2,6-Dichloro­aniline–4-(2,6-dichloro­anilino)­pent-3-en-2-one (1/2)

Venter, G.J.S.; Steyl, G.; Roodt, A.

doi:10.1107/S1600536812049227

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Pages o34-o35

https://doi.org/10.1107/S1600536812049227

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2,6-Dichloroaniline–4-(2,6-dichloroanilino)pent-3-en-2-one (1/2)

Gertruida J. S. Venter,^a ^* Gideon Steyl ^a and Andreas Roodt ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein, 9300, South Africa
^*Correspondence e-mail: ventergjs@ufs.ac.za

(Received 27 September 2012; accepted 30 November 2012; online 8 December 2012)

The asymmetric unit of the title compound, C₆H₅Cl₂N·2C₁₁H₁₁Cl₂NO, is composed of one molecule of an enamino–ketone [i.e. –(2,6-dichlorophenylamino)pent-3-en-2-one] and half a molecule of 2,6-dichloroaniline, the whole molecule of the latter component being generated by twofold rotational symmetry. In this latter molecule, there are two intramolecular N—H⋯Cl contacts. In the enamino–ketone molecule, there is an N—H⋯O hydrogen bond of moderate strength, and the dihedral angle between the benzene ring and pentanone fragment [C—C(—N)=C—C(=O)—C; planar within 0.005 (1) Å] is 81.85 (7)°. In the crystal, two molecules of the enamino–ketone are bridged by a molecule of 2,6-dichloroaniline via N—H⋯O hydrogen bonds of moderate strength. There are also π–π interactions present, involving the benzene rings of inversion-related enamino–ketone molecules [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_r = 650.23
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.027
wR(F²) = 0.077
S = 1.04
3785 reflections
186 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.23 e Å⁻³

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)

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812049227/fb2272sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049227/fb2272Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812049227/fb2272Isup3.cml

checkCIF report

Comment top

The β-diketone compound AcacH (acetylacetone; or acetylacetonato if it is coordinated) has been studied extensively, and a large number of its derivatives have been synthesized up to date. One of these derivative types is known as enamino–ketones, which contain an unsaturated C═C bond as well as nitrogen and oxygen atoms. enamino–ketones are of interest in various fields including liquid crystals (Pyżuk et al., 1993), fluorescence studies (Xia et al., 2008), medicine (Tan et al., 2008) and catalysis (Roodt & Steyn, 2000; Brink et al., 2010).

The title enamino–ketone (Fig. 1) is a derivative of 4-(phenylamino)pent-3-en-2-one (PhonyH; Shaheen et al., 2006). The 2,6-dichloroaniline molecule is located on a two-fold rotation axis. The pertinent two-fold axis passes through atoms N21, C211, C214 and H214. The molecule thus has symmetry of point group 2. The dihedral angle between the phenyl ring and the mean plane of the pentanone fragment [C1-C2(-N11)═ C3-C4(═O12)-C5; maximum deviation 0.005 (1) Å for atom C4] in the title enamino–ketone, where the substituents are situated in the ortho position on the phenyl ring, is 81.85 (7) °. This angle is dependent on the position of the substituent on the phenyl ring, for example compounds with para substituents usually display smaller dihedral angles (Venter et al., 2010).

In the enamino–ketone molecule there is an intramolecular hydrogen-bond (Table 1 and Fig. 1) of moderate strength (Gilli & Gilli, 2009) in which the N_{secondary amine}—H···O_keto is involved. There are two intramolecular contacts, N_{primary amine}—H···Cl, observed in the 2,6-dichloroaniline molecule (Table 1 and Fig. 1).

In the crystal, two molecules of 4-(2,6-dichlorophenylamino)-pent-3-en-2-one and one molecule of 2,6-dichloroaniline are linked by N_{primary amine}—H···O_keto intermolecular hydrogen bonds of moderate strength (Table 1 and Fig. 1). There are also π-π interactions present between the phenyl rings of the inversion-related 4-(2,6-dichlorophenylamino)-pent-3-en-2-one molecules, with a distance of 3.724 (4) Å between their centroids [symmetry operation: -x, -y+2, -z]. The packing style resulting from the respective interactions, with clearly visible π-π-stacking, is illustrated in Fig. 2.

As expected the bond distances in the title enamino–ketone differ significantly from the respective distances in compounds where the enamino–ketone is coordinated to rhodium (Venter, Steyl et al., 2012; Damoense et al., 1994; see Table 2), but they display similar bond distances to those observed in analogous enamino–ketones (Venter et al., 2010; Venter, Brink et al., 2012). The difference between the C2–C3 bond distance [1.376 (2) Å] and the C3–C4 bond distance [1.457 (3) °] indicates an unsaturated C2═C3 bond in the pentenone backbone, which is consistent with the definition of an enamino–ketone. The N11···O12 distance is longer by ca. 0.2 Å upon coordination when comparing the title structure and selected compounds (II) and (III) with complexes (IV) and (V), as indicated in Table 2.

Related literature top

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 enaminoketonato 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 top

A solution of acetylacetone (11.07 g, 0.1106 mol), 2,6-dichloroaniline (16.25 g, 0.1001 mol) and 2 drops of H₂SO₄(conc.) in 150 ml benzene was refluxed for 24 h in a Dean-Stark trap. The mixture was then filtered and left to crystallize by slow evaporation of the solvent yielding 23.53 g (72.37%) of cuboid crystals with lengths of up to 4 mm. The title compound is stable in air and light over a period of several months.

Structure description top

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 enaminoketonato 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).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); 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).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level [Symmetry code: (i) -x, y, -z + 1/2]. The various intramolecular hydrogen bonds and contacts are shown as dashed lines.
	Fig. 2. A view of the unit cell along the b axis of the crystal structure of the title compound, illustrating the intra- and intermolecular N—H···O hydrogen bonds (dashed yellow lines).

2,6-Dichloroaniline–4-(2,6-dichloroanilino)pent-3-en-2-one (1/2) top

Crystal data top

C₆H₅Cl₂N·2C₁₁H₁₁Cl₂NO	F(000) = 1336
M_r = 650.23	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0394P)² + 2.1199P] where P = (F_o² + 2F_c²)/3
3785 reflections	(Δ/σ)_max = 0.002
186 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³
46 constraints

Crystal data top

C₆H₅Cl₂N·2C₁₁H₁₁Cl₂NO	V = 3046.81 (9) Å³
M_r = 650.23	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.7140 (1) Å	µ = 0.60 mm⁻¹
b = 8.7210 (2) Å	T = 100 K
c = 22.9950 (4) Å	0.31 × 0.25 × 0.19 mm
β = 104.794 (1)°

Data collection top

Bruker X8 APEXII 4K KappaCCD diffractometer	3785 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3305 reflections with I > 2σ(I)
T_min = 0.837, T_max = 0.895	R_int = 0.034
34421 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.32 e Å⁻³
3785 reflections	Δρ_min = −0.23 e Å⁻³
186 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	C₆H₅Cl₂N·2C₁₁H₁₁Cl₂NO
M_r	650.23
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	15.7140 (1), 8.7210 (2), 22.9950 (4)
β (°)	104.794 (1)
V (Å³)	3046.81 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.31 × 0.25 × 0.19

Data collection
Diffractometer	Bruker X8 APEXII 4K KappaCCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.837, 0.895
No. of measured, independent and observed [I > 2σ(I)] reflections	34421, 3785, 3305
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.077, 1.04
No. of reflections	3785
No. of parameters	186
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.23

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

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)

Table 2. Comparative geometrical parameters (Å, °) for free N,O-bidendate (N,O-bid) compounds and coordinated dicarbonyl N,O-bidendate rhodium [Rh(N,O-bid)(CO)₂] complexes. top

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)	-

(I) This work. (II) 4-((2-Chloro-phenyl)amino)pent-3-en-2-one (Venter, Brink et al., 2012). (III) 4-(4-Methylphenylamino)pent-3-en-2-onate (Venter et al., 2010). (IV) Dicarbonyl-(4-(2,6-dimethylphenylamino)pent-3-en-2-onato- κ²N,O)-rhodium(I) (Venter, Steyl et al., 2012). (V) (2-Imino-4-pentanonato-κ²N,O) -carbonyl-triphenylphosphine-rhodium(I) (Damoense et al., 1994)]. a) The torsion angle between the phenyl ring and pentenone fragments.

Acknowledgements

Mr Leo Kirsten is thanked for the XRD data collection. Financial assistance from the University of the Free State Strategic Academic Cluster Initiative, SASOL, the South African National Research Foundation (SA-NRF/THRIP) and the Inkaba ye Afrika Research Initiative is gratefully acknowledged. Part of this material is based on work supported by the SA-NRF/THRIP under grant No. GUN 2068915. Opinions, findings, conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the SA-NRF.

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