)C17—C181.371 (3)
C4—H40.9300C17—H170.9300
C5—C61.394 (2)C18—H180.9300
C5—H50.9300
C7—N1—N2120.17 (13)C10—C9—C8119.78 (15)
C7—N1—H7119.9C10—C9—H9120.1
N2—N1—H7119.9C8—C9—H9120.1
C2—C1—C6120.52 (16)C11—C10—C9119.62 (16)
C2—C1—H1119.7C11—C10—H10120.2
C6—C1—H1119.7C9—C10—H10120.2
C13—N2—N1118.27 (12)C12—C11—C10117.75 (15)
C3—C2—C1119.78 (16)C12—C11—H11121.1
C3—C2—H2120.1C10—C11—H11121.1
C1—C2—H2120.1N3—C12—C11123.82 (16)
C12—N3—C8118.61 (14)N3—C12—H12118.1
C4—C3—C2120.29 (16)C11—C12—H12118.1
C4—C3—H3119.9N2—C13—C8127.81 (14)
C2—C3—H3119.9N2—C13—C14112.79 (13)
C18—N4—C14116.92 (15)C8—C13—C14119.29 (13)
C3—C4—C5120.30 (16)N4—C14—C15122.42 (15)
C3—C4—H4119.8N4—C14—C13116.60 (14)
C5—C4—H4119.8C15—C14—C13120.98 (14)
C4—C5—C6120.28 (16)C16—C15—C14119.18 (16)
C4—C5—H5119.9C16—C15—H15120.4
C6—C5—H5119.9C14—C15—H15120.4
C1—C6—C5118.80 (15)C15—C16—C17118.97 (17)
C1—C6—C7123.43 (14)C15—C16—H16120.5
C5—C6—C7117.76 (14)C17—C16—H16120.5
O1—C7—N1124.24 (15)C18—C17—C16118.30 (17)
O1—C7—C6122.38 (14)C18—C17—H17120.8
N1—C7—C6113.37 (13)C16—C17—H17120.9
N3—C8—C9120.41 (14)N4—C18—C17124.18 (17)
N3—C8—C13117.62 (13)N4—C18—H18117.9
C9—C8—C13121.88 (14)C17—C18—H18117.9
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H7···N30.861.942.624 (2)136
C9—H9···N40.932.452.973 (2)115

Experimental details

Crystal data
Chemical formulaC18H14N4O
Mr302.33
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)8.2741 (5), 22.1436 (14), 8.8006 (5)
β (°) 108.974 (2)
V3)1524.82 (15)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.50 × 0.30 × 0.10
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku/MSC, 2007)
Tmin, Tmax0.968, 0.989
No. of measured, independent and
observed [I > 2δ(I)] reflections
33115, 3491, 2329
Rint0.050
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.169, 0.99
No. of reflections3491
No. of parameters208
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H7···N30.861.942.624 (2)135.7
C9—H9···N40.932.452.973 (2)115
 

Acknowledgements

IW and SAR thank SABIC for financial support.

References

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First citationK. Brandenburg (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationGrell, J., Bernstein, J. & Tinhofer, G. (1999). Acta Cryst. B55, 1030–1043.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationMotherwell, W. D. S., Shields, G. P. & Allen, F. H. (1999). Acta Cryst. B55, 1044–1056.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationRaparti, V., Chitre, T., Bothara, K., Kumar, V., Dangre, S., Khachane, C., Gore, S. & Deshmane, B. (2009). Eur. J. Med. Chem. In the press.  Google Scholar
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First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar
First citationZhong, X., Wei, H.-L., Liu, W.-S., Wang, D. K. & Wang, X. (2007). Bioorg. Med. Chem. Lett. 17, 3774–3777.  Web of Science CSD CrossRef PubMed CAS Google Scholar

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