2-Amino-7,7-dimethyl-5-oxo-4-[3-(trifluoro­meth­yl)phen­yl]-5,6,7,8-tetra­hydro-4H-chromene-3-carbonitrile

Kant, R.; Gupta, V.K.; Kapoor, K.; Patil, D.R.; Chandam, D.R.; Deshmukh, M.B.

doi:10.1107/S1600536813004522

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Pages o417-o418

doi:10.1107/S1600536813004522

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2-Amino-7,7-dimethyl-5-oxo-4-[3-(trifluoromethyl)phenyl]-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile

Rajni Kant,^a ^* Vivek K. Gupta,^a Kamini Kapoor,^a D. R. Patil,^b D. R. Chandam ^b and Madhukar B. Deshmukh ^b

^aX-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and ^bDepartment of Chemistry, Shivaji University, Kolhapur 416 004 (MS), India
^*Correspondence e-mail: rkvk.paper11@gmail.com

(Received 11 February 2013; accepted 15 February 2013; online 20 February 2013)

In the title molecule, C₁₉H₁₇F₃N₂O₂, the fused cyclohexene and pyran rings adopt sofa and flattened boat conformations, respectively. The four essentially planar atoms of the pyran ring [maximum deviation = 0.008 (2) Å] form a dihedral angle of 88.13 (9)° with the benzene ring. The F atoms of the trifluoromethyl group were refined as disordered over three sets of sites in a 0.507 (7):0.330 (7):0.163 (3) ratio. In the crystal, molecules are connected into inversion dimers via pairs of N—H⋯N hydrogen bonds and these dimers are further linked by N—H⋯O hydrogen bonds into a two-dimensional network parallel to (100).

Related literature

For the biological activity of 4H-pyran derivatives, see: Bhattacharyya et al.(2012 ); Khaksar et al. (2012 ); Fotouhi et al. (2007 ). For related structures, see: Wang (2011 ); Anthal et al. (2012 ); Kant et al. (2013 ). For ring conformations, see: Duax & Norton (1975 ).

Experimental

Crystal data

C₁₉H₁₇F₃N₂O₂
M_r = 362.35
Monoclinic, C 2/c
a = 23.7543 (6) Å
b = 9.3871 (2) Å
c = 15.8857 (4) Å
β = 94.704 (2)°
V = 3530.33 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.766, T_max = 1.000
40937 measured reflections
3467 independent reflections
2538 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.126
S = 1.03
3467 reflections
258 parameters
10 restraints
H-atom parameters constrained
Δρ_max = 0.26 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
N21—H21A⋯N20ⁱ	0.86	2.17	3.025 (3)	171
N21—H21B⋯O2ⁱⁱ	0.86	2.10	2.934 (2)	163
Symmetry codes: (i) -x, -y+2, -z+2; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813004522/lh5585sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813004522/lh5585Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813004522/lh5585Isup3.cml

checkCIF report

Comment top

Polyfunctionalized 4H-pyran derivatives are used as anti-coagulants, anticancer agents, spasmolytics, anti-anaphylactics, anti-microbial and immunomodulating activities (Khaksar et al., 2012; Bhattacharyya et al., 2012). Furthermore, these compounds can be employed as pigments, photoactive materials and used as biodegradable agrochemicals (Fotouhi et al., 2007). In this paper, we report the crystal structure of the title compound, (I).

In (I) (Fig.1), all bond lengths and angles are normal and correspond to those observed in related structures (Wang et al.,2011; Anthal et al., 2012; Kant et al.,2013). The cyclohexene ring (C5/C6/C7/C8/C8A/C4A) and and pyran ring (O1/C2/C3/C4/C4A/C8A) exhibit sofa and boat conformations, respectively, with asymmetry parameters (ΔCs(C7) = 9.78 & ΔCs(C4) = 2.36, ΔCs(C2-C3)= 9.4)(Duax & Norton, 1975) with atom C7 forming the flap in the cyclohexene ring. The four essentially planar atoms (C2/C3/C4A/C8A) of pyran ring (maximum deviation = -0.008 (2)Å for C8A) form a dihedral angle of 88.13 (9)° with benzene the ring. The F atoms of the trifluoromethyl group were refined as disordered over three sets of sites in a 0.507 (7) : 0.330 (7) : 0.163 (3) ratio. In the crystal, molecules are connected into dimers via N21—H21A···N20ⁱ hydrogen bonds and these dimers are further connected by N21—H21B···O2ⁱⁱ (Table 1) hydrogen bonds into a two-dimensional network (Fig. 2) parallel to (100).

Related literature top

For the biological activity of 4H-pyran derivatives, see: Bhattacharyya et al.(2012); Khaksar et al. (2012); Fotouhi et al. (2007). For related structures, see: Wang (2011); Anthal et al. (2012); Kant et al. (2013). For ring conformations, see: Duax & Norton (1975).

Experimental top

In a 50 ml round bottom flask charged with 1mmole of dimedone, 1 mmole of 3-(trifluoromethyl)benzaldehyde and 1 mmole of malononitrile were added. Then 5 ml of aqueous ethanol (1:1) and 20 mol% of NH₄Cl was added and the reaction mixture stirred for 30-45 min. at 323-328 K. The reaction was monitored by TLC. After completion of the reaction, the mixture was poured onto crushed ice and stirred. The solid precipitated was filtered and recrystallized from ethanol to afford pure product as crystal suitable for X-ray diffraction.

m.p.: 503-504 K, Yield: 82%.

1H NMR (300MHz,DMSO-d6): δ 0.94(s, 3H, CH3), 1.02(s, 3H, CH3), 2.05-2.20(m,2H, CH2), 2.44-2.49(m, 2H, CH2), 4.18(s, 1H, CH), 6.73(s, 2H,NH2), 6.81-6.87(m, 2H, Ar-H), 6.92-6.95(m, 1H, Ar-H), 7.18-7.25(m, 1H, Ar-H).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with ellipsoids drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii. The F atoms are disorded over three sets of sites.
	Fig. 2. The packing arrangement of molecules viewed along the a axis. The dashed lines show intermolecular N—H···O and N—H···N hydrogen bonds. The disorder is not shown.

2-Amino-7,7-dimethyl-5-oxo-4-[3-(trifluoromethyl)phenyl]-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile top

Crystal data top

C₁₉H₁₇F₃N₂O₂	F(000) = 1504
M_r = 362.35	D_x = 1.363 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 18267 reflections
a = 23.7543 (6) Å	θ = 3.4–29.1°
b = 9.3871 (2) Å	µ = 0.11 mm⁻¹
c = 15.8857 (4) Å	T = 293 K
β = 94.704 (2)°	Block, colorless
V = 3530.33 (15) Å³	0.3 × 0.2 × 0.2 mm
Z = 8

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	3467 independent reflections
Radiation source: fine-focus sealed tube	2538 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
Detector resolution: 16.1049 pixels mm^-1	θ_max = 26.0°, θ_min = 3.4°
ω scans	h = −29→29
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→11
T_min = 0.766, T_max = 1.000	l = −19→19
40937 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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0389P)² + 5.1587P] where P = (F_o² + 2F_c²)/3
3467 reflections	(Δ/σ)_max = 0.001
258 parameters	Δρ_max = 0.26 e Å⁻³
10 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₉H₁₇F₃N₂O₂	V = 3530.33 (15) Å³
M_r = 362.35	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 23.7543 (6) Å	µ = 0.11 mm⁻¹
b = 9.3871 (2) Å	T = 293 K
c = 15.8857 (4) Å	0.3 × 0.2 × 0.2 mm
β = 94.704 (2)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	3467 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	2538 reflections with I > 2σ(I)
T_min = 0.766, T_max = 1.000	R_int = 0.065
40937 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	10 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.03	Δρ_max = 0.26 e Å⁻³
3467 reflections	Δρ_min = −0.32 e Å⁻³
258 parameters

Special details top

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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)
O1	0.08902 (7)	0.55303 (15)	1.02901 (8)	0.0401 (4)
C2	0.06233 (9)	0.6806 (2)	1.01297 (12)	0.0324 (5)
O2	0.06995 (8)	0.41341 (18)	0.74350 (9)	0.0506 (5)
C3	0.04766 (9)	0.7238 (2)	0.93258 (12)	0.0308 (5)
C4	0.06583 (9)	0.6445 (2)	0.85626 (12)	0.0319 (5)
H4	0.0335	0.6405	0.8138	0.038*
C4A	0.08096 (9)	0.4945 (2)	0.88253 (12)	0.0313 (5)
C5	0.08182 (9)	0.3842 (2)	0.81766 (13)	0.0358 (5)
C6	0.09581 (11)	0.2348 (2)	0.84666 (15)	0.0431 (6)
H6A	0.1117	0.1836	0.8011	0.052*
H6B	0.0612	0.1869	0.8588	0.052*
C7	0.13766 (10)	0.2287 (2)	0.92539 (14)	0.0394 (5)
C8	0.11327 (11)	0.3177 (2)	0.99442 (14)	0.0402 (6)
H8A	0.0821	0.2663	1.0161	0.048*
H8B	0.1421	0.3309	1.0407	0.048*
C8A	0.09300 (9)	0.4593 (2)	0.96338 (13)	0.0319 (5)
C9	0.11372 (10)	0.7223 (2)	0.81771 (12)	0.0337 (5)
C10	0.16874 (10)	0.7180 (2)	0.85477 (13)	0.0377 (5)
H10	0.1772	0.6617	0.9023	0.045*
C11	0.21092 (11)	0.7965 (3)	0.82186 (15)	0.0454 (6)
C12	0.19901 (13)	0.8810 (3)	0.75148 (17)	0.0575 (7)
H12	0.2275	0.9335	0.7292	0.069*
C13	0.14458 (14)	0.8865 (3)	0.71472 (16)	0.0636 (8)
H13	0.1360	0.9440	0.6677	0.076*
C14	0.10264 (11)	0.8071 (3)	0.74738 (14)	0.0498 (7)
H14	0.0661	0.8107	0.7214	0.060*
C15	0.26941 (13)	0.7941 (4)	0.8631 (2)	0.0643 (8)
C19	0.01734 (9)	0.8518 (2)	0.91848 (12)	0.0328 (5)
N20	−0.00772 (9)	0.9545 (2)	0.90387 (12)	0.0495 (6)
N21	0.05451 (9)	0.7470 (2)	1.08480 (11)	0.0446 (5)
H21A	0.0381	0.8288	1.0839	0.054*
H21B	0.0658	0.7083	1.1323	0.054*
C22	0.19433 (11)	0.2886 (3)	0.90370 (18)	0.0583 (7)
H22A	0.1887	0.3805	0.8779	0.088*
H22B	0.2109	0.2254	0.8652	0.088*
H22C	0.2190	0.2975	0.9544	0.088*
C23	0.14521 (13)	0.0752 (3)	0.95659 (17)	0.0592 (8)
H23A	0.1580	0.0171	0.9122	0.089*
H23B	0.1098	0.0395	0.9727	0.089*
H23C	0.1726	0.0727	1.0044	0.089*
F1A	0.2811 (5)	0.8968 (12)	0.9208 (6)	0.089 (2)	0.507 (7)
F2A	0.2806 (3)	0.6766 (7)	0.9151 (5)	0.0813 (17)	0.507 (7)
F3A	0.3113 (2)	0.7874 (11)	0.8116 (4)	0.091 (2)	0.507 (7)
F1B	0.2694 (8)	0.861 (2)	0.9364 (9)	0.089 (2)	0.330 (7)
F2B	0.2877 (5)	0.6587 (9)	0.8792 (8)	0.0813 (17)	0.330 (7)
F3B	0.3049 (4)	0.8668 (14)	0.8182 (7)	0.091 (2)	0.330 (7)
F1C	0.2904 (6)	0.9254 (11)	0.8551 (10)	0.089 (2)	0.163 (3)
F2C	0.2730 (6)	0.7466 (19)	0.9427 (6)	0.0813 (17)	0.163 (3)
F3C	0.2982 (6)	0.7011 (16)	0.8215 (10)	0.091 (2)	0.163 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0604 (11)	0.0333 (8)	0.0262 (7)	0.0141 (7)	0.0006 (7)	−0.0023 (6)
C2	0.0373 (13)	0.0274 (10)	0.0326 (11)	0.0049 (9)	0.0042 (9)	−0.0011 (9)
O2	0.0679 (12)	0.0506 (10)	0.0325 (9)	0.0070 (9)	−0.0012 (8)	−0.0119 (8)
C3	0.0333 (12)	0.0291 (10)	0.0299 (11)	0.0049 (9)	0.0027 (8)	−0.0011 (8)
C4	0.0365 (13)	0.0338 (11)	0.0246 (10)	0.0056 (9)	−0.0024 (8)	−0.0015 (8)
C4A	0.0303 (12)	0.0325 (11)	0.0311 (11)	0.0007 (9)	0.0023 (8)	−0.0036 (9)
C5	0.0316 (12)	0.0403 (12)	0.0358 (12)	−0.0004 (10)	0.0042 (9)	−0.0079 (10)
C6	0.0495 (15)	0.0323 (12)	0.0480 (13)	−0.0001 (11)	0.0073 (11)	−0.0114 (10)
C7	0.0436 (14)	0.0307 (11)	0.0450 (13)	0.0061 (10)	0.0101 (10)	−0.0006 (10)
C8	0.0524 (15)	0.0311 (11)	0.0377 (12)	0.0061 (11)	0.0075 (10)	0.0026 (10)
C8A	0.0344 (13)	0.0288 (11)	0.0328 (11)	0.0009 (9)	0.0055 (9)	−0.0025 (9)
C9	0.0438 (14)	0.0323 (11)	0.0255 (10)	0.0066 (10)	0.0057 (9)	−0.0034 (9)
C10	0.0438 (14)	0.0376 (12)	0.0322 (11)	0.0059 (10)	0.0058 (10)	0.0014 (10)
C11	0.0484 (15)	0.0464 (14)	0.0431 (13)	0.0029 (12)	0.0151 (11)	−0.0079 (11)
C12	0.063 (2)	0.0597 (17)	0.0531 (16)	−0.0032 (14)	0.0267 (14)	0.0068 (13)
C13	0.078 (2)	0.0712 (19)	0.0429 (15)	0.0045 (16)	0.0142 (14)	0.0259 (14)
C14	0.0539 (17)	0.0607 (16)	0.0345 (13)	0.0068 (13)	0.0022 (11)	0.0116 (12)
C15	0.0492 (18)	0.077 (2)	0.0679 (19)	−0.0027 (16)	0.0137 (14)	0.0023 (17)
C19	0.0381 (13)	0.0354 (12)	0.0248 (10)	0.0012 (10)	0.0023 (9)	−0.0033 (9)
N20	0.0636 (15)	0.0412 (12)	0.0423 (11)	0.0166 (11)	−0.0040 (10)	−0.0042 (9)
N21	0.0708 (15)	0.0362 (10)	0.0270 (9)	0.0175 (10)	0.0058 (9)	−0.0005 (8)
C22	0.0380 (15)	0.0703 (18)	0.0675 (17)	0.0098 (14)	0.0094 (12)	0.0119 (15)
C23	0.080 (2)	0.0344 (13)	0.0647 (17)	0.0141 (13)	0.0142 (15)	−0.0008 (12)
F1A	0.061 (5)	0.119 (6)	0.085 (3)	−0.017 (3)	−0.006 (3)	−0.031 (5)
F2A	0.057 (3)	0.098 (3)	0.089 (5)	0.029 (2)	0.005 (3)	−0.004 (3)
F3A	0.0386 (17)	0.154 (7)	0.0855 (18)	0.008 (3)	0.0329 (12)	0.012 (4)
F1B	0.061 (5)	0.119 (6)	0.085 (3)	−0.017 (3)	−0.006 (3)	−0.031 (5)
F2B	0.057 (3)	0.098 (3)	0.089 (5)	0.029 (2)	0.005 (3)	−0.004 (3)
F3B	0.0386 (17)	0.154 (7)	0.0855 (18)	0.008 (3)	0.0329 (12)	0.012 (4)
F1C	0.061 (5)	0.119 (6)	0.085 (3)	−0.017 (3)	−0.006 (3)	−0.031 (5)
F2C	0.057 (3)	0.098 (3)	0.089 (5)	0.029 (2)	0.005 (3)	−0.004 (3)
F3C	0.0386 (17)	0.154 (7)	0.0855 (18)	0.008 (3)	0.0329 (12)	0.012 (4)

Geometric parameters (Å, º) top

O1—C2	1.369 (2)	C11—C12	1.381 (4)
O1—C8A	1.373 (2)	C11—C15	1.487 (4)
C2—N21	1.327 (3)	C12—C13	1.375 (4)
C2—C3	1.358 (3)	C12—H12	0.9300
O2—C5	1.220 (3)	C13—C14	1.379 (4)
C3—C19	1.409 (3)	C13—H13	0.9300
C3—C4	1.515 (3)	C14—H14	0.9300
C4—C4A	1.504 (3)	C15—F3C	1.320 (8)
C4—C9	1.522 (3)	C15—F1B	1.321 (8)
C4—H4	0.9800	C15—F3B	1.336 (7)
C4A—C8A	1.334 (3)	C15—F2C	1.337 (8)
C4A—C5	1.462 (3)	C15—F3A	1.339 (5)
C5—C6	1.505 (3)	C15—F1C	1.340 (8)
C6—C7	1.534 (3)	C15—F1A	1.344 (5)
C6—H6A	0.9700	C15—F2B	1.360 (7)
C6—H6B	0.9700	C15—F2A	1.389 (5)
C7—C22	1.524 (3)	C19—N20	1.147 (3)
C7—C23	1.529 (3)	N21—H21A	0.8600
C7—C8	1.530 (3)	N21—H21B	0.8600
C8—C8A	1.484 (3)	C22—H22A	0.9600
C8—H8A	0.9700	C22—H22B	0.9600
C8—H8B	0.9700	C22—H22C	0.9600
C9—C14	1.379 (3)	C23—H23A	0.9600
C9—C10	1.389 (3)	C23—H23B	0.9600
C10—C11	1.380 (3)	C23—H23C	0.9600
C10—H10	0.9300

C2—O1—C8A	118.60 (15)	C9—C14—C13	121.4 (2)
N21—C2—C3	128.71 (19)	C9—C14—H14	119.3
N21—C2—O1	110.26 (17)	C13—C14—H14	119.3
C3—C2—O1	121.03 (18)	F3C—C15—F1B	142.4 (12)
C2—C3—C19	119.51 (18)	F3C—C15—F3B	72.2 (8)
C2—C3—C4	122.53 (18)	F1B—C15—F3B	105.9 (9)
C19—C3—C4	117.84 (17)	F3C—C15—F2C	104.9 (10)
C4A—C4—C3	108.37 (16)	F3B—C15—F2C	132.9 (9)
C4A—C4—C9	113.05 (18)	F1B—C15—F3A	127.9 (8)
C3—C4—C9	110.95 (17)	F2C—C15—F3A	124.6 (7)
C4A—C4—H4	108.1	F3C—C15—F1C	110.4 (10)
C3—C4—H4	108.1	F1B—C15—F1C	71.1 (10)
C9—C4—H4	108.1	F2C—C15—F1C	113.6 (10)
C8A—C4A—C5	119.27 (19)	F3A—C15—F1C	71.6 (8)
C8A—C4A—C4	121.77 (18)	F3C—C15—F1A	136.9 (9)
C5—C4A—C4	118.96 (17)	F3B—C15—F1A	83.9 (6)
O2—C5—C4A	120.4 (2)	F2C—C15—F1A	66.4 (10)
O2—C5—C6	122.18 (19)	F3A—C15—F1A	109.1 (5)
C4A—C5—C6	117.37 (18)	F1B—C15—F2B	107.4 (12)
C5—C6—C7	113.39 (18)	F3B—C15—F2B	111.8 (7)
C5—C6—H6A	108.9	F2C—C15—F2B	61.1 (8)
C7—C6—H6A	108.9	F3A—C15—F2B	80.2 (5)
C5—C6—H6B	108.9	F1C—C15—F2B	139.6 (8)
C7—C6—H6B	108.9	F1A—C15—F2B	119.8 (9)
H6A—C6—H6B	107.7	F3C—C15—F2A	72.0 (8)
C22—C7—C23	109.8 (2)	F1B—C15—F2A	82.3 (11)
C22—C7—C8	110.7 (2)	F3B—C15—F2A	128.6 (6)
C23—C7—C8	108.87 (19)	F3A—C15—F2A	102.1 (4)
C22—C7—C6	109.1 (2)	F1C—C15—F2A	137.0 (7)
C23—C7—C6	110.5 (2)	F1A—C15—F2A	98.3 (7)
C8—C7—C6	107.79 (19)	F3C—C15—C11	107.1 (7)
C8A—C8—C7	112.50 (18)	F1B—C15—C11	108.2 (9)
C8A—C8—H8A	109.1	F3B—C15—C11	111.4 (6)
C7—C8—H8A	109.1	F2C—C15—C11	114.0 (7)
C8A—C8—H8B	109.1	F3A—C15—C11	116.4 (4)
C7—C8—H8B	109.1	F1C—C15—C11	106.6 (6)
H8A—C8—H8B	107.8	F1A—C15—C11	115.0 (6)
C4A—C8A—O1	123.33 (18)	F2B—C15—C11	111.7 (6)
C4A—C8A—C8	125.43 (19)	F2A—C15—C11	113.6 (4)
O1—C8A—C8	111.23 (17)	N20—C19—C3	177.4 (2)
C14—C9—C10	118.1 (2)	C2—N21—H21A	120.0
C14—C9—C4	120.2 (2)	C2—N21—H21B	120.0
C10—C9—C4	121.58 (18)	H21A—N21—H21B	120.0
C11—C10—C9	120.7 (2)	C7—C22—H22A	109.5
C11—C10—H10	119.6	C7—C22—H22B	109.5
C9—C10—H10	119.6	H22A—C22—H22B	109.5
C10—C11—C12	120.4 (2)	C7—C22—H22C	109.5
C10—C11—C15	120.4 (2)	H22A—C22—H22C	109.5
C12—C11—C15	119.2 (2)	H22B—C22—H22C	109.5
C13—C12—C11	119.2 (2)	C7—C23—H23A	109.5
C13—C12—H12	120.4	C7—C23—H23B	109.5
C11—C12—H12	120.4	H23A—C23—H23B	109.5
C12—C13—C14	120.2 (2)	C7—C23—H23C	109.5
C12—C13—H13	119.9	H23A—C23—H23C	109.5
C14—C13—H13	119.9	H23B—C23—H23C	109.5

C8A—O1—C2—N21	170.12 (19)	C7—C8—C8A—O1	−159.98 (19)
C8A—O1—C2—C3	−9.9 (3)	C4A—C4—C9—C14	138.3 (2)
N21—C2—C3—C19	−3.7 (4)	C3—C4—C9—C14	−99.8 (2)
O1—C2—C3—C19	176.4 (2)	C4A—C4—C9—C10	−46.0 (3)
N21—C2—C3—C4	172.3 (2)	C3—C4—C9—C10	76.0 (2)
O1—C2—C3—C4	−7.7 (3)	C14—C9—C10—C11	0.0 (3)
C2—C3—C4—C4A	21.0 (3)	C4—C9—C10—C11	−175.90 (19)
C19—C3—C4—C4A	−163.03 (19)	C9—C10—C11—C12	0.2 (3)
C2—C3—C4—C9	−103.7 (2)	C9—C10—C11—C15	178.5 (2)
C19—C3—C4—C9	72.3 (2)	C10—C11—C12—C13	0.3 (4)
C3—C4—C4A—C8A	−19.2 (3)	C15—C11—C12—C13	−178.1 (3)
C9—C4—C4A—C8A	104.2 (2)	C11—C12—C13—C14	−0.8 (4)
C3—C4—C4A—C5	160.06 (18)	C10—C9—C14—C13	−0.5 (4)
C9—C4—C4A—C5	−76.5 (2)	C4—C9—C14—C13	175.4 (2)
C8A—C4A—C5—O2	178.7 (2)	C12—C13—C14—C9	0.9 (4)
C4—C4A—C5—O2	−0.7 (3)	C10—C11—C15—F3C	97.7 (9)
C8A—C4A—C5—C6	0.7 (3)	C12—C11—C15—F3C	−83.9 (9)
C4—C4A—C5—C6	−178.6 (2)	C10—C11—C15—F1B	−69.1 (11)
O2—C5—C6—C7	149.3 (2)	C12—C11—C15—F1B	109.3 (10)
C4A—C5—C6—C7	−32.8 (3)	C10—C11—C15—F3B	174.8 (7)
C5—C6—C7—C22	−65.0 (3)	C12—C11—C15—F3B	−6.8 (8)
C5—C6—C7—C23	174.1 (2)	C10—C11—C15—F2C	−17.9 (10)
C5—C6—C7—C8	55.3 (3)	C12—C11—C15—F2C	160.5 (9)
C22—C7—C8—C8A	71.6 (3)	C10—C11—C15—F3A	138.6 (6)
C23—C7—C8—C8A	−167.6 (2)	C12—C11—C15—F3A	−43.0 (6)
C6—C7—C8—C8A	−47.7 (3)	C10—C11—C15—F1C	−144.1 (8)
C5—C4A—C8A—O1	−174.82 (19)	C12—C11—C15—F1C	34.3 (9)
C4—C4A—C8A—O1	4.5 (3)	C10—C11—C15—F1A	−91.9 (6)
C5—C4A—C8A—C8	6.5 (3)	C12—C11—C15—F1A	86.5 (6)
C4—C4A—C8A—C8	−174.2 (2)	C10—C11—C15—F2B	49.0 (7)
C2—O1—C8A—C4A	11.7 (3)	C12—C11—C15—F2B	−132.6 (6)
C2—O1—C8A—C8	−169.41 (19)	C10—C11—C15—F2A	20.3 (5)
C7—C8—C8A—C4A	18.8 (3)	C12—C11—C15—F2A	−161.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21A···N20ⁱ	0.86	2.17	3.025 (3)	171
N21—H21B···O2ⁱⁱ	0.86	2.10	2.934 (2)	163

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

Experimental details

Crystal data
Chemical formula	C₁₉H₁₇F₃N₂O₂
M_r	362.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	23.7543 (6), 9.3871 (2), 15.8857 (4)
β (°)	94.704 (2)
V (Å³)	3530.33 (15)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.766, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	40937, 3467, 2538
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.126, 1.03
No. of reflections	3467
No. of parameters	258
No. of restraints	10
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.32

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21A···N20ⁱ	0.86	2.17	3.025 (3)	171
N21—H21B···O2ⁱⁱ	0.86	2.10	2.934 (2)	163

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

Acknowledgements

RK acknowledges the Department of Science & Technology for access to the single-crystal X-ray diffractometer sanctioned as a national facility under project No. SR/S2/CMP-47/2003.

References

Anthal, S., Brahmachari, G., Laskar, S., Banerjee, B., Kant, R. & Gupta, V. K. (2012). Acta Cryst. E68, o2592–o2593. CSD CrossRef IUCr Journals Google Scholar
Bhattacharyya, P., Pradhan, K., Paul, S. & Das, A. S. (2012). Tetrahedron Lett. 53, 4687–4691. Web of Science CSD CrossRef CAS Google Scholar
Duax, W. L. & Norton, D. A. (1975). Atlas of Steroid Structures, Vol. 1. New York: Plenum Press. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fotouhi, L., Heravi, M. M., Fatehi, A. & Bakhtiari, K. (2007). Tetrahedron Lett. 48, 5379–5381. Web of Science CrossRef CAS Google Scholar
Kant, R., Gupta, V. K., Kapoor, K., Patil, D. R., Mulik, A. G. & Deshmukh, M. B. (2013). Acta Cryst. E69, o105. CSD CrossRef IUCr Journals Google Scholar
Khaksar, S., Rouhollahpour, A. & Talesh, S. M. (2012). J. Fluorine Chem. 141, 12–15. Web of Science CrossRef Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. 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
Wang, X. (2011). Acta Cryst. E67, o832. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 69| Part 3| March 2013| Pages o417-o418

doi:10.1107/S1600536813004522

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-Amino-7,7-di­methyl-5-oxo-4-[3-(tri­fluoro­meth­yl)phen­yl]-5,6,7,8-tetra­hydro-4H-chromene-3-carbo­nitrile

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-Amino-7,7-dimethyl-5-oxo-4-[3-(trifluoromethyl)phenyl]-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile