2-Amino-6-[(2,6-dichloro­phen­yl)imino]-3-oxocyclo­hexa-1,4-dienecarbaldehyde

Neves, C.M.B.; Fernandes, J.A.; Simões, M.M.Q.; Neves, M.G.P.M.S.; Cavaleiro, J.A.S.; Almeida Paz, F.A.

doi:10.1107/S1600536811042619

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages o3022-o3023

doi:10.1107/S1600536811042619

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2-Amino-6-[(2,6-dichlorophenyl)imino]-3-oxocyclohexa-1,4-dienecarbaldehyde

Cláudia M. B. Neves,^a José A. Fernandes,^b Mário M. Q. Simões,^a M. Graça P. M. S. Neves,^a José A. S. Cavaleiro ^a and Filipe A. Almeida Paz ^b ^*

^aDepartment of Chemistry, University of Aveiro, QOPNA, 3810-193 Aveiro, Portugal, and ^bDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 10 October 2011; accepted 14 October 2011; online 22 October 2011)

The title compound, C₁₃H₈Cl₂N₂O₂, was obtained by the oxidation of diclofenac {systematic name: 2-[2-(2,6-dichlorophenylamino)phenyl]acetic acid}, an anti-inflammatory drug, with hydrogen peroxide catalysed by chlorido[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]manganese(III), using ammonium acetate as co-catalyst. The asymmetric unit contains two crystallographically independent molecules of the title compound (Z′ = 2). The close packing of individual molecules is mediated by a series of strong and rather directional N—H⋯Cl and N—H⋯O hydrogen bonds, plus weak π–π [distance between the individual double bonds of symmetry-related iminoquinone rings = 3.7604 (13) Å] and Cl⋯O interactions [3.0287 (18) Å].

Related literature

For background to diclofenac oxidation reactions using metalloporphyrins as catalysts, see: Othman et al. (2000 ). For oxidation of other drugs and other organic compounds by hydrogen peroxide catalysed by metalloporphyrins, see: Othman et al. (2000); Bernadou & Meunier (2004 ); Mansuy (2007 ); Neves et al. (2011 ); Simões et al. (2009 ); Rebelo et al. (2004a ,b , 2005 ). For crystallographic studies from our research group of compounds with biological activity, see: Fernandes et al. (2010 , 2011 ); Loughzail et al. (2011 ). For a description of the graph-set notation, see: Grell et al. (1999 ).

Experimental

Crystal data

C₁₃H₈Cl₂N₂O₂
M_r = 295.11
Monoclinic, P 2₁ /c
a = 17.1738 (14) Å
b = 10.5718 (8) Å
c = 14.1457 (11) Å
β = 101.192 (5)°
V = 2519.4 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 150 K
0.07 × 0.04 × 0.01 mm

Data collection

Bruker X8 KappaCCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.965, T_max = 0.995
24324 measured reflections
4600 independent reflections
3466 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.085
S = 1.02
4600 reflections
355 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2X⋯Cl1ⁱ	0.92 (1)	2.60 (1)	3.4590 (18)	156 (2)
N2—H2Y⋯O1	0.92 (1)	2.08 (2)	2.722 (2)	126 (2)
N2—H2Y⋯O4ⁱ	0.92 (1)	2.26 (2)	2.933 (2)	130 (2)
N4—H4X⋯O1ⁱ	0.93 (1)	2.04 (1)	2.916 (2)	155 (2)
N4—H4Y⋯O3	0.92 (1)	2.01 (2)	2.666 (3)	127 (2)
Symmetry code: (i) -x+1, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2005 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811042619/tk2799sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042619/tk2799Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811042619/tk2799Isup3.cml

checkCIF report

Comment top

The possibility of using synthetic metalloporphyrins as biomimetic catalysts, which are able to mimic cytochrome P450 enzymes, has attracted the interest of many research groups (Othman et al., 2000; Bernadou et al., 2004; Mansuy, 2007), including ours (Neves et al., 2011; Simões et al., 2009; Rebelo et al., 2004a, 2004b, 2005). In particular, our current research is focused on the preparation of putative metabolites by the in vitro oxidation of drugs. These studies will allow the production of metabolites in the amounts of milligrams, the isolation and identification of unstable intermediates and the understanding of the mechanism of action of drugs (Bernadou et al., 2004). The title compound, C₁₃H₈Cl₂N₂O₂, was obtained by the oxidation of 2-(2-(2,6-dichlorophenylamino)phenyl)acetic acid (diclofenac), an anti-inflammatory drug, with hydrogen peroxide catalysed by chloro[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]manganese(III) using ammonium acetate as co-catalyst. Following our on-going interest on the structural features of compounds with biological activity (Fernandes et al., 2010, 2011; Loughzail et al. 2011) here we wish to report the crystal structure of the oxidation product of diclofenac.

The asymmetric unit of the title compound comprises two whole molecules of C₁₃H₈Cl₂N₂O₂ (Fig. 1). A comparison between the geometrical features of the two molecules reveals that bond distances and angles involving equivalent atoms are very similar (deviations smaller than 0.012 Å and 1.6°, respectively). There are, however, some considerable differences concerning torsion angles, namely those subtended by the two six-membered rings in each molecule: 71.97 (10)° for molecule A and 75.89 (10)° for molecule B.

The crystal is rich in supramolecular interactions, namely π–π (involving the individual double bonds of the iminoquinone rings), Cl···O and hydrogen bonding interactions. The π–π interactions occur between pairs of molecules A involving the aromatic and the iminoquinone rings, or two iminoquinone rings [distance between centroids of 3.7604 (13) and 3.9595 (13) Å, respectively - purple dashed bonds in Figure 2]. A pair of B molecules also exhibits a short Cl···O interaction (Cl···O distance 3.0287 (18) Å, not shown].

The two crystallographically independent molecules have a different behaviour concerning the hydrogen bonding network in which they are involved (Figure 2 and Table 1 for geometric details). Molecule A is engaged in a bifurcated N—H···(O,O) hydrogen bond, which is shared by the aldehyde group (intramolecular) and the ketone group of a neighbouring B molecule. The remaining N—H moiety of molecule A donates the hydrogen atom to a Cl atom of a neighbouring A molecule. The NH₂ group of molecule B participates in two N—H···O_aldehyde interactions, of which one is intramolecular and the other occurs with molecule A. The hydrogen bonds form discrete clusters (violet dashed lines in Fig. 2) which can be described as the merging of two rings with a graph set notations R¹₁(6) and R²₂(11), respectively (Grell et al., 1999).

Unequivocally, the strongest connection among adjacent molecules corresponds to that of the latter graph set, which leads to the formation of dimers as depicted in Fig. 2. The crystal packing is, thus, promoted by the close packing of such dimers: firstly, and mediated by the aforementioned weak π–π contacts, dimers form columnar arrangements along the c-axis of the unit cell. Secondly, columns pack in the ab plane in a typical brick-wall-type fashion as depicted in Fig. 3.

Related literature top

For background to diclofenac oxidation reactions using metalloporphyrins as catalysts, see: Othman et al. (2000). For oxidation of other drugs and other organic compounds by hydrogen peroxide catalysed by metalloporphyrins, see: Othman et al. (2000); Bernadou & Meunier (2004); Mansuy (2007); Neves et al. (2011); Simões et al. (2009); Rebelo et al. (2004a,b, 2005). For crystallographic studies from our research group of compounds with biological activity, see: Fernandes et al. (2010, 2011); Loughzail et al. (2011). For a description of the graph-set notation, see: Grell et al. (1999).

Experimental top

All chemicals were purchased from commercial sources and were used as received without further purification.

The oxidation reactions were carried out using 0.1 mmol of diclofenac (sodium salt, Sigma-Aldrich), 1.33 µmol of chloro[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]manganese(III) ([Mn(TDCPP)Cl, as catalyst) and 15 mg of co-catalyst (ammonium acetate, Fluka) in CH₃CN: H₂O (10:1), in a total volume of 2.0 ml under normal atmosphere at 30 °C. The oxidant employed was aqueous hydrogen peroxide 30% (w/w) (Riedel-de Haën) diluted 1:5 in CH₃CN. The oxidant (0.05 mmol) was added to the reaction mixture every 15 min. After 8 h of reaction, the mixture was extracted with dichloromethane and purified by preparative TLC using the same solvent as eluent. The product was dissolved in a minimum amount of dichloromethane and crystallized in hexane at around -16 °C to isolate crystals of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit of the title compound showing the two crystallographic independent molecular units coined A and B. Displacement ellipsoids are drawn at the 50% probability level and the atomic labeling is provided for all non-hydrogen atoms. Hydrogen atoms are represented as small spheres with arbitrary radius.
	Fig. 2. Supramolecular contacts interconnecting adjacent molecules A and B of the title compound. On the left the strong N—H···O and N—H···Cl hydrogen bonds can be grouped into two graph set motifs: R¹₁(6) and R²₂(11). On the right, weak π–π contacts involving double bonds of the iminoquinone and aromatic rings further ensure supramolecular connections among A molecules. For geometric details on the represented hydrogen bonds see Table 1. Symmetry transformations used to generate equivalent atoms have been omitted for simplicity.
	Fig. 3. Crystal packing of the title compound viewed in perspective along the [001] direction of the unit cell. Supramolecular interactions have been omitted for clarity.

2-Amino-6-[(2,6-dichlorophenyl)imino]-3-oxocyclohexa-1,4-dienecarbaldehyde top

Crystal data top

C₁₃H₈Cl₂N₂O₂	F(000) = 1200
M_r = 295.11	D_x = 1.556 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5810 reflections
a = 17.1738 (14) Å	θ = 2.4–25.3°
b = 10.5718 (8) Å	µ = 0.51 mm⁻¹
c = 14.1457 (11) Å	T = 150 K
β = 101.192 (5)°	Plate, red
V = 2519.4 (3) Å³	0.07 × 0.04 × 0.01 mm
Z = 8

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	4600 independent reflections
Radiation source: fine-focus sealed tube	3466 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω and ϕ scans	θ_max = 25.4°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −20→20
T_min = 0.965, T_max = 0.995	k = −12→11
24324 measured reflections	l = −16→17

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) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0396P)² + 1.1952P] where P = (F_o² + 2F_c²)/3
4600 reflections	(Δ/σ)_max = 0.001
355 parameters	Δρ_max = 0.24 e Å⁻³
6 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₃H₈Cl₂N₂O₂	V = 2519.4 (3) Å³
M_r = 295.11	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.1738 (14) Å	µ = 0.51 mm⁻¹
b = 10.5718 (8) Å	T = 150 K
c = 14.1457 (11) Å	0.07 × 0.04 × 0.01 mm
β = 101.192 (5)°

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	4600 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	3466 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.995	R_int = 0.040
24324 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	6 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.24 e Å⁻³
4600 reflections	Δρ_min = −0.24 e Å⁻³
355 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
Cl1	0.49916 (4)	0.47039 (5)	0.65986 (4)	0.03327 (15)
Cl2	0.26299 (4)	0.18196 (7)	0.74680 (4)	0.04150 (17)
Cl3	−0.05691 (3)	0.62367 (6)	0.53847 (4)	0.03368 (16)
Cl4	0.12169 (4)	0.98217 (6)	0.40871 (5)	0.04362 (18)
O1	0.58372 (8)	0.22644 (14)	1.02574 (10)	0.0271 (3)
O2	0.36779 (9)	0.51109 (15)	1.11813 (10)	0.0308 (4)
O3	0.13914 (10)	0.96716 (17)	0.83068 (11)	0.0381 (4)
O4	0.36096 (9)	0.70522 (15)	0.73428 (10)	0.0317 (4)
N1	0.42445 (10)	0.31116 (17)	0.78706 (12)	0.0254 (4)
N2	0.49446 (10)	0.36348 (17)	1.12812 (12)	0.0234 (4)
H2X	0.4811 (12)	0.396 (2)	1.1829 (11)	0.035*
H2Y	0.5399 (9)	0.3149 (19)	1.1359 (14)	0.035*
N3	0.06269 (10)	0.83177 (18)	0.56257 (12)	0.0282 (4)
N4	0.27682 (11)	0.84936 (19)	0.83330 (12)	0.0294 (4)
H4X	0.3282 (7)	0.826 (2)	0.8623 (15)	0.044*
H4Y	0.2502 (11)	0.900 (2)	0.8693 (14)	0.044*
C1	0.37540 (13)	0.3337 (2)	0.69673 (14)	0.0246 (5)
C2	0.40534 (13)	0.4033 (2)	0.62735 (15)	0.0264 (5)
C3	0.36328 (15)	0.4175 (2)	0.53380 (15)	0.0324 (6)
H3	0.3847	0.4657	0.4883	0.039*
C4	0.28988 (15)	0.3606 (2)	0.50764 (15)	0.0351 (6)
H4	0.2604	0.3707	0.4439	0.042*
C5	0.25886 (14)	0.2893 (2)	0.57318 (16)	0.0340 (6)
H5	0.2086	0.2496	0.5547	0.041*
C6	0.30200 (13)	0.2760 (2)	0.66665 (15)	0.0293 (5)
C7	0.41077 (12)	0.36167 (19)	0.86545 (14)	0.0208 (4)
C8	0.46514 (12)	0.33341 (19)	0.95584 (14)	0.0189 (4)
C9	0.45032 (12)	0.38251 (19)	1.04179 (14)	0.0205 (4)
C10	0.37993 (12)	0.4683 (2)	1.04199 (15)	0.0234 (5)
C11	0.33030 (13)	0.4983 (2)	0.94897 (15)	0.0266 (5)
H11	0.2869	0.5547	0.9464	0.032*
C12	0.34440 (12)	0.4484 (2)	0.86732 (15)	0.0241 (5)
H12	0.3103	0.4699	0.8083	0.029*
C13	0.53477 (12)	0.25818 (19)	0.95380 (15)	0.0223 (5)
H13	0.5436	0.2311	0.8927	0.027*
C14	0.03131 (12)	0.7975 (2)	0.46603 (14)	0.0260 (5)
C15	−0.02731 (13)	0.7046 (2)	0.44466 (14)	0.0273 (5)
C16	−0.06283 (14)	0.6751 (2)	0.35062 (15)	0.0312 (5)
H16	−0.1021	0.6107	0.3381	0.037*
C17	−0.04074 (14)	0.7399 (2)	0.27537 (15)	0.0340 (6)
H17	−0.0651	0.7203	0.2109	0.041*
C18	0.01639 (14)	0.8329 (2)	0.29324 (15)	0.0322 (6)
H18	0.0317	0.8772	0.2413	0.039*
C19	0.05143 (13)	0.8613 (2)	0.38746 (16)	0.0295 (5)
C20	0.13475 (12)	0.8026 (2)	0.60230 (14)	0.0228 (5)
C21	0.16673 (12)	0.8469 (2)	0.69960 (14)	0.0224 (5)
C22	0.24313 (12)	0.8152 (2)	0.74440 (14)	0.0228 (5)
C23	0.29463 (13)	0.7359 (2)	0.69351 (15)	0.0253 (5)
C24	0.26042 (14)	0.6948 (2)	0.59531 (15)	0.0317 (5)
H24	0.2919	0.6462	0.5605	0.038*
C25	0.18613 (13)	0.7242 (2)	0.55375 (15)	0.0286 (5)
H25	0.1656	0.6936	0.4907	0.034*
C26	0.11859 (13)	0.9265 (2)	0.74825 (16)	0.0299 (5)
H26	0.0673	0.9490	0.7140	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0426 (3)	0.0302 (3)	0.0295 (3)	0.0019 (3)	0.0133 (3)	−0.0011 (2)
Cl2	0.0421 (4)	0.0542 (4)	0.0276 (3)	−0.0097 (3)	0.0050 (3)	0.0044 (3)
Cl3	0.0358 (3)	0.0457 (4)	0.0196 (3)	−0.0011 (3)	0.0053 (2)	0.0034 (2)
Cl4	0.0342 (3)	0.0497 (4)	0.0439 (4)	−0.0070 (3)	−0.0002 (3)	0.0110 (3)
O1	0.0270 (8)	0.0292 (8)	0.0224 (8)	0.0023 (7)	−0.0018 (7)	0.0026 (7)
O2	0.0319 (9)	0.0377 (9)	0.0247 (8)	0.0008 (7)	0.0101 (7)	−0.0064 (7)
O3	0.0365 (9)	0.0512 (11)	0.0256 (8)	0.0079 (8)	0.0039 (7)	−0.0143 (8)
O4	0.0248 (8)	0.0420 (10)	0.0261 (8)	0.0089 (7)	−0.0003 (7)	0.0023 (7)
N1	0.0298 (10)	0.0297 (10)	0.0165 (9)	0.0040 (8)	0.0036 (8)	0.0028 (8)
N2	0.0255 (10)	0.0270 (10)	0.0174 (9)	−0.0026 (8)	0.0036 (8)	−0.0011 (8)
N3	0.0258 (10)	0.0383 (11)	0.0189 (9)	0.0050 (9)	0.0008 (8)	−0.0034 (8)
N4	0.0281 (10)	0.0381 (12)	0.0190 (9)	0.0055 (9)	−0.0028 (8)	−0.0049 (8)
C1	0.0306 (12)	0.0250 (12)	0.0173 (10)	0.0116 (10)	0.0023 (9)	0.0003 (9)
C2	0.0377 (13)	0.0222 (12)	0.0207 (10)	0.0101 (10)	0.0087 (9)	−0.0006 (9)
C3	0.0524 (16)	0.0274 (13)	0.0182 (11)	0.0140 (12)	0.0093 (10)	0.0022 (10)
C4	0.0501 (16)	0.0367 (14)	0.0155 (10)	0.0157 (12)	−0.0014 (10)	−0.0010 (10)
C5	0.0338 (13)	0.0406 (14)	0.0250 (12)	0.0088 (11)	−0.0007 (10)	−0.0064 (11)
C6	0.0341 (13)	0.0324 (13)	0.0209 (11)	0.0082 (11)	0.0038 (10)	0.0028 (10)
C7	0.0212 (11)	0.0206 (11)	0.0205 (10)	−0.0022 (9)	0.0040 (9)	0.0032 (9)
C8	0.0204 (10)	0.0177 (10)	0.0182 (10)	−0.0027 (8)	0.0027 (8)	0.0023 (8)
C9	0.0209 (10)	0.0197 (11)	0.0206 (10)	−0.0065 (9)	0.0032 (9)	0.0026 (9)
C10	0.0230 (11)	0.0233 (11)	0.0248 (11)	−0.0064 (9)	0.0067 (9)	−0.0017 (9)
C11	0.0230 (11)	0.0273 (12)	0.0288 (11)	0.0018 (10)	0.0033 (9)	0.0004 (10)
C12	0.0246 (11)	0.0236 (11)	0.0224 (11)	0.0023 (9)	0.0002 (9)	0.0019 (9)
C13	0.0261 (11)	0.0194 (11)	0.0212 (10)	−0.0030 (9)	0.0041 (9)	0.0000 (9)
C14	0.0220 (11)	0.0367 (13)	0.0186 (10)	0.0096 (10)	0.0018 (9)	−0.0012 (10)
C15	0.0266 (12)	0.0361 (13)	0.0188 (10)	0.0048 (10)	0.0036 (9)	0.0015 (10)
C16	0.0308 (13)	0.0394 (14)	0.0221 (11)	0.0013 (11)	0.0016 (10)	−0.0003 (10)
C17	0.0362 (13)	0.0468 (15)	0.0164 (10)	0.0046 (12)	−0.0011 (10)	−0.0023 (10)
C18	0.0332 (13)	0.0421 (14)	0.0210 (11)	0.0095 (11)	0.0046 (10)	0.0074 (10)
C19	0.0220 (11)	0.0357 (13)	0.0298 (12)	0.0043 (10)	0.0029 (9)	0.0028 (10)
C20	0.0233 (11)	0.0257 (12)	0.0193 (10)	0.0016 (9)	0.0035 (9)	0.0024 (9)
C21	0.0239 (11)	0.0247 (12)	0.0189 (10)	0.0009 (9)	0.0046 (9)	−0.0011 (9)
C22	0.0229 (11)	0.0256 (11)	0.0194 (10)	−0.0007 (9)	0.0031 (9)	0.0008 (9)
C23	0.0245 (12)	0.0289 (12)	0.0219 (10)	0.0032 (10)	0.0029 (9)	0.0029 (9)
C24	0.0323 (13)	0.0386 (14)	0.0234 (11)	0.0126 (11)	0.0032 (10)	−0.0069 (10)
C25	0.0321 (12)	0.0335 (13)	0.0188 (10)	0.0060 (10)	0.0015 (9)	−0.0054 (10)
C26	0.0245 (12)	0.0380 (14)	0.0265 (12)	0.0036 (10)	0.0030 (9)	−0.0023 (11)

Geometric parameters (Å, º) top

Cl1—C2	1.738 (2)	C7—C12	1.467 (3)
Cl2—C6	1.737 (2)	C8—C9	1.390 (3)
Cl3—C15	1.736 (2)	C8—C13	1.441 (3)
Cl4—C19	1.743 (2)	C9—C10	1.512 (3)
O1—C13	1.234 (2)	C10—C11	1.457 (3)
O2—C10	1.223 (2)	C11—C12	1.334 (3)
O3—C26	1.229 (3)	C11—H11	0.9500
O4—C23	1.217 (2)	C12—H12	0.9500
N1—C7	1.293 (3)	C13—H13	0.9500
N1—C1	1.408 (3)	C14—C15	1.397 (3)
N2—C9	1.322 (2)	C14—C19	1.400 (3)
N2—H2X	0.917 (9)	C15—C16	1.387 (3)
N2—H2Y	0.922 (9)	C16—C17	1.380 (3)
N3—C20	1.293 (3)	C16—H16	0.9500
N3—C14	1.414 (3)	C17—C18	1.377 (3)
N4—C22	1.328 (3)	C17—H17	0.9500
N4—H4X	0.931 (9)	C18—C19	1.385 (3)
N4—H4Y	0.921 (9)	C18—H18	0.9500
C1—C6	1.390 (3)	C20—C21	1.456 (3)
C1—C2	1.402 (3)	C20—C25	1.474 (3)
C2—C3	1.387 (3)	C21—C22	1.383 (3)
C3—C4	1.381 (3)	C21—C26	1.444 (3)
C3—H3	0.9500	C22—C23	1.501 (3)
C4—C5	1.380 (3)	C23—C24	1.465 (3)
C4—H4	0.9500	C24—C25	1.334 (3)
C5—C6	1.392 (3)	C24—H24	0.9500
C5—H5	0.9500	C25—H25	0.9500
C7—C8	1.460 (3)	C26—H26	0.9500

C7—N1—C1	122.17 (18)	C7—C12—H12	118.8
C9—N2—H2X	122.1 (13)	O1—C13—C8	124.65 (19)
C9—N2—H2Y	121.0 (13)	O1—C13—H13	117.7
H2X—N2—H2Y	116.9 (14)	C8—C13—H13	117.7
C20—N3—C14	120.77 (18)	C15—C14—C19	116.48 (19)
C22—N4—H4X	123.3 (13)	C15—C14—N3	120.83 (19)
C22—N4—H4Y	120.7 (13)	C19—C14—N3	122.5 (2)
H4X—N4—H4Y	116.0 (14)	C16—C15—C14	122.0 (2)
C6—C1—C2	116.73 (19)	C16—C15—Cl3	118.86 (18)
C6—C1—N1	123.4 (2)	C14—C15—Cl3	119.13 (16)
C2—C1—N1	119.2 (2)	C17—C16—C15	119.5 (2)
C3—C2—C1	122.0 (2)	C17—C16—H16	120.2
C3—C2—Cl1	119.52 (18)	C15—C16—H16	120.2
C1—C2—Cl1	118.43 (16)	C18—C17—C16	120.4 (2)
C4—C3—C2	119.2 (2)	C18—C17—H17	119.8
C4—C3—H3	120.4	C16—C17—H17	119.8
C2—C3—H3	120.4	C17—C18—C19	119.5 (2)
C5—C4—C3	120.6 (2)	C17—C18—H18	120.2
C5—C4—H4	119.7	C19—C18—H18	120.2
C3—C4—H4	119.7	C18—C19—C14	122.1 (2)
C4—C5—C6	119.3 (2)	C18—C19—Cl4	118.83 (18)
C4—C5—H5	120.3	C14—C19—Cl4	119.07 (17)
C6—C5—H5	120.3	N3—C20—C21	119.18 (19)
C1—C6—C5	122.1 (2)	N3—C20—C25	122.72 (19)
C1—C6—Cl2	119.52 (16)	C21—C20—C25	118.09 (18)
C5—C6—Cl2	118.42 (19)	C22—C21—C26	120.17 (19)
N1—C7—C8	118.35 (18)	C22—C21—C20	120.36 (19)
N1—C7—C12	123.02 (19)	C26—C21—C20	119.46 (18)
C8—C7—C12	118.62 (18)	N4—C22—C21	124.6 (2)
C9—C8—C13	121.14 (18)	N4—C22—C23	114.66 (18)
C9—C8—C7	119.67 (18)	C21—C22—C23	120.70 (18)
C13—C8—C7	119.16 (17)	O4—C23—C24	122.5 (2)
N2—C9—C8	125.56 (19)	O4—C23—C22	120.41 (19)
N2—C9—C10	113.89 (18)	C24—C23—C22	117.07 (18)
C8—C9—C10	120.53 (18)	C25—C24—C23	121.5 (2)
O2—C10—C11	123.0 (2)	C25—C24—H24	119.3
O2—C10—C9	119.78 (19)	C23—C24—H24	119.3
C11—C10—C9	117.17 (18)	C24—C25—C20	122.3 (2)
C12—C11—C10	121.5 (2)	C24—C25—H25	118.9
C12—C11—H11	119.2	C20—C25—H25	118.9
C10—C11—H11	119.2	O3—C26—C21	124.8 (2)
C11—C12—C7	122.34 (19)	O3—C26—H26	117.6
C11—C12—H12	118.8	C21—C26—H26	117.6

C7—N1—C1—C6	−77.3 (3)	C20—N3—C14—C15	110.1 (2)
C7—N1—C1—C2	111.9 (2)	C20—N3—C14—C19	−75.8 (3)
C6—C1—C2—C3	1.7 (3)	C19—C14—C15—C16	1.2 (3)
N1—C1—C2—C3	173.0 (2)	N3—C14—C15—C16	175.7 (2)
C6—C1—C2—Cl1	−176.76 (16)	C19—C14—C15—Cl3	−178.67 (16)
N1—C1—C2—Cl1	−5.4 (3)	N3—C14—C15—Cl3	−4.2 (3)
C1—C2—C3—C4	−0.4 (3)	C14—C15—C16—C17	−0.8 (3)
Cl1—C2—C3—C4	177.98 (17)	Cl3—C15—C16—C17	179.07 (18)
C2—C3—C4—C5	−0.8 (3)	C15—C16—C17—C18	0.3 (4)
C3—C4—C5—C6	0.7 (3)	C16—C17—C18—C19	−0.2 (3)
C2—C1—C6—C5	−1.8 (3)	C17—C18—C19—C14	0.7 (3)
N1—C1—C6—C5	−172.7 (2)	C17—C18—C19—Cl4	−178.31 (18)
C2—C1—C6—Cl2	177.02 (16)	C15—C14—C19—C18	−1.1 (3)
N1—C1—C6—Cl2	6.1 (3)	N3—C14—C19—C18	−175.5 (2)
C4—C5—C6—C1	0.7 (3)	C15—C14—C19—Cl4	177.85 (17)
C4—C5—C6—Cl2	−178.15 (17)	N3—C14—C19—Cl4	3.5 (3)
C1—N1—C7—C8	−179.69 (19)	C14—N3—C20—C21	175.9 (2)
C1—N1—C7—C12	−1.3 (3)	C14—N3—C20—C25	−5.1 (3)
N1—C7—C8—C9	−177.60 (19)	N3—C20—C21—C22	178.9 (2)
C12—C7—C8—C9	3.9 (3)	C25—C20—C21—C22	−0.2 (3)
N1—C7—C8—C13	4.4 (3)	N3—C20—C21—C26	−2.5 (3)
C12—C7—C8—C13	−174.09 (18)	C25—C20—C21—C26	178.5 (2)
C13—C8—C9—N2	−2.5 (3)	C26—C21—C22—N4	2.5 (3)
C7—C8—C9—N2	179.58 (19)	C20—C21—C22—N4	−178.8 (2)
C13—C8—C9—C10	175.95 (18)	C26—C21—C22—C23	−178.1 (2)
C7—C8—C9—C10	−2.0 (3)	C20—C21—C22—C23	0.5 (3)
N2—C9—C10—O2	−1.2 (3)	N4—C22—C23—O4	1.6 (3)
C8—C9—C10—O2	−179.80 (19)	C21—C22—C23—O4	−177.8 (2)
N2—C9—C10—C11	177.42 (18)	N4—C22—C23—C24	179.7 (2)
C8—C9—C10—C11	−1.2 (3)	C21—C22—C23—C24	0.3 (3)
O2—C10—C11—C12	−178.9 (2)	O4—C23—C24—C25	176.6 (2)
C9—C10—C11—C12	2.5 (3)	C22—C23—C24—C25	−1.5 (3)
C10—C11—C12—C7	−0.6 (3)	C23—C24—C25—C20	1.9 (4)
N1—C7—C12—C11	178.9 (2)	N3—C20—C25—C24	179.9 (2)
C8—C7—C12—C11	−2.7 (3)	C21—C20—C25—C24	−1.0 (3)
C9—C8—C13—O1	3.6 (3)	C22—C21—C26—O3	−2.6 (4)
C7—C8—C13—O1	−178.44 (19)	C20—C21—C26—O3	178.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2X···Cl1ⁱ	0.92 (1)	2.60 (1)	3.4590 (18)	156 (2)
N2—H2Y···O1	0.92 (1)	2.08 (2)	2.722 (2)	126 (2)
N2—H2Y···O4ⁱ	0.92 (1)	2.26 (2)	2.933 (2)	130 (2)
N4—H4X···O1ⁱ	0.93 (1)	2.04 (1)	2.916 (2)	155 (2)
N4—H4Y···O3	0.92 (1)	2.01 (2)	2.666 (3)	127 (2)

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₃H₈Cl₂N₂O₂
M_r	295.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	17.1738 (14), 10.5718 (8), 14.1457 (11)
β (°)	101.192 (5)
V (Å³)	2519.4 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.07 × 0.04 × 0.01

Data collection
Diffractometer	Bruker X8 KappaCCD APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.965, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	24324, 4600, 3466
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.02
No. of reflections	4600
No. of parameters	355
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.24

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2X···Cl1ⁱ	0.917 (9)	2.601 (13)	3.4590 (18)	156.0 (19)
N2—H2Y···O1	0.922 (9)	2.080 (16)	2.722 (2)	125.5 (16)
N2—H2Y···O4ⁱ	0.922 (9)	2.259 (18)	2.933 (2)	129.5 (16)
N4—H4X···O1ⁱ	0.931 (9)	2.044 (14)	2.916 (2)	155 (2)
N4—H4Y···O3	0.921 (9)	2.008 (17)	2.666 (3)	127.0 (17)

Symmetry code: (i) −x+1, −y+1, −z+2.

Acknowledgements

We are grateful to the Fundação para a Ciência e a Tecnologia (FCT/FEDER, Portugal) for their general financial support to QOPNA and CICECO, and for the post-doctoral research grant No. SFRH/BPD/63736/2009 (to JAF). Thanks are also due to the FCT for specific funding toward the purchase of the single-crystal diffractometer.

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