N′-[(E)-3-Bromo­benzyl­idene]pyrazine-2-carbohydrazide

Ahmad, M.; Hameed, S.; Tahir, M.N.; Anwar, M.; Israr, M.

doi:10.1107/S1600536813027426

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1635

doi:10.1107/S1600536813027426

Open

access

N′-[(E)-3-Bromobenzylidene]pyrazine-2-carbohydrazide

Mushtaq Ahmad,^a,^b Shahid Hameed,^a M. Nawaz Tahir,^c ^* Muhammad Anwar ^d and Muhammad Israr ^d

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan, ^bMedicinal Botanic Centre, PCSIR Laboratories Complex, Peshawar, Pakistan, ^cUniversity of Sargodha, Department of Physics, Sargodha, Pakistan, and ^dDepartment of Chemistry, Kohat University of Science and Technology, Kohat, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 6 October 2013; accepted 6 October 2013; online 12 October 2013)

In the title compound, C₁₂H₉BrN₄O, the dihedral angle between the aromatic rings is 12.16 (12)°. An intramolecular N—H⋯N hydrogen bond closes an S(5) ring. In the crystal, C—H⋯O hydrogen bonds link the molecules into C(6) chains propagating in [010]. Very weak aromatic π–π stacking [centroid–centroid separations = 3.9189 (15) and 3.9357 (15) Å] is also observed.

CCDC reference: 965079

Related literature

For related structures, see: Hameed et al. (2013a ,b ).

Experimental

Crystal data

C₁₂H₉BrN₄O
M_r = 305.14
Monoclinic, C 2/c
a = 14.4115 (8) Å
b = 6.2128 (3) Å
c = 27.5992 (15) Å
β = 104.379 (2)°
V = 2393.7 (2) Å³
Z = 8
Mo Kα radiation
μ = 3.43 mm⁻¹
T = 296 K
0.34 × 0.25 × 0.23 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.389, T_max = 0.506
9373 measured reflections
2415 independent reflections
1670 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.075
S = 1.02
2415 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.30 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
N3—H3A⋯N2	0.86	2.24	2.646 (3)	109
C6—H6⋯O1ⁱ	0.93	2.26	3.150 (3)	160
Symmetry code: (i) x, y-1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON.

Supporting information

CCDC reference: 965079

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813027426/hb7147sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813027426/hb7147Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813027426/hb7147Isup3.cml

checkCIF report

Comment top

The title compound (I), (Fig. 1) has been prepared in continuation of synthesizing different compounds containing pyrazine-2-carbohydrazide moiety (Hameed et al., 2013a, 2013b).

In (I) the parts A (C1–C5/N1—N4/O1) and B (C6—C12/Br1) of pyrazine-2-carbohydrazide and 3-bromobenzaldehyde moieties are close to planar with r.m. s. deviations of 0.0259 Å and 0.0149 Å, respectively. The dihedral angle between A/B is 13.950 (54)°. There exist intramolecular H-bondings of N—H····N type (Table 1, Fig. 2) forming S(5) ring motif. Molecules are linked due to H-bonding of C—H····O type (Table 1, Fig. 2) forming C (6) chains. There exist π–π interactions at a distance of 3.9190 Å [Cg1—Cg2ⁱ & Cg2—Cg1ⁱ: i = 1/2 - x, 1/2 - y, -z] and 3.9356 Å [Cg1—Cg2ⁱⁱ & Cg2—Cg1ⁱⁱ: ii = 1 - x, 1 - y, -z], between the centroids of Cg1 (C1/C2/N1/C3/C4/N2) and Cg2 (C7—C12), respectively.

Related literature top

For related structures, see: Hameed et al. (2013a,b).

Experimental top

The title compound was synthesized by the condensation of equimolar ratio of pyrazine-2-carbohydrazide with 3-bromobenzaldehyde, both dissolved in methanol. The resulting reaction mixture was stirred well and then refluxed for 5 h and allowed to cool over night. The precipitated solid was filtered, washed with petroleum ether and recrystallized from chloroform in pet ether and dried under reduced pressure over CaCl₂ giving white crystalline compound. The crystals were re-grown in the same solvent system for crystallographic studies, yielding colourless prisms (m.p. 475–476 K).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title compound, showing that molecules form polymeric chains.

N'-[(E)-3-Bromobenzylidene]pyrazine-2-carbohydrazide top

Crystal data top

C₁₂H₉BrN₄O	F(000) = 1216
M_r = 305.14	D_x = 1.693 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.4115 (8) Å	Cell parameters from 1670 reflections
b = 6.2128 (3) Å	θ = 1.5–26.3°
c = 27.5992 (15) Å	µ = 3.43 mm⁻¹
β = 104.379 (2)°	T = 296 K
V = 2393.7 (2) Å³	Prism, colorless
Z = 8	0.34 × 0.25 × 0.23 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2415 independent reflections
Radiation source: fine-focus sealed tube	1670 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 8.00 pixels mm^-1	θ_max = 26.3°, θ_min = 1.5°
ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −5→7
T_min = 0.389, T_max = 0.506	l = −34→34
9373 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0348P)² + 1.0725P] where P = (F_o² + 2F_c²)/3
2415 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₂H₉BrN₄O	V = 2393.7 (2) Å³
M_r = 305.14	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.4115 (8) Å	µ = 3.43 mm⁻¹
b = 6.2128 (3) Å	T = 296 K
c = 27.5992 (15) Å	0.34 × 0.25 × 0.23 mm
β = 104.379 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2415 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1670 reflections with I > 2σ(I)
T_min = 0.389, T_max = 0.506	R_int = 0.029
9373 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.02	Δρ_max = 0.30 e Å⁻³
2415 reflections	Δρ_min = −0.34 e Å⁻³
163 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
Br1	0.62227 (2)	0.43755 (5)	0.23030 (2)	0.07124 (14)
O1	0.34544 (12)	0.8178 (3)	−0.01354 (6)	0.0572 (5)
N1	0.15137 (16)	0.8142 (4)	−0.15404 (8)	0.0650 (6)
N2	0.23320 (14)	0.4402 (3)	−0.10560 (7)	0.0489 (5)
N3	0.35102 (14)	0.4532 (3)	−0.01526 (7)	0.0501 (5)
H3A	0.3313	0.3401	−0.0328	0.060*
N4	0.41296 (14)	0.4300 (3)	0.03159 (7)	0.0470 (5)
C1	0.25220 (16)	0.6348 (4)	−0.08500 (8)	0.0421 (5)
C2	0.21160 (18)	0.8185 (5)	−0.10872 (9)	0.0565 (7)
H2	0.2266	0.9502	−0.0927	0.068*
C3	0.13278 (19)	0.6199 (5)	−0.17444 (10)	0.0620 (8)
H3	0.0911	0.6087	−0.2060	0.074*
C4	0.17254 (18)	0.4358 (5)	−0.15084 (9)	0.0567 (7)
H4	0.1568	0.3041	−0.1668	0.068*
C5	0.32089 (16)	0.6472 (4)	−0.03412 (8)	0.0432 (6)
C6	0.43789 (17)	0.2363 (4)	0.04277 (8)	0.0488 (6)
H6	0.4144	0.1287	0.0195	0.059*
C7	0.50180 (16)	0.1759 (4)	0.09064 (8)	0.0429 (5)
C8	0.52751 (15)	0.3190 (4)	0.13043 (8)	0.0441 (6)
H8	0.5043	0.4593	0.1274	0.053*
C9	0.58834 (16)	0.2486 (4)	0.17454 (8)	0.0457 (6)
C10	0.62372 (18)	0.0415 (4)	0.17990 (10)	0.0557 (7)
H10	0.6649	−0.0027	0.2098	0.067*
C11	0.59711 (19)	−0.0986 (4)	0.14028 (11)	0.0599 (7)
H11	0.6210	−0.2383	0.1434	0.072*
C12	0.53564 (19)	−0.0348 (4)	0.09608 (10)	0.0538 (6)
H12	0.5167	−0.1322	0.0699	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0841 (2)	0.0729 (2)	0.04238 (16)	−0.00330 (16)	−0.01146 (13)	−0.00346 (13)
O1	0.0665 (11)	0.0511 (11)	0.0501 (10)	−0.0134 (9)	0.0073 (8)	−0.0144 (8)
N1	0.0630 (15)	0.0746 (17)	0.0523 (13)	0.0077 (13)	0.0045 (11)	0.0107 (12)
N2	0.0511 (11)	0.0532 (13)	0.0392 (10)	−0.0028 (11)	0.0048 (9)	−0.0096 (10)
N3	0.0553 (12)	0.0501 (13)	0.0367 (10)	−0.0022 (11)	−0.0042 (9)	−0.0109 (9)
N4	0.0491 (11)	0.0522 (13)	0.0345 (9)	−0.0025 (10)	0.0004 (8)	−0.0063 (9)
C1	0.0402 (13)	0.0502 (15)	0.0365 (11)	−0.0016 (11)	0.0110 (10)	−0.0043 (10)
C2	0.0604 (16)	0.0557 (17)	0.0519 (14)	0.0006 (14)	0.0110 (12)	−0.0003 (13)
C3	0.0508 (16)	0.089 (2)	0.0411 (13)	−0.0007 (15)	0.0011 (12)	0.0039 (14)
C4	0.0538 (15)	0.0694 (19)	0.0416 (13)	−0.0048 (14)	0.0018 (11)	−0.0103 (13)
C5	0.0432 (13)	0.0496 (15)	0.0375 (12)	−0.0041 (12)	0.0113 (10)	−0.0053 (11)
C6	0.0544 (15)	0.0505 (16)	0.0385 (12)	−0.0080 (13)	0.0058 (10)	−0.0083 (11)
C7	0.0425 (13)	0.0453 (15)	0.0408 (12)	−0.0035 (11)	0.0102 (10)	−0.0001 (10)
C8	0.0458 (13)	0.0422 (14)	0.0412 (12)	−0.0002 (11)	0.0048 (10)	0.0016 (11)
C9	0.0432 (13)	0.0499 (15)	0.0418 (12)	−0.0046 (12)	0.0064 (10)	0.0019 (11)
C10	0.0482 (14)	0.0611 (18)	0.0537 (15)	0.0025 (13)	0.0049 (11)	0.0138 (13)
C11	0.0620 (17)	0.0510 (17)	0.0680 (17)	0.0106 (13)	0.0183 (14)	0.0095 (13)
C12	0.0620 (16)	0.0472 (15)	0.0547 (15)	0.0002 (13)	0.0195 (13)	−0.0038 (12)

Geometric parameters (Å, º) top

Br1—C9	1.901 (2)	C3—H3	0.9300
O1—C5	1.213 (3)	C4—H4	0.9300
N1—C3	1.331 (4)	C6—C7	1.459 (3)
N1—C2	1.334 (3)	C6—H6	0.9300
N2—C4	1.335 (3)	C7—C8	1.390 (3)
N2—C1	1.335 (3)	C7—C12	1.392 (4)
N3—C5	1.341 (3)	C8—C9	1.383 (3)
N3—N4	1.384 (2)	C8—H8	0.9300
N3—H3A	0.8600	C9—C10	1.378 (4)
N4—C6	1.272 (3)	C10—C11	1.376 (4)
C1—C2	1.372 (3)	C10—H10	0.9300
C1—C5	1.506 (3)	C11—C12	1.376 (4)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.369 (4)	C12—H12	0.9300

C3—N1—C2	115.5 (2)	N4—C6—C7	122.6 (2)
C4—N2—C1	115.7 (2)	N4—C6—H6	118.7
C5—N3—N4	121.85 (19)	C7—C6—H6	118.7
C5—N3—H3A	119.1	C8—C7—C12	119.9 (2)
N4—N3—H3A	119.1	C8—C7—C6	122.4 (2)
C6—N4—N3	113.77 (18)	C12—C7—C6	117.7 (2)
N2—C1—C2	122.1 (2)	C9—C8—C7	118.7 (2)
N2—C1—C5	117.5 (2)	C9—C8—H8	120.7
C2—C1—C5	120.4 (2)	C7—C8—H8	120.7
N1—C2—C1	122.1 (3)	C10—C9—C8	121.8 (2)
N1—C2—H2	118.9	C10—C9—Br1	118.40 (18)
C1—C2—H2	118.9	C8—C9—Br1	119.78 (19)
N1—C3—C4	122.7 (2)	C11—C10—C9	118.9 (2)
N1—C3—H3	118.7	C11—C10—H10	120.6
C4—C3—H3	118.7	C9—C10—H10	120.6
N2—C4—C3	121.8 (3)	C10—C11—C12	120.9 (2)
N2—C4—H4	119.1	C10—C11—H11	119.6
C3—C4—H4	119.1	C12—C11—H11	119.6
O1—C5—N3	125.1 (2)	C11—C12—C7	119.9 (2)
O1—C5—C1	121.9 (2)	C11—C12—H12	120.1
N3—C5—C1	113.0 (2)	C7—C12—H12	120.1

C5—N3—N4—C6	−176.9 (2)	C2—C1—C5—N3	177.4 (2)
C4—N2—C1—C2	0.3 (4)	N3—N4—C6—C7	−179.2 (2)
C4—N2—C1—C5	−179.6 (2)	N4—C6—C7—C8	10.8 (4)
C3—N1—C2—C1	0.5 (4)	N4—C6—C7—C12	−170.6 (2)
N2—C1—C2—N1	−0.7 (4)	C12—C7—C8—C9	1.3 (3)
C5—C1—C2—N1	179.2 (2)	C6—C7—C8—C9	179.9 (2)
C2—N1—C3—C4	−0.1 (4)	C7—C8—C9—C10	0.0 (4)
C1—N2—C4—C3	0.1 (4)	C7—C8—C9—Br1	−178.32 (17)
N1—C3—C4—N2	−0.3 (4)	C8—C9—C10—C11	−0.4 (4)
N4—N3—C5—O1	1.9 (4)	Br1—C9—C10—C11	177.9 (2)
N4—N3—C5—C1	−178.7 (2)	C9—C10—C11—C12	−0.5 (4)
N2—C1—C5—O1	176.8 (2)	C10—C11—C12—C7	1.8 (4)
C2—C1—C5—O1	−3.1 (4)	C8—C7—C12—C11	−2.3 (4)
N2—C1—C5—N3	−2.7 (3)	C6—C7—C12—C11	179.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2	0.86	2.24	2.646 (3)	109
C6—H6···O1ⁱ	0.93	2.26	3.150 (3)	160

Symmetry code: (i) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2	0.86	2.24	2.646 (3)	109
C6—H6···O1ⁱ	0.93	2.26	3.150 (3)	160

Symmetry code: (i) x, y−1, z.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors are also thankful to the Higher Education Commission (HEC) of Pakistan for financial support. M. Ahmad is thankful to the Pakistan Council of Scientific and Industrial Research (PCSIR) Laboratories of Pakistan for financial support throughout his study leave.

References

Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hameed, S., Ahmad, M., Tahir, M. N., Israr, M. & Anwar, M. (2013a). Acta Cryst. E69, o1419. CSD CrossRef IUCr Journals Google Scholar
Hameed, S., Ahmad, M., Tahir, M. N., Shah, M. A. & Shad, H. A. (2013b). Acta Cryst. E69, o1141. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar