(1Z)-1-(2,4-Dichloro-phen-yl)ethan-1-one semicarbazone.

In the title compound, C(9)H(9)Cl(2)N(3)O, the semicarbazone group is approximately planar, with an r.m.s deviation from the mean plane of 0.011 (2) Å. The dihedral angle between the least-squares planes through the semicarbazone group and the benzene ring is 38.76 (9)°. The crystal structure is further stabilized by N-H⋯O and C-H⋯O hydrogen bonding.

Related literature

For applications of semicarbazone derivatives, see: Warren et al. (1977 ▶); Chandra & Gupta (2005 ▶); Jain et al. (2002 ▶); Pilgram (1978 ▶); Yogeeswari et al. (2004 ▶); For semicarbazide preparations, see: Furniss et al. (1978 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C9H9Cl2N3O

M = 246.09

Monoclinic,

a = 37.8079 (17) Å

b = 3.8097 (2) Å

c = 14.4920 (7) Å

β = 98.852 (2)°

V = 2062.52 (17) Å3

Z = 8

Mo Kα radiation

μ = 0.60 mm−1

T = 100 K

0.42 × 0.14 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.707, T max = 0.974

32124 measured reflections

4202 independent reflections

3654 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.072

wR(F 2) = 0.192

S = 1.11

4202 reflections

149 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 3.37 e Å−3

Δρmin = −0.82 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/S1600536809029900/bq2153sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029900/bq2153Isup2.hkl

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

C9H9Cl2N3O	F(000) = 1008
Mr = 246.09	Dx = 1.585 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9961 reflections
a = 37.8079 (17) Å	θ = 2.9–34.0°
b = 3.8097 (2) Å	µ = 0.60 mm−1
c = 14.4920 (7) Å	T = 100 K
β = 98.852 (2)°	Plate, colorless
V = 2062.52 (17) Å3	0.42 × 0.14 × 0.04 mm
Z = 8

Bruker SMART APEXII CCD area-detector diffractometer	4202 independent reflections
Radiation source: fine-focus sealed tube	3654 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 34.1°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −59→58
Tmin = 0.707, Tmax = 0.974	k = −5→5
32124 measured reflections	l = −22→22

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.192	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ2(Fo2) + (0.1176P)2 + 5.115P] where P = (Fo2 + 2Fc2)/3
4202 reflections	(Δ/σ)max = 0.001
149 parameters	Δρmax = 3.37 e Å−3
0 restraints	Δρmin = −0.82 e Å−3

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

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Cl1	0.254197 (12)	1.14825 (12)	0.14159 (3)	0.01486 (13)
Cl2	0.149699 (12)	0.64254 (12)	−0.11406 (3)	0.01413 (13)
O1	−0.00572 (4)	0.4635 (5)	0.11828 (10)	0.0162 (3)
N1	0.08094 (4)	0.7191 (5)	0.08948 (11)	0.0127 (3)
N2	0.04458 (4)	0.6666 (5)	0.06771 (12)	0.0141 (3)
N3	0.04484 (5)	0.5433 (7)	0.22395 (13)	0.0222 (4)
C1	0.14889 (5)	1.0482 (6)	0.14140 (13)	0.0132 (3)
H1A	0.1327	1.0954	0.1819	0.016*
C2	0.18500 (5)	1.1187 (5)	0.17051 (14)	0.0132 (3)
H2A	0.1928	1.2131	0.2293	0.016*
C3	0.20913 (5)	1.0451 (5)	0.10974 (13)	0.0120 (3)
C4	0.19805 (5)	0.9013 (5)	0.02261 (13)	0.0124 (3)
H4A	0.2145	0.8508	−0.0172	0.015*
C5	0.16165 (5)	0.8336 (5)	−0.00436 (13)	0.0112 (3)
C6	0.13617 (5)	0.9086 (5)	0.05322 (13)	0.0112 (3)
C7	0.09697 (5)	0.8539 (5)	0.02541 (13)	0.0116 (3)
C8	0.02647 (5)	0.5559 (6)	0.13727 (14)	0.0152 (3)
C9	0.07833 (5)	0.9765 (5)	−0.06811 (13)	0.0123 (3)
H9A	0.0571	1.1034	−0.0601	0.018*
H9B	0.0720	0.7772	−0.1078	0.018*
H9C	0.0940	1.1272	−0.0962	0.018*
H1N2	0.0320 (9)	0.660 (8)	0.014 (2)	0.016 (7)*
H1N3	0.0663 (10)	0.636 (10)	0.231 (3)	0.028 (9)*
H2N3	0.0324 (10)	0.484 (10)	0.262 (3)	0.028 (9)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0092 (2)	0.0180 (2)	0.0168 (2)	−0.00196 (13)	0.00036 (15)	−0.00011 (14)
Cl2	0.0141 (2)	0.0179 (2)	0.0105 (2)	−0.00169 (14)	0.00232 (15)	−0.00251 (14)
O1	0.0090 (6)	0.0283 (8)	0.0111 (6)	−0.0027 (5)	0.0010 (5)	0.0002 (5)
N1	0.0076 (6)	0.0192 (7)	0.0111 (7)	−0.0008 (5)	0.0009 (5)	0.0005 (5)
N2	0.0084 (6)	0.0238 (8)	0.0097 (7)	−0.0026 (5)	0.0005 (5)	0.0012 (5)
N3	0.0114 (7)	0.0461 (12)	0.0088 (7)	−0.0060 (8)	0.0002 (6)	0.0043 (7)
C1	0.0100 (7)	0.0191 (8)	0.0104 (7)	−0.0019 (6)	0.0016 (6)	−0.0020 (6)
C2	0.0114 (7)	0.0163 (8)	0.0114 (7)	−0.0007 (6)	0.0005 (6)	−0.0018 (6)
C3	0.0082 (7)	0.0140 (8)	0.0135 (8)	−0.0007 (6)	0.0006 (6)	0.0011 (6)
C4	0.0119 (7)	0.0126 (7)	0.0130 (8)	−0.0005 (6)	0.0027 (6)	−0.0004 (6)
C5	0.0113 (7)	0.0127 (7)	0.0097 (7)	0.0001 (5)	0.0021 (6)	−0.0005 (5)
C6	0.0104 (7)	0.0130 (7)	0.0101 (7)	−0.0007 (6)	0.0015 (5)	0.0013 (6)
C7	0.0099 (7)	0.0141 (8)	0.0105 (7)	−0.0007 (5)	0.0009 (6)	−0.0003 (5)
C8	0.0109 (7)	0.0234 (9)	0.0116 (8)	−0.0011 (7)	0.0025 (6)	0.0017 (7)
C9	0.0107 (7)	0.0140 (8)	0.0114 (7)	−0.0011 (6)	−0.0010 (6)	0.0017 (6)

Cl1—C3	1.7403 (19)	C1—H1A	0.9300
Cl2—C5	1.7436 (19)	C2—C3	1.391 (3)
O1—C8	1.256 (2)	C2—H2A	0.9300
N1—C7	1.291 (2)	C3—C4	1.381 (3)
N1—N2	1.377 (2)	C4—C5	1.395 (3)
N2—C8	1.369 (2)	C4—H4A	0.9300
N2—H1N2	0.85 (3)	C5—C6	1.398 (3)
N3—C8	1.339 (3)	C6—C7	1.489 (3)
N3—H1N3	0.88 (4)	C7—C9	1.503 (3)
N3—H2N3	0.81 (4)	C9—H9A	0.9600
C1—C2	1.392 (3)	C9—H9B	0.9600
C1—C6	1.399 (3)	C9—H9C	0.9600
C7—N1—N2	117.12 (16)	C4—C5—C6	122.38 (17)
C8—N2—N1	118.08 (16)	C4—C5—Cl2	116.02 (14)
C8—N2—H1N2	113 (2)	C6—C5—Cl2	121.59 (15)
N1—N2—H1N2	128 (2)	C5—C6—C1	116.83 (17)
C8—N3—H1N3	115 (2)	C5—C6—C7	123.95 (17)
C8—N3—H2N3	112 (3)	C1—C6—C7	119.21 (16)
H1N3—N3—H2N3	131 (4)	N1—C7—C6	114.76 (16)
C2—C1—C6	122.24 (17)	N1—C7—C9	124.43 (17)
C2—C1—H1A	118.9	C6—C7—C9	120.65 (16)
C6—C1—H1A	118.9	O1—C8—N3	122.71 (18)
C3—C2—C1	118.53 (17)	O1—C8—N2	120.16 (18)
C3—C2—H2A	120.7	N3—C8—N2	117.11 (18)
C1—C2—H2A	120.7	C7—C9—H9A	109.5
C4—C3—C2	121.52 (17)	C7—C9—H9B	109.5
C4—C3—Cl1	118.62 (14)	H9A—C9—H9B	109.5
C2—C3—Cl1	119.83 (15)	C7—C9—H9C	109.5
C3—C4—C5	118.48 (17)	H9A—C9—H9C	109.5
C3—C4—H4A	120.8	H9B—C9—H9C	109.5
C5—C4—H4A	120.8
C7—N1—N2—C8	−173.82 (19)	Cl2—C5—C6—C7	−3.6 (3)
C6—C1—C2—C3	−0.4 (3)	C2—C1—C6—C5	1.6 (3)
C1—C2—C3—C4	−0.7 (3)	C2—C1—C6—C7	−177.46 (18)
C1—C2—C3—Cl1	177.08 (15)	N2—N1—C7—C6	179.31 (17)
C2—C3—C4—C5	0.7 (3)	N2—N1—C7—C9	4.0 (3)
Cl1—C3—C4—C5	−177.15 (14)	C5—C6—C7—N1	137.72 (19)
C3—C4—C5—C6	0.5 (3)	C1—C6—C7—N1	−43.3 (3)
C3—C4—C5—Cl2	−178.54 (15)	C5—C6—C7—C9	−46.8 (3)
C4—C5—C6—C1	−1.6 (3)	C1—C6—C7—C9	132.2 (2)
Cl2—C5—C6—C1	177.39 (15)	N1—N2—C8—O1	−171.2 (2)
C4—C5—C6—C7	177.37 (18)	N1—N2—C8—N3	7.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1i	0.85 (3)	2.07 (3)	2.907 (2)	168 (3)
N3—H2N3···O1ii	0.81 (4)	2.13 (4)	2.924 (2)	164 (4)
C9—H9A···O1iii	0.96	2.59	3.465 (2)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1i	0.85 (3)	2.07 (3)	2.907 (2)	168 (3)
N3—H2N3⋯O1ii	0.81 (4)	2.13 (4)	2.924 (2)	164 (4)
C9—H9A⋯O1iii	0.96	2.59	3.465 (2)	152

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