Ethyl 4-(2,4-difluoro­phen­yl)-6-methyl-2-oxo-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate

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

doi:10.1107/S1600536809015918

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages o1188-o1189

doi:10.1107/S1600536809015918

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Ethyl 4-(2,4-difluorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate

Hoong-Kun Fun,^a ^*‡ Chin Sing Yeap,^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 24 April 2009; accepted 28 April 2009; online 7 May 2009)

In the title compound, C₁₄H₁₄F₂N₂O₃, the dihydropyrimidinone ring adopts a flattened boat conformation. The difluorophenyl group is disordered over two orientations with occupancies of 0.544 (3) and 0.456 (3). The methoxycarbonyl group is disordered over two positions with occupancies of 0.580 (8) and 0.420 (8). In the crystal, molecules are linked into centrosymmetric dimers by paired N—H⋯O hydrogen bonds and the dimers are linked into a ribbon-like structure along [100] by further N—H⋯O hydrogen bonds.

Related literature

For general background and pharmaceutical applications of pyrimidinones, see: Kalluraya & Rai (2003 ); Atwal (1990 ); Sadanandam et al. (1992 ); Steele et al. (1998 ); Manjula et al. (2004 ). 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

C₁₄H₁₄F₂N₂O₃
M_r = 296.27
Triclinic, $[P \overline 1]$
a = 7.5176 (1) Å
b = 8.0483 (1) Å
c = 11.9323 (2) Å
α = 90.147 (1)°
β = 100.839 (1)°
γ = 108.421 (1)°
V = 671.25 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.43 × 0.32 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.949, T_max = 0.985
17515 measured reflections
3075 independent reflections
2703 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.173
S = 1.08
3075 reflections
266 parameters
45 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2ⁱ	0.89 (3)	2.14 (3)	3.007 (2)	165 (2)
N2—H1N2⋯O1ⁱⁱ	0.86 (3)	1.99 (3)	2.840 (2)	177 (3)
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y, -z.

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/S1600536809015918/ci2792sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015918/ci2792Isup2.hkl

checkCIF report

Comment top

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 and Rai, 2003). 3,4-Dihydro-pyrimidinones are compounds that have drawn wide-spread attention, due to their pharmaceutical applications (Atwal, 1990; Sadanandam et al., 1992). The common synthetic routes to these compounds generally involve multi-step transformation, which 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 synthesized the title compound by means of Robinson's annulation employing the microwave technique, and its crystal structure is reported here.

Bond lengths (Allen et al., 1987) and angles in the title molecule (Fig. 1) are within normal ranges. The dihydropyrimidinone ring adopts a flattened boat conformation, with puckering parameters Q = 0.170 (2) Å, Θ = 97.4 (7)° and ϕ = 254.4 (7)°.

The difluorophenyl group is disordered over two positions with occupancies of 0.544 (3) and 0.456 (3). The caboxylate methyl group is also disordered over two positions with occupancies of 0.580 (8) and 0.420 (8).

In the crystal structure, the molecules are linked into centrosymmetric dimers by means of paired N—H···O hydrogen bonds (Table 1). The dimers are linked into a chain along the [100] again by N—H···O hydrogen bonds (Fig. 2).

Related literature top

For general background and pharmaceutical applications of pyrimidinones, see: Kalluraya & Rai (2003); Atwal (1990); Sadanandam et al. (1992); Steele et al. (1998); Manjula et al. (2004). 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 2,4-difluoro 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 microwave oven for 3 min 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 recrystallisation from ethanol. Single crystals suitable for X-ray analysis were obtained from ethanol by slow evaporation.

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, with atom labels and 50% probability displacement ellipsoids for non-H atoms. All disorder components are shown.
	Fig. 2. The crystal packing of the title compound, viewed down the b axis, showing chains along the [100]. Hydrogen bonds are shown as dashed lines. Only major disorder components are shown.

Ethyl 4-(2,4-difluorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate top

Crystal data top

C₁₄H₁₄F₂N₂O₃	Z = 2
M_r = 296.27	F(000) = 308
Triclinic, P1	D_x = 1.466 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5176 (1) Å	Cell parameters from 7927 reflections
b = 8.0483 (1) Å	θ = 2.7–34.4°
c = 11.9323 (2) Å	µ = 0.12 mm⁻¹
α = 90.147 (1)°	T = 100 K
β = 100.839 (1)°	Plate, colourless
γ = 108.421 (1)°	0.43 × 0.32 × 0.13 mm
V = 671.25 (2) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3075 independent reflections
Radiation source: fine-focus sealed tube	2703 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.949, T_max = 0.985	k = −10→10
17515 measured reflections	l = −15→15

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0607P)² + 0.8775P] where P = (F_o² + 2F_c²)/3
3075 reflections	(Δ/σ)_max = 0.001
266 parameters	Δρ_max = 0.66 e Å⁻³
45 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

C₁₄H₁₄F₂N₂O₃	γ = 108.421 (1)°
M_r = 296.27	V = 671.25 (2) Å³
Triclinic, P1	Z = 2
a = 7.5176 (1) Å	Mo Kα radiation
b = 8.0483 (1) Å	µ = 0.12 mm⁻¹
c = 11.9323 (2) Å	T = 100 K
α = 90.147 (1)°	0.43 × 0.32 × 0.13 mm
β = 100.839 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3075 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2703 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.985	R_int = 0.028
17515 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	45 restraints
wR(F²) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.66 e Å⁻³
3075 reflections	Δρ_min = −0.84 e Å⁻³
266 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 100.0 (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	Occ. (<1)
F1A	0.7550 (6)	0.3028 (5)	0.3410 (3)	0.0598 (8)	0.544 (3)
F1B	0.8268 (7)	0.8571 (6)	0.2813 (4)	0.0598 (8)	0.456 (3)
O1	0.3876 (2)	0.1588 (2)	0.01956 (16)	0.0352 (4)
O2	1.2723 (2)	0.5461 (2)	0.14780 (15)	0.0298 (4)
O3	1.1456 (2)	0.7375 (2)	0.20789 (18)	0.0428 (5)
N1	0.5906 (2)	0.4172 (2)	0.10712 (14)	0.0207 (4)
N2	0.7014 (2)	0.1862 (2)	0.07956 (16)	0.0234 (4)
F2A	0.7967 (7)	0.7696 (9)	0.6102 (3)	0.0959 (19)	0.544 (3)
C1A	0.7750 (7)	0.4770 (8)	0.3704 (4)	0.0279 (8)	0.544 (3)
C2A	0.7792 (9)	0.5355 (13)	0.4811 (5)	0.0557 (19)	0.544 (3)
H2AA	0.7719	0.4586	0.5394	0.067*	0.544 (3)
C3A	0.7941 (12)	0.7054 (15)	0.5035 (6)	0.061 (2)	0.544 (3)
C4A	0.8048 (8)	0.8278 (10)	0.4216 (5)	0.0520 (16)	0.544 (3)
H4AA	0.8131	0.9433	0.4381	0.062*	0.544 (3)
C5A	0.8022 (7)	0.7640 (8)	0.3129 (5)	0.0332 (10)	0.544 (3)
H5AA	0.8107	0.8423	0.2554	0.040*	0.544 (3)
C6A	0.788 (3)	0.5949 (12)	0.2835 (7)	0.0180 (17)	0.544 (3)
F2B	0.7660 (6)	0.6163 (6)	0.6323 (2)	0.0479 (11)	0.456 (3)
C1B	0.8051 (8)	0.7153 (9)	0.3476 (5)	0.0279 (8)	0.456 (3)
C2B	0.8046 (11)	0.7414 (8)	0.4604 (6)	0.0255 (14)	0.456 (3)
H2BA	0.8265	0.8519	0.4945	0.031*	0.456 (3)
C3B	0.7694 (10)	0.5921 (9)	0.5204 (5)	0.0275 (13)	0.456 (3)
C4B	0.7384 (11)	0.4271 (8)	0.4734 (5)	0.0345 (14)	0.456 (3)
H4BA	0.7125	0.3326	0.5193	0.041*	0.456 (3)
C5B	0.7443 (9)	0.3954 (11)	0.3573 (5)	0.0332 (10)	0.456 (3)
H5BA	0.7301	0.2853	0.3256	0.040*	0.456 (3)
C6B	0.774 (3)	0.5502 (15)	0.2934 (11)	0.025 (3)	0.456 (3)
C7	0.7793 (3)	0.5371 (3)	0.16198 (16)	0.0182 (4)
H7A	0.7995	0.6433	0.1195	0.022*	0.580 (8)
H7B	0.7985	0.6385	0.1178	0.022*	0.420 (8)
C8	0.5505 (3)	0.2516 (3)	0.06653 (18)	0.0234 (4)
C9	0.8906 (3)	0.2904 (3)	0.11002 (16)	0.0197 (4)
C10	0.9344 (3)	0.4608 (3)	0.14452 (15)	0.0179 (4)
C11	1.1330 (3)	0.5786 (3)	0.16561 (16)	0.0198 (4)
C12	1.3361 (4)	0.8646 (4)	0.2385 (3)	0.0541 (9)
H12A	1.3717	0.9251	0.1718	0.065*	0.580 (8)
H12B	1.4283	0.8057	0.2670	0.065*	0.580 (8)
H12C	1.4223	0.8259	0.2019	0.065*	0.420 (8)
H12D	1.3332	0.9763	0.2093	0.065*	0.420 (8)
C13A	1.3350 (6)	0.9926 (6)	0.3285 (4)	0.0367 (13)	0.580 (8)
H13A	1.4629	1.0700	0.3559	0.055*	0.580 (8)
H13B	1.2866	0.9305	0.3908	0.055*	0.580 (8)
H13C	1.2546	1.0599	0.2970	0.055*	0.580 (8)
C13B	1.4024 (9)	0.8870 (8)	0.3480 (5)	0.0355 (17)	0.420 (8)
H13D	1.4307	0.7841	0.3750	0.053*	0.420 (8)
H13E	1.3085	0.9070	0.3861	0.053*	0.420 (8)
H13F	1.5170	0.9866	0.3640	0.053*	0.420 (8)
C14	1.0280 (3)	0.1943 (3)	0.09888 (19)	0.0242 (4)
H14A	1.1389	0.2365	0.1591	0.036*
H14B	1.0657	0.2138	0.0262	0.036*
H14C	0.9676	0.0710	0.1042	0.036*
H1N1	0.493 (4)	0.458 (4)	0.105 (2)	0.034 (7)*
H1N2	0.674 (4)	0.081 (4)	0.052 (2)	0.035 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1A	0.078 (2)	0.0668 (19)	0.0584 (16)	0.0393 (16)	0.0423 (15)	0.0248 (14)
F1B	0.078 (2)	0.0668 (19)	0.0584 (16)	0.0393 (16)	0.0423 (15)	0.0248 (14)
O1	0.0139 (7)	0.0315 (8)	0.0586 (11)	0.0057 (6)	0.0059 (7)	−0.0174 (8)
O2	0.0166 (7)	0.0307 (8)	0.0447 (9)	0.0085 (6)	0.0107 (6)	0.0018 (7)
O3	0.0160 (8)	0.0346 (9)	0.0721 (13)	−0.0006 (7)	0.0104 (8)	−0.0262 (9)
N1	0.0141 (8)	0.0243 (9)	0.0253 (8)	0.0088 (7)	0.0032 (6)	−0.0036 (7)
N2	0.0160 (8)	0.0206 (8)	0.0350 (10)	0.0063 (7)	0.0081 (7)	−0.0045 (7)
F2A	0.081 (3)	0.165 (5)	0.0359 (19)	0.034 (3)	0.0086 (18)	−0.043 (3)
C1A	0.0253 (17)	0.047 (2)	0.0141 (15)	0.0144 (16)	0.0068 (12)	0.0079 (16)
C2A	0.039 (3)	0.102 (6)	0.023 (3)	0.018 (4)	0.008 (2)	0.002 (4)
C3A	0.039 (3)	0.112 (7)	0.026 (4)	0.018 (5)	0.003 (3)	−0.023 (4)
C4A	0.030 (3)	0.071 (4)	0.049 (3)	0.012 (3)	0.002 (2)	−0.039 (3)
C5A	0.0261 (18)	0.051 (3)	0.0162 (16)	0.0024 (17)	0.0063 (13)	−0.0106 (19)
C6A	0.010 (3)	0.031 (5)	0.012 (2)	0.004 (4)	0.0039 (16)	−0.003 (2)
F2B	0.079 (3)	0.073 (3)	0.0113 (13)	0.051 (2)	0.0125 (14)	0.0029 (15)
C1B	0.0253 (17)	0.047 (2)	0.0141 (15)	0.0144 (16)	0.0068 (12)	0.0079 (16)
C2B	0.040 (3)	0.017 (2)	0.025 (3)	0.019 (2)	0.002 (3)	−0.002 (2)
C3B	0.041 (3)	0.036 (3)	0.015 (3)	0.023 (3)	0.008 (2)	0.005 (2)
C4B	0.058 (4)	0.028 (3)	0.028 (3)	0.023 (3)	0.016 (3)	0.011 (2)
C5B	0.0261 (18)	0.051 (3)	0.0162 (16)	0.0024 (17)	0.0063 (13)	−0.0106 (19)
C6B	0.016 (4)	0.025 (5)	0.036 (5)	0.008 (5)	0.005 (3)	−0.005 (3)
C7	0.0150 (9)	0.0218 (9)	0.0189 (9)	0.0073 (7)	0.0039 (7)	−0.0009 (7)
C8	0.0159 (9)	0.0252 (10)	0.0304 (10)	0.0067 (8)	0.0080 (8)	−0.0038 (8)
C9	0.0156 (9)	0.0262 (10)	0.0196 (9)	0.0084 (8)	0.0062 (7)	0.0020 (7)
C10	0.0144 (9)	0.0250 (10)	0.0159 (8)	0.0081 (7)	0.0043 (7)	0.0012 (7)
C11	0.0173 (9)	0.0269 (10)	0.0162 (8)	0.0082 (8)	0.0041 (7)	0.0013 (7)
C12	0.0205 (12)	0.0508 (17)	0.078 (2)	−0.0088 (11)	0.0148 (13)	−0.0355 (15)
C13A	0.033 (2)	0.028 (2)	0.042 (2)	0.0054 (17)	−0.0014 (18)	−0.0057 (17)
C13B	0.032 (3)	0.035 (3)	0.034 (3)	0.007 (2)	−0.001 (2)	−0.006 (2)
C14	0.0198 (10)	0.0261 (10)	0.0308 (11)	0.0112 (8)	0.0085 (8)	0.0002 (8)

Geometric parameters (Å, º) top

F1A—C1A	1.398 (6)	C3B—C4B	1.373 (8)
F1B—C1B	1.375 (7)	C4B—C5B	1.418 (8)
O1—C8	1.238 (3)	C4B—H4BA	0.93
O2—C11	1.211 (2)	C5B—C6B	1.441 (12)
O3—C11	1.342 (3)	C5B—H5BA	0.93
O3—C12	1.451 (3)	C6B—C7	1.579 (12)
N1—C8	1.337 (3)	C7—C10	1.524 (3)
N1—C7	1.468 (2)	C7—H7A	0.98
N1—H1N1	0.89 (3)	C7—H7B	0.96
N2—C8	1.379 (3)	C9—C10	1.349 (3)
N2—C9	1.382 (3)	C9—C14	1.496 (3)
N2—H1N2	0.86 (3)	C10—C11	1.467 (3)
F2A—C3A	1.367 (7)	C12—C13B	1.299 (7)
C1A—C2A	1.392 (8)	C12—C13A	1.490 (5)
C1A—C6A	1.404 (9)	C12—H12A	0.97
C2A—C3A	1.358 (11)	C12—H12B	0.97
C2A—H2AA	0.93	C12—H12C	0.97
C3A—C4A	1.384 (11)	C12—H12D	0.97
C4A—C5A	1.388 (7)	C13A—H12D	1.4259
C4A—H4AA	0.93	C13A—H13A	0.96
C5A—C6A	1.371 (11)	C13A—H13B	0.96
C5A—H5AA	0.93	C13A—H13C	0.96
C6A—C7	1.505 (8)	C13B—H13D	0.96
F2B—C3B	1.355 (6)	C13B—H13E	0.96
C1B—C2B	1.362 (8)	C13B—H13F	0.96
C1B—C6B	1.409 (12)	C14—H14A	0.96
C2B—C3B	1.378 (7)	C14—H14B	0.96
C2B—H2BA	0.93	C14—H14C	0.96

C11—O3—C12	116.68 (18)	C10—C7—H7B	104.8
C8—N1—C7	126.65 (17)	C6B—C7—H7B	121.4
C8—N1—H1N1	117.3 (18)	O1—C8—N1	123.06 (19)
C7—N1—H1N1	115.9 (18)	O1—C8—N2	120.41 (19)
C8—N2—C9	123.28 (18)	N1—C8—N2	116.53 (18)
C8—N2—H1N2	115 (2)	C10—C9—N2	119.93 (18)
C9—N2—H1N2	120 (2)	C10—C9—C14	126.95 (18)
C2A—C1A—F1A	122.6 (6)	N2—C9—C14	113.12 (17)
C2A—C1A—C6A	119.6 (7)	C9—C10—C11	120.89 (17)
F1A—C1A—C6A	117.9 (5)	C9—C10—C7	121.08 (17)
C3A—C2A—C1A	119.6 (6)	C11—C10—C7	118.04 (17)
C3A—C2A—H2AA	120.2	O2—C11—O3	121.61 (18)
C1A—C2A—H2AA	120.2	O2—C11—C10	127.53 (19)
C2A—C3A—F2A	122.2 (8)	O3—C11—C10	110.85 (16)
C2A—C3A—C4A	123.8 (6)	C13B—C12—O3	113.2 (4)
F2A—C3A—C4A	114.0 (8)	C13B—C12—C13A	46.9 (3)
C3A—C4A—C5A	114.5 (6)	O3—C12—C13A	108.3 (3)
C3A—C4A—H4AA	122.7	C13B—C12—H12A	135.7
C5A—C4A—H4AA	122.7	O3—C12—H12A	110.0
C6A—C5A—C4A	125.2 (7)	C13A—C12—H12A	110.0
C6A—C5A—H5AA	117.4	C13B—C12—H12B	64.7
C4A—C5A—H5AA	117.4	O3—C12—H12B	110.0
C5A—C6A—C1A	117.2 (6)	C13A—C12—H12B	110.0
C5A—C6A—C7	121.1 (7)	H12A—C12—H12B	108.4
C1A—C6A—C7	121.6 (7)	C13B—C12—H12C	108.9
C2B—C1B—F1B	118.1 (6)	O3—C12—H12C	108.9
C2B—C1B—C6B	124.0 (7)	C13A—C12—H12C	141.9
F1B—C1B—C6B	117.9 (6)	H12A—C12—H12C	63.9
C1B—C2B—C3B	115.2 (5)	H12B—C12—H12C	48.0
C1B—C2B—H2BA	122.4	C13B—C12—H12D	109.0
C3B—C2B—H2BA	122.4	O3—C12—H12D	109.0
F2B—C3B—C4B	120.2 (5)	C13A—C12—H12D	67.0
F2B—C3B—C2B	115.7 (6)	H12A—C12—H12D	46.1
C4B—C3B—C2B	124.1 (5)	H12B—C12—H12D	139.4
C3B—C4B—C5B	122.4 (6)	H12C—C12—H12D	107.8
C3B—C4B—H4BA	118.8	C12—C13A—H13A	109.5
C5B—C4B—H4BA	118.8	H12D—C13A—H13A	100.8
C4B—C5B—C6B	113.6 (8)	C12—C13A—H13B	109.5
C4B—C5B—H5BA	123.2	H12D—C13A—H13B	143.5
C6B—C5B—H5BA	123.2	C12—C13A—H13C	109.5
C1B—C6B—C5B	120.6 (9)	H12D—C13A—H13C	77.8
C1B—C6B—C7	119.2 (7)	C12—C13B—H13D	109.5
C5B—C6B—C7	120.1 (8)	C12—C13B—H13E	109.5
N1—C7—C6A	113.1 (6)	H13D—C13B—H13E	109.5
N1—C7—C10	109.82 (15)	C12—C13B—H13F	109.5
C6A—C7—C10	115.3 (7)	H13D—C13B—H13F	109.5
N1—C7—C6B	105.6 (8)	H13E—C13B—H13F	109.5
C10—C7—C6B	110.0 (8)	C9—C14—H14A	109.5
N1—C7—H7A	105.9	C9—C14—H14B	109.5
C6A—C7—H7A	105.9	H14A—C14—H14B	109.5
C10—C7—H7A	105.9	C9—C14—H14C	109.5
C6B—C7—H7A	119.3	H14A—C14—H14C	109.5
N1—C7—H7B	104.8	H14B—C14—H14C	109.5
C6A—C7—H7B	108.1

F1A—C1A—C2A—C3A	−178.4 (6)	C5A—C6A—C7—C6B	−168 (8)
C6A—C1A—C2A—C3A	0.7 (12)	C1A—C6A—C7—C6B	10 (5)
C1A—C2A—C3A—F2A	179.2 (6)	C1B—C6B—C7—N1	−120.8 (15)
C1A—C2A—C3A—C4A	0.3 (12)	C5B—C6B—C7—N1	60.9 (18)
C2A—C3A—C4A—C5A	−1.0 (11)	C1B—C6B—C7—C6A	5 (5)
F2A—C3A—C4A—C5A	−180.0 (5)	C5B—C6B—C7—C6A	−173 (8)
C3A—C4A—C5A—C6A	0.8 (12)	C1B—C6B—C7—C10	120.7 (15)
C4A—C5A—C6A—C1A	0.1 (18)	C5B—C6B—C7—C10	−57.6 (18)
C4A—C5A—C6A—C7	177.7 (8)	C7—N1—C8—O1	−178.9 (2)
C2A—C1A—C6A—C5A	−0.9 (17)	C7—N1—C8—N2	1.3 (3)
F1A—C1A—C6A—C5A	178.2 (9)	C9—N2—C8—O1	166.8 (2)
C2A—C1A—C6A—C7	−178.4 (9)	C9—N2—C8—N1	−13.3 (3)
F1A—C1A—C6A—C7	0.6 (17)	C8—N2—C9—C10	9.5 (3)
F1B—C1B—C2B—C3B	175.8 (6)	C8—N2—C9—C14	−169.96 (19)
C6B—C1B—C2B—C3B	−0.7 (16)	N2—C9—C10—C11	−173.48 (17)
C1B—C2B—C3B—F2B	−179.1 (5)	C14—C9—C10—C11	6.0 (3)
C1B—C2B—C3B—C4B	0.7 (12)	N2—C9—C10—C7	6.1 (3)
F2B—C3B—C4B—C5B	−178.7 (6)	C14—C9—C10—C7	−174.45 (18)
C2B—C3B—C4B—C5B	1.5 (12)	N1—C7—C10—C9	−15.5 (2)
C3B—C4B—C5B—C6B	−3.4 (14)	C6A—C7—C10—C9	113.7 (5)
C2B—C1B—C6B—C5B	−1 (3)	C6B—C7—C10—C9	100.3 (6)
F1B—C1B—C6B—C5B	−178.0 (13)	N1—C7—C10—C11	164.14 (16)
C2B—C1B—C6B—C7	−179.8 (10)	C6A—C7—C10—C11	−66.7 (5)
F1B—C1B—C6B—C7	4 (2)	C6B—C7—C10—C11	−80.1 (6)
C4B—C5B—C6B—C1B	3 (2)	C12—O3—C11—O2	−4.1 (3)
C4B—C5B—C6B—C7	−178.4 (12)	C12—O3—C11—C10	176.8 (2)
C8—N1—C7—C6A	−118.4 (5)	C9—C10—C11—O2	6.0 (3)
C8—N1—C7—C10	12.0 (3)	C7—C10—C11—O2	−173.63 (19)
C8—N1—C7—C6B	−106.5 (7)	C9—C10—C11—O3	−174.99 (18)
C5A—C6A—C7—N1	−109.7 (12)	C7—C10—C11—O3	5.4 (2)
C1A—C6A—C7—N1	67.8 (15)	C11—O3—C12—C13B	−104.0 (4)
C5A—C6A—C7—C10	122.8 (12)	C11—O3—C12—C13A	−154.2 (3)
C1A—C6A—C7—C10	−59.7 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2ⁱ	0.89 (3)	2.14 (3)	3.007 (2)	165 (2)
N2—H1N2···O1ⁱⁱ	0.86 (3)	1.99 (3)	2.840 (2)	177 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄F₂N₂O₃
M_r	296.27
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.5176 (1), 8.0483 (1), 11.9323 (2)
α, β, γ (°)	90.147 (1), 100.839 (1), 108.421 (1)
V (Å³)	671.25 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.43 × 0.32 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.949, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	17515, 3075, 2703
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.173, 1.08
No. of reflections	3075
No. of parameters	266
No. of restraints	45
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.84

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···O2ⁱ	0.89 (3)	2.14 (3)	3.007 (2)	165 (2)
N2—H1N2···O1ⁱⁱ	0.86 (3)	1.99 (3)	2.840 (2)	177 (3)

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5523-2009.

Acknowledgements

HKF thanks Universiti Sains Malaysia for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). CSY thanks the Malaysian Government and Universiti Sains Malaysia for the award of a post of research officer under the Science Fund (grant No. 305/PFIZIK/613312).

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