2,6-Dichloro-aniline-4-(2,6-dichloro-anilino)-pent-3-en-2-one (1/2).

The asymmetric unit of the title compound, C6H5Cl2N·2C11H11Cl2NO, is composed of one mol-ecule of an enamino-ketone [i.e. -(2,6-dichloro-phenyl-amino)-pent-3-en-2-one] and half a mol-ecule of 2,6-dichloro-aniline, the whole mol-ecule of the latter component being generated by twofold rotational symmetry. In this latter mol-ecule, there are two intra-molecular N-H⋯Cl contacts. In the enamino-ketone mol-ecule, there is an N-H⋯O hydrogen bond of moderate strength, and the dihedral angle between the benzene ring and penta-none fragment [C-C(-N)=C-C(=O)-C; planar within 0.005 (1) Å] is 81.85 (7)°. In the crystal, two mol-ecules of the enamino-ketone are bridged by a mol-ecule of 2,6-dichloro-aniline via N-H⋯O hydrogen bonds of moderate strength. There are also π-π inter-actions present, involving the benzene rings of inversion-related enamino-ketone mol-ecules [centroid-centroid distance = 3.724 (4) Å].

Related literature

For the properties of enamino–ketones as liquid crystals, see: Pyżuk et al. (1993 ▶). For fluorescence studies of enamino–ketones, see: Xia et al. (2008 ▶). For the use of enamino–ketones in medicine, see: Tan et al. (2008 ▶); and in catalysis, see: Roodt & Steyn (2000 ▶); Brink et al. (2010 ▶). For background to the ligand preparation, see: Shaheen et al. (2006 ▶); Venter et al. (2010 ▶); Venter, Brink et al. (2012 ▶). For applications of rhodium compounds containing bidentate ligand systems, see: Pyżuk et al. (1993 ▶); Tan et al. (2008 ▶); Xia et al. (2008 ▶). For related rhodium enamino–­ketonato complexes, see: Brink et al. (2010 ▶); Damoense et al. (1994 ▶); Roodt & Steyn (2000 ▶); Venter, Steyl et al. (2012 ▶). For classification of hydrogen bonds, see: Gilli & Gilli (2009 ▶).

Experimental

Crystal data

C6H5Cl2N·2C11H11Cl2NO

M = 650.23

Monoclinic,

a = 15.7140 (1) Å

b = 8.7210 (2) Å

c = 22.9950 (4) Å

β = 104.794 (1)°

V = 3046.81 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.60 mm−1

T = 100 K

0.31 × 0.25 × 0.19 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.837, T max = 0.895

34421 measured reflections

3785 independent reflections

3305 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.077

S = 1.04

3785 reflections

186 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812049227/fb2272sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812049227/fb2272Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812049227/fb2272Isup3.cml

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

C6H5Cl2N·2C11H11Cl2NO	F(000) = 1336
Mr = 650.23	Dx = 1.418 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9993 reflections
a = 15.7140 (1) Å	θ = 2.8–28.2°
b = 8.7210 (2) Å	µ = 0.60 mm−1
c = 22.9950 (4) Å	T = 100 K
β = 104.794 (1)°	Cuboid, colourless
V = 3046.81 (9) Å3	0.31 × 0.25 × 0.19 mm
Z = 4

Bruker X8 APEXII 4K KappaCCD diffractometer	3785 independent reflections
Radiation source: fine-focus sealed tube	3305 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω and φ scans	θmax = 28.4°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −20→20
Tmin = 0.837, Tmax = 0.895	k = −11→11
34421 measured reflections	l = −30→30

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)] = 0.027	Hydrogen site location: difference Fourier map
wR(F2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0394P)2 + 2.1199P] where P = (Fo2 + 2Fc2)/3
3785 reflections	(Δ/σ)max = 0.002
186 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.23 e Å−3
46 constraints

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 > 2σ(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
C1	0.29987 (9)	1.0652 (2)	0.10718 (6)	0.0321 (3)
H1A	0.3066	0.9907	0.0768	0.048*
H1B	0.3555	1.0741	0.1382	0.048*
H1C	0.2839	1.1653	0.0881	0.048*
C2	0.22871 (8)	1.01235 (15)	0.13549 (6)	0.0223 (3)
C3	0.24331 (9)	0.99643 (17)	0.19672 (6)	0.0261 (3)
H3	0.3002	1.0201	0.2213	0.031*
C4	0.17787 (8)	0.94637 (14)	0.22541 (6)	0.0214 (2)
C5	0.20270 (10)	0.9341 (2)	0.29307 (6)	0.0344 (3)
H5A	0.2077	1.0371	0.3107	0.052*
H5B	0.2593	0.8809	0.3065	0.052*
H5C	0.1573	0.8763	0.3060	0.052*
C111	0.12706 (7)	0.99074 (14)	0.03518 (5)	0.0174 (2)
C112	0.10240 (8)	1.12965 (14)	0.00548 (6)	0.0211 (2)
C113	0.07626 (8)	1.13817 (16)	−0.05687 (6)	0.0252 (3)
H113	0.0594	1.2337	−0.0762	0.030*
C114	0.07507 (8)	1.00632 (17)	−0.09046 (6)	0.0271 (3)
H114	0.0572	1.0116	−0.1331	0.032*
C115	0.09966 (9)	0.86664 (16)	−0.06261 (6)	0.0256 (3)
H115	0.0991	0.7764	−0.0858	0.031*
C116	0.12516 (8)	0.86044 (14)	−0.00031 (6)	0.0201 (2)
C211	0.0000	0.53418 (19)	0.2500	0.0181 (3)
C212	0.02876 (8)	0.44701 (14)	0.20698 (5)	0.0183 (2)
C213	0.03042 (8)	0.28839 (14)	0.20718 (5)	0.0217 (3)
H213	0.0523	0.2345	0.1781	0.026*
C214	0.0000	0.2083 (2)	0.2500	0.0244 (4)
H214	0.0000	0.0993	0.2500	0.029*
N11	0.14928 (7)	0.98030 (13)	0.09874 (5)	0.0198 (2)
H11	0.1130 (10)	0.9500 (18)	0.1164 (7)	0.024*
N21	0.0000	0.68981 (18)	0.2500	0.0275 (4)
H21	0.0252 (11)	0.737 (2)	0.2268 (7)	0.033*
O12	0.10094 (6)	0.91464 (10)	0.19690 (4)	0.02136 (19)
Cl12	0.10261 (2)	1.29453 (4)	0.047476 (17)	0.03288 (10)
Cl16	0.15505 (2)	0.68546 (4)	0.034586 (16)	0.03104 (10)
Cl22	0.06336 (2)	0.54706 (3)	0.151471 (13)	0.02337 (9)

	U11	U22	U33	U12	U13	U23
C1	0.0179 (6)	0.0563 (9)	0.0219 (6)	−0.0084 (6)	0.0044 (5)	0.0032 (6)
C2	0.0167 (6)	0.0298 (6)	0.0201 (6)	−0.0027 (5)	0.0040 (5)	0.0004 (5)
C3	0.0184 (6)	0.0399 (7)	0.0182 (6)	−0.0047 (5)	0.0016 (5)	0.0014 (5)
C4	0.0231 (6)	0.0223 (6)	0.0181 (6)	0.0001 (5)	0.0042 (5)	0.0011 (5)
C5	0.0301 (7)	0.0548 (9)	0.0176 (6)	−0.0073 (7)	0.0049 (5)	0.0035 (6)
C111	0.0136 (5)	0.0222 (6)	0.0167 (5)	−0.0025 (4)	0.0044 (4)	0.0011 (4)
C112	0.0173 (6)	0.0208 (6)	0.0260 (6)	−0.0024 (5)	0.0069 (5)	0.0012 (5)
C113	0.0172 (6)	0.0305 (7)	0.0274 (6)	−0.0005 (5)	0.0048 (5)	0.0124 (5)
C114	0.0196 (6)	0.0446 (8)	0.0169 (6)	−0.0019 (6)	0.0045 (5)	0.0051 (5)
C115	0.0233 (6)	0.0333 (7)	0.0209 (6)	−0.0025 (5)	0.0066 (5)	−0.0055 (5)
C116	0.0182 (6)	0.0208 (6)	0.0213 (6)	0.0001 (5)	0.0049 (5)	0.0024 (5)
C211	0.0154 (8)	0.0176 (8)	0.0196 (8)	0.000	0.0012 (6)	0.000
C212	0.0180 (6)	0.0196 (6)	0.0159 (5)	0.0012 (4)	0.0017 (4)	0.0016 (4)
C213	0.0246 (6)	0.0200 (6)	0.0182 (6)	0.0029 (5)	0.0013 (5)	−0.0025 (4)
C214	0.0318 (10)	0.0155 (8)	0.0228 (9)	0.000	0.0010 (7)	0.000
N11	0.0171 (5)	0.0275 (5)	0.0151 (5)	−0.0050 (4)	0.0049 (4)	0.0001 (4)
N21	0.0375 (9)	0.0165 (7)	0.0372 (9)	0.000	0.0258 (8)	0.000
O12	0.0201 (4)	0.0243 (4)	0.0197 (4)	−0.0032 (4)	0.0052 (3)	0.0020 (3)
Cl12	0.03494 (19)	0.01929 (16)	0.0452 (2)	−0.00228 (13)	0.01176 (16)	−0.00467 (13)
Cl16	0.0402 (2)	0.02055 (16)	0.03423 (19)	0.00503 (13)	0.01296 (15)	0.00368 (12)
Cl22	0.02857 (17)	0.02216 (15)	0.02189 (15)	0.00499 (11)	0.01100 (12)	0.00329 (11)

C1—C2	1.5028 (18)	C113—C114	1.383 (2)
C1—H1A	0.9800	C113—H113	0.9500
C1—H1B	0.9800	C114—C115	1.385 (2)
C1—H1C	0.9800	C114—H114	0.9500
C2—N11	1.3458 (16)	C115—C116	1.3867 (18)
C2—C3	1.3745 (17)	C115—H115	0.9500
C3—C4	1.4248 (18)	C116—Cl16	1.7322 (12)
C3—H3	0.9500	C211—N21	1.357 (2)
C4—O12	1.2501 (15)	C211—C212i	1.4103 (15)
C4—C5	1.5082 (18)	C211—C212	1.4104 (15)
C5—H5A	0.9800	C212—C213	1.3835 (17)
C5—H5B	0.9800	C212—Cl22	1.7437 (12)
C5—H5C	0.9800	C213—C214	1.3880 (16)
C111—C116	1.3948 (17)	C213—H213	0.9500
C111—C112	1.3960 (17)	C214—C213i	1.3881 (16)
C111—N11	1.4162 (15)	C214—H214	0.9500
C112—C113	1.3889 (18)	N11—H11	0.825 (16)
C112—Cl12	1.7316 (13)	N21—H21	0.850 (17)
C2—C1—H1A	109.5	C114—C113—H113	120.3
C2—C1—H1B	109.5	C112—C113—H113	120.3
H1A—C1—H1B	109.5	C113—C114—C115	120.73 (12)
C2—C1—H1C	109.5	C113—C114—H114	119.6
H1A—C1—H1C	109.5	C115—C114—H114	119.6
H1B—C1—H1C	109.5	C114—C115—C116	119.02 (12)
N11—C2—C3	120.52 (12)	C114—C115—H115	120.5
N11—C2—C1	117.71 (11)	C116—C115—H115	120.5
C3—C2—C1	121.77 (12)	C115—C116—C111	122.00 (11)
C2—C3—C4	123.62 (12)	C115—C116—Cl16	119.05 (10)
C2—C3—H3	118.2	C111—C116—Cl16	118.95 (9)
C4—C3—H3	118.2	N21—C211—C212i	122.62 (7)
O12—C4—C3	122.73 (11)	N21—C211—C212	122.62 (8)
O12—C4—C5	119.08 (12)	C212i—C211—C212	114.76 (15)
C3—C4—C5	118.18 (11)	C213—C212—C211	123.07 (12)
C4—C5—H5A	109.5	C213—C212—Cl22	119.58 (10)
C4—C5—H5B	109.5	C211—C212—Cl22	117.35 (9)
H5A—C5—H5B	109.5	C212—C213—C214	119.74 (12)
C4—C5—H5C	109.5	C212—C213—H213	120.1
H5A—C5—H5C	109.5	C214—C213—H213	120.1
H5B—C5—H5C	109.5	C213—C214—C213i	119.55 (16)
C116—C111—C112	117.33 (11)	C213—C214—H214	120.2
C116—C111—N11	120.94 (11)	C213i—C214—H214	120.2
C112—C111—N11	121.67 (11)	C2—N11—C111	125.41 (11)
C113—C112—C111	121.56 (12)	C2—N11—H11	113.8 (11)
C113—C112—Cl12	119.29 (10)	C111—N11—H11	120.7 (11)
C111—C112—Cl12	119.15 (10)	C211—N21—H21	119.2 (12)
C114—C113—C112	119.37 (12)
N11—C2—C3—C4	0.0 (2)	N11—C111—C116—C115	176.95 (11)
C1—C2—C3—C4	−179.84 (14)	C112—C111—C116—Cl16	−179.90 (9)
C2—C3—C4—O12	−1.0 (2)	N11—C111—C116—Cl16	−2.72 (16)
C2—C3—C4—C5	−179.94 (14)	N21—C211—C212—C213	178.88 (9)
C116—C111—C112—C113	0.53 (18)	C212i—C211—C212—C213	−1.13 (9)
N11—C111—C112—C113	−176.62 (11)	N21—C211—C212—Cl22	−1.17 (10)
C116—C111—C112—Cl12	179.39 (9)	C212i—C211—C212—Cl22	178.83 (10)
N11—C111—C112—Cl12	2.24 (16)	C211—C212—C213—C214	2.23 (17)
C111—C112—C113—C114	−0.40 (19)	Cl22—C212—C213—C214	−177.73 (7)
Cl12—C112—C113—C114	−179.26 (10)	C212—C213—C214—C213i	−1.07 (8)
C112—C113—C114—C115	−0.05 (19)	C3—C2—N11—C111	−179.21 (13)
C113—C114—C115—C116	0.35 (19)	C1—C2—N11—C111	0.7 (2)
C114—C115—C116—C111	−0.20 (19)	C116—C111—N11—C2	99.59 (15)
C114—C115—C116—Cl16	179.47 (10)	C112—C111—N11—C2	−83.36 (16)
C112—C111—C116—C115	−0.23 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···Cl22	0.850 (17)	2.578 (17)	2.9710 (7)	109.4 (13)
N11—H11···O12	0.825 (16)	1.932 (16)	2.6223 (13)	140.7 (14)
N21—H21···O12	0.850 (17)	2.167 (17)	2.9732 (13)	158.4 (16)

Parameters	I	II	III	IV	V
N11-C111	1.416 (2)	1.408 (2)	1.417 (2)	1.451 (2)	-
N11-C2	1.346 (2)	1.347 (2)	1.348 (1)	1.324 (2)	1.303 (6)
O12-C4	1.250 (1)	1.249 (2)	1.253 (1)	1.295 (2)	1.281 (6)
C2-C3	1.375 (2)	1.379 (2)	1.384 (2)	1.419 (3)	1.396 (7)
C3-C4	1.425 (2)	1.428 (2)	1.424 (2)	1.378 (3)	1.388 (8)
N11···O12	2.622 (2)	2.633 (2)	2.646 (1)	2.890 (2)	2.826 (6)
N11-C2···C4-O12	-0.8 (1)	5.5 (1)	1.70 (9)	1.6 (2)	1.2 (4)
Dihedral angle a	81.87 (5)	46.52 (5)	29.90 (3)	89.82 (6)	-

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21⋯Cl22	0.850 (17)	2.578 (17)	2.9710 (7)	109.4 (13)
N11—H11⋯O12	0.825 (16)	1.932 (16)	2.6223 (13)	140.7 (14)
N21—H21⋯O12	0.850 (17)	2.167 (17)	2.9732 (13)	158.4 (16)