(E)-1-(4-Bromo-phen-yl)ethan-1-one semicarbazone.

In the title compound, C(9)H(10)BrN(3)O, the hydrazone portion and aliphatic chain are essentially coplanar [maximum deviation 0.057 (15) Å] and the mean plane makes a dihedral angle of 70.9 (6)° with the benzene ring. The main feature of the crystal structure is the inter-molecular N-H⋯O hydrogen bond, which links mol-ecules into zigzag chains along the a axis. These chains are further stacked along the b axis. The crystal structure features non-classical inter-molecular C-H⋯O inter-actions. The crystal studied was a nonmerohedral twin, with a twin ratio of 0.505 (1):0.495 (1).

Related literature

For general background and applications of semicarbazone derivatives, see: Chandra & Gupta (2005 ▶); Jain et al. (2002 ▶); Pilgram (1978 ▶); Warren et al. (1977 ▶); Yogeeswari et al. (2004 ▶). For the preparation, see: Furniss et al. (1978 ▶). For bond-length data, see: Allen et al. (1987 ▶). For a related structure, see: Fun et al. (2009 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C9H10BrN3O

M = 256.11

Monoclinic,

a = 17.6700 (8) Å

b = 7.3426 (4) Å

c = 7.9082 (4) Å

β = 102.953 (3)°

V = 999.93 (9) Å3

Z = 4

Mo Kα radiation

μ = 4.08 mm−1

T = 100 K

0.22 × 0.12 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.466, T max = 0.733

12017 measured reflections

2945 independent reflections

2105 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.080

wR(F 2) = 0.249

S = 1.16

2945 reflections

129 parameters

1 restraint

H-atom parameters constrained

Δρmax = 3.03 e Å−3

Δρmin = −1.11 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022284/ng2596sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022284/ng2596Isup2.hkl

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

C9H10BrN3O	F(000) = 512
Mr = 256.11	Dx = 1.701 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3514 reflections
a = 17.6700 (8) Å	θ = 3.0–28.2°
b = 7.3426 (4) Å	µ = 4.08 mm−1
c = 7.9082 (4) Å	T = 100 K
β = 102.953 (3)°	Block, colourless
V = 999.93 (9) Å3	0.22 × 0.12 × 0.08 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	2945 independent reflections
Radiation source: fine-focus sealed tube	2105 reflections with I > 2σ(I)
graphite	Rint = 0.053
φ and ω scans	θmax = 30.2°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −24→24
Tmin = 0.466, Tmax = 0.733	k = −10→10
12017 measured reflections	l = −11→11

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.249	H-atom parameters constrained
S = 1.16	w = 1/[σ2(Fo2) + (0.1217P)2 + 9.4338P] where P = (Fo2 + 2Fc2)/3
2945 reflections	(Δ/σ)max < 0.000
129 parameters	Δρmax = 3.03 e Å−3
1 restraint	Δρmin = −1.11 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

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.

	x	y	z	Uiso*/Ueq
Br1	0.03467 (5)	0.43707 (10)	0.2675 (2)	0.0212 (2)
N3	0.4198 (6)	0.1238 (13)	0.8352 (16)	0.034 (2)
H3A	0.4430	0.0237	0.8214	0.041*
H3B	0.3772	0.1214	0.8704	0.041*
N1	0.3450 (5)	0.4205 (11)	0.899 (2)	0.039 (3)
N2	0.4105 (5)	0.4401 (11)	0.8290 (14)	0.027 (2)
H2B	0.4257	0.5459	0.8038	0.032*
O1	0.5113 (4)	0.2902 (11)	0.7512 (13)	0.032 (2)
C1	0.1856 (7)	0.6630 (14)	0.6881 (14)	0.026 (2)
H1A	0.1894	0.7729	0.7479	0.032*
C2	0.1231 (6)	0.6387 (14)	0.5429 (16)	0.027 (2)
H2A	0.0876	0.7317	0.5050	0.032*
C3	0.1165 (6)	0.4722 (15)	0.4594 (13)	0.023 (2)
C4	0.1698 (7)	0.3367 (14)	0.5184 (14)	0.025 (2)
H4A	0.1638	0.2236	0.4642	0.030*
C5	0.2310 (7)	0.3651 (14)	0.6544 (16)	0.028 (2)
H5A	0.2671	0.2725	0.6885	0.033*
C6	0.2409 (6)	0.5321 (14)	0.7448 (17)	0.027 (2)
C7	0.3094 (5)	0.5625 (12)	0.911 (3)	0.0244 (19)
C8	0.4503 (7)	0.2840 (13)	0.8017 (14)	0.025 (2)
C9	0.3368 (5)	0.7556 (12)	0.914 (3)	0.030 (2)
H9A	0.3911	0.7610	0.9682	0.045*
H9B	0.3081	0.8292	0.9779	0.045*
H9C	0.3288	0.8004	0.7971	0.045*

	U11	U22	U33	U12	U13	U23
Br1	0.0269 (4)	0.0173 (4)	0.0201 (8)	−0.0037 (3)	0.0067 (17)	−0.0023 (5)
N3	0.039 (5)	0.013 (4)	0.057 (7)	0.000 (4)	0.026 (5)	−0.004 (5)
N1	0.019 (3)	0.015 (4)	0.083 (11)	0.001 (3)	0.011 (6)	−0.004 (6)
N2	0.033 (5)	0.009 (4)	0.043 (6)	0.001 (3)	0.018 (4)	−0.004 (4)
O1	0.029 (3)	0.037 (5)	0.038 (4)	−0.003 (3)	0.021 (4)	−0.001 (5)
C1	0.043 (6)	0.013 (4)	0.023 (5)	−0.003 (4)	0.008 (5)	−0.004 (4)
C2	0.023 (5)	0.019 (4)	0.039 (6)	−0.005 (4)	0.008 (5)	−0.003 (5)
C3	0.020 (4)	0.034 (6)	0.016 (4)	−0.001 (4)	0.008 (4)	0.005 (4)
C4	0.035 (5)	0.019 (5)	0.019 (5)	−0.008 (4)	0.002 (4)	0.004 (4)
C5	0.033 (5)	0.013 (4)	0.034 (6)	0.000 (4)	0.004 (5)	−0.005 (4)
C6	0.024 (5)	0.020 (5)	0.040 (6)	0.000 (4)	0.014 (5)	0.004 (4)
C7	0.021 (3)	0.016 (3)	0.036 (6)	0.003 (3)	0.005 (8)	−0.016 (6)
C8	0.046 (6)	0.007 (4)	0.024 (5)	0.007 (4)	0.009 (5)	−0.002 (4)
C9	0.022 (4)	0.011 (3)	0.060 (8)	−0.003 (3)	0.018 (8)	0.009 (8)

Br1—C3	1.865 (10)	C2—C3	1.382 (16)
N3—C8	1.344 (14)	C2—H2A	0.9300
N3—H3A	0.8600	C3—C4	1.378 (15)
N3—H3B	0.8600	C4—C5	1.359 (15)
N1—C7	1.233 (11)	C4—H4A	0.9300
N1—N2	1.397 (9)	C5—C6	1.410 (15)
N2—C8	1.387 (12)	C5—H5A	0.9300
N2—H2B	0.8600	C6—C7	1.59 (2)
O1—C8	1.232 (13)	C7—C9	1.496 (12)
C1—C6	1.373 (15)	C9—H9A	0.9600
C1—C2	1.415 (16)	C9—H9B	0.9600
C1—H1A	0.9300	C9—H9C	0.9600
C8—N3—H3A	120.0	C4—C5—C6	121.4 (11)
C8—N3—H3B	120.0	C4—C5—H5A	119.3
H3A—N3—H3B	120.0	C6—C5—H5A	119.3
C7—N1—N2	115.2 (10)	C1—C6—C5	116.4 (11)
C8—N2—N1	118.1 (8)	C1—C6—C7	121.7 (9)
C8—N2—H2B	121.0	C5—C6—C7	121.8 (9)
N1—N2—H2B	121.0	N1—C7—C9	129.3 (10)
C6—C1—C2	123.1 (10)	N1—C7—C6	97.0 (12)
C6—C1—H1A	118.5	C9—C7—C6	109.2 (13)
C2—C1—H1A	118.5	O1—C8—N3	121.0 (9)
C3—C2—C1	117.8 (10)	O1—C8—N2	122.1 (9)
C3—C2—H2A	121.1	N3—C8—N2	116.9 (10)
C1—C2—H2A	121.1	C7—C9—H9A	109.5
C4—C3—C2	119.9 (10)	C7—C9—H9B	109.5
C4—C3—Br1	121.5 (8)	H9A—C9—H9B	109.5
C2—C3—Br1	118.6 (8)	C7—C9—H9C	109.5
C5—C4—C3	121.3 (10)	H9A—C9—H9C	109.5
C5—C4—H4A	119.4	H9B—C9—H9C	109.5
C3—C4—H4A	119.4
C7—N1—N2—C8	−176.1 (14)	C4—C5—C6—C7	176.3 (13)
C6—C1—C2—C3	2.4 (17)	N2—N1—C7—C9	−20 (3)
C1—C2—C3—C4	0.1 (15)	N2—N1—C7—C6	101.6 (13)
C1—C2—C3—Br1	−179.9 (8)	C1—C6—C7—N1	−174.6 (12)
C2—C3—C4—C5	−2.4 (16)	C5—C6—C7—N1	9.4 (17)
Br1—C3—C4—C5	177.5 (9)	C1—C6—C7—C9	−38.6 (17)
C3—C4—C5—C6	2.4 (18)	C5—C6—C7—C9	145.3 (12)
C2—C1—C6—C5	−2.4 (17)	N1—N2—C8—O1	−175.3 (12)
C2—C1—C6—C7	−178.7 (12)	N1—N2—C8—N3	3.9 (16)
C4—C5—C6—C1	0.0 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1i	0.86	2.21	3.052 (12)	168
N3—H3A···O1ii	0.86	2.03	2.885 (13)	171
C9—H9A···O1iii	0.96	2.51	3.34 (2)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O1i	0.86	2.21	3.052 (12)	168
N3—H3A⋯O1ii	0.86	2.03	2.885 (13)	171
C9—H9A⋯O1iii	0.96	2.51	3.34 (2)	144

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