N-(3,5-Dichloro­phen­yl)maleamic acid

Gowda, B.T.; Tokarčík, M.; Kožíšek, J.; Shakuntala, K.; Fuess, H.

doi:10.1107/S1600536809051484

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o51

doi:10.1107/S1600536809051484

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N-(3,5-Dichlorophenyl)maleamic acid

B. Thimme Gowda,^a ^* Miroslav Tokarčík,^b Jozef Kožíšek,^b K. Shakuntala ^a and Hartmut Fuess ^c

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, ^bFaculty of Chemical and Food Technology, Slovak Technical University, Radlinského 9, SK-812 37 Bratislava, Slovak Republic, and ^cInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287, Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 20 November 2009; accepted 29 November 2009; online 4 December 2009)

In the title compound, C₁₀H₇Cl₂NO₃, the asymmetric unit contains four independent molecules, which are linked to each other by N—H⋯O hydrogen bonds. The molecular structure is stabilized by a short intramolecular O—H⋯O hydrogen bond within each maleamic acid unit. In the crystal, the molecules are linked into networks through N—H⋯O hydrogen bonds and intermolecular C—Cl⋯O=C contacts [Cl⋯O = 3.0897 (12) and 3.0797 (13) Å].

Related literature

For studies on the effect of ring- and side-chain substitutions on the crystal structures of amides, see: Gowda, Foro et al. (2009 ); Gowda, Tokarčík et al. (2009 ); Lo & Ng (2009 ); Prasad et al. (2002 ); Shakuntala et al. (2009 ). For short halogen–oxygen contacts, see: Fourmigué (2009 ). Kubicki (2004 ).

Experimental

Crystal data

C₁₀H₇Cl₂NO₃
M_r = 260.07
Triclinic, $[P \overline 1]$
a = 8.13786 (12) Å
b = 16.5293 (3) Å
c = 17.4170 (3) Å
α = 103.4502 (17)°
β = 100.6466 (15)°
γ = 99.5964 (15)°
V = 2184.79 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 295 K
0.59 × 0.51 × 0.22 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: analytical (CrysAlis PRO, Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.728, T_max = 0.887
46919 measured reflections
8204 independent reflections
6694 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.088
S = 1.09
8204 reflections
581 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O33ⁱ	0.86	2.07	2.9254 (17)	172
N21—H21⋯O13	0.86	2.05	2.8748 (18)	161
N31—H31⋯O43	0.86	2.09	2.9244 (19)	165
N41—H41⋯O23	0.86	2.07	2.9186 (18)	168
O12—H12A⋯O11	0.82	1.65	2.4680 (18)	175
O22—H22A⋯O21	0.82	1.64	2.4613 (17)	177
O32—H32A⋯O31	0.82	1.66	2.4772 (17)	177
O42—H42A⋯O41	0.82	1.65	2.4684 (18)	172
Symmetry code: (i) x+1, y-1, z-1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2002 ); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ) and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051484/dn2519sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051484/dn2519Isup2.hkl

checkCIF report

Comment top

In the present work, as a part of studying the effect of ring and side chain substitutions on the crystal structures of biologically significant amides (Gowda, Foro et al.,2009; Gowda, Tokarčík et al., 2009; Shakuntala et al., 2009; Prasad et al., 2002), the crystal structure of N-(3,5-dichlorophenyl)maleamic acid (I) has been determined.

The asymmetric unit of (I) contains four independent molecules linked to each other through N-H···O intermolecular hydrogen bonds(Table 1, Fig. 1). The conformations of the N—H and C=O bonds in the amide segment of the structure are anti to each other and those of the amide O atom and the carbonyl O atom of the acid segment are also anti to each other. But the amide O atom is anti to the H atom attached to the adjacent C atom, while the carboxyl O atom is syn to the H atom attached to its adjacent C atom (Fig.1). In the structure of (I), relatively rare anti conformation of the C=O and O—H bonds of the acid group has been observed, similar to that obsrved in N-phenylmaleamic acid (Lo & Ng, 2009), N-(3,4-dimethylphenyl)maleamic acid, N-(2,4,6-trimethylphenyl)- maleamic acid (Gowda,Tokarčík et al., 2009) and N-(2,5-dichlorophenyl)maleamic acid (Shakuntala et al., 2009).

Each maleamic unit includes a short intramolecular hydrogen O—H···O bond (Table 1). Bond lengths C12–C13 =1.329 (2), C22–C23 =1.336 (2), C32–C33 =1.335 (2) and C42–C43 =1.329 (2)Å clearly indicate the double bond character.

The dihedral angles between the dichloro-substituted phenyl ring and the amido group –NHCO– are 4.5 (3), 8.4 (2), 10.4 (2) and 8.3 (3)° in the four independent molecules.

In the crystal structure, the intermolecular N–H···O hydrogen bonds link the molecules into infinite chain running parallel to the [-1 1 1] vector. The relatively short Cl···O contacts build up a two-dimensional network. Part of the crystal structure is shown in Fig. 2. The molecule containing the amido atom N11 forms an inversion dimer, which is is stabilized by two short Cl···O contacts with the length of 3.0897 (12)Å. Another short Cl···O contact between the atoms Cl12 and O41(iii) has the length of 3.0797 (13) Å. [Symmetry code (iii): x, y-1, z-1].

Our data for the C–Cl···O halogen bonds are in agreement with the observations of others (Kubicki, 2004; Fourmigué 2009).

Related literature top

For sudies on the effect of ring- and side-chain substitutions on the crystal structures of amides, see: Gowda, Foro et al. (2009); Gowda, Tokarčík et al. (2009); Lo & Ng (2009); Prasad et al. (2002); Shakuntala et al. (2009). For short halogen–oxygen contacts, see: Fourmigué (2009). Kubicki (2004)

Experimental top

The solution of maleic anhydride (0.025 mol) in toluene (25 ml) was treated dropwise with the solution of 3,5-dichloroaniline (0.025 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was warmed with stirring for over 30 min and set aside for an additional 30 min at room temperature for completion of the reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 3,5-dichloroaniline. The resultant solid N-(3,5-dichlorophenyl)maleamic acid was filtered under suction and washed thoroughly with water to remove the unreacted maleic anhydride and maleic acid. It was recrystallized to constant melting point from ethanol. The purity of the compound was checked by elemental analysis and characterized by its infrared spectra. Colourless single crystals used in X-ray diffraction studies were grown in an ethanol solution by slow evaporation at room temperature.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of (I) showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. Part of crystal structure of (I) showing the chain of molecules linked by N–H···O hydrogen bonds (represented by dashed lines). The molecule with the amido atom N11 forms an inversion dimer stabilized via short Cl···O contacts involving the atoms Cl11 and O11.H atoms not involved in hydrogen bonding were omitted for clarity.[Symmetry code (ii): -x, -y, -z]

N-(3,5-Dichlorophenyl)maleamic acid top

Crystal data top

C₁₀H₇Cl₂NO₃	Z = 8
M_r = 260.07	F(000) = 1056
Triclinic, P1	D_x = 1.581 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.13786 (12) Å	Cell parameters from 29193 reflections
b = 16.5293 (3) Å	θ = 2.0–29.5°
c = 17.4170 (3) Å	µ = 0.58 mm⁻¹
α = 103.4502 (17)°	T = 295 K
β = 100.6466 (15)°	Block, colourless
γ = 99.5964 (15)°	0.59 × 0.51 × 0.22 mm
V = 2184.79 (7) Å³

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	8204 independent reflections
Graphite monochromator	6694 reflections with I > 2σ(I)
Detector resolution: 10.434 pixels mm^-1	R_int = 0.017
ω scans	θ_max = 25.6°, θ_min = 2.0°
Absorption correction: analytical (CrysAlis PRO, Oxford Diffraction, 2009)	h = −9→9
T_min = 0.728, T_max = 0.887	k = −20→20
46919 measured reflections	l = −21→21

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0445P)² + 0.4698P] where P = (F_o² + 2F_c²)/3
8204 reflections	(Δ/σ)_max = 0.001
581 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₀H₇Cl₂NO₃	γ = 99.5964 (15)°
M_r = 260.07	V = 2184.79 (7) Å³
Triclinic, P1	Z = 8
a = 8.13786 (12) Å	Mo Kα radiation
b = 16.5293 (3) Å	µ = 0.58 mm⁻¹
c = 17.4170 (3) Å	T = 295 K
α = 103.4502 (17)°	0.59 × 0.51 × 0.22 mm
β = 100.6466 (15)°

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	8204 independent reflections
Absorption correction: analytical (CrysAlis PRO, Oxford Diffraction, 2009)	6694 reflections with I > 2σ(I)
T_min = 0.728, T_max = 0.887	R_int = 0.017
46919 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.09	Δρ_max = 0.45 e Å⁻³
8204 reflections	Δρ_min = −0.38 e Å⁻³
581 parameters

Special details top

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 > 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.

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

	x	y	z	U_iso*/U_eq
Cl11	−0.12991 (7)	−0.13131 (3)	−0.04861 (4)	0.07207 (17)
Cl12	0.08943 (6)	−0.35296 (3)	−0.26076 (3)	0.05786 (14)
O11	0.38762 (19)	0.06550 (8)	−0.04674 (10)	0.0728 (5)
O12	0.51265 (18)	0.21919 (9)	0.01320 (10)	0.0688 (4)
H12A	0.4669	0.1684	−0.0054	0.103*
O13	0.72670 (19)	0.30909 (8)	0.00178 (9)	0.0716 (4)
N11	0.42407 (17)	−0.04601 (8)	−0.14019 (8)	0.0403 (3)
H11	0.4904	−0.0625	−0.1709	0.048*
C11	0.4692 (2)	0.03579 (11)	−0.09563 (10)	0.0439 (4)
C12	0.6215 (2)	0.08687 (11)	−0.10927 (11)	0.0473 (4)
H12	0.6767	0.0576	−0.1453	0.057*
C13	0.6907 (2)	0.16943 (11)	−0.07690 (11)	0.0499 (4)
H13	0.7879	0.1886	−0.0941	0.060*
C14	0.6420 (2)	0.23697 (11)	−0.01833 (11)	0.0465 (4)
C15	0.2796 (2)	−0.10786 (10)	−0.14214 (9)	0.0369 (3)
C16	0.1585 (2)	−0.08976 (11)	−0.09764 (11)	0.0448 (4)
H16	0.1701	−0.0354	−0.0641	0.054*
C17	0.0209 (2)	−0.15445 (11)	−0.10443 (11)	0.0449 (4)
C18	−0.0017 (2)	−0.23577 (11)	−0.15278 (10)	0.0424 (4)
H18	−0.0949	−0.2785	−0.1558	0.051*
C19	0.1201 (2)	−0.25142 (10)	−0.19677 (10)	0.0391 (4)
C20	0.2594 (2)	−0.18954 (10)	−0.19278 (10)	0.0382 (4)
H20	0.3390	−0.2019	−0.2233	0.046*
Cl21	0.84361 (9)	0.77742 (3)	0.13652 (4)	0.07855 (19)
Cl22	0.89486 (6)	0.54211 (3)	−0.12381 (3)	0.05692 (13)
O21	0.54916 (18)	0.52453 (8)	0.20423 (8)	0.0567 (3)
O22	0.4351 (2)	0.49126 (8)	0.31739 (8)	0.0650 (4)
H22A	0.4712	0.5037	0.2797	0.097*
O23	0.36320 (18)	0.37768 (9)	0.35801 (8)	0.0615 (4)
N21	0.63526 (17)	0.45503 (8)	0.09578 (8)	0.0396 (3)
H21	0.6386	0.4052	0.0680	0.048*
C21	0.5655 (2)	0.45722 (10)	0.16001 (10)	0.0391 (4)
C22	0.5086 (2)	0.37266 (11)	0.17328 (10)	0.0420 (4)
H22	0.5174	0.3261	0.1336	0.050*
C23	0.4463 (2)	0.35426 (11)	0.23449 (10)	0.0428 (4)
H23	0.4192	0.2963	0.2306	0.051*
C24	0.4128 (2)	0.40956 (12)	0.30745 (10)	0.0446 (4)
C25	0.7041 (2)	0.52430 (10)	0.06799 (10)	0.0381 (4)
C26	0.7260 (2)	0.60907 (11)	0.11038 (10)	0.0436 (4)
H26	0.6886	0.6236	0.1581	0.052*
C27	0.8047 (2)	0.67118 (11)	0.07996 (11)	0.0488 (4)
C28	0.8582 (2)	0.65292 (12)	0.00858 (11)	0.0491 (4)
H28	0.9105	0.6959	−0.0108	0.059*
C29	0.8309 (2)	0.56830 (12)	−0.03288 (10)	0.0428 (4)
C30	0.7562 (2)	0.50368 (11)	−0.00454 (10)	0.0407 (4)
H30	0.7407	0.4470	−0.0335	0.049*
Cl31	0.55958 (9)	1.27986 (3)	0.76423 (5)	0.0959 (2)
Cl32	0.82403 (7)	1.05115 (3)	0.58042 (4)	0.07005 (16)
O31	0.12442 (17)	1.02362 (8)	0.74663 (8)	0.0571 (3)
O32	−0.15047 (18)	0.99017 (9)	0.78660 (10)	0.0684 (4)
H32A	−0.0581	1.0026	0.7750	0.103*
O33	−0.36446 (17)	0.87993 (9)	0.75591 (9)	0.0645 (4)
N31	0.25893 (18)	0.96191 (9)	0.65386 (9)	0.0436 (3)
H31	0.2552	0.9152	0.6185	0.052*
C31	0.1331 (2)	0.96077 (10)	0.69387 (10)	0.0411 (4)
C32	0.0088 (2)	0.87797 (11)	0.67137 (10)	0.0433 (4)
H32	0.0355	0.8333	0.6359	0.052*
C33	−0.1363 (2)	0.85857 (11)	0.69501 (11)	0.0450 (4)
H33	−0.1929	0.8016	0.6743	0.054*
C34	−0.2235 (2)	0.91137 (12)	0.74824 (11)	0.0485 (4)
C35	0.3974 (2)	1.03050 (10)	0.66258 (10)	0.0412 (4)
C36	0.4083 (2)	1.11348 (11)	0.70717 (11)	0.0496 (4)
H36	0.3236	1.1269	0.7340	0.060*
C37	0.5476 (3)	1.17524 (11)	0.71059 (12)	0.0547 (5)
C38	0.6779 (2)	1.15837 (12)	0.67291 (12)	0.0549 (5)
H38	0.7719	1.2011	0.6770	0.066*
C39	0.6626 (2)	1.07548 (11)	0.62901 (12)	0.0487 (4)
C40	0.5251 (2)	1.01120 (11)	0.62243 (11)	0.0461 (4)
H40	0.5174	0.9559	0.5918	0.055*
Cl41	−0.02282 (7)	0.37735 (4)	0.72019 (3)	0.06395 (15)
Cl42	0.24811 (9)	0.16293 (3)	0.52385 (4)	0.07410 (17)
O41	0.1923 (2)	0.57709 (8)	0.57929 (9)	0.0737 (5)
O42	0.2233 (2)	0.73192 (9)	0.59737 (10)	0.0750 (5)
H42A	0.2170	0.6815	0.5957	0.112*
O43	0.3060 (2)	0.81990 (8)	0.53013 (9)	0.0711 (4)
N41	0.24994 (17)	0.46304 (8)	0.49887 (8)	0.0410 (3)
H41	0.2850	0.4450	0.4557	0.049*
C41	0.2470 (2)	0.54591 (10)	0.52001 (10)	0.0425 (4)
C42	0.3126 (2)	0.59666 (11)	0.46873 (10)	0.0432 (4)
H42	0.3481	0.5668	0.4248	0.052*
C43	0.3275 (2)	0.67973 (11)	0.47709 (11)	0.0439 (4)
H43	0.3736	0.6988	0.4377	0.053*
C44	0.2847 (2)	0.74820 (11)	0.53737 (11)	0.0469 (4)
C45	0.2013 (2)	0.40192 (10)	0.54029 (10)	0.0385 (4)
C46	0.1217 (2)	0.41867 (11)	0.60458 (10)	0.0442 (4)
H46	0.0955	0.4716	0.6220	0.053*
C47	0.0823 (2)	0.35548 (12)	0.64202 (10)	0.0455 (4)
C48	0.1202 (2)	0.27686 (12)	0.61936 (11)	0.0501 (4)
H48	0.0949	0.2355	0.6462	0.060*
C49	0.1980 (2)	0.26185 (11)	0.55458 (11)	0.0474 (4)
C50	0.2381 (2)	0.32229 (11)	0.51464 (10)	0.0429 (4)
H50	0.2892	0.3100	0.4710	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl11	0.0741 (3)	0.0627 (3)	0.0933 (4)	0.0149 (3)	0.0646 (3)	0.0126 (3)
Cl12	0.0638 (3)	0.0411 (2)	0.0622 (3)	0.0011 (2)	0.0306 (2)	−0.0035 (2)
O11	0.0714 (9)	0.0484 (8)	0.0902 (10)	−0.0030 (7)	0.0571 (8)	−0.0163 (7)
O12	0.0658 (9)	0.0464 (8)	0.0823 (10)	0.0011 (6)	0.0405 (8)	−0.0155 (7)
O13	0.0817 (10)	0.0399 (8)	0.0843 (10)	−0.0005 (7)	0.0403 (8)	−0.0067 (7)
N11	0.0392 (7)	0.0373 (7)	0.0449 (8)	0.0084 (6)	0.0224 (6)	0.0021 (6)
C11	0.0439 (9)	0.0402 (9)	0.0457 (10)	0.0085 (7)	0.0197 (8)	0.0013 (7)
C12	0.0458 (9)	0.0426 (9)	0.0522 (10)	0.0093 (8)	0.0263 (8)	−0.0011 (8)
C13	0.0464 (10)	0.0436 (10)	0.0564 (11)	0.0031 (8)	0.0254 (9)	0.0015 (8)
C14	0.0483 (10)	0.0400 (10)	0.0467 (10)	0.0091 (8)	0.0138 (8)	0.0014 (8)
C15	0.0374 (8)	0.0384 (8)	0.0378 (8)	0.0094 (7)	0.0155 (7)	0.0097 (7)
C16	0.0499 (10)	0.0393 (9)	0.0482 (10)	0.0107 (7)	0.0257 (8)	0.0055 (7)
C17	0.0474 (9)	0.0476 (10)	0.0494 (10)	0.0155 (8)	0.0301 (8)	0.0137 (8)
C18	0.0420 (9)	0.0423 (9)	0.0464 (10)	0.0060 (7)	0.0195 (8)	0.0142 (8)
C19	0.0444 (9)	0.0367 (8)	0.0371 (9)	0.0101 (7)	0.0141 (7)	0.0073 (7)
C20	0.0389 (8)	0.0412 (9)	0.0383 (9)	0.0125 (7)	0.0176 (7)	0.0086 (7)
Cl21	0.1164 (5)	0.0404 (3)	0.0771 (4)	0.0009 (3)	0.0463 (3)	0.0053 (2)
Cl22	0.0648 (3)	0.0712 (3)	0.0456 (3)	0.0192 (2)	0.0299 (2)	0.0205 (2)
O21	0.0796 (9)	0.0398 (7)	0.0569 (8)	0.0105 (6)	0.0441 (7)	0.0048 (6)
O22	0.0947 (11)	0.0524 (8)	0.0509 (8)	0.0086 (7)	0.0460 (8)	0.0027 (6)
O23	0.0785 (9)	0.0694 (9)	0.0479 (7)	0.0176 (7)	0.0363 (7)	0.0195 (7)
N21	0.0481 (8)	0.0355 (7)	0.0384 (7)	0.0110 (6)	0.0213 (6)	0.0062 (6)
C21	0.0393 (8)	0.0412 (9)	0.0369 (8)	0.0082 (7)	0.0161 (7)	0.0053 (7)
C22	0.0486 (9)	0.0392 (9)	0.0395 (9)	0.0103 (7)	0.0207 (8)	0.0046 (7)
C23	0.0453 (9)	0.0417 (9)	0.0434 (9)	0.0087 (7)	0.0185 (8)	0.0096 (7)
C24	0.0418 (9)	0.0541 (11)	0.0377 (9)	0.0076 (8)	0.0163 (7)	0.0087 (8)
C25	0.0348 (8)	0.0431 (9)	0.0390 (9)	0.0095 (7)	0.0124 (7)	0.0124 (7)
C26	0.0469 (9)	0.0433 (9)	0.0414 (9)	0.0086 (7)	0.0183 (8)	0.0079 (7)
C27	0.0556 (11)	0.0399 (9)	0.0498 (10)	0.0067 (8)	0.0178 (9)	0.0083 (8)
C28	0.0523 (10)	0.0485 (10)	0.0506 (11)	0.0068 (8)	0.0193 (9)	0.0186 (8)
C29	0.0386 (9)	0.0576 (11)	0.0378 (9)	0.0142 (8)	0.0152 (7)	0.0160 (8)
C30	0.0422 (9)	0.0440 (9)	0.0377 (9)	0.0131 (7)	0.0137 (7)	0.0087 (7)
Cl31	0.1081 (5)	0.0399 (3)	0.1330 (6)	−0.0019 (3)	0.0686 (4)	−0.0086 (3)
Cl32	0.0627 (3)	0.0547 (3)	0.1095 (5)	0.0189 (2)	0.0499 (3)	0.0271 (3)
O31	0.0623 (8)	0.0436 (7)	0.0635 (8)	0.0072 (6)	0.0343 (7)	−0.0014 (6)
O32	0.0652 (9)	0.0518 (8)	0.0915 (11)	0.0138 (7)	0.0504 (8)	0.0001 (7)
O33	0.0522 (8)	0.0674 (9)	0.0782 (10)	0.0122 (7)	0.0375 (7)	0.0113 (7)
N31	0.0513 (8)	0.0350 (7)	0.0469 (8)	0.0084 (6)	0.0234 (7)	0.0070 (6)
C31	0.0454 (9)	0.0399 (9)	0.0425 (9)	0.0141 (7)	0.0181 (8)	0.0101 (7)
C32	0.0480 (9)	0.0381 (9)	0.0457 (9)	0.0127 (7)	0.0201 (8)	0.0058 (7)
C33	0.0466 (9)	0.0407 (9)	0.0484 (10)	0.0093 (7)	0.0191 (8)	0.0076 (8)
C34	0.0488 (10)	0.0524 (11)	0.0527 (11)	0.0176 (8)	0.0249 (9)	0.0153 (9)
C35	0.0481 (9)	0.0390 (9)	0.0409 (9)	0.0102 (7)	0.0163 (7)	0.0143 (7)
C36	0.0581 (11)	0.0413 (9)	0.0537 (11)	0.0109 (8)	0.0260 (9)	0.0106 (8)
C37	0.0675 (12)	0.0364 (9)	0.0604 (12)	0.0077 (8)	0.0254 (10)	0.0075 (8)
C38	0.0542 (11)	0.0417 (10)	0.0703 (13)	0.0037 (8)	0.0220 (10)	0.0172 (9)
C39	0.0502 (10)	0.0453 (10)	0.0608 (11)	0.0153 (8)	0.0240 (9)	0.0217 (9)
C40	0.0529 (10)	0.0376 (9)	0.0540 (11)	0.0131 (8)	0.0221 (8)	0.0143 (8)
Cl41	0.0705 (3)	0.0751 (3)	0.0505 (3)	0.0069 (3)	0.0327 (2)	0.0171 (2)
Cl42	0.1134 (5)	0.0526 (3)	0.0719 (4)	0.0381 (3)	0.0316 (3)	0.0251 (3)
O41	0.1289 (13)	0.0460 (8)	0.0721 (9)	0.0321 (8)	0.0727 (10)	0.0180 (7)
O42	0.1258 (13)	0.0440 (8)	0.0763 (10)	0.0302 (9)	0.0658 (10)	0.0158 (7)
O43	0.1044 (12)	0.0400 (8)	0.0795 (10)	0.0188 (7)	0.0456 (9)	0.0158 (7)
N41	0.0503 (8)	0.0369 (7)	0.0386 (7)	0.0099 (6)	0.0229 (6)	0.0058 (6)
C41	0.0498 (10)	0.0388 (9)	0.0419 (9)	0.0124 (7)	0.0206 (8)	0.0070 (7)
C42	0.0509 (10)	0.0430 (9)	0.0402 (9)	0.0142 (8)	0.0226 (8)	0.0077 (7)
C43	0.0477 (9)	0.0433 (9)	0.0453 (10)	0.0106 (7)	0.0200 (8)	0.0135 (8)
C44	0.0528 (10)	0.0375 (10)	0.0507 (10)	0.0097 (8)	0.0177 (8)	0.0083 (8)
C45	0.0377 (8)	0.0378 (8)	0.0381 (9)	0.0043 (7)	0.0111 (7)	0.0077 (7)
C46	0.0455 (9)	0.0420 (9)	0.0443 (9)	0.0063 (7)	0.0175 (8)	0.0070 (8)
C47	0.0408 (9)	0.0547 (11)	0.0373 (9)	0.0012 (8)	0.0125 (7)	0.0094 (8)
C48	0.0530 (10)	0.0519 (11)	0.0455 (10)	0.0040 (8)	0.0106 (8)	0.0194 (8)
C49	0.0526 (10)	0.0426 (9)	0.0461 (10)	0.0119 (8)	0.0090 (8)	0.0110 (8)
C50	0.0453 (9)	0.0436 (9)	0.0392 (9)	0.0098 (7)	0.0135 (7)	0.0072 (7)

Geometric parameters (Å, º) top

Cl11—C17	1.7383 (15)	Cl31—C37	1.7410 (18)
Cl12—C19	1.7347 (16)	Cl32—C39	1.7412 (18)
O11—C11	1.2370 (19)	O31—C31	1.2383 (19)
O12—C14	1.297 (2)	O32—C34	1.299 (2)
O12—H12A	0.8200	O32—H32A	0.8200
O13—C14	1.209 (2)	O33—C34	1.222 (2)
N11—C11	1.344 (2)	N31—C31	1.341 (2)
N11—C15	1.413 (2)	N31—C35	1.417 (2)
N11—H11	0.8600	N31—H31	0.8600
C11—C12	1.469 (2)	C31—C32	1.481 (2)
C12—C13	1.329 (2)	C32—C33	1.335 (2)
C12—H12	0.9300	C32—H32	0.9300
C13—C14	1.487 (2)	C33—C34	1.483 (2)
C13—H13	0.9300	C33—H33	0.9300
C15—C16	1.390 (2)	C35—C36	1.390 (2)
C15—C20	1.395 (2)	C35—C40	1.395 (2)
C16—C17	1.380 (2)	C36—C37	1.375 (3)
C16—H16	0.9300	C36—H36	0.9300
C17—C18	1.372 (2)	C37—C38	1.380 (3)
C18—C19	1.382 (2)	C38—C39	1.378 (3)
C18—H18	0.9300	C38—H38	0.9300
C19—C20	1.374 (2)	C39—C40	1.376 (2)
C20—H20	0.9300	C40—H40	0.9300
Cl21—C27	1.7462 (18)	Cl41—C47	1.7382 (17)
Cl22—C29	1.7400 (16)	Cl42—C49	1.7383 (18)
O21—C21	1.2399 (19)	O41—C41	1.236 (2)
O22—C24	1.298 (2)	O42—C44	1.301 (2)
O22—H22A	0.8200	O42—H42A	0.8200
O23—C24	1.222 (2)	O43—C44	1.208 (2)
N21—C21	1.341 (2)	N41—C41	1.339 (2)
N21—C25	1.415 (2)	N41—C45	1.417 (2)
N21—H21	0.8600	N41—H41	0.8600
C21—C22	1.482 (2)	C41—C42	1.470 (2)
C22—C23	1.336 (2)	C42—C43	1.329 (2)
C22—H22	0.9300	C42—H42	0.9300
C23—C24	1.482 (2)	C43—C44	1.490 (2)
C23—H23	0.9300	C43—H43	0.9300
C25—C26	1.388 (2)	C45—C50	1.389 (2)
C25—C30	1.392 (2)	C45—C46	1.391 (2)
C26—C27	1.380 (2)	C46—C47	1.379 (2)
C26—H26	0.9300	C46—H46	0.9300
C27—C28	1.377 (2)	C47—C48	1.371 (3)
C28—C29	1.376 (2)	C48—C49	1.386 (3)
C28—H28	0.9300	C48—H48	0.9300
C29—C30	1.376 (2)	C49—C50	1.374 (2)
C30—H30	0.9300	C50—H50	0.9300

C14—O12—H12A	109.5	C34—O32—H32A	109.5
C11—N11—C15	127.15 (13)	C31—N31—C35	128.06 (14)
C11—N11—H11	116.4	C31—N31—H31	116.0
C15—N11—H11	116.4	C35—N31—H31	116.0
O11—C11—N11	122.01 (15)	O31—C31—N31	122.38 (16)
O11—C11—C12	122.74 (15)	O31—C31—C32	122.95 (15)
N11—C11—C12	115.25 (13)	N31—C31—C32	114.65 (14)
C13—C12—C11	128.48 (15)	C33—C32—C31	128.94 (15)
C13—C12—H12	115.8	C33—C32—H32	115.5
C11—C12—H12	115.8	C31—C32—H32	115.5
C12—C13—C14	132.18 (16)	C32—C33—C34	131.68 (17)
C12—C13—H13	113.9	C32—C33—H33	114.2
C14—C13—H13	113.9	C34—C33—H33	114.2
O13—C14—O12	119.44 (16)	O33—C34—O32	120.35 (16)
O13—C14—C13	119.61 (16)	O33—C34—C33	119.38 (17)
O12—C14—C13	120.92 (15)	O32—C34—C33	120.27 (15)
C16—C15—C20	120.07 (15)	C36—C35—C40	120.31 (16)
C16—C15—N11	122.84 (14)	C36—C35—N31	123.30 (15)
C20—C15—N11	117.07 (13)	C40—C35—N31	116.38 (15)
C17—C16—C15	118.37 (15)	C37—C36—C35	118.29 (16)
C17—C16—H16	120.8	C37—C36—H36	120.9
C15—C16—H16	120.8	C35—C36—H36	120.9
C18—C17—C16	123.10 (15)	C36—C37—C38	123.09 (17)
C18—C17—Cl11	118.80 (13)	C36—C37—Cl31	118.59 (14)
C16—C17—Cl11	118.10 (13)	C38—C37—Cl31	118.31 (14)
C17—C18—C19	117.05 (15)	C39—C38—C37	117.04 (17)
C17—C18—H18	121.5	C39—C38—H38	121.5
C19—C18—H18	121.5	C37—C38—H38	121.5
C20—C19—C18	122.50 (15)	C40—C39—C38	122.49 (16)
C20—C19—Cl12	119.90 (12)	C40—C39—Cl32	118.83 (14)
C18—C19—Cl12	117.58 (12)	C38—C39—Cl32	118.68 (14)
C19—C20—C15	118.89 (14)	C39—C40—C35	118.75 (16)
C19—C20—H20	120.6	C39—C40—H40	120.6
C15—C20—H20	120.6	C35—C40—H40	120.6
C24—O22—H22A	109.5	C44—O42—H42A	109.5
C21—N21—C25	128.20 (14)	C41—N41—C45	126.76 (13)
C21—N21—H21	115.9	C41—N41—H41	116.6
C25—N21—H21	115.9	C45—N41—H41	116.6
O21—C21—N21	122.61 (15)	O41—C41—N41	121.40 (16)
O21—C21—C22	122.90 (14)	O41—C41—C42	122.65 (15)
N21—C21—C22	114.48 (13)	N41—C41—C42	115.95 (13)
C23—C22—C21	128.81 (15)	C43—C42—C41	128.27 (15)
C23—C22—H22	115.6	C43—C42—H42	115.9
C21—C22—H22	115.6	C41—C42—H42	115.9
C22—C23—C24	131.60 (16)	C42—C43—C44	132.34 (16)
C22—C23—H23	114.2	C42—C43—H43	113.8
C24—C23—H23	114.2	C44—C43—H43	113.8
O23—C24—O22	120.20 (16)	O43—C44—O42	119.42 (16)
O23—C24—C23	119.55 (17)	O43—C44—C43	119.52 (17)
O22—C24—C23	120.24 (15)	O42—C44—C43	121.06 (16)
C26—C25—C30	120.11 (15)	C50—C45—C46	119.75 (15)
C26—C25—N21	123.43 (14)	C50—C45—N41	117.07 (14)
C30—C25—N21	116.42 (14)	C46—C45—N41	123.17 (15)
C27—C26—C25	118.29 (15)	C47—C46—C45	118.83 (16)
C27—C26—H26	120.9	C47—C46—H46	120.6
C25—C26—H26	120.9	C45—C46—H46	120.6
C28—C27—C26	123.00 (16)	C48—C47—C46	122.88 (16)
C28—C27—Cl21	118.79 (14)	C48—C47—Cl41	119.41 (14)
C26—C27—Cl21	118.18 (13)	C46—C47—Cl41	117.70 (14)
C29—C28—C27	117.17 (16)	C47—C48—C49	116.89 (16)
C29—C28—H28	121.4	C47—C48—H48	121.6
C27—C28—H28	121.4	C49—C48—H48	121.6
C30—C29—C28	122.29 (15)	C50—C49—C48	122.50 (16)
C30—C29—Cl22	118.87 (13)	C50—C49—Cl42	119.14 (14)
C28—C29—Cl22	118.84 (13)	C48—C49—Cl42	118.36 (14)
C29—C30—C25	119.10 (15)	C49—C50—C45	119.13 (15)
C29—C30—H30	120.4	C49—C50—H50	120.4
C25—C30—H30	120.4	C45—C50—H50	120.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O33ⁱ	0.86	2.07	2.9254 (17)	172
N21—H21···O13	0.86	2.05	2.8748 (18)	161
N31—H31···O43	0.86	2.09	2.9244 (19)	165
N41—H41···O23	0.86	2.07	2.9186 (18)	168
O12—H12A···O11	0.82	1.65	2.4680 (18)	175
O22—H22A···O21	0.82	1.64	2.4613 (17)	177
O32—H32A···O31	0.82	1.66	2.4772 (17)	177
O42—H42A···O41	0.82	1.65	2.4684 (18)	172

Symmetry code: (i) x+1, y−1, z−1.

Experimental details

Crystal data
Chemical formula	C₁₀H₇Cl₂NO₃
M_r	260.07
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	8.13786 (12), 16.5293 (3), 17.4170 (3)
α, β, γ (°)	103.4502 (17), 100.6466 (15), 99.5964 (15)
V (Å³)	2184.79 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.59 × 0.51 × 0.22

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction	Analytical (CrysAlis PRO, Oxford Diffraction, 2009)
T_min, T_max	0.728, 0.887
No. of measured, independent and observed [I > 2σ(I)] reflections	46919, 8204, 6694
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.088, 1.09
No. of reflections	8204
No. of parameters	581
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.38

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O33ⁱ	0.86	2.07	2.9254 (17)	171.6
N21—H21···O13	0.86	2.05	2.8748 (18)	160.5
N31—H31···O43	0.86	2.09	2.9244 (19)	165.0
N41—H41···O23	0.86	2.07	2.9186 (18)	168.0
O12—H12A···O11	0.82	1.65	2.4680 (18)	175.3
O22—H22A···O21	0.82	1.64	2.4613 (17)	177.0
O32—H32A···O31	0.82	1.66	2.4772 (17)	176.8
O42—H42A···O41	0.82	1.65	2.4684 (18)	172.4

Symmetry code: (i) x+1, y−1, z−1.

Acknowledgements

MT and JK thank the Grant Agency of the Slovak Republic (VEGA 1/0817/08) and Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer.

References

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