N-(2-Fluoro­phen­yl)-2,6-dimethyl-1,3-dioxan-4-amine

Fatima, Z.; Rambabu, G.; Reddy, B.P.; Vijayakumar, V.; Velmurugan, D.

doi:10.1107/S1600536813024732

organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page o1524

doi:10.1107/S1600536813024732

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N-(2-Fluorophenyl)-2,6-dimethyl-1,3-dioxan-4-amine

Zeenat Fatima,^a Gottimukkala Rambabu,^b Bandapalli Palakshi Reddy,^b Vijayaparthasarathi Vijayakumar ^c and Devadasan Velmurugan ^a ^*

^aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, ^bChemistry Department, GEBH, Sree Vidyanikethan Engineering College, A. Rangampet, Tirupati 517102, India, and ^cCentre for Organic and Medicinal Chemistry, VIT University, Vellore 632 014, India
^*Correspondence e-mail: shirai2011@gmail.com

(Received 1 September 2013; accepted 5 September 2013; online 12 September 2013)

In the title compound, C₁₂H₁₆FNO₃, the dioxane ring adopts a chair conformation with the methyl groups and amine N atom in equatorial positions. The best plane through the dioxane ring makes a dihedral angle of 43.16 (8)° with the phenyl ring. In the crystal, pairs of C—H⋯O hydrogen bonds link the molecules into centrosymmetric R₂²(8) dimers, which are linked into [100] chains by further C—H⋯O hydrogen bonds. The N—H group does not participate in hydrogen bonding.

Related literature

Dioxane rings are frequently encountered in structural motifs in many bioactive molecules such as cytotoxic agents (Aubele et al., 2005 ) and antimuscarinic agents (Marucci et al., 2005 ). For applications of this class of compounds, see: Wang, Yuan, Liu et al. (1996 ); Wang, Yuan, Lei & Liu (1996 ); Yuan et al. (2005 ). For related crystal structures, see: Chuprunov et al. (1981 ).

Experimental

Crystal data

C₁₂H₁₆FNO₂
M_r = 225.26
Monoclinic, C 2/c
a = 19.6219 (13) Å
b = 8.1603 (6) Å
c = 15.2396 (10) Å
β = 95.950 (3)°
V = 2427.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.617, T_max = 0.746
11540 measured reflections
3020 independent reflections
1973 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.137
S = 1.03
3020 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O2ⁱ	0.97	2.60	3.5563 (17)	169
C11—H11⋯O1ⁱⁱ	0.93	2.54	3.473 (2)	177
Symmetry codes: (i) -x, -y, -z+2; (ii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813024732/hb7132sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813024732/hb7132Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813024732/hb7132Isup3.cml

checkCIF report

Comment top

Oxygen heterocycles play a vital role as basic building blocks in pharmaceutical preparations. This class of compounds has useful insecticidal as well as anti-foaming properties (Yuan et al., 2005). Dioxane rings are frequently encountered in structural motifs in many bioactive molecules such as cytotoxic agents (Aubele et al., 2005) and antimuscarinic agents (Marucci et al., 2005). As part of our studies in this area, we have undertaken a single-crystal structure determination of the title compound.

In the title compound, C₁₂H₁₆F₁N₁O₃ (Fig.1), pairs of C—H···O hydrogen bonds link the molecules into centrosymmetric R₂²(8) dimers (Fig.2). The dimers are linked into an infinite chain propagating along the 'a' axis by further C—H···O hydrogen bonds. The dioxane ring adopts a chair conformation and the best plane through the dioxane ring makes a dihedral angle of 43.16 (8)° with the phenyl ring.

Related literature top

Dioxane rings are frequently encountered in structural motifs in many bioactive molecules such as cytotoxic agents (Aubele et al., 2005) and antimuscarinic agents (Marucci et al., 2005). For applications of this class of compounds, see: Wang, Yuan, Liu et al. (1996); Wang, Yuan, Lei & Liu (1996); Yuan et al. (2005). For related crystal structures, see: Chuprunov et al. (1981).

Experimental top

To 2-fluoroaniline (1 mmol), acetaldehyde (3 mmol) was added dropwise and stirred for about 4 h at 0 °C. The progress of the reaction was monitored through TLC. The reaction mixture was washed with petroleum ether. Resultant was dissolved in diethylether and allowed to evaporate. Solid product obtained was recrystallized for diethylether solution to yield colourless blocks.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed down b axis. H-atoms not involved in H-bonds have been excluded for clarity.

N-(2-Fluorophenyl)-2,6-dimethyl-1,3-dioxan-4-amine top

Crystal data top

C₁₂H₁₆FNO₂	F(000) = 960
M_r = 225.26	D_x = 1.233 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3020 reflections
a = 19.6219 (13) Å	θ = 2.7–28.4°
b = 8.1603 (6) Å	µ = 0.09 mm⁻¹
c = 15.2396 (10) Å	T = 293 K
β = 95.950 (3)°	Block, colourless
V = 2427.0 (3) Å³	0.25 × 0.20 × 0.15 mm
Z = 8

Data collection top

Bruker SMART APEXII CCD diffractometer	3020 independent reflections
Radiation source: fine-focus sealed tube	1973 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω and ϕ scans	θ_max = 28.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −26→25
T_min = 0.617, T_max = 0.746	k = −10→10
11540 measured reflections	l = −17→20

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) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0629P)² + 0.5739P] where P = (F_o² + 2F_c²)/3
3020 reflections	(Δ/σ)_max = 0.001
153 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₁₆FNO₂	V = 2427.0 (3) Å³
M_r = 225.26	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 19.6219 (13) Å	µ = 0.09 mm⁻¹
b = 8.1603 (6) Å	T = 293 K
c = 15.2396 (10) Å	0.25 × 0.20 × 0.15 mm
β = 95.950 (3)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3020 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1973 reflections with I > 2σ(I)
T_min = 0.617, T_max = 0.746	R_int = 0.026
11540 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.18 e Å⁻³
3020 reflections	Δρ_min = −0.23 e Å⁻³
153 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
H1	−0.0550 (9)	0.220 (2)	1.0096 (12)	0.074 (5)*
H3	0.1172 (8)	0.1912 (19)	0.8533 (10)	0.058 (4)*
O1	0.13369 (5)	0.02783 (12)	0.94558 (6)	0.0592 (3)
O2	0.02809 (4)	0.13036 (11)	0.88947 (6)	0.0535 (3)
C4	0.02808 (7)	0.25397 (16)	0.95733 (9)	0.0526 (3)
H4	0.0476	0.3552	0.9360	0.063*
C5	0.07197 (7)	0.19735 (17)	1.03878 (9)	0.0545 (3)
H5A	0.0500	0.1056	1.0649	0.065*
H5B	0.0767	0.2854	1.0817	0.065*
N1	−0.04050 (7)	0.28505 (17)	0.97514 (9)	0.0617 (3)
C2	0.14205 (7)	0.14617 (18)	1.01572 (9)	0.0561 (3)
H2	0.1657	0.2425	0.9953	0.067*
C3	0.09501 (7)	0.0917 (2)	0.87025 (9)	0.0562 (4)
C7	−0.08824 (7)	0.35496 (17)	0.91321 (10)	0.0598 (4)
F1	−0.16772 (6)	0.33920 (15)	1.01790 (9)	0.1024 (4)
C6	0.09070 (10)	−0.0353 (3)	0.79920 (11)	0.0828 (6)
H6A	0.1360	−0.0620	0.7852	0.124*
H6B	0.0642	0.0064	0.7475	0.124*
H6C	0.0691	−0.1320	0.8192	0.124*
C12	−0.15451 (8)	0.3829 (2)	0.93551 (13)	0.0723 (5)
C1	0.18616 (9)	0.0692 (2)	1.09141 (10)	0.0745 (5)
H1A	0.2296	0.0394	1.0725	0.112*
H1B	0.1639	−0.0270	1.1108	0.112*
H1C	0.1931	0.1460	1.1392	0.112*
C8	−0.07505 (9)	0.4054 (2)	0.83014 (11)	0.0733 (5)
H8	−0.0318	0.3885	0.8120	0.088*
C9	−0.12519 (11)	0.4808 (2)	0.77326 (12)	0.0899 (6)
H9	−0.1151	0.5158	0.7180	0.108*
C11	−0.20465 (10)	0.4542 (3)	0.88042 (17)	0.0926 (7)
H11	−0.2482	0.4692	0.8979	0.111*
C10	−0.18988 (12)	0.5039 (3)	0.79822 (16)	0.0989 (7)
H10	−0.2236	0.5532	0.7596	0.119*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0587 (6)	0.0740 (6)	0.0451 (5)	0.0204 (5)	0.0063 (4)	−0.0013 (4)
O2	0.0435 (5)	0.0652 (5)	0.0531 (5)	0.0060 (4)	0.0112 (4)	−0.0052 (4)
C4	0.0477 (8)	0.0510 (7)	0.0608 (8)	0.0028 (6)	0.0144 (6)	−0.0025 (6)
C5	0.0596 (9)	0.0530 (7)	0.0523 (8)	0.0005 (6)	0.0128 (6)	−0.0070 (6)
N1	0.0521 (7)	0.0665 (7)	0.0695 (8)	0.0106 (6)	0.0208 (6)	−0.0006 (7)
C2	0.0533 (8)	0.0627 (8)	0.0526 (8)	0.0015 (6)	0.0068 (6)	0.0016 (6)
C3	0.0474 (8)	0.0767 (9)	0.0461 (7)	0.0128 (7)	0.0113 (6)	0.0061 (7)
C7	0.0516 (8)	0.0563 (7)	0.0721 (10)	0.0061 (6)	0.0093 (7)	−0.0185 (7)
F1	0.0756 (7)	0.1085 (8)	0.1316 (10)	0.0213 (6)	0.0513 (7)	0.0091 (7)
C6	0.0734 (11)	0.1247 (15)	0.0507 (8)	0.0338 (10)	0.0076 (8)	−0.0165 (9)
C12	0.0542 (9)	0.0690 (9)	0.0948 (12)	0.0079 (7)	0.0129 (9)	−0.0202 (9)
C1	0.0746 (11)	0.0911 (11)	0.0554 (9)	0.0164 (9)	−0.0043 (8)	−0.0047 (8)
C8	0.0689 (10)	0.0814 (10)	0.0697 (10)	0.0192 (8)	0.0081 (8)	−0.0148 (8)
C9	0.1005 (16)	0.0957 (13)	0.0703 (11)	0.0248 (11)	−0.0069 (10)	−0.0226 (10)
C11	0.0544 (10)	0.0973 (13)	0.1236 (18)	0.0145 (9)	−0.0033 (11)	−0.0348 (13)
C10	0.0798 (14)	0.1034 (14)	0.1047 (16)	0.0290 (11)	−0.0316 (12)	−0.0404 (13)

Geometric parameters (Å, º) top

O1—C3	1.4087 (16)	C7—C12	1.396 (2)
O1—C2	1.4373 (17)	F1—C12	1.356 (2)
O2—C3	1.4105 (16)	C6—H6A	0.9600
O2—C4	1.4446 (16)	C6—H6B	0.9600
C4—N1	1.4228 (17)	C6—H6C	0.9600
C4—C5	1.508 (2)	C12—C11	1.357 (3)
C4—H4	0.9800	C1—H1A	0.9600
C5—C2	1.513 (2)	C1—H1B	0.9600
C5—H5A	0.9700	C1—H1C	0.9600
C5—H5B	0.9700	C8—C9	1.386 (2)
N1—C7	1.382 (2)	C8—H8	0.9300
N1—H1	0.820 (18)	C9—C10	1.375 (3)
C2—C1	1.506 (2)	C9—H9	0.9300
C2—H2	0.9800	C11—C10	1.376 (3)
C3—C6	1.495 (2)	C11—H11	0.9300
C3—H3	0.969 (16)	C10—H10	0.9300
C7—C8	1.381 (2)

C3—O1—C2	111.59 (11)	C8—C7—C12	116.24 (16)
C3—O2—C4	111.98 (10)	N1—C7—C12	118.92 (15)
N1—C4—O2	109.35 (11)	C3—C6—H6A	109.5
N1—C4—C5	111.61 (11)	C3—C6—H6B	109.5
O2—C4—C5	109.44 (10)	H6A—C6—H6B	109.5
N1—C4—H4	108.8	C3—C6—H6C	109.5
O2—C4—H4	108.8	H6A—C6—H6C	109.5
C5—C4—H4	108.8	H6B—C6—H6C	109.5
C4—C5—C2	110.40 (11)	F1—C12—C11	119.33 (17)
C4—C5—H5A	109.6	F1—C12—C7	117.05 (16)
C2—C5—H5A	109.6	C11—C12—C7	123.6 (2)
C4—C5—H5B	109.6	C2—C1—H1A	109.5
C2—C5—H5B	109.6	C2—C1—H1B	109.5
H5A—C5—H5B	108.1	H1A—C1—H1B	109.5
C7—N1—C4	122.05 (13)	C2—C1—H1C	109.5
C7—N1—H1	116.8 (13)	H1A—C1—H1C	109.5
C4—N1—H1	113.9 (13)	H1B—C1—H1C	109.5
O1—C2—C1	107.55 (12)	C7—C8—C9	121.15 (18)
O1—C2—C5	108.78 (11)	C7—C8—H8	119.4
C1—C2—C5	113.66 (12)	C9—C8—H8	119.4
O1—C2—H2	108.9	C10—C9—C8	120.2 (2)
C1—C2—H2	108.9	C10—C9—H9	119.9
C5—C2—H2	108.9	C8—C9—H9	119.9
O1—C3—O2	110.36 (10)	C12—C11—C10	118.84 (19)
O1—C3—C6	108.61 (13)	C12—C11—H11	120.6
O2—C3—C6	108.76 (13)	C10—C11—H11	120.6
O1—C3—H3	107.9 (9)	C9—C10—C11	119.91 (19)
O2—C3—H3	108.7 (9)	C9—C10—H10	120.0
C6—C3—H3	112.5 (9)	C11—C10—H10	120.0
C8—C7—N1	124.81 (14)

C3—O2—C4—N1	−178.72 (11)	C4—N1—C7—C8	−1.8 (2)
C3—O2—C4—C5	−56.18 (14)	C4—N1—C7—C12	−179.59 (13)
N1—C4—C5—C2	173.31 (11)	C8—C7—C12—F1	−177.83 (14)
O2—C4—C5—C2	52.12 (15)	N1—C7—C12—F1	0.2 (2)
O2—C4—N1—C7	−65.93 (17)	C8—C7—C12—C11	0.4 (2)
C5—C4—N1—C7	172.83 (12)	N1—C7—C12—C11	178.40 (16)
C3—O1—C2—C1	−177.76 (12)	N1—C7—C8—C9	−177.28 (16)
C3—O1—C2—C5	58.73 (14)	C12—C7—C8—C9	0.6 (2)
C4—C5—C2—O1	−53.33 (14)	C7—C8—C9—C10	−1.2 (3)
C4—C5—C2—C1	−173.11 (12)	F1—C12—C11—C10	177.44 (17)
C2—O1—C3—O2	−62.98 (16)	C7—C12—C11—C10	−0.7 (3)
C2—O1—C3—C6	177.87 (13)	C8—C9—C10—C11	0.9 (3)
C4—O2—C3—O1	61.46 (15)	C12—C11—C10—C9	0.1 (3)
C4—O2—C3—C6	−179.49 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O2ⁱ	0.97	2.60	3.5563 (17)	169
C11—H11···O1ⁱⁱ	0.93	2.54	3.473 (2)	177

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O2ⁱ	0.97	2.60	3.5563 (17)	169
C11—H11···O1ⁱⁱ	0.93	2.54	3.473 (2)	177

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

Acknowledgements

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection. ZF and DV acknowledge the UGC (SAP–CAS) for the departmental facilties. ZF also thanks the UGC for a meritorious fellowship.

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