5-Chloro-3,6-dimethyl-1-phenyl-1H,4H-pyrano[2,3-c]pyrazol-4-one

Asiri, A.M.; Faidallah, H.M.; Alamry, K.A.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812028528

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2257

https://doi.org/10.1107/S1600536812028528

Open

access

5-Chloro-3,6-dimethyl-1-phenyl-1H,4H-pyrano[2,3-c]pyrazol-4-one

Abdullah M. Asiri,^a,^b ‡ Hassan M. Faidallah,^b Khalid A. Alamry,^a,^b Seik Weng Ng ^c and Edward R. T. Tiekink ^c ^*

^aCenter of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, ^bChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 21 June 2012; accepted 23 June 2012; online 30 June 2012)

In the title compound, C₁₄H₁₁ClN₂O₂, two independent molecules (A and B) comprise the asymmetric unit with the main difference between them being the relative orientation of the pendent phenyl ring with respect to the fused-ring system [dihedral angles = 8.32 (8)° (A) and 28.32 (8)° (B)]. In the crystal, the A molecules are connected into a linear supramolecular chain along the a axis via C—H⋯O interactions and linked to this via C—H⋯Cl interactions are the B molecules. The chains are connected into layers in the ab plane by π–π interactions between pyrazole (A) and pyran (B) rings, and between pyrazole (B) and pyran (A) rings [centroid–centroid distances = 3.5442 (11) and 3.4022 (10) Å, respectively].

Related literature

For the analgesic and anti-inflammatory activity of pyrano[2,3-c]pyrazole derivatives, see: Kuo et al. (1984 ). For the synthesis, see: Gelin et al. (1983 ). For the structure of the derivative without a chloro substituent, see: Asiri et al. (2012 ).

Experimental

Crystal data

C₁₄H₁₁ClN₂O₂
M_r = 274.70
Orthorhombic, P b c a
a = 11.8864 (4) Å
b = 13.6276 (5) Å
c = 31.0273 (10) Å
V = 5025.9 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 100 K
0.40 × 0.20 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.817, T_max = 1.000
17994 measured reflections
5796 independent reflections
4522 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.117
S = 1.03
5796 reflections
347 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O2ⁱ	0.95	2.32	3.203 (2)	154
C14—H14⋯Cl2ⁱ	0.95	2.74	3.448 (2)	132
Symmetry code: (i) x+1, y, z.

Data collection: CrysAlis PRO (Agilent, 2012); 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, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812028528/su2466sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028528/su2466Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028528/su2466Isup3.cml

checkCIF report

Comment top

In connection with reports that pyrano[2,3-c]pyrazole derivatives possess analgesic and anti-inflammatory activities (Kuo et al., 1984), the title compound (I) was synthesized, following a literature procedure (Gelin et al., 1983), and its crystal and molecular structure are reported on herein.

In (I), Fig. 1, two independent molecules comprise the asymmetric unit. As seen from the overlay diagram, Fig. 2, these are virtually super-imposable. The primary difference between the molecules relates to the relative orientation of the pendent phenyl ring with respect to the fused-ring system [r.m.s. deviations = 0.024 and 0.021 Å, respectively] as seen in the dihedral angles of 8.32 (8) and 28.32 (8)°, respectively. In the structure of the derivative without a chloro substituent, the molecule is planar with the r.m.s. of all non-hydrogen atoms being 0.038 Å (Asiri et al., 2012).

In the crystal, the Cl1-containing molecules are connected into a linear supramolecular chain along the a axis via C—H···O interactions and linked to this via C—H···Cl interactions are the Cl2-containing molecules, Fig. 3 and Table 1. Chains are connected into layers in the ab plane by π—π interactions with the closest of these occurring between the five-membered and six-membered in an alternating sequence of the independent molecules [ring centroid(N1-pyrazole)···(O3-pyrano)ⁱ = 3.5442 (11) Å, angle of inclination = 2.29 (11)° for i: -x+1, -y, -z+1; ring centroid(N3-pyrazole)···(O1-pyrano)ⁱⁱ = 3.4022 (10) Å, angle of inclination = 5.38 (8)° for ii: x+1/2, -y+1/2, -z+1]. The layers stack along the c axis with no specific intermolecular interactions between them, Fig. 4.

Related literature top

For the analgesic and anti-inflammatory activity of pyrano[2,3-c]pyrazole derivatives, see: Kuo et al. (1984). For the synthesis, see: Gelin et al. (1983). For the structure of the derivative without a chloro substituent, see: Asiri et al. (2012).

Experimental top

To a solution of 4-(acetoacetyl)-3-methyl-1-phenyl-2-pyrazolin-5-one (0.01 M), made following a literature procedure (Gelin et al., 1983), in dry methylene chloride (20 ml) was added drop-wise sulfuryl chloride (1.35 g, 0.01 M). The mixture was allowed to stand at room temperature for 2 h and then poured into a 10% aqueous K₂CO₃ solution (50 ml) with stirring for 5 min. The aqueous layer was acidified with 10% HCl and extracted with chloroform. The combined organic extracts were washed with water and dried (Na₂SO₄). Removal of the solvent gave 4-(aceto-chloroacetyl)-3-methyl-1-phenyl-2-pyrazolin-5-one. Concentrated sulfuric acid (1 ml) was then added drop-wise. After 4 h at room temperature, the mixture was poured into ice-water (200 ml). The precipitate was extracted with chloroform. The chloroform layer was washed with 5% aqueous K₂CO₃ solution, dried and evaporated to give the title compound which was recrystallized from ethanol. M.p: 413–415 K cf. Lit. M.p. 413 K (Gelin et al., 1983). Yield: 68%.

Structure description top

For the analgesic and anti-inflammatory activity of pyrano[2,3-c]pyrazole derivatives, see: Kuo et al. (1984). For the synthesis, see: Gelin et al. (1983). For the structure of the derivative without a chloro substituent, see: Asiri et al. (2012).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the two independent molecules of (I), showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. Super-imposition of the fused-ring systems of the two independent molecules in (I). The Cl1 and and Cl2-containing molecules are shown as red and blue images, respectively.
	Fig. 3. A view of the supramolecular chain along the a axis in (I) mediated by C—H···O and C—H···Cl interactions shown as orange and blue dashed lines, respectively.
	Fig. 4. A view in projection down the a axis of the unit-cell contents of (I) highlighting the stacks of supramolecular layers along the c axis. The C—H···O, C—H···Cl and π—π interactions are shown as orange, blue and purple dashed lines, respectively.

5-Chloro-3,6-dimethyl-1-phenyl-1H,4H- pyrano[2,3-c]pyrazol-4-one top

Crystal data top

C₁₄H₁₁ClN₂O₂	F(000) = 2272
M_r = 274.70	D_x = 1.452 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5991 reflections
a = 11.8864 (4) Å	θ = 2.3–27.5°
b = 13.6276 (5) Å	µ = 0.30 mm⁻¹
c = 31.0273 (10) Å	T = 100 K
V = 5025.9 (3) Å³	Prism, colourless
Z = 16	0.40 × 0.20 × 0.20 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	5796 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4522 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.041
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 2.4°
ω scan	h = −14→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −17→10
T_min = 0.817, T_max = 1.000	l = −23→40
17994 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0556P)² + 1.8272P] where P = (F_o² + 2F_c²)/3
5796 reflections	(Δ/σ)_max = 0.001
347 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₄H₁₁ClN₂O₂	V = 5025.9 (3) Å³
M_r = 274.70	Z = 16
Orthorhombic, Pbca	Mo Kα radiation
a = 11.8864 (4) Å	µ = 0.30 mm⁻¹
b = 13.6276 (5) Å	T = 100 K
c = 31.0273 (10) Å	0.40 × 0.20 × 0.20 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	5796 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	4522 reflections with I > 2σ(I)
T_min = 0.817, T_max = 1.000	R_int = 0.041
17994 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.03	Δρ_max = 0.56 e Å⁻³
5796 reflections	Δρ_min = −0.37 e Å⁻³
347 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	0.47784 (4)	0.10807 (4)	0.536902 (15)	0.02329 (13)
Cl2	0.02904 (4)	0.13031 (4)	0.482067 (16)	0.02722 (14)
O1	0.80047 (10)	0.08977 (9)	0.56939 (4)	0.0182 (3)
O2	0.49310 (11)	0.08983 (10)	0.63216 (5)	0.0250 (3)
O3	0.10832 (10)	0.18078 (9)	0.36014 (4)	0.0182 (3)
O4	0.27633 (11)	0.13467 (10)	0.47565 (4)	0.0241 (3)
N1	0.87843 (13)	0.06692 (12)	0.63947 (5)	0.0173 (3)
N2	0.83780 (13)	0.05555 (11)	0.68112 (5)	0.0190 (3)
N3	0.29023 (13)	0.18475 (11)	0.32886 (5)	0.0187 (3)
N4	0.40146 (12)	0.17885 (12)	0.34252 (5)	0.0204 (3)
C1	0.72337 (17)	0.10797 (16)	0.49990 (6)	0.0240 (4)
H1A	0.6531	0.1003	0.4837	0.036*
H1B	0.7769	0.0573	0.4909	0.036*
H1C	0.7553	0.1730	0.4942	0.036*
C2	0.70039 (15)	0.09791 (13)	0.54658 (6)	0.0186 (4)
C3	0.59974 (15)	0.09712 (14)	0.56689 (6)	0.0192 (4)
C4	0.58537 (15)	0.08820 (13)	0.61417 (6)	0.0186 (4)
C5	0.69231 (15)	0.07793 (13)	0.63565 (6)	0.0168 (4)
C6	0.79054 (15)	0.07976 (13)	0.61251 (6)	0.0164 (4)
C7	0.65511 (17)	0.05340 (15)	0.71804 (6)	0.0237 (4)
H7A	0.7022	0.0369	0.7429	0.035*
H7B	0.5990	0.0017	0.7136	0.035*
H7C	0.6169	0.1160	0.7233	0.035*
C8	0.72680 (15)	0.06198 (13)	0.67899 (6)	0.0184 (4)
C9	0.99726 (15)	0.06552 (13)	0.63192 (6)	0.0172 (4)
C10	1.06841 (16)	0.04123 (15)	0.66587 (6)	0.0221 (4)
H10	1.0387	0.0267	0.6936	0.027*
C11	1.18377 (16)	0.03853 (16)	0.65855 (7)	0.0256 (4)
H11	1.2330	0.0215	0.6815	0.031*
C12	1.22826 (16)	0.06032 (15)	0.61829 (7)	0.0235 (4)
H12	1.3072	0.0582	0.6136	0.028*
C13	1.15581 (16)	0.08529 (15)	0.58498 (7)	0.0240 (4)
H13	1.1856	0.1008	0.5574	0.029*
C14	1.04043 (16)	0.08789 (15)	0.59154 (6)	0.0221 (4)
H14	0.9913	0.1048	0.5686	0.027*
C15	−0.07309 (16)	0.17796 (15)	0.39208 (6)	0.0216 (4)
H15A	−0.1128	0.1366	0.4130	0.032*
H15B	−0.0929	0.1574	0.3628	0.032*
H15C	−0.0949	0.2466	0.3963	0.032*
C16	0.05018 (16)	0.16775 (13)	0.39842 (6)	0.0181 (4)
C17	0.10543 (16)	0.15005 (14)	0.43572 (6)	0.0189 (4)
C18	0.22949 (16)	0.14778 (13)	0.44089 (6)	0.0176 (4)
C19	0.28413 (15)	0.16257 (13)	0.39974 (6)	0.0177 (4)
C20	0.22119 (15)	0.17546 (13)	0.36295 (6)	0.0169 (4)
C21	0.50367 (16)	0.15383 (15)	0.41053 (7)	0.0240 (4)
H21A	0.5689	0.1630	0.3916	0.036*
H21B	0.5061	0.0880	0.4232	0.036*
H21C	0.5053	0.2030	0.4336	0.036*
C22	0.39769 (15)	0.16529 (13)	0.38481 (6)	0.0187 (4)
C23	0.26647 (16)	0.19886 (13)	0.28403 (6)	0.0186 (4)
C24	0.34540 (16)	0.24761 (14)	0.25905 (6)	0.0213 (4)
H24	0.4129	0.2716	0.2716	0.026*
C25	0.32434 (17)	0.26094 (15)	0.21537 (6)	0.0257 (4)
H25	0.3779	0.2940	0.1979	0.031*
C26	0.22545 (17)	0.22611 (15)	0.19720 (6)	0.0264 (5)
H26	0.2114	0.2355	0.1673	0.032*
C27	0.14728 (17)	0.17781 (15)	0.22247 (6)	0.0234 (4)
H27	0.0796	0.1542	0.2099	0.028*
C28	0.16698 (16)	0.16358 (15)	0.26614 (6)	0.0218 (4)
H28	0.1134	0.1303	0.2835	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0166 (2)	0.0292 (3)	0.0240 (3)	0.00225 (19)	−0.00503 (18)	−0.0020 (2)
Cl2	0.0242 (3)	0.0396 (3)	0.0178 (2)	−0.0002 (2)	0.00323 (18)	0.0053 (2)
O1	0.0145 (6)	0.0254 (7)	0.0146 (7)	0.0014 (5)	−0.0003 (5)	−0.0012 (5)
O2	0.0145 (7)	0.0334 (8)	0.0270 (8)	0.0006 (6)	0.0026 (6)	−0.0034 (6)
O3	0.0147 (6)	0.0240 (7)	0.0161 (7)	0.0002 (5)	−0.0003 (5)	0.0024 (5)
O4	0.0233 (7)	0.0314 (8)	0.0178 (7)	0.0013 (6)	−0.0047 (5)	0.0031 (6)
N1	0.0139 (7)	0.0234 (8)	0.0146 (8)	−0.0006 (6)	0.0011 (6)	−0.0014 (6)
N2	0.0179 (8)	0.0240 (8)	0.0150 (8)	−0.0006 (7)	0.0027 (6)	−0.0019 (6)
N3	0.0155 (8)	0.0240 (8)	0.0165 (8)	0.0009 (6)	−0.0017 (6)	0.0012 (6)
N4	0.0155 (8)	0.0241 (8)	0.0215 (9)	−0.0006 (7)	−0.0035 (6)	0.0019 (7)
C1	0.0196 (10)	0.0339 (11)	0.0184 (10)	0.0001 (9)	−0.0028 (7)	−0.0002 (8)
C2	0.0164 (9)	0.0207 (9)	0.0187 (9)	0.0021 (8)	−0.0039 (7)	−0.0016 (8)
C3	0.0158 (9)	0.0207 (9)	0.0212 (10)	0.0018 (8)	−0.0041 (7)	−0.0031 (8)
C4	0.0171 (9)	0.0179 (9)	0.0209 (10)	−0.0010 (7)	−0.0010 (7)	−0.0025 (7)
C5	0.0154 (9)	0.0187 (9)	0.0164 (9)	−0.0006 (7)	0.0016 (7)	−0.0025 (7)
C6	0.0169 (9)	0.0165 (9)	0.0159 (9)	−0.0005 (7)	0.0007 (7)	−0.0023 (7)
C7	0.0213 (10)	0.0313 (11)	0.0184 (10)	−0.0020 (8)	0.0042 (8)	−0.0025 (8)
C8	0.0188 (9)	0.0186 (9)	0.0177 (10)	−0.0006 (7)	−0.0009 (7)	−0.0014 (7)
C9	0.0129 (9)	0.0189 (9)	0.0197 (10)	−0.0001 (7)	0.0006 (7)	−0.0040 (7)
C10	0.0175 (9)	0.0316 (11)	0.0172 (10)	−0.0002 (8)	−0.0008 (7)	−0.0026 (8)
C11	0.0179 (10)	0.0354 (11)	0.0237 (11)	0.0016 (9)	−0.0085 (8)	−0.0047 (9)
C12	0.0129 (9)	0.0293 (11)	0.0283 (11)	−0.0003 (8)	−0.0010 (8)	−0.0071 (9)
C13	0.0200 (10)	0.0310 (11)	0.0209 (10)	−0.0020 (8)	0.0022 (8)	−0.0007 (8)
C14	0.0196 (10)	0.0287 (10)	0.0182 (10)	0.0007 (8)	−0.0012 (7)	0.0009 (8)
C15	0.0183 (9)	0.0263 (10)	0.0201 (10)	−0.0006 (8)	−0.0008 (7)	0.0027 (8)
C16	0.0189 (9)	0.0180 (9)	0.0174 (9)	−0.0007 (7)	0.0013 (7)	−0.0008 (7)
C17	0.0204 (10)	0.0197 (9)	0.0167 (9)	−0.0009 (8)	0.0018 (7)	0.0011 (7)
C18	0.0203 (9)	0.0160 (8)	0.0166 (9)	0.0008 (7)	−0.0012 (7)	0.0001 (7)
C19	0.0177 (9)	0.0174 (9)	0.0180 (9)	0.0002 (7)	−0.0025 (7)	0.0008 (7)
C20	0.0163 (9)	0.0163 (8)	0.0182 (9)	0.0012 (7)	0.0005 (7)	0.0002 (7)
C21	0.0182 (10)	0.0300 (11)	0.0239 (11)	−0.0017 (8)	−0.0047 (8)	0.0028 (9)
C22	0.0174 (9)	0.0184 (9)	0.0202 (10)	−0.0014 (7)	−0.0008 (7)	0.0016 (7)
C23	0.0217 (9)	0.0194 (9)	0.0147 (9)	0.0046 (8)	−0.0012 (7)	0.0005 (7)
C24	0.0201 (10)	0.0232 (9)	0.0207 (10)	0.0016 (8)	−0.0002 (7)	−0.0022 (8)
C25	0.0272 (11)	0.0319 (11)	0.0181 (10)	0.0012 (9)	0.0058 (8)	0.0018 (8)
C26	0.0318 (11)	0.0321 (11)	0.0153 (10)	0.0069 (9)	0.0001 (8)	0.0002 (8)
C27	0.0216 (10)	0.0287 (10)	0.0197 (10)	0.0040 (8)	−0.0033 (8)	−0.0020 (8)
C28	0.0200 (10)	0.0268 (10)	0.0185 (10)	0.0013 (8)	0.0001 (7)	0.0022 (8)

Geometric parameters (Å, º) top

Cl1—C3	1.7285 (19)	C10—H10	0.9500
Cl2—C17	1.7218 (19)	C11—C12	1.389 (3)
O1—C6	1.350 (2)	C11—H11	0.9500
O1—C2	1.389 (2)	C12—C13	1.388 (3)
O2—C4	1.231 (2)	C12—H12	0.9500
O3—C20	1.346 (2)	C13—C14	1.387 (3)
O3—C16	1.386 (2)	C13—H13	0.9500
O4—C18	1.227 (2)	C14—H14	0.9500
N1—C6	1.350 (2)	C15—C16	1.485 (3)
N1—N2	1.388 (2)	C15—H15A	0.9800
N1—C9	1.432 (2)	C15—H15B	0.9800
N2—C8	1.324 (2)	C15—H15C	0.9800
N3—C20	1.345 (2)	C16—C17	1.352 (3)
N3—N4	1.391 (2)	C17—C18	1.484 (3)
N3—C23	1.432 (2)	C18—C19	1.447 (3)
N4—C22	1.326 (2)	C19—C20	1.376 (2)
C1—C2	1.480 (3)	C19—C22	1.428 (3)
C1—H1A	0.9800	C21—C22	1.499 (3)
C1—H1B	0.9800	C21—H21A	0.9800
C1—H1C	0.9800	C21—H21B	0.9800
C2—C3	1.352 (3)	C21—H21C	0.9800
C3—C4	1.482 (3)	C23—C24	1.386 (3)
C4—C5	1.442 (3)	C23—C28	1.392 (3)
C5—C6	1.371 (2)	C24—C25	1.390 (3)
C5—C8	1.423 (3)	C24—H24	0.9500
C7—C8	1.486 (3)	C25—C26	1.387 (3)
C7—H7A	0.9800	C25—H25	0.9500
C7—H7B	0.9800	C26—C27	1.382 (3)
C7—H7C	0.9800	C26—H26	0.9500
C9—C14	1.388 (3)	C27—C28	1.389 (3)
C9—C10	1.391 (3)	C27—H27	0.9500
C10—C11	1.390 (3)	C28—H28	0.9500

C6—O1—C2	115.99 (14)	C14—C13—H13	119.6
C20—O3—C16	115.74 (14)	C12—C13—H13	119.6
C6—N1—N2	108.79 (14)	C13—C14—C9	119.50 (18)
C6—N1—C9	131.59 (16)	C13—C14—H14	120.2
N2—N1—C9	119.60 (14)	C9—C14—H14	120.2
C8—N2—N1	107.03 (15)	C16—C15—H15A	109.5
C20—N3—N4	109.56 (15)	C16—C15—H15B	109.5
C20—N3—C23	131.01 (16)	H15A—C15—H15B	109.5
N4—N3—C23	119.42 (15)	C16—C15—H15C	109.5
C22—N4—N3	106.12 (15)	H15A—C15—H15C	109.5
C2—C1—H1A	109.5	H15B—C15—H15C	109.5
C2—C1—H1B	109.5	C17—C16—O3	120.95 (16)
H1A—C1—H1B	109.5	C17—C16—C15	127.54 (17)
C2—C1—H1C	109.5	O3—C16—C15	111.49 (15)
H1A—C1—H1C	109.5	C16—C17—C18	125.37 (17)
H1B—C1—H1C	109.5	C16—C17—Cl2	119.11 (15)
C3—C2—O1	121.32 (17)	C18—C17—Cl2	115.51 (14)
C3—C2—C1	128.32 (17)	O4—C18—C19	126.34 (18)
O1—C2—C1	110.36 (15)	O4—C18—C17	123.30 (17)
C2—C3—C4	124.33 (17)	C19—C18—C17	110.36 (16)
C2—C3—Cl1	119.35 (15)	C20—C19—C22	103.99 (16)
C4—C3—Cl1	116.32 (14)	C20—C19—C18	120.39 (17)
O2—C4—C5	125.28 (18)	C22—C19—C18	135.59 (17)
O2—C4—C3	123.38 (17)	O3—C20—N3	123.50 (16)
C5—C4—C3	111.33 (16)	O3—C20—C19	127.05 (17)
C6—C5—C8	104.63 (16)	N3—C20—C19	109.44 (16)
C6—C5—C4	120.46 (17)	C22—C21—H21A	109.5
C8—C5—C4	134.88 (17)	C22—C21—H21B	109.5
O1—C6—N1	124.03 (16)	H21A—C21—H21B	109.5
O1—C6—C5	126.54 (16)	C22—C21—H21C	109.5
N1—C6—C5	109.41 (16)	H21A—C21—H21C	109.5
C8—C7—H7A	109.5	H21B—C21—H21C	109.5
C8—C7—H7B	109.5	N4—C22—C19	110.89 (16)
H7A—C7—H7B	109.5	N4—C22—C21	120.85 (17)
C8—C7—H7C	109.5	C19—C22—C21	128.26 (17)
H7A—C7—H7C	109.5	C24—C23—C28	121.18 (17)
H7B—C7—H7C	109.5	C24—C23—N3	118.27 (17)
N2—C8—C5	110.14 (16)	C28—C23—N3	120.55 (17)
N2—C8—C7	121.71 (17)	C23—C24—C25	119.05 (18)
C5—C8—C7	128.14 (17)	C23—C24—H24	120.5
C14—C9—C10	120.74 (17)	C25—C24—H24	120.5
C14—C9—N1	120.63 (16)	C26—C25—C24	120.27 (19)
C10—C9—N1	118.63 (17)	C26—C25—H25	119.9
C11—C10—C9	118.84 (18)	C24—C25—H25	119.9
C11—C10—H10	120.6	C27—C26—C25	120.13 (19)
C9—C10—H10	120.6	C27—C26—H26	119.9
C12—C11—C10	121.11 (18)	C25—C26—H26	119.9
C12—C11—H11	119.4	C26—C27—C28	120.43 (19)
C10—C11—H11	119.4	C26—C27—H27	119.8
C11—C12—C13	119.08 (18)	C28—C27—H27	119.8
C11—C12—H12	120.5	C27—C28—C23	118.95 (18)
C13—C12—H12	120.5	C27—C28—H28	120.5
C14—C13—C12	120.71 (19)	C23—C28—H28	120.5

C6—N1—N2—C8	−0.26 (19)	C10—C9—C14—C13	0.4 (3)
C9—N1—N2—C8	178.57 (16)	N1—C9—C14—C13	−179.52 (17)
C20—N3—N4—C22	0.45 (19)	C20—O3—C16—C17	−0.6 (2)
C23—N3—N4—C22	−179.61 (16)	C20—O3—C16—C15	178.27 (15)
C6—O1—C2—C3	0.9 (2)	O3—C16—C17—C18	3.4 (3)
C6—O1—C2—C1	−179.75 (15)	C15—C16—C17—C18	−175.20 (18)
O1—C2—C3—C4	0.3 (3)	O3—C16—C17—Cl2	−177.84 (13)
C1—C2—C3—C4	−178.98 (18)	C15—C16—C17—Cl2	3.5 (3)
O1—C2—C3—Cl1	179.71 (13)	C16—C17—C18—O4	177.47 (18)
C1—C2—C3—Cl1	0.5 (3)	Cl2—C17—C18—O4	−1.3 (2)
C2—C3—C4—O2	178.32 (18)	C16—C17—C18—C19	−2.8 (3)
Cl1—C3—C4—O2	−1.1 (2)	Cl2—C17—C18—C19	178.44 (13)
C2—C3—C4—C5	−1.5 (3)	O4—C18—C19—C20	179.30 (18)
Cl1—C3—C4—C5	179.05 (13)	C17—C18—C19—C20	−0.4 (2)
O2—C4—C5—C6	−178.18 (18)	O4—C18—C19—C22	1.6 (3)
C3—C4—C5—C6	1.6 (2)	C17—C18—C19—C22	−178.2 (2)
O2—C4—C5—C8	4.2 (3)	C16—O3—C20—N3	178.86 (16)
C3—C4—C5—C8	−176.02 (19)	C16—O3—C20—C19	−2.8 (3)
C2—O1—C6—N1	177.20 (16)	N4—N3—C20—O3	178.15 (15)
C2—O1—C6—C5	−0.7 (3)	C23—N3—C20—O3	−1.8 (3)
N2—N1—C6—O1	−177.71 (15)	N4—N3—C20—C19	−0.4 (2)
C9—N1—C6—O1	3.6 (3)	C23—N3—C20—C19	179.65 (17)
N2—N1—C6—C5	0.5 (2)	C22—C19—C20—O3	−178.29 (17)
C9—N1—C6—C5	−178.13 (18)	C18—C19—C20—O3	3.3 (3)
C8—C5—C6—O1	177.63 (16)	C22—C19—C20—N3	0.2 (2)
C4—C5—C6—O1	−0.6 (3)	C18—C19—C20—N3	−178.16 (16)
C8—C5—C6—N1	−0.5 (2)	N3—N4—C22—C19	−0.3 (2)
C4—C5—C6—N1	−178.81 (16)	N3—N4—C22—C21	178.95 (16)
N1—N2—C8—C5	−0.1 (2)	C20—C19—C22—N4	0.1 (2)
N1—N2—C8—C7	−179.79 (16)	C18—C19—C22—N4	178.07 (19)
C6—C5—C8—N2	0.4 (2)	C20—C19—C22—C21	−179.13 (18)
C4—C5—C8—N2	178.28 (19)	C18—C19—C22—C21	−1.1 (3)
C6—C5—C8—C7	−179.94 (18)	C20—N3—C23—C24	152.03 (19)
C4—C5—C8—C7	−2.0 (3)	N4—N3—C23—C24	−27.9 (2)
C6—N1—C9—C14	6.0 (3)	C20—N3—C23—C28	−28.5 (3)
N2—N1—C9—C14	−172.56 (16)	N4—N3—C23—C28	151.54 (17)
C6—N1—C9—C10	−173.99 (18)	C28—C23—C24—C25	−0.2 (3)
N2—N1—C9—C10	7.5 (2)	N3—C23—C24—C25	179.24 (17)
C14—C9—C10—C11	−0.8 (3)	C23—C24—C25—C26	0.2 (3)
N1—C9—C10—C11	179.18 (17)	C24—C25—C26—C27	−0.1 (3)
C9—C10—C11—C12	0.5 (3)	C25—C26—C27—C28	−0.1 (3)
C10—C11—C12—C13	0.1 (3)	C26—C27—C28—C23	0.1 (3)
C11—C12—C13—C14	−0.5 (3)	C24—C23—C28—C27	0.0 (3)
C12—C13—C14—C9	0.2 (3)	N3—C23—C28—C27	−179.40 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O2ⁱ	0.95	2.32	3.203 (2)	154
C14—H14···Cl2ⁱ	0.95	2.74	3.448 (2)	132

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁ClN₂O₂
M_r	274.70
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	11.8864 (4), 13.6276 (5), 31.0273 (10)
V (Å³)	5025.9 (3)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.817, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	17994, 5796, 4522
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.117, 1.03
No. of reflections	5796
No. of parameters	347
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.37

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O2ⁱ	0.95	2.32	3.203 (2)	154
C14—H14···Cl2ⁱ	0.95	2.74	3.448 (2)	132

Symmetry code: (i) x+1, y, z.

Footnotes

‡Additional correspondence author, e-mail: aasiri2@kau.edu.sa.

Acknowledgements

The authors are grateful to King Abdulaziz University for providing research facilities. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Asiri, A. M., Faidallah, H. M., Hameed, S. A., Ng, S. W. & Tiekink, E. R. T. (2012). Acta Cryst. E68, o1120. CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gelin, S., Chantegrel, B. & Nadi, A. I. (1983). J. Org. Chem. 48, 4078–4082. CrossRef CAS Web of Science Google Scholar
Kuo, S.-C., Huang, L.-J. & Nakamura, H. (1984). J. Med. Chem. 27, 539–544. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar