2-Bromo-N'-[(2Z)-butan-2-yl-idene]-5-methoxy-benzohydrazide.

In the title compound, C(12)H(15)BrN(2)O(2), the dihedral angle between the benzene ring and the mean plane of the amide grouping is 77.7 (8)°. In the crystal, inversion dimers linked by pairs of N-H⋯O hydrogen bonds occur, and the packing is further supported by C-H⋯O and C-H⋯Br inter-actions and weak π-π ring stacking inter-actions.

Related literature

Hydrazides and their corresponding Schiff bases are useful precursors in the synthesis of several heterocyclic systems, see: Narayana et al. (2005 ▶; 2005a ▶). For the biological activity of substituted hydrazides, see: Cajocorius et al. (1977 ▶). Hydrazides are inter­mediates in the production of many pharmaceutically important compounds, see: Liu et al. (2006 ▶). For related structures, see: Butcher et al. (2007 ▶); Hou (2009 ▶); Li & Ban (2009 ▶); Sarojini et al. (2007a ▶,b ▶,c ▶,d ▶). For the MOPAC AM1 calculations, see: Schmidt & Polik (2007 ▶).

Experimental

Crystal data

C12H15BrN2O2

M = 299.17

Monoclinic,

a = 8.0942 (1) Å

b = 14.2475 (2) Å

c = 11.2974 (2) Å

β = 91.1519 (13)°

V = 1302.58 (3) Å3

Z = 4

Cu Kα radiation

μ = 4.25 mm−1

T = 200 K

0.56 × 0.47 × 0.35 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.452, T max = 1.000

7962 measured reflections

2577 independent reflections

2484 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.122

S = 1.07

2577 reflections

157 parameters

H-atom parameters constrained

Δρmax = 0.73 e Å−3

Δρmin = −1.07 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044869/ds2010sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044869/ds2010Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H15BrN2O2	F(000) = 608
Mr = 299.17	Dx = 1.526 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 8517 reflections
a = 8.0942 (1) Å	θ = 5.0–73.4°
b = 14.2475 (2) Å	µ = 4.25 mm−1
c = 11.2974 (2) Å	T = 200 K
β = 91.1519 (13)°	Chunk, colorless
V = 1302.58 (3) Å3	0.56 × 0.47 × 0.35 mm
Z = 4

Oxford Diffraction Gemini R CCD diffractometer	2577 independent reflections
Radiation source: fine-focus sealed tube	2484 reflections with I > 2σ(I)
graphite	Rint = 0.023
Detector resolution: 10.5081 pixels mm-1	θmax = 73.6°, θmin = 5.0°
φ and ω scans	h = −10→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −16→17
Tmin = 0.452, Tmax = 1.000	l = −9→13
7962 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0673P)2 + 1.7115P] where P = (Fo2 + 2Fc2)/3
2577 reflections	(Δ/σ)max < 0.001
157 parameters	Δρmax = 0.73 e Å−3
0 restraints	Δρmin = −1.07 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br	−0.00062 (5)	0.75926 (3)	0.23886 (3)	0.05362 (18)
O1	0.3113 (3)	1.07458 (17)	−0.03054 (18)	0.0478 (6)
O2	−0.0433 (2)	1.01275 (15)	0.35066 (16)	0.0358 (5)
N1	0.1775 (3)	0.93324 (16)	0.42004 (18)	0.0306 (5)
H1A	0.1550	0.9465	0.4941	0.037*
N2	0.3148 (3)	0.87860 (17)	0.39363 (19)	0.0318 (5)
C1	0.0954 (3)	0.85866 (18)	0.1528 (2)	0.0305 (5)
C2	0.1316 (4)	0.8445 (2)	0.0351 (2)	0.0361 (6)
H2A	0.1073	0.7858	−0.0012	0.043*
C3	0.2033 (3)	0.9154 (2)	−0.0303 (2)	0.0316 (6)
H3A	0.2285	0.9056	−0.1111	0.038*
C4	0.2379 (3)	1.00067 (19)	0.0234 (2)	0.0294 (5)
C5	0.1981 (3)	1.01479 (18)	0.1415 (2)	0.0285 (5)
H5A	0.2195	1.0739	0.1775	0.034*
C6	0.1282 (3)	0.94403 (17)	0.2066 (2)	0.0244 (5)
C7	0.3619 (4)	1.0618 (3)	−0.1501 (3)	0.0525 (9)
H7A	0.4202	1.1181	−0.1766	0.079*
H7B	0.2644	1.0512	−0.2012	0.079*
H7C	0.4357	1.0075	−0.1544	0.079*
C8	0.0802 (3)	0.96538 (18)	0.3318 (2)	0.0258 (5)
C9	0.4048 (3)	0.8504 (2)	0.4794 (2)	0.0357 (6)
C10	0.3829 (5)	0.8738 (3)	0.6083 (3)	0.0624 (12)
H10A	0.2676	0.8632	0.6295	0.094*
H10B	0.4118	0.9397	0.6221	0.094*
H10C	0.4551	0.8336	0.6570	0.094*
C11	0.5478 (4)	0.7880 (3)	0.4479 (3)	0.0485 (8)
H11A	0.5308	0.7253	0.4835	0.058*
H11B	0.5486	0.7800	0.3609	0.058*
C12	0.7109 (5)	0.8246 (4)	0.4882 (5)	0.0764 (13)
H12A	0.7969	0.7786	0.4702	0.115*
H12B	0.7097	0.8357	0.5738	0.115*
H12C	0.7339	0.8837	0.4472	0.115*

	U11	U22	U33	U12	U13	U23
Br	0.0949 (4)	0.0345 (2)	0.0315 (2)	−0.01786 (16)	0.00182 (18)	0.00284 (12)
O1	0.0666 (14)	0.0508 (13)	0.0261 (11)	−0.0214 (11)	0.0079 (9)	−0.0005 (9)
O2	0.0396 (10)	0.0467 (12)	0.0210 (9)	0.0198 (8)	−0.0009 (7)	−0.0063 (8)
N1	0.0373 (11)	0.0386 (12)	0.0159 (10)	0.0145 (9)	0.0007 (8)	−0.0042 (8)
N2	0.0371 (11)	0.0346 (12)	0.0238 (11)	0.0125 (9)	0.0026 (9)	−0.0023 (9)
C1	0.0452 (14)	0.0245 (12)	0.0219 (12)	0.0002 (10)	0.0004 (10)	−0.0003 (10)
C2	0.0576 (17)	0.0292 (13)	0.0212 (13)	0.0033 (12)	−0.0032 (11)	−0.0081 (10)
C3	0.0397 (13)	0.0395 (15)	0.0157 (11)	0.0066 (11)	0.0019 (9)	−0.0066 (10)
C4	0.0322 (12)	0.0352 (14)	0.0206 (12)	−0.0005 (10)	−0.0021 (10)	−0.0007 (10)
C5	0.0342 (12)	0.0283 (12)	0.0230 (12)	0.0015 (10)	−0.0020 (9)	−0.0070 (10)
C6	0.0281 (11)	0.0275 (12)	0.0175 (11)	0.0092 (9)	−0.0018 (8)	−0.0033 (9)
C7	0.0564 (19)	0.076 (2)	0.0250 (15)	−0.0218 (17)	0.0066 (13)	0.0033 (15)
C8	0.0327 (12)	0.0255 (12)	0.0192 (11)	0.0047 (9)	−0.0004 (9)	−0.0039 (9)
C9	0.0391 (14)	0.0418 (15)	0.0263 (13)	0.0132 (12)	0.0014 (10)	0.0018 (11)
C10	0.060 (2)	0.104 (3)	0.0233 (15)	0.040 (2)	−0.0041 (14)	0.0002 (17)
C11	0.0513 (18)	0.0549 (19)	0.0393 (17)	0.0250 (15)	0.0012 (13)	0.0036 (15)
C12	0.050 (2)	0.100 (4)	0.079 (3)	0.016 (2)	0.004 (2)	0.004 (3)

Br—C1	1.894 (3)	C5—H5A	0.9500
O1—C4	1.359 (3)	C6—C8	1.506 (3)
O1—C7	1.431 (4)	C7—H7A	0.9800
O2—C8	1.228 (3)	C7—H7B	0.9800
N1—C8	1.338 (3)	C7—H7C	0.9800
N1—N2	1.394 (3)	C9—C10	1.507 (4)
N1—H1A	0.8800	C9—C11	1.508 (4)
N2—C9	1.266 (4)	C10—H10A	0.9800
C1—C2	1.382 (4)	C10—H10B	0.9800
C1—C6	1.383 (3)	C10—H10C	0.9800
C2—C3	1.386 (4)	C11—C12	1.482 (6)
C2—H2A	0.9500	C11—H11A	0.9900
C3—C4	1.383 (4)	C11—H11B	0.9900
C3—H3A	0.9500	C12—H12A	0.9800
C4—C5	1.393 (4)	C12—H12B	0.9800
C5—C6	1.376 (4)	C12—H12C	0.9800
C4—O1—C7	117.4 (2)	H7A—C7—H7C	109.5
C8—N1—N2	119.4 (2)	H7B—C7—H7C	109.5
C8—N1—H1A	120.3	O2—C8—N1	121.9 (2)
N2—N1—H1A	120.3	O2—C8—C6	120.0 (2)
C9—N2—N1	117.5 (2)	N1—C8—C6	118.2 (2)
C2—C1—C6	120.6 (2)	N2—C9—C10	126.3 (3)
C2—C1—Br	118.8 (2)	N2—C9—C11	116.0 (3)
C6—C1—Br	120.59 (19)	C10—C9—C11	117.6 (3)
C1—C2—C3	120.3 (2)	C9—C10—H10A	109.5
C1—C2—H2A	119.9	C9—C10—H10B	109.5
C3—C2—H2A	119.9	H10A—C10—H10B	109.5
C4—C3—C2	119.4 (2)	C9—C10—H10C	109.5
C4—C3—H3A	120.3	H10A—C10—H10C	109.5
C2—C3—H3A	120.3	H10B—C10—H10C	109.5
O1—C4—C3	124.8 (2)	C12—C11—C9	113.8 (3)
O1—C4—C5	115.4 (2)	C12—C11—H11A	108.8
C3—C4—C5	119.8 (2)	C9—C11—H11A	108.8
C6—C5—C4	120.8 (2)	C12—C11—H11B	108.8
C6—C5—H5A	119.6	C9—C11—H11B	108.8
C4—C5—H5A	119.6	H11A—C11—H11B	107.7
C5—C6—C1	119.1 (2)	C11—C12—H12A	109.5
C5—C6—C8	118.1 (2)	C11—C12—H12B	109.5
C1—C6—C8	122.7 (2)	H12A—C12—H12B	109.5
O1—C7—H7A	109.5	C11—C12—H12C	109.5
O1—C7—H7B	109.5	H12A—C12—H12C	109.5
H7A—C7—H7B	109.5	H12B—C12—H12C	109.5
O1—C7—H7C	109.5
C8—N1—N2—C9	179.2 (3)	Br—C1—C6—C5	179.97 (19)
C6—C1—C2—C3	0.8 (4)	C2—C1—C6—C8	175.6 (2)
Br—C1—C2—C3	−179.4 (2)	Br—C1—C6—C8	−4.2 (3)
C1—C2—C3—C4	−0.2 (4)	N2—N1—C8—O2	179.0 (3)
C7—O1—C4—C3	−2.5 (4)	N2—N1—C8—C6	−2.5 (4)
C7—O1—C4—C5	177.0 (3)	C5—C6—C8—O2	74.8 (3)
C2—C3—C4—O1	178.4 (3)	C1—C6—C8—O2	−101.1 (3)
C2—C3—C4—C5	−1.0 (4)	C5—C6—C8—N1	−103.7 (3)
O1—C4—C5—C6	−177.9 (2)	C1—C6—C8—N1	80.4 (3)
C3—C4—C5—C6	1.6 (4)	N1—N2—C9—C10	−3.0 (5)
C4—C5—C6—C1	−0.9 (4)	N1—N2—C9—C11	177.4 (3)
C4—C5—C6—C8	−177.0 (2)	N2—C9—C11—C12	122.5 (4)
C2—C1—C6—C5	−0.3 (4)	C10—C9—C11—C12	−57.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O2i	0.98	2.60	3.561 (4)	166
C10—H10A···Brii	0.98	3.07	3.949 (5)	151
C10—H10A···O2iii	0.98	2.55	3.231 (4)	127
C11—H11A···O1iv	0.99	2.55	3.373 (4)	141
N1—H1A···O2iii	0.88	2.07	2.932 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O2i	0.98	2.60	3.561 (4)	166
C10—H10A⋯Brii	0.98	3.07	3.949 (5)	151
C10—H10A⋯O2iii	0.98	2.55	3.231 (4)	127
C11—H11A⋯O1iv	0.99	2.55	3.373 (4)	141
N1—H1A⋯O2iii	0.88	2.07	2.932 (3)	165

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .