N-(2,4,5-Trichloro­phen­yl)maleamic acid

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

doi:10.1107/S1600536809052520

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Pages o182-o183

doi:10.1107/S1600536809052520

Open

access

N-(2,4,5-Trichlorophenyl)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 26 November 2009; accepted 7 December 2009; online 16 December 2009)

The title compound, C₁₀H₆Cl₃NO₃, crystallizes with two independent molecules in the asymmetric unit. The molecular structure is stabilized by a short intramolecular O—H⋯O hydrogen bond within the maleamic unit. In the crystal, each molecule self-associates via N—H⋯O hydrogen bonds into chains, each running along the b axis. Two short intermolecular Cl⋯O contacts [3.1267 (15) and 3.0523 (12) Å] and C—H⋯O interactions interconnect these chains into a three-dimensional network.

Related literature

For studies on the effect of ring- and side-chain substitutions on the crystal structures of amides, see: Gowda et al. (2009 , 2010 ); Lo & Ng (2009 ); Prasad et al. (2002 ); Shakuntala et al. (2009 ). For the concept of orthogonality of halogen and hydrogen bonds, see: Voth et al. (2009 ). For a review on short halogen–oxygen contacts, see: Fourmigué (2009 ); Kubicki (2004 ).

Experimental

Crystal data

C₁₀H₆Cl₃NO₃
M_r = 294.51
Monoclinic, P 2₁ /c
a = 10.8979 (2) Å
b = 11.0225 (2) Å
c = 19.4739 (3) Å
β = 95.4761 (9)°
V = 2328.57 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 295 K
0.34 × 0.25 × 0.22 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.794, T_max = 0.852
49446 measured reflections
4424 independent reflections
3825 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.079
S = 1.06
4424 reflections
315 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1	0.82	1.69	2.5080 (15)	175
O5—H5A⋯O4	0.82	1.72	2.5332 (17)	175
N1—H1N⋯O3ⁱ	0.77 (2)	2.30 (2)	3.0356 (18)	161.2 (19)
N2—H2N⋯O6ⁱⁱ	0.81 (2)	2.481 (19)	3.0775 (19)	131.3 (16)
N1—H1N⋯Cl1	0.77 (2)	2.56 (2)	2.9628 (14)	114.2 (17)
N2—H2N⋯Cl4	0.81 (2)	2.519 (18)	2.9476 (14)	114.3 (15)
C2—H2⋯O3ⁱ	0.93	2.29	3.123 (2)	149
C12—H12⋯O2	0.93	2.47	3.330 (2)	154
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Halogen-bond geometry (Å, °)

C—Cl⋯O	Cl⋯O	C—Cl⋯O
C9—Cl3⋯O6ⁱⁱⁱ	3.1267 (15)	158.99 (6)
C16—Cl4⋯O1	3.0523 (12)	159.62 (7)
Symmetry code: (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}.]$

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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/S1600536809052520/tk2591sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052520/tk2591Isup2.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 et al., 2009, 2010; Shakuntala et al., 2009; Prasad et al., 2002), the crystal structure of N-(2,4,5-trichlorophenyl)-maleamic acid (I) has been determined. The asymmetric unit of (I) contains two independent molecules (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 the amide-O atom and the carbonyl-O atom of the acid segment are also anti to each other. Further, the amide-O atom is anti to the H atom attached to the adjacent C atom, while the carbonyl-O atom is syn to the H atom attached to its adjacent C atom (Fig.1). In the structure, a rare anti conformation of the C=O and O—H bonds of the acid group has been observed, similar to that observed in N-phenylmaleamic acid (Lo & Ng, 2009), N-(2,5-dichlorophenyl)maleamic acid (Shakuntala et al., 2009), N-(3,5-dichlorophenyl)maleamic acid (Gowda et al., 2010) and N-(2,4,6-dimethylphenyl)maleamic acid (Gowda et al., 2009). Further, the conformation of the N—H bond is syn to the 2-Cl in the phenyl ring, while it is anti to the 5-Cl in the ring. Each maleamic unit includes a short intramolecular hydrogen O—H···O bond (Table 1). The bond lengths of C2–C3 and C12–C13 (i.e. 1.329 (2) and 1.328 (2) Å) clearly indicate double bond character.

In both the molecules, the dihedral angle between the amido group –NHCO– and the tri-substituted phenyl ring is 6.1 (3)°. The two N—H···O hydrogen bonds have quite different geometry, as seen in the N—H···O angles (Table 1). Remarkably small N2—H2N···O6ⁱⁱ angle of 131.3 (16)° can be attributed to the competing effect of the neighbouring C9—Cl3···O6ⁱⁱⁱ halogen bond. The angle Cl3···O6ⁱⁱⁱ···H2N =78.24 (6)° is close to 90° and can be interpreted within the concept of orthogonality of halogen and hydrogen bonds (Voth et al., 2009). The N1—H1N···O3ⁱ hydrogen bond with the angle of 161.2 (19)° is much less influenced by the near C6—Cl1···O3ⁱ halogen bond, which is weaker as indicated by the Cl1···O3ⁱ contact of 3.2372 (13) A. [Symmetry codes: (i) -x + 1, y + 1/2, -z + 3/2; (ii) -x, y + 1/2, -z + 3/2; (iii) x, -y + 1/2, z - 1/2.]

In the crystal of (I), the intermolecular N–H···O hydrogen bonds link the molecules, which self-associate, into infinite chains running along the b axis. These chains are connected through relatively short Cl···O contacts: Cl4···O1 =3.0523 (12), Cl3···O6(iii) =3.1267 (15) Å. [Symmetry codes: (iii) x, -y + 1/2, z - 1/2].(iii) x, -y + 1/2, z - 1/2] as well as C–H···O contacts to consolidate the crystal packing. Fig. 2 outlines part of the crystal structure of (I) with the N–H···O hydrogen bonding and Cl···O contacts highlighted. The data for the C–Cl···O halogen bonds are in agreement with others (Kubicki, 2004; Fourmigué, 2009).

Related literature top

For studies on the effect of ring- and side-chain substitutions on the crystal structures of amides, see: Gowda et al. (2009, 2010); Lo & Ng (2009); Prasad et al. (2002); Shakuntala et al. (2009). For the concept of orthogonality of halogen and hydrogen bonds, see: Voth et al. (2009). For a review on 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 drop-wise with the solution of 2,4,5-trichloroaniline (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 2,4,5-trichloroaniline. The resultant solid N-(2,4,5-trichlorophenyl)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 the two independent molecules comprising the asymmetric unit in (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.
	Fig. 2. Part of crystal structure of (I) showing the main intermolecular interactions: N–H···O hydrogen bonds and short Cl···O contacts (all represented by dashed lines). Symmetry codes: (i) -x + 1, y + 1/2, -z + 3/2; (ii) -x, y + 1/2, -z + 3/2; (iii) x, -y + 1/2, z - 1/2.

N-(2,4,5-Trichlorophenyl)maleamic acid top

Crystal data top

C₁₀H₆Cl₃NO₃	F(000) = 1184
M_r = 294.51	D_x = 1.68 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 30027 reflections
a = 10.8979 (2) Å	θ = 1.8–29.5°
b = 11.0225 (2) Å	µ = 0.78 mm⁻¹
c = 19.4739 (3) Å	T = 295 K
β = 95.4761 (9)°	Block, colourless
V = 2328.57 (7) Å³	0.34 × 0.25 × 0.22 mm
Z = 8

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector	4424 independent reflections
Graphite monochromator	3825 reflections with I > 2σ(I)
Detector resolution: 10.434 pixels mm^-1	R_int = 0.022
ω scans	θ_max = 25.7°, θ_min = 1.9°
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009)	h = −13→13
T_min = 0.794, T_max = 0.852	k = −13→13
49446 measured reflections	l = −23→23

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0464P)² + 0.5233P] where P = (F_o² + 2F_c²)/3
4424 reflections	(Δ/σ)_max = 0.001
315 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₀H₆Cl₃NO₃	V = 2328.57 (7) Å³
M_r = 294.51	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.8979 (2) Å	µ = 0.78 mm⁻¹
b = 11.0225 (2) Å	T = 295 K
c = 19.4739 (3) Å	0.34 × 0.25 × 0.22 mm
β = 95.4761 (9)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector	4424 independent reflections
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009)	3825 reflections with I > 2σ(I)
T_min = 0.794, T_max = 0.852	R_int = 0.022
49446 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.28 e Å⁻³
4424 reflections	Δρ_min = −0.32 e Å⁻³
315 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 > 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
C1	0.44390 (14)	0.49367 (14)	0.63260 (8)	0.0359 (3)
C2	0.49027 (16)	0.44723 (15)	0.70185 (8)	0.0435 (4)
H2	0.5531	0.4921	0.7254	0.052*
C3	0.45354 (16)	0.34984 (16)	0.73449 (8)	0.0437 (4)
H3	0.4945	0.3395	0.7782	0.052*
C4	0.36034 (14)	0.25383 (14)	0.71553 (8)	0.0353 (3)
C5	0.47664 (14)	0.65859 (13)	0.55063 (8)	0.0338 (3)
C6	0.55197 (15)	0.75667 (14)	0.53696 (8)	0.0390 (4)
C7	0.52840 (17)	0.82580 (15)	0.47808 (9)	0.0447 (4)
H7	0.5787	0.8917	0.4705	0.054*
C8	0.43056 (16)	0.79770 (15)	0.43042 (8)	0.0418 (4)
C9	0.35753 (15)	0.69853 (15)	0.44191 (8)	0.0385 (4)
C10	0.37961 (15)	0.63019 (14)	0.50161 (8)	0.0374 (3)
H10	0.3289	0.5645	0.5090	0.045*
N1	0.50133 (13)	0.59440 (12)	0.61283 (7)	0.0364 (3)
H1N	0.5504 (19)	0.6210 (18)	0.6398 (10)	0.047 (6)*
O1	0.36099 (12)	0.44379 (11)	0.59559 (6)	0.0524 (3)
O2	0.29633 (10)	0.25568 (10)	0.65501 (6)	0.0440 (3)
H2A	0.3156	0.3154	0.6334	0.053*
O3	0.34614 (11)	0.17281 (10)	0.75610 (6)	0.0439 (3)
Cl1	0.67690 (5)	0.79432 (5)	0.59434 (2)	0.06029 (15)
Cl2	0.40225 (5)	0.88690 (4)	0.35759 (3)	0.06031 (15)
Cl3	0.23559 (4)	0.65766 (5)	0.38355 (2)	0.05600 (14)
C11	−0.01578 (14)	0.08037 (14)	0.62405 (8)	0.0356 (3)
C12	0.05760 (15)	0.08711 (15)	0.69170 (8)	0.0405 (4)
H12	0.1200	0.1450	0.6953	0.049*
C13	0.04666 (15)	0.02176 (16)	0.74809 (8)	0.0429 (4)
H13	0.1058	0.0398	0.7843	0.051*
C14	−0.04107 (16)	−0.07430 (17)	0.76485 (9)	0.0468 (4)
C15	−0.04415 (14)	0.19115 (14)	0.51309 (7)	0.0348 (3)
C16	−0.00319 (16)	0.29029 (15)	0.47665 (8)	0.0393 (4)
C17	−0.05759 (17)	0.32085 (16)	0.41215 (8)	0.0450 (4)
H17	−0.0298	0.3880	0.3892	0.054*
C18	−0.15340 (16)	0.25164 (15)	0.38159 (8)	0.0410 (4)
C19	−0.19375 (15)	0.15206 (15)	0.41656 (8)	0.0374 (3)
C20	−0.14062 (15)	0.12225 (14)	0.48168 (8)	0.0380 (4)
H20	−0.1696	0.0557	0.5046	0.046*
N2	0.01228 (14)	0.16733 (13)	0.57959 (7)	0.0393 (3)
H2N	0.0613 (18)	0.2172 (17)	0.5962 (9)	0.044 (5)*
O4	−0.09307 (13)	0.00116 (12)	0.60847 (6)	0.0572 (4)
O5	−0.12126 (16)	−0.11735 (15)	0.71730 (7)	0.0818 (5)
H5A	−0.1146	−0.0818	0.6808	0.098*
O6	−0.03687 (14)	−0.11161 (13)	0.82354 (7)	0.0629 (4)
Cl4	0.11807 (5)	0.37788 (4)	0.51289 (2)	0.05662 (14)
Cl5	−0.22020 (5)	0.29035 (5)	0.30038 (2)	0.06325 (15)
Cl6	−0.31341 (4)	0.06298 (4)	0.38018 (2)	0.05475 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0387 (8)	0.0346 (8)	0.0336 (8)	−0.0062 (6)	−0.0006 (6)	−0.0020 (6)
C2	0.0481 (10)	0.0433 (9)	0.0364 (8)	−0.0128 (7)	−0.0103 (7)	−0.0004 (7)
C3	0.0486 (10)	0.0459 (9)	0.0335 (8)	−0.0075 (8)	−0.0123 (7)	0.0040 (7)
C4	0.0341 (8)	0.0345 (8)	0.0363 (8)	0.0035 (6)	−0.0014 (6)	0.0018 (7)
C5	0.0366 (8)	0.0325 (8)	0.0326 (7)	−0.0023 (6)	0.0044 (6)	−0.0035 (6)
C6	0.0420 (9)	0.0372 (8)	0.0376 (8)	−0.0096 (7)	0.0035 (7)	−0.0066 (7)
C7	0.0546 (10)	0.0372 (9)	0.0435 (9)	−0.0113 (7)	0.0107 (8)	−0.0004 (7)
C8	0.0498 (10)	0.0393 (9)	0.0372 (8)	0.0034 (7)	0.0095 (7)	0.0047 (7)
C9	0.0371 (8)	0.0426 (9)	0.0354 (8)	0.0011 (7)	0.0007 (7)	−0.0016 (7)
C10	0.0367 (8)	0.0378 (8)	0.0373 (8)	−0.0074 (7)	0.0012 (7)	0.0012 (7)
N1	0.0387 (7)	0.0359 (7)	0.0331 (7)	−0.0101 (6)	−0.0049 (6)	−0.0018 (6)
O1	0.0594 (8)	0.0510 (7)	0.0427 (6)	−0.0255 (6)	−0.0165 (6)	0.0126 (5)
O2	0.0467 (7)	0.0429 (6)	0.0398 (6)	−0.0156 (5)	−0.0099 (5)	0.0095 (5)
O3	0.0487 (7)	0.0372 (6)	0.0441 (6)	−0.0003 (5)	−0.0035 (5)	0.0105 (5)
Cl1	0.0609 (3)	0.0657 (3)	0.0520 (3)	−0.0323 (2)	−0.0066 (2)	−0.0027 (2)
Cl2	0.0741 (3)	0.0548 (3)	0.0516 (3)	0.0010 (2)	0.0036 (2)	0.0191 (2)
Cl3	0.0502 (3)	0.0696 (3)	0.0451 (2)	−0.0060 (2)	−0.01197 (19)	0.0054 (2)
C11	0.0355 (8)	0.0389 (8)	0.0320 (8)	−0.0030 (7)	0.0002 (6)	0.0020 (6)
C12	0.0358 (8)	0.0466 (9)	0.0377 (8)	−0.0102 (7)	−0.0041 (7)	0.0043 (7)
C13	0.0402 (9)	0.0516 (10)	0.0347 (8)	−0.0073 (7)	−0.0081 (7)	0.0046 (7)
C14	0.0491 (10)	0.0495 (10)	0.0403 (9)	−0.0074 (8)	−0.0043 (8)	0.0098 (8)
C15	0.0392 (8)	0.0366 (8)	0.0278 (7)	−0.0015 (6)	−0.0002 (6)	−0.0009 (6)
C16	0.0424 (9)	0.0405 (9)	0.0341 (8)	−0.0096 (7)	−0.0008 (7)	−0.0007 (7)
C17	0.0541 (10)	0.0454 (9)	0.0346 (8)	−0.0102 (8)	−0.0006 (7)	0.0069 (7)
C18	0.0465 (9)	0.0473 (9)	0.0282 (7)	−0.0003 (7)	−0.0024 (7)	0.0022 (7)
C19	0.0386 (8)	0.0404 (9)	0.0325 (8)	−0.0033 (7)	−0.0006 (6)	−0.0039 (6)
C20	0.0419 (9)	0.0375 (8)	0.0339 (8)	−0.0056 (7)	0.0006 (7)	0.0010 (6)
N2	0.0435 (8)	0.0411 (8)	0.0316 (7)	−0.0117 (6)	−0.0057 (6)	0.0031 (6)
O4	0.0698 (8)	0.0597 (8)	0.0385 (6)	−0.0307 (7)	−0.0139 (6)	0.0111 (6)
O5	0.0967 (12)	0.0929 (12)	0.0499 (8)	−0.0596 (10)	−0.0235 (8)	0.0280 (8)
O6	0.0715 (9)	0.0722 (9)	0.0433 (7)	−0.0173 (7)	−0.0040 (6)	0.0210 (6)
Cl4	0.0632 (3)	0.0586 (3)	0.0450 (2)	−0.0288 (2)	−0.0107 (2)	0.0078 (2)
Cl5	0.0709 (3)	0.0774 (3)	0.0373 (2)	−0.0156 (3)	−0.0160 (2)	0.0162 (2)
Cl6	0.0557 (3)	0.0606 (3)	0.0443 (2)	−0.0203 (2)	−0.0140 (2)	0.0024 (2)

Geometric parameters (Å, º) top

C1—O1	1.2304 (18)	C11—O4	1.2309 (19)
C1—N1	1.349 (2)	C11—N2	1.346 (2)
C1—C2	1.485 (2)	C11—C12	1.476 (2)
C2—C3	1.329 (2)	C12—C13	1.328 (2)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.489 (2)	C13—C14	1.484 (2)
C3—H3	0.9300	C13—H13	0.9300
C4—O3	1.2121 (18)	C14—O6	1.211 (2)
C4—O2	1.3111 (18)	C14—O5	1.301 (2)
C5—C10	1.391 (2)	C15—C20	1.390 (2)
C5—C6	1.398 (2)	C15—C16	1.399 (2)
C5—N1	1.406 (2)	C15—N2	1.404 (2)
C6—C7	1.380 (2)	C16—C17	1.379 (2)
C6—Cl1	1.7274 (16)	C16—Cl4	1.7315 (16)
C7—C8	1.380 (3)	C17—C18	1.381 (2)
C7—H7	0.9300	C17—H17	0.9300
C8—C9	1.383 (2)	C18—C19	1.385 (2)
C8—Cl2	1.7292 (16)	C18—Cl5	1.7301 (16)
C9—C10	1.387 (2)	C19—C20	1.382 (2)
C9—Cl3	1.7240 (16)	C19—Cl6	1.7292 (16)
C10—H10	0.9300	C20—H20	0.9300
N1—H1N	0.77 (2)	N2—H2N	0.81 (2)
O2—H2A	0.8200	O5—H5A	0.8200

O1—C1—N1	122.38 (14)	O4—C11—N2	122.58 (14)
O1—C1—C2	123.03 (14)	O4—C11—C12	123.73 (14)
N1—C1—C2	114.58 (13)	N2—C11—C12	113.65 (14)
C3—C2—C1	128.39 (15)	C13—C12—C11	128.82 (15)
C3—C2—H2	115.8	C13—C12—H12	115.6
C1—C2—H2	115.8	C11—C12—H12	115.6
C2—C3—C4	133.25 (15)	C12—C13—C14	132.80 (15)
C2—C3—H3	113.4	C12—C13—H13	113.6
C4—C3—H3	113.4	C14—C13—H13	113.6
O3—C4—O2	120.49 (14)	O6—C14—O5	120.67 (16)
O3—C4—C3	119.25 (14)	O6—C14—C13	118.86 (16)
O2—C4—C3	120.25 (13)	O5—C14—C13	120.47 (15)
C10—C5—C6	117.71 (14)	C20—C15—C16	117.90 (14)
C10—C5—N1	123.25 (14)	C20—C15—N2	123.35 (14)
C6—C5—N1	119.04 (14)	C16—C15—N2	118.74 (14)
C7—C6—C5	121.26 (15)	C17—C16—C15	121.51 (15)
C7—C6—Cl1	118.52 (13)	C17—C16—Cl4	118.70 (13)
C5—C6—Cl1	120.22 (12)	C15—C16—Cl4	119.79 (12)
C6—C7—C8	120.35 (15)	C16—C17—C18	119.95 (15)
C6—C7—H7	119.8	C16—C17—H17	120.0
C8—C7—H7	119.8	C18—C17—H17	120.0
C7—C8—C9	119.22 (15)	C17—C18—C19	119.22 (14)
C7—C8—Cl2	119.33 (13)	C17—C18—Cl5	119.50 (13)
C9—C8—Cl2	121.46 (13)	C19—C18—Cl5	121.28 (13)
C8—C9—C10	120.56 (15)	C20—C19—C18	120.96 (15)
C8—C9—Cl3	121.27 (13)	C20—C19—Cl6	118.32 (12)
C10—C9—Cl3	118.16 (13)	C18—C19—Cl6	120.72 (12)
C9—C10—C5	120.85 (14)	C19—C20—C15	120.44 (15)
C9—C10—H10	119.6	C19—C20—H20	119.8
C5—C10—H10	119.6	C15—C20—H20	119.8
C1—N1—C5	127.17 (14)	C11—N2—C15	128.30 (14)
C1—N1—H1N	115.5 (15)	C11—N2—H2N	114.0 (13)
C5—N1—H1N	117.3 (15)	C15—N2—H2N	117.0 (13)
C4—O2—H2A	109.5	C14—O5—H5A	109.5

O1—C1—C2—C3	0.1 (3)	O4—C11—C12—C13	−7.6 (3)
N1—C1—C2—C3	−178.97 (18)	N2—C11—C12—C13	174.36 (18)
C1—C2—C3—C4	1.6 (3)	C11—C12—C13—C14	−2.5 (3)
C2—C3—C4—O3	179.39 (19)	C12—C13—C14—O6	−173.1 (2)
C2—C3—C4—O2	0.8 (3)	C12—C13—C14—O5	6.7 (3)
C10—C5—C6—C7	2.3 (2)	C20—C15—C16—C17	1.2 (2)
N1—C5—C6—C7	−177.16 (15)	N2—C15—C16—C17	−177.78 (16)
C10—C5—C6—Cl1	−178.08 (12)	C20—C15—C16—Cl4	−179.11 (13)
N1—C5—C6—Cl1	2.4 (2)	N2—C15—C16—Cl4	1.9 (2)
C5—C6—C7—C8	−1.3 (3)	C15—C16—C17—C18	−1.2 (3)
Cl1—C6—C7—C8	179.06 (13)	Cl4—C16—C17—C18	179.12 (14)
C6—C7—C8—C9	−0.9 (3)	C16—C17—C18—C19	0.1 (3)
C6—C7—C8—Cl2	179.30 (13)	C16—C17—C18—Cl5	−179.56 (14)
C7—C8—C9—C10	2.0 (2)	C17—C18—C19—C20	0.8 (3)
Cl2—C8—C9—C10	−178.14 (13)	Cl5—C18—C19—C20	−179.46 (13)
C7—C8—C9—Cl3	−178.97 (13)	C17—C18—C19—Cl6	180.00 (14)
Cl2—C8—C9—Cl3	0.9 (2)	Cl5—C18—C19—Cl6	−0.3 (2)
C8—C9—C10—C5	−1.0 (2)	C18—C19—C20—C15	−0.8 (3)
Cl3—C9—C10—C5	179.95 (12)	Cl6—C19—C20—C15	−179.99 (12)
C6—C5—C10—C9	−1.1 (2)	C16—C15—C20—C19	−0.2 (2)
N1—C5—C10—C9	178.32 (15)	N2—C15—C20—C19	178.71 (15)
O1—C1—N1—C5	1.4 (3)	O4—C11—N2—C15	5.9 (3)
C2—C1—N1—C5	−179.53 (15)	C12—C11—N2—C15	−176.01 (16)
C10—C5—N1—C1	5.1 (3)	C20—C15—N2—C11	−1.6 (3)
C6—C5—N1—C1	−175.47 (15)	C16—C15—N2—C11	177.28 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.82	1.69	2.5080 (15)	175
O5—H5A···O4	0.82	1.72	2.5332 (17)	175
N1—H1N···O3ⁱ	0.77 (2)	2.30 (2)	3.0356 (18)	161.2 (19)
N2—H2N···O6ⁱⁱ	0.81 (2)	2.481 (19)	3.0775 (19)	131.3 (16)
N1—H1N···Cl1	0.77 (2)	2.56 (2)	2.9628 (14)	114.2 (17)
N2—H2N···Cl4	0.81 (2)	2.519 (18)	2.9476 (14)	114.3 (15)
C2—H2···O3ⁱ	0.93	2.29	3.123 (2)	149
C12—H12···O2	0.93	2.47	3.330 (2)	154

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₆Cl₃NO₃
M_r	294.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	10.8979 (2), 11.0225 (2), 19.4739 (3)
β (°)	95.4761 (9)
V (Å³)	2328.57 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.78
Crystal size (mm)	0.34 × 0.25 × 0.22

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector
Absorption correction	Analytical (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.794, 0.852
No. of measured, independent and observed [I > 2σ(I)] reflections	49446, 4424, 3825
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.079, 1.06
No. of reflections	4424
No. of parameters	315
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.32

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
O2—H2A···O1	0.82	1.69	2.5080 (15)	175
O5—H5A···O4	0.82	1.72	2.5332 (17)	175
N1—H1N···O3ⁱ	0.77 (2)	2.30 (2)	3.0356 (18)	161.2 (19)
N2—H2N···O6ⁱⁱ	0.81 (2)	2.481 (19)	3.0775 (19)	131.3 (16)
N1—H1N···Cl1	0.77 (2)	2.56 (2)	2.9628 (14)	114.2 (17)
N2—H2N···Cl4	0.81 (2)	2.519 (18)	2.9476 (14)	114.3 (15)
C2—H2···O3ⁱ	0.93	2.29	3.123 (2)	149
C12—H12···O2	0.93	2.47	3.330 (2)	154

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2.

Table 2. Halogen-bond geometry (Å, °). top

C–Cl···O	Cl···O	C–Cl···O
C9–Cl3···O6ⁱⁱⁱ	3.1267 (15)	158.99 (6)
C16–Cl4···O1	3.0523 (12)	159.62 (7)

Symmetry code: (iii) x, -y+1/2, z-1/2.

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. KS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement programme

References

Brandenburg, K. (2002). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Fourmigué, M. (2009). Curr. Opin. Solid State Mater. Sci. 13, 36–45. Google Scholar
Gowda, B. T., Tokarčík, M., Kožíšek, J., Shakuntala, K. & Fuess, H. (2009). Acta Cryst. E65, o2945. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gowda, B. T., Tokarčík, M., Kožíšek, J., Shakuntala, K. & Fuess, H. (2010). Acta Cryst. E66, o51. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kubicki, M. (2004). J. Mol. Struct. 698, 67–73. Web of Science CSD CrossRef CAS Google Scholar
Lo, K. M. & Ng, S. W. (2009). Acta Cryst. E65, o1101. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Prasad, S. M., Sinha, R. B. P., Mandal, D. K. & Rani, A. (2002). Acta Cryst. E58, o1296–o1297. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shakuntala, K., Gowda, B. T., Tokarčík, M. & Kožíšek, J. (2009). Acta Cryst. E65, o3119. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Voth, A. R., Khuu, P., Oishi, K. & Ho, P. S. (2009). Nat. Chem. 1, 74–79. Web of Science CrossRef CAS PubMed Google Scholar