Ethyl 4-[3,5-bis­(trifluoro­meth­yl)phen­yl]-6-methyl-2-oxo-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate

Fun, H.-K.; Quah, C.K.; Babu, M.; Kalluraya, B.

doi:10.1107/S1600536809019035

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages o1404-o1405

doi:10.1107/S1600536809019035

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Ethyl 4-[3,5-bis(trifluoromethyl)phenyl]-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § M. Babu ^b and B. Kalluraya ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 8 May 2009; accepted 19 May 2009; online 29 May 2009)

In the title compound, C₁₆H₁₄F₆N₂O₃, the dihydropyrimidinone ring adopts an envelope conformation. In the crystal, molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds into a ribbon-like structure along the b axis. In the ribbon, a pair of bifurcated acceptor N—H⋯O and C—H⋯O bonds generate an R₂¹(6) ring motif. Adjacent ribbons are linked via C—H⋯F hydrogen bonds.

Related literature

For general background and the pharmaceutical applications of pyrimidinones, see: Kalluraya & Rai (2003 ); Atwal (1990 ); Steele et al. (1998 ); Manjula et al. (2004 ); Matsuda & Hirao (1965 ). For a related structure, see: Fun et al. (2009 ). For ring conformations, see: Cremer & Pople (1975 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₆H₁₄F₆N₂O₃
M_r = 396.29
Monoclinic, P 2₁ /c
a = 12.6876 (2) Å
b = 7.3073 (1) Å
c = 19.9547 (3) Å
β = 114.443 (1)°
V = 1684.23 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 110 K
0.45 × 0.25 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.908, T_max = 0.967
22326 measured reflections
7151 independent reflections
5660 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.134
S = 1.04
7151 reflections
254 parameters
36 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1ⁱ	0.86 (2)	2.05 (2)	2.8641 (13)	157 (1)
N2—H1N2⋯O3ⁱⁱ	0.86 (2)	2.13 (2)	2.9796 (12)	166 (1)
C5—H5⋯O1ⁱⁱⁱ	0.95	2.46	3.3797 (14)	162
C14—H14B⋯O3ⁱⁱ	0.98	2.46	3.3571 (13)	153
C12—H12B⋯F3^iv	0.99	2.47	3.2308 (15)	133
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y+1, z; (iii) x, y-1, z; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019035/ci2801sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019035/ci2801Isup2.hkl

checkCIF report

Comment top

3,4-Dihydropyrimidinones are compounds that have been drawn wide-spread attention due to their pharmaceutical applications. A variety of dihydropyrimidinone derivatives have been screened for antihypertension (Atwal, 1990) and antibacterial (Matsuda & Hirao, 1965) activities. Michael addition followed by aldol condensation known as the Robinson's annulation is synthetically a very useful reaction for the construction of six-membered cyclic compounds (Kalluraya & Rai, 2003). The common synthetic routes to these compounds generally involve multi-step transformations that are essentially based on the Biginelli condensation methodology (Steele et al., 1998). These pyrimidinones are also associated with activities like calcium channel blocking (Manjula et al., 2004). We report here the crystal structure of the title compound which was synthesized by means of Robinson's annulation employing microwave technique.

The bond lengths (Allen et al., 1987) and angles in the molecule (Fig. 1) are within normal ranges, and are comparable to those observed in a closely related structure (Fun et al., 2009). The dihydropyrimidinone ring adopts an envelope conformation with atom C7 as the flap. The puckering parameters (Cremer & Pople, 1975) are Q = 0.288 (1) Å; Θ = 72.0 (2)° and ϕ = 52.3 (2)°. The dihedral angle formed by benzene ring (C1—C6) and the N1/C8/N2/C9-/C10 plane is 89.33 (3)°.

In the solid state, the molecules are linked into a ribbon-like structure (Fig. 2) along the [010] by N–H···O and C–H···O hydrogen bonds (Table 1). In the ribbon, C14–H14B···O3 and N2–H1N2···O3 interactions form a pair of bifurcated acceptor bonds, generating an R₂¹(6) ring motif (Bernstein et al., 1995). The adjacent ribbons are linked via C—H···F hydrogen bonds (Fig. 3).

Related literature top

For general background and the pharmaceutical applications of pyrimidinones, see: Kalluraya & Rai (2003); Atwal (1990); Steele et al. (1998); Manjula et al. (2004); Matsuda & Hirao (1965). For a related structure, see: Fun et al. (2009). For ring conformations, see: Cremer & Pople (1975). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

A mixture of 3,5-bis(trifluoromethyl)benzaldehyde (0.01 mol), ethyl acetoacetate (0.015 mol), thiourea (0.01 mol) and conc. H₂SO₄ (2 drops) in absolute alcohol (10 ml) taken in a beaker (100 ml) was zapped inside a MW oven for a duration of 3 minutes (at 160 Watt i.e, 25% MW power). The reaction mixture was then allowed to stand at room temperature and the product formed was filtered, washed with ethanol followed by water and dried. Further purification was done by recrystallization from ethanol. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title compound, viewed along the [101]. Intermolecular interactions are shown as dashed lines.
	Fig. 3. The crystal packing viewed along the b axis. Intermolecular interactions are shown as dashed lines.

Ethyl 4-[3,5-bis(trifluoromethyl)phenyl]-6-methyl-2-oxo-1,2,3,4- tetrahydropyrimidine-5-carboxylate top

Crystal data top

C₁₆H₁₄F₆N₂O₃	F(000) = 808
M_r = 396.29	D_x = 1.563 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9602 reflections
a = 12.6876 (2) Å	θ = 3.2–35.0°
b = 7.3073 (1) Å	µ = 0.15 mm⁻¹
c = 19.9547 (3) Å	T = 110 K
β = 114.443 (1)°	Block, colourless
V = 1684.23 (5) Å³	0.45 × 0.25 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7151 independent reflections
Radiation source: fine-focus sealed tube	5660 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 35.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −20→20
T_min = 0.908, T_max = 0.967	k = −11→11
22326 measured reflections	l = −32→32

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0681P)² + 0.4398P] where P = (F_o² + 2F_c²)/3
7151 reflections	(Δ/σ)_max = 0.001
254 parameters	Δρ_max = 0.49 e Å⁻³
36 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₁₆H₁₄F₆N₂O₃	V = 1684.23 (5) Å³
M_r = 396.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.6876 (2) Å	µ = 0.15 mm⁻¹
b = 7.3073 (1) Å	T = 110 K
c = 19.9547 (3) Å	0.45 × 0.25 × 0.22 mm
β = 114.443 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7151 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5660 reflections with I > 2σ(I)
T_min = 0.908, T_max = 0.967	R_int = 0.025
22326 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	36 restraints
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.49 e Å⁻³
7151 reflections	Δρ_min = −0.45 e Å⁻³
254 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 110.0 (1) K.

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 > 2sigma(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
F1	1.02153 (7)	1.04916 (15)	0.79988 (6)	0.0546 (3)
F2	1.12550 (8)	0.80663 (18)	0.82674 (7)	0.0625 (3)
F3	1.08940 (8)	0.94509 (16)	0.90918 (5)	0.0510 (3)
F4	0.96398 (11)	0.31292 (16)	0.94197 (6)	0.0734 (4)
F5	0.78290 (13)	0.33990 (15)	0.91770 (7)	0.0721 (4)
F6	0.83618 (9)	0.18885 (11)	0.84630 (5)	0.0416 (2)
O1	0.54733 (7)	1.21425 (11)	0.72029 (5)	0.02532 (16)
O2	0.65993 (7)	0.70237 (10)	0.50892 (4)	0.02120 (15)
O3	0.63160 (7)	0.49775 (10)	0.58404 (4)	0.01973 (14)
N1	0.56554 (7)	0.90955 (12)	0.70349 (5)	0.01736 (15)
H1N1	0.5326 (13)	0.881 (2)	0.7321 (8)	0.024 (4)*
N2	0.62532 (7)	1.12340 (12)	0.64147 (5)	0.01722 (15)
H1N2	0.6307 (13)	1.238 (2)	0.6327 (8)	0.025 (4)*
C1	0.83363 (8)	0.82264 (14)	0.76186 (5)	0.01796 (16)
H1	0.8281	0.9301	0.7338	0.022*
C2	0.93726 (9)	0.77888 (16)	0.82033 (5)	0.02191 (19)
C3	0.94750 (10)	0.62163 (17)	0.86221 (6)	0.0247 (2)
H3	1.0185	0.5927	0.9024	0.030*
C4	0.85233 (10)	0.50878 (15)	0.84400 (5)	0.02311 (19)
C5	0.74728 (9)	0.55033 (14)	0.78490 (5)	0.01934 (17)
H5	0.6829	0.4704	0.7727	0.023*
C6	0.73721 (8)	0.70860 (13)	0.74415 (5)	0.01511 (15)
C7	0.62140 (7)	0.75947 (13)	0.68172 (5)	0.01453 (15)
H7	0.5695	0.6501	0.6705	0.017*
C8	0.57787 (8)	1.08737 (14)	0.69151 (5)	0.01731 (16)
C9	0.64143 (7)	0.99139 (13)	0.59672 (5)	0.01476 (15)
C10	0.63470 (7)	0.81180 (12)	0.61226 (5)	0.01376 (14)
C11	0.64206 (7)	0.65599 (13)	0.56809 (5)	0.01450 (15)
C12	0.66444 (9)	0.55645 (15)	0.46087 (5)	0.02057 (18)
H12A	0.5860	0.5072	0.4317	0.025*
H12B	0.7146	0.4556	0.4900	0.025*
C13	0.71342 (13)	0.64003 (19)	0.41112 (7)	0.0337 (3)
H13A	0.7119	0.5496	0.3745	0.051*
H13B	0.7935	0.6785	0.4404	0.051*
H13C	0.6669	0.7466	0.3861	0.051*
C14	0.66536 (10)	1.06995 (14)	0.53478 (5)	0.02129 (18)
H14A	0.7385	1.0205	0.5369	0.032*
H14B	0.6709	1.2035	0.5394	0.032*
H14C	0.6023	1.0371	0.4876	0.032*
C15	0.85946 (13)	0.33881 (18)	0.88774 (7)	0.0338 (3)
C16	1.04253 (10)	0.8954 (2)	0.83865 (7)	0.0314 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0302 (4)	0.0609 (6)	0.0583 (6)	−0.0195 (4)	0.0037 (4)	0.0275 (5)
F2	0.0249 (4)	0.0770 (8)	0.0886 (8)	−0.0072 (4)	0.0266 (5)	−0.0217 (7)
F3	0.0464 (5)	0.0600 (7)	0.0342 (4)	−0.0237 (5)	0.0044 (4)	−0.0086 (4)
F4	0.0821 (8)	0.0439 (6)	0.0514 (6)	−0.0039 (5)	−0.0152 (5)	0.0284 (5)
F5	0.1372 (11)	0.0420 (6)	0.0831 (8)	0.0306 (6)	0.0916 (9)	0.0335 (6)
F6	0.0642 (6)	0.0183 (4)	0.0462 (5)	0.0014 (4)	0.0267 (4)	0.0044 (3)
O1	0.0308 (4)	0.0193 (4)	0.0354 (4)	0.0011 (3)	0.0233 (3)	−0.0065 (3)
O2	0.0373 (4)	0.0144 (3)	0.0191 (3)	−0.0018 (3)	0.0188 (3)	−0.0016 (3)
O3	0.0293 (3)	0.0120 (3)	0.0219 (3)	−0.0003 (3)	0.0147 (3)	0.0004 (2)
N1	0.0207 (3)	0.0156 (4)	0.0226 (3)	−0.0005 (3)	0.0157 (3)	−0.0004 (3)
N2	0.0235 (4)	0.0112 (3)	0.0226 (3)	−0.0007 (3)	0.0151 (3)	−0.0012 (3)
C1	0.0194 (4)	0.0180 (4)	0.0178 (3)	−0.0003 (3)	0.0091 (3)	0.0019 (3)
C2	0.0198 (4)	0.0257 (5)	0.0193 (4)	0.0002 (4)	0.0072 (3)	0.0008 (4)
C3	0.0265 (5)	0.0266 (5)	0.0185 (4)	0.0059 (4)	0.0069 (3)	0.0033 (4)
C4	0.0358 (5)	0.0166 (4)	0.0181 (4)	0.0036 (4)	0.0123 (4)	0.0029 (3)
C5	0.0284 (4)	0.0149 (4)	0.0176 (4)	−0.0010 (3)	0.0123 (3)	0.0005 (3)
C6	0.0203 (4)	0.0134 (4)	0.0146 (3)	0.0000 (3)	0.0103 (3)	0.0000 (3)
C7	0.0178 (3)	0.0128 (4)	0.0164 (3)	−0.0020 (3)	0.0104 (3)	−0.0009 (3)
C8	0.0175 (4)	0.0165 (4)	0.0218 (4)	−0.0004 (3)	0.0120 (3)	−0.0025 (3)
C9	0.0175 (3)	0.0126 (4)	0.0161 (3)	−0.0003 (3)	0.0088 (3)	−0.0001 (3)
C10	0.0174 (3)	0.0120 (4)	0.0143 (3)	−0.0008 (3)	0.0090 (3)	0.0000 (3)
C11	0.0167 (3)	0.0138 (4)	0.0143 (3)	−0.0002 (3)	0.0077 (3)	0.0001 (3)
C12	0.0268 (4)	0.0195 (4)	0.0191 (4)	−0.0007 (4)	0.0131 (3)	−0.0049 (3)
C13	0.0535 (7)	0.0306 (6)	0.0308 (5)	0.0104 (5)	0.0313 (5)	0.0070 (5)
C14	0.0348 (5)	0.0140 (4)	0.0210 (4)	−0.0005 (4)	0.0175 (4)	0.0021 (3)
C15	0.0523 (7)	0.0227 (6)	0.0262 (5)	0.0061 (5)	0.0159 (5)	0.0083 (4)
C16	0.0201 (4)	0.0404 (7)	0.0290 (5)	−0.0035 (4)	0.0054 (4)	0.0029 (5)

Geometric parameters (Å, º) top

F1—C16	1.3271 (17)	C3—C4	1.3809 (17)
F2—C16	1.3388 (16)	C3—H3	0.95
F3—C16	1.3317 (15)	C4—C5	1.3994 (15)
F4—C15	1.3334 (17)	C4—C15	1.4991 (16)
F5—C15	1.3348 (17)	C5—C6	1.3890 (13)
F6—C15	1.3302 (16)	C5—H5	0.95
O1—C8	1.2344 (11)	C6—C7	1.5278 (13)
O2—C11	1.3350 (10)	C7—C10	1.5129 (11)
O2—C12	1.4508 (12)	C7—H7	1.00
O3—C11	1.2210 (12)	C9—C10	1.3593 (13)
N1—C8	1.3420 (13)	C9—C14	1.5034 (12)
N1—C7	1.4659 (12)	C10—C11	1.4663 (12)
N1—H1N1	0.860 (15)	C12—C13	1.5017 (15)
N2—C9	1.3859 (12)	C12—H12A	0.99
N2—C8	1.3879 (11)	C12—H12B	0.99
N2—H1N2	0.866 (17)	C13—H13A	0.98
C1—C2	1.3867 (14)	C13—H13B	0.98
C1—C6	1.3993 (13)	C13—H13C	0.98
C1—H1	0.95	C14—H14A	0.98
C2—C3	1.3949 (16)	C14—H14B	0.98
C2—C16	1.4961 (16)	C14—H14C	0.98

C11—O2—C12	117.75 (8)	C9—C10—C11	125.94 (8)
C8—N1—C7	124.42 (7)	C9—C10—C7	119.63 (8)
C8—N1—H1N1	118.3 (11)	C11—C10—C7	114.42 (8)
C7—N1—H1N1	116.5 (11)	O3—C11—O2	123.19 (8)
C9—N2—C8	123.71 (8)	O3—C11—C10	122.54 (8)
C9—N2—H1N2	120.0 (10)	O2—C11—C10	114.26 (8)
C8—N2—H1N2	115.0 (10)	O2—C12—C13	106.15 (9)
C2—C1—C6	120.04 (9)	O2—C12—H12A	110.5
C2—C1—H1	120.0	C13—C12—H12A	110.5
C6—C1—H1	120.0	O2—C12—H12B	110.5
C1—C2—C3	120.99 (10)	C13—C12—H12B	110.5
C1—C2—C16	120.94 (10)	H12A—C12—H12B	108.7
C3—C2—C16	118.04 (10)	C12—C13—H13A	109.5
C4—C3—C2	118.67 (9)	C12—C13—H13B	109.5
C4—C3—H3	120.7	H13A—C13—H13B	109.5
C2—C3—H3	120.7	C12—C13—H13C	109.5
C3—C4—C5	121.09 (10)	H13A—C13—H13C	109.5
C3—C4—C15	120.40 (10)	H13B—C13—H13C	109.5
C5—C4—C15	118.51 (11)	C9—C14—H14A	109.5
C6—C5—C4	119.92 (9)	C9—C14—H14B	109.5
C6—C5—H5	120.0	H14A—C14—H14B	109.5
C4—C5—H5	120.0	C9—C14—H14C	109.5
C5—C6—C1	119.28 (9)	H14A—C14—H14C	109.5
C5—C6—C7	120.29 (8)	H14B—C14—H14C	109.5
C1—C6—C7	120.42 (8)	F6—C15—F4	106.15 (12)
N1—C7—C10	109.47 (7)	F6—C15—F5	105.53 (12)
N1—C7—C6	111.10 (7)	F4—C15—F5	107.51 (12)
C10—C7—C6	111.98 (7)	F6—C15—C4	112.10 (10)
N1—C7—H7	108.0	F4—C15—C4	112.97 (12)
C10—C7—H7	108.0	F5—C15—C4	112.09 (11)
C6—C7—H7	108.0	F1—C16—F3	106.23 (12)
O1—C8—N1	124.21 (8)	F1—C16—F2	106.83 (12)
O1—C8—N2	120.35 (9)	F3—C16—F2	106.23 (11)
N1—C8—N2	115.41 (8)	F1—C16—C2	113.32 (10)
C10—C9—N2	119.02 (8)	F3—C16—C2	112.12 (10)
C10—C9—C14	127.54 (8)	F2—C16—C2	111.64 (12)
N2—C9—C14	113.44 (8)

C6—C1—C2—C3	0.11 (15)	N2—C9—C10—C7	−5.85 (13)
C6—C1—C2—C16	177.92 (10)	C14—C9—C10—C7	173.99 (9)
C1—C2—C3—C4	0.49 (16)	N1—C7—C10—C9	26.13 (11)
C16—C2—C3—C4	−177.37 (10)	C6—C7—C10—C9	−97.55 (10)
C2—C3—C4—C5	−0.12 (15)	N1—C7—C10—C11	−155.34 (7)
C2—C3—C4—C15	−179.77 (10)	C6—C7—C10—C11	80.98 (10)
C3—C4—C5—C6	−0.86 (15)	C12—O2—C11—O3	1.37 (14)
C15—C4—C5—C6	178.79 (9)	C12—O2—C11—C10	−177.99 (8)
C4—C5—C6—C1	1.46 (13)	C9—C10—C11—O3	−177.59 (9)
C4—C5—C6—C7	−177.28 (8)	C7—C10—C11—O3	4.00 (13)
C2—C1—C6—C5	−1.09 (14)	C9—C10—C11—O2	1.78 (13)
C2—C1—C6—C7	177.64 (8)	C7—C10—C11—O2	−176.63 (8)
C8—N1—C7—C10	−31.69 (12)	C11—O2—C12—C13	−166.51 (9)
C8—N1—C7—C6	92.51 (11)	C3—C4—C15—F6	−120.88 (13)
C5—C6—C7—N1	104.84 (9)	C5—C4—C15—F6	59.46 (15)
C1—C6—C7—N1	−73.88 (10)	C3—C4—C15—F4	−1.01 (17)
C5—C6—C7—C10	−132.40 (9)	C5—C4—C15—F4	179.34 (11)
C1—C6—C7—C10	48.88 (11)	C3—C4—C15—F5	120.64 (14)
C7—N1—C8—O1	−167.27 (9)	C5—C4—C15—F5	−59.01 (15)
C7—N1—C8—N2	14.68 (14)	C1—C2—C16—F1	7.46 (17)
C9—N2—C8—O1	−167.38 (9)	C3—C2—C16—F1	−174.67 (11)
C9—N2—C8—N1	10.76 (14)	C1—C2—C16—F3	127.71 (12)
C8—N2—C9—C10	−14.76 (14)	C3—C2—C16—F3	−54.42 (16)
C8—N2—C9—C14	165.38 (9)	C1—C2—C16—F2	−113.22 (13)
N2—C9—C10—C11	175.81 (8)	C3—C2—C16—F2	64.65 (14)
C14—C9—C10—C11	−4.35 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.86 (2)	2.05 (2)	2.8641 (13)	157 (1)
N2—H1N2···O3ⁱⁱ	0.86 (2)	2.13 (2)	2.9796 (12)	166 (1)
C5—H5···O1ⁱⁱⁱ	0.95	2.46	3.3797 (14)	162
C14—H14B···O3ⁱⁱ	0.98	2.46	3.3571 (13)	153
C12—H12B···F3^iv	0.99	2.47	3.2308 (15)	133

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄F₆N₂O₃
M_r	396.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	110
a, b, c (Å)	12.6876 (2), 7.3073 (1), 19.9547 (3)
β (°)	114.443 (1)
V (Å³)	1684.23 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.45 × 0.25 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.908, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	22326, 7151, 5660
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.134, 1.04
No. of reflections	7151
No. of parameters	254
No. of restraints	36
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.45

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.86 (2)	2.05 (2)	2.8641 (13)	157 (1)
N2—H1N2···O3ⁱⁱ	0.86 (2)	2.13 (2)	2.9796 (12)	166 (1)
C5—H5···O1ⁱⁱⁱ	0.95	2.46	3.3797 (14)	162
C14—H14B···O3ⁱⁱ	0.98	2.46	3.3571 (13)	153
C12—H12B···F3^iv	0.99	2.47	3.2308 (15)	133

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

HKF and CKQ thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). CKQ also thanks USM for a Research Fellowship.

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