Synthesis, X-ray crystal structure, Hirshfeld surface analysis and DFT studies of (E)-N′-(2-bromo­benzyl­idene)-4-methylbenzohydrazide

Anitha, A.G.; Arunagiri, C.; Subashini, A.

doi:10.1107/S2056989018017978

Synthesis, X-ray crystal structure, Hirshfeld surface analysis and DFT studies of (E)-N′-(2-bromobenzylidene)-4-methylbenzohydrazide

A. G. Anitha, C. Arunagiri and A. Subashini

The title molecule displays a trans configuration with respect to the C=N double bond. The dihedral angle between the bromo- and the methyl-substituted benzene rings is 16.1 (3)°. In the crystal, molecules are connected by N—H

O and weak C—H

O hydrogen bonds, forming $R_{2}^{1}$ (6) ring motifs and generating chains along the a–axis direction.

Keywords: crystal structure; hydrogen bonding; DFT; Hirshfeld surface analysis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989018017978/lh5887sup1.cif Contains datablocks global, I, 80R
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989018017978/lh5887Isup2.cml Supplementary material

CCDC reference: 1580647

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Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.008 Å
R factor = 0.037
wR factor = 0.097
Data-to-parameter ratio = 15.6

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No syntax errors found



Alert level C
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0082 Ang.

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          2 Note
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....         C7 Check
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2018 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(E)-4-Methyl-N'-(2-bromobenzylidene)benzohydrazide top

Crystal data top

C₁₅H₁₃BrN₂O	F(000) = 640
M_r = 317.18	D_x = 1.509 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 6594 reflections
a = 9.6002 (10) Å	θ = 2.4–26.0°
b = 11.5584 (13) Å	µ = 2.94 mm⁻¹
c = 12.5823 (12) Å	T = 296 K
V = 1396.2 (3) Å³	Block, brown
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2744 independent reflections
Radiation source: fine-focus sealed tube	1837 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω and φ scan	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→11
T_min = 0.473, T_max = 0.591	k = −14→14
17816 measured reflections	l = −15→15

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0208P)² + 2.2419P] where P = (F_o² + 2F_c²)/3
2744 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 0.42 e Å⁻³
2 restraints	Δρ_min = −0.47 e Å⁻³

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
Br1	0.27412 (5)	0.49846 (5)	0.50267 (12)	0.06555 (18)
O1	0.7807 (3)	0.1961 (4)	0.2048 (3)	0.0633 (11)
N1	0.5643 (4)	0.2641 (4)	0.2337 (3)	0.0430 (10)
N2	0.5965 (5)	0.2925 (4)	0.3373 (3)	0.0464 (11)
C1	0.6174 (5)	0.1750 (4)	0.0649 (3)	0.0390 (10)
C2	0.6886 (5)	0.0846 (4)	0.0191 (5)	0.0529 (14)
H2	0.7632	0.0514	0.0551	0.064*
C3	0.6512 (7)	0.0427 (5)	−0.0791 (5)	0.0632 (15)
H3	0.7000	−0.0193	−0.1080	0.076*
C4	0.5433 (6)	0.0907 (5)	−0.1352 (4)	0.0546 (14)
C5	0.4721 (6)	0.1827 (5)	−0.0902 (4)	0.0526 (13)
H5	0.3987	0.2165	−0.1271	0.063*
C6	0.5085 (4)	0.2251 (4)	0.0089 (5)	0.0446 (10)
H6	0.4599	0.2872	0.0378	0.054*
C7	0.4998 (11)	0.0447 (6)	−0.2424 (6)	0.0834 (19)
H7C	0.4230	0.0894	−0.2689	0.125*
H7A	0.4723	−0.0348	−0.2356	0.125*
H7B	0.5766	0.0503	−0.2910	0.125*
C8	0.6621 (5)	0.2130 (4)	0.1724 (4)	0.0429 (11)
C9	0.4964 (5)	0.3296 (4)	0.3937 (4)	0.0446 (12)
H9	0.4093	0.3413	0.3632	0.053*
C10	0.5182 (5)	0.3543 (3)	0.5071 (5)	0.0435 (10)
C11	0.4290 (6)	0.4236 (4)	0.5651 (4)	0.0530 (13)
C12	0.4514 (8)	0.4419 (5)	0.6726 (4)	0.0726 (19)
H12	0.3908	0.4882	0.7115	0.087*
C13	0.5642 (9)	0.3908 (6)	0.7213 (5)	0.082 (2)
H13	0.5807	0.4039	0.7931	0.098*
C14	0.6504 (9)	0.3224 (6)	0.6660 (5)	0.083 (2)
H14	0.7239	0.2857	0.7004	0.100*
C15	0.6313 (7)	0.3059 (5)	0.5591 (4)	0.0608 (15)
H15	0.6951	0.2617	0.5210	0.073*
H1	0.480 (3)	0.268 (5)	0.217 (4)	0.051 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0673 (3)	0.0624 (3)	0.0669 (3)	0.0056 (3)	0.0118 (6)	−0.0006 (3)
O1	0.0301 (18)	0.111 (3)	0.049 (2)	0.006 (2)	−0.0069 (16)	0.001 (2)
N1	0.033 (2)	0.061 (3)	0.035 (2)	−0.001 (2)	−0.0091 (19)	−0.003 (2)
N2	0.045 (3)	0.058 (3)	0.035 (2)	0.000 (2)	−0.009 (2)	−0.002 (2)
C1	0.035 (2)	0.049 (3)	0.033 (2)	−0.004 (2)	0.001 (2)	0.003 (2)
C2	0.046 (3)	0.058 (3)	0.055 (4)	0.011 (2)	0.003 (3)	0.006 (3)
C3	0.067 (4)	0.059 (3)	0.063 (4)	0.002 (3)	0.008 (3)	−0.008 (3)
C4	0.061 (3)	0.062 (3)	0.041 (3)	−0.013 (3)	0.005 (3)	−0.007 (3)
C5	0.052 (3)	0.066 (3)	0.040 (3)	−0.001 (3)	−0.013 (2)	−0.001 (3)
C6	0.038 (2)	0.055 (3)	0.041 (2)	0.0026 (19)	−0.005 (3)	−0.003 (3)
C7	0.097 (4)	0.095 (5)	0.058 (3)	−0.016 (6)	−0.009 (3)	−0.021 (5)
C8	0.029 (2)	0.059 (3)	0.040 (3)	−0.003 (2)	0.000 (2)	0.008 (2)
C9	0.049 (3)	0.046 (3)	0.039 (3)	−0.003 (2)	−0.013 (2)	−0.002 (2)
C10	0.057 (3)	0.041 (2)	0.033 (2)	−0.008 (2)	−0.006 (3)	−0.002 (3)
C11	0.070 (4)	0.045 (3)	0.043 (3)	−0.014 (3)	0.000 (3)	−0.002 (2)
C12	0.116 (6)	0.059 (4)	0.042 (4)	−0.021 (4)	0.016 (4)	−0.006 (3)
C13	0.152 (7)	0.059 (4)	0.034 (3)	−0.030 (4)	−0.021 (4)	−0.003 (3)
C14	0.117 (6)	0.082 (5)	0.050 (4)	−0.001 (5)	−0.043 (4)	0.002 (4)
C15	0.075 (4)	0.054 (3)	0.053 (3)	−0.002 (3)	−0.020 (3)	0.003 (3)

Geometric parameters (Å, º) top

Br1—C11	1.891 (6)	C6—H6	0.9300
O1—C8	1.225 (6)	C7—H7C	0.9600
N1—C8	1.351 (6)	C7—H7A	0.9600
N1—N2	1.379 (5)	C7—H7B	0.9600
N1—H1	0.837 (19)	C9—C10	1.470 (8)
N2—C9	1.270 (6)	C9—H9	0.9300
C1—C2	1.375 (7)	C10—C11	1.381 (7)
C1—C6	1.389 (6)	C10—C15	1.386 (7)
C1—C8	1.485 (6)	C11—C12	1.385 (7)
C2—C3	1.375 (8)	C12—C13	1.378 (10)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.371 (8)	C13—C14	1.340 (10)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.386 (7)	C14—C15	1.370 (8)
C4—C7	1.508 (9)	C14—H14	0.9300
C5—C6	1.384 (8)	C15—H15	0.9300
C5—H5	0.9300

C8—N1—N2	119.2 (4)	H7C—C7—H7B	109.5
C8—N1—H1	123 (4)	H7A—C7—H7B	109.5
N2—N1—H1	117 (4)	O1—C8—N1	121.7 (4)
C9—N2—N1	116.0 (4)	O1—C8—C1	121.6 (4)
C2—C1—C6	118.6 (5)	N1—C8—C1	116.6 (4)
C2—C1—C8	117.6 (4)	N2—C9—C10	120.1 (4)
C6—C1—C8	123.8 (5)	N2—C9—H9	120.0
C1—C2—C3	121.0 (5)	C10—C9—H9	120.0
C1—C2—H2	119.5	C11—C10—C15	118.1 (5)
C3—C2—H2	119.5	C11—C10—C9	122.5 (5)
C4—C3—C2	121.2 (5)	C15—C10—C9	119.4 (5)
C4—C3—H3	119.4	C10—C11—C12	120.5 (6)
C2—C3—H3	119.4	C10—C11—Br1	122.2 (4)
C3—C4—C5	118.2 (5)	C12—C11—Br1	117.2 (5)
C3—C4—C7	121.8 (6)	C13—C12—C11	119.4 (6)
C5—C4—C7	120.0 (6)	C13—C12—H12	120.3
C6—C5—C4	121.1 (5)	C11—C12—H12	120.3
C6—C5—H5	119.5	C14—C13—C12	120.5 (6)
C4—C5—H5	119.5	C14—C13—H13	119.8
C5—C6—C1	120.0 (5)	C12—C13—H13	119.8
C5—C6—H6	120.0	C13—C14—C15	120.6 (7)
C1—C6—H6	120.0	C13—C14—H14	119.7
C4—C7—H7C	109.5	C15—C14—H14	119.7
C4—C7—H7A	109.5	C14—C15—C10	120.8 (6)
H7C—C7—H7A	109.5	C14—C15—H15	119.6
C4—C7—H7B	109.5	C10—C15—H15	119.6

C8—N1—N2—C9	−173.3 (5)	C6—C1—C8—N1	26.3 (7)
C6—C1—C2—C3	−1.5 (7)	N1—N2—C9—C10	175.7 (4)
C8—C1—C2—C3	178.4 (5)	N2—C9—C10—C11	161.4 (5)
C1—C2—C3—C4	1.0 (8)	N2—C9—C10—C15	−19.2 (7)
C2—C3—C4—C5	−0.2 (8)	C15—C10—C11—C12	−1.2 (7)
C2—C3—C4—C7	−179.2 (6)	C9—C10—C11—C12	178.2 (5)
C3—C4—C5—C6	−0.1 (8)	C15—C10—C11—Br1	178.1 (4)
C7—C4—C5—C6	178.9 (6)	C9—C10—C11—Br1	−2.5 (6)
C4—C5—C6—C1	−0.3 (8)	C10—C11—C12—C13	0.4 (8)
C2—C1—C6—C5	1.1 (7)	Br1—C11—C12—C13	−178.9 (5)
C8—C1—C6—C5	−178.8 (5)	C11—C12—C13—C14	−1.1 (10)
N2—N1—C8—O1	−3.5 (7)	C12—C13—C14—C15	2.8 (11)
N2—N1—C8—C1	174.6 (4)	C13—C14—C15—C10	−3.6 (10)
C2—C1—C8—O1	24.6 (7)	C11—C10—C15—C14	2.8 (8)
C6—C1—C8—O1	−155.5 (5)	C9—C10—C15—C14	−176.6 (6)
C2—C1—C8—N1	−153.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.84 (3)	1.96 (3)	2.785 (5)	167 (5)
C9—H9···O1ⁱ	0.93	2.38	3.166 (6)	142

Symmetry code: (i) x−1/2, −y+1/2, z.

Selected geometric parameters of XRD and DFT (Å,°) top

	XRD	DFT
Br1—C11	1.891 (6)	1.925
O1—C8	1.225 (6)	1.219
N1—N2	1.379 (5)	1.364
N1—C8	1.351 (6)	1.383
N2—C9	1.270 (6)	1.285
N1—H1	0.837 (19)	1.006
C1—C8	1.485 (6)	1.501
C9—C10	1.470 (8)	1.470
C9—H9	0.930	1.082

N2—N1—C8	119.2 (4)	120.00
C8—N1—H1	123 (4)	117.84
N2—N1—H1	117 (4)	111.31
N1—C8—C1	116.6 (4)	114.46
O1—C8—C1	121.6 (4)	122.20
O1—C8—N1	121.7 (4)	123.33
N2—C9—C10	120.1 (4)	118.62
N2—C9—H9	120.00	122.79

C8—N1—N2—C9	-173.3 (5)	-179.68
N2—N1—C8—O1	-3.5 (7)	2.54
N2—N1—C8—C1	174.64)	-178.45
C2—C1—C8—O1	24.6 (7)	22.94
C2—C1—C8—N1	-153.6 (5)	-156.06
N2—C9—C10—C11	161.4 (5)	-179.93
N2—C9—C10—C15	-19.2 (7)	-0.14
C6—C1—C8—N1	26.3 (7)	25.79

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Synthesis, X-ray crystal structure, Hirshfeld surface analysis and DFT studies of (E)-N′-(2-bromo­benzyl­idene)-4-methylbenzohydrazide

Supporting information

Key indicators

checkCIF/PLATON results

Synthesis, X-ray crystal structure, Hirshfeld surface analysis and DFT studies of (E)-N′-(2-bromobenzylidene)-4-methylbenzohydrazide