(E)-1-(4-Chloro-phen-yl)ethanone semi-carbazone.

In the title compound, C(9)H(10)ClN(3)O, the semicarbazone group is approximately planar, with an r.m.s. deviation from the mean plane of 0.054 (1) Å. The dihedral angle between the least-squares planes through the semicarbazone group and the benzene ring is 30.46 (5)°. In the solid state, mol-ecules are linked via inter-molecular N-H⋯O and N-H⋯N hydrogen bonds, generating R(2) (2)(9) ring motifs which, together with R(2) (2)(8) ring motifs formed by pairs of inter-molecular N-H⋯O hydrogen bonds, lead to the formation of a seldom-observed mol-ecular trimer. Furthermore, N-H⋯O hydrogen bonds form R(2) (1)(7) ring motifs with C-H⋯O hydrogen bonds, further consolidating the crystal structure. Mol-ecules are linked by these inter-molecular inter-actions, forming two-dimensional networks parallel to (100).

Related literature

For the synthetic utility and applications of semicarbazone derivatives, see: Warren et al. (1977 ▶); Chandra & Gupta (2005 ▶); Jain et al. (2002 ▶); Pilgram (1978 ▶); Yogeeswari et al. (2004 ▶). For a related structure, see: Fun et al. (2009 ▶). For the preparation, see: Furniss et al. (1978 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C9H10ClN3O

M = 211.65

Monoclinic,

a = 21.8191 (4) Å

b = 7.0484 (1) Å

c = 13.7249 (2) Å

β = 109.633 (1)°

V = 1988.04 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.35 mm−1

T = 100 K

0.41 × 0.20 × 0.03 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.867, T max = 0.991

28636 measured reflections

3539 independent reflections

2912 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.101

S = 1.04

3539 reflections

167 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.45 e Å−3

Δρmin = −0.27 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/S160053680902279X/sj2631sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902279X/sj2631Isup2.hkl

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

C9H10ClN3O	F(000) = 880
Mr = 211.65	Dx = 1.414 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6351 reflections
a = 21.8191 (4) Å	θ = 3.1–32.1°
b = 7.0484 (1) Å	µ = 0.35 mm−1
c = 13.7249 (2) Å	T = 100 K
β = 109.633 (1)°	Plate, colourless
V = 1988.04 (6) Å3	0.41 × 0.20 × 0.03 mm
Z = 8

Bruker SMART APEXII CCD area-detector diffractometer	3539 independent reflections
Radiation source: fine-focus sealed tube	2912 reflections with I > 2σ(I)
graphite	Rint = 0.052
φ and ω scans	θmax = 32.3°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −32→32
Tmin = 0.867, Tmax = 0.991	k = −10→10
28636 measured reflections	l = −20→20

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.049P)2 + 1.2937P] where P = (Fo2 + 2Fc2)/3
3539 reflections	(Δ/σ)max = 0.001
167 parameters	Δρmax = 0.45 e Å−3
0 restraints	Δρmin = −0.27 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 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
Cl1	0.023375 (16)	−0.37949 (4)	0.13113 (2)	0.02330 (9)
O1	0.28038 (4)	0.80096 (12)	0.13075 (6)	0.01675 (17)
N1	0.18652 (5)	0.38677 (13)	0.08164 (7)	0.01332 (18)
N2	0.22047 (5)	0.53956 (13)	0.06342 (7)	0.01416 (18)
N3	0.24395 (6)	0.61942 (14)	0.23627 (8)	0.0176 (2)
C1	0.11370 (6)	−0.05633 (16)	−0.01844 (9)	0.0167 (2)
C2	0.08397 (6)	−0.21004 (16)	0.01146 (10)	0.0178 (2)
C3	0.06045 (6)	−0.18847 (16)	0.09274 (9)	0.0172 (2)
C4	0.06590 (6)	−0.01713 (17)	0.14505 (9)	0.0184 (2)
C5	0.09612 (6)	0.13476 (16)	0.11541 (9)	0.0167 (2)
C6	0.12052 (6)	0.11705 (15)	0.03359 (9)	0.0136 (2)
C7	0.15469 (6)	0.27915 (15)	0.00516 (9)	0.0137 (2)
C8	0.24965 (6)	0.65995 (15)	0.14448 (8)	0.0136 (2)
C9	0.15172 (7)	0.30648 (18)	−0.10430 (9)	0.0189 (2)
H1	0.1299 (8)	−0.071 (2)	−0.0751 (13)	0.022 (4)*
H2	0.0807 (8)	−0.332 (3)	−0.0235 (13)	0.029 (4)*
H4	0.0472 (8)	−0.007 (2)	0.2047 (13)	0.026 (4)*
H5	0.0998 (8)	0.254 (2)	0.1502 (13)	0.024 (4)*
H9A	0.1211 (11)	0.237 (3)	−0.1478 (18)	0.053 (6)*
H9B	0.1901 (12)	0.271 (3)	−0.1107 (18)	0.064 (7)*
H9C	0.1416 (9)	0.433 (3)	−0.1261 (15)	0.036 (5)*
H1N2	0.2197 (8)	0.579 (3)	0.0019 (14)	0.028 (4)*
H1N3	0.2668 (8)	0.684 (2)	0.2863 (13)	0.022 (4)*
H2N3	0.2271 (8)	0.522 (2)	0.2487 (12)	0.020 (4)*

	U11	U22	U33	U12	U13	U23
Cl1	0.02608 (17)	0.01993 (15)	0.02367 (16)	−0.00699 (11)	0.00806 (12)	0.00422 (10)
O1	0.0227 (4)	0.0154 (4)	0.0128 (4)	−0.0054 (3)	0.0067 (3)	−0.0010 (3)
N1	0.0157 (4)	0.0121 (4)	0.0120 (4)	−0.0013 (3)	0.0044 (3)	0.0007 (3)
N2	0.0202 (5)	0.0127 (4)	0.0100 (4)	−0.0042 (3)	0.0056 (4)	−0.0007 (3)
N3	0.0272 (6)	0.0163 (4)	0.0102 (4)	−0.0065 (4)	0.0076 (4)	−0.0015 (3)
C1	0.0176 (5)	0.0165 (5)	0.0163 (5)	−0.0024 (4)	0.0064 (4)	−0.0024 (4)
C2	0.0183 (6)	0.0141 (5)	0.0204 (6)	−0.0024 (4)	0.0055 (4)	−0.0019 (4)
C3	0.0165 (5)	0.0148 (5)	0.0188 (5)	−0.0024 (4)	0.0039 (4)	0.0037 (4)
C4	0.0200 (6)	0.0194 (5)	0.0166 (5)	−0.0019 (4)	0.0074 (4)	0.0013 (4)
C5	0.0200 (6)	0.0151 (5)	0.0158 (5)	−0.0013 (4)	0.0073 (4)	−0.0010 (4)
C6	0.0138 (5)	0.0142 (5)	0.0121 (5)	−0.0004 (4)	0.0034 (4)	0.0013 (4)
C7	0.0158 (5)	0.0127 (4)	0.0121 (5)	−0.0006 (4)	0.0040 (4)	0.0003 (4)
C8	0.0164 (5)	0.0129 (4)	0.0109 (5)	−0.0002 (4)	0.0040 (4)	−0.0005 (4)
C9	0.0266 (7)	0.0185 (5)	0.0124 (5)	−0.0052 (5)	0.0077 (5)	−0.0008 (4)

Cl1—C3	1.7410 (12)	C2—C3	1.3842 (18)
O1—C8	1.2481 (13)	C2—H2	0.977 (18)
N1—C7	1.2922 (14)	C3—C4	1.3895 (17)
N1—N2	1.3768 (13)	C4—C5	1.3882 (16)
N2—C8	1.3737 (14)	C4—H4	1.033 (17)
N2—H1N2	0.883 (18)	C5—C6	1.4006 (16)
N3—C8	1.3378 (14)	C5—H5	0.958 (17)
N3—H1N3	0.835 (18)	C6—C7	1.4863 (15)
N3—H2N3	0.826 (17)	C7—C9	1.4943 (16)
C1—C2	1.3935 (16)	C9—H9A	0.88 (2)
C1—C6	1.3979 (15)	C9—H9B	0.91 (2)
C1—H1	0.963 (16)	C9—H9C	0.94 (2)
C7—N1—N2	119.12 (9)	C4—C5—C6	120.81 (11)
C8—N2—N1	117.86 (9)	C4—C5—H5	120.0 (10)
C8—N2—H1N2	115.9 (12)	C6—C5—H5	119.1 (10)
N1—N2—H1N2	125.4 (12)	C1—C6—C5	118.92 (10)
C8—N3—H1N3	116.1 (12)	C1—C6—C7	120.97 (10)
C8—N3—H2N3	124.2 (11)	C5—C6—C7	120.08 (10)
H1N3—N3—H2N3	118.0 (16)	N1—C7—C6	114.71 (10)
C2—C1—C6	120.63 (11)	N1—C7—C9	124.82 (10)
C2—C1—H1	119.1 (10)	C6—C7—C9	120.46 (10)
C6—C1—H1	120.3 (10)	O1—C8—N3	122.47 (10)
C3—C2—C1	119.16 (11)	O1—C8—N2	119.73 (10)
C3—C2—H2	120.4 (10)	N3—C8—N2	117.80 (10)
C1—C2—H2	120.4 (10)	C7—C9—H9A	112.1 (14)
C2—C3—C4	121.43 (11)	C7—C9—H9B	109.4 (15)
C2—C3—Cl1	119.65 (9)	H9A—C9—H9B	107 (2)
C4—C3—Cl1	118.92 (9)	C7—C9—H9C	111.6 (11)
C5—C4—C3	119.04 (11)	H9A—C9—H9C	105.6 (19)
C5—C4—H4	122.2 (10)	H9B—C9—H9C	110.9 (19)
C3—C4—H4	118.7 (10)
C7—N1—N2—C8	175.03 (10)	C4—C5—C6—C7	−177.97 (11)
C6—C1—C2—C3	0.79 (18)	N2—N1—C7—C6	179.22 (9)
C1—C2—C3—C4	−0.05 (18)	N2—N1—C7—C9	0.30 (17)
C1—C2—C3—Cl1	−179.84 (9)	C1—C6—C7—N1	−146.43 (11)
C2—C3—C4—C5	−0.55 (19)	C5—C6—C7—N1	31.82 (15)
Cl1—C3—C4—C5	179.24 (9)	C1—C6—C7—C9	32.55 (16)
C3—C4—C5—C6	0.41 (18)	C5—C6—C7—C9	−149.20 (12)
C2—C1—C6—C5	−0.92 (18)	N1—N2—C8—O1	−179.37 (10)
C2—C1—C6—C7	177.35 (11)	N1—N2—C8—N3	0.92 (16)
C4—C5—C6—C1	0.32 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1i	0.884 (19)	2.007 (19)	2.8866 (12)	173.3 (19)
N3—H1N3···N1ii	0.835 (18)	2.264 (18)	3.0904 (14)	170.5 (16)
N3—H2N3···O1iii	0.826 (17)	2.316 (17)	3.0499 (13)	148.4 (15)
C9—H9C···O1i	0.94 (2)	2.55 (2)	3.2162 (16)	128.1 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1i	0.884 (19)	2.007 (19)	2.8866 (12)	173.3 (19)
N3—H1N3⋯N1ii	0.835 (18)	2.264 (18)	3.0904 (14)	170.5 (16)
N3—H2N3⋯O1iii	0.826 (17)	2.316 (17)	3.0499 (13)	148.4 (15)
C9—H9C⋯O1i	0.94 (2)	2.55 (2)	3.2162 (16)	128.1 (16)

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