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

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

doi:10.1107/S1600536813026561

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1602

doi:10.1107/S1600536813026561

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

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

^aChemistry Department, GEBH, Sree Vidyanikethan Engineering College, A. Rangampet, Tirupati 517 102, India, ^bCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^cCentre for Organic and Medicinal Chemistry, VIT University, Vellore 632 014, India
^*Correspondence e-mail: shirai2011@gmail.com

(Received 10 September 2013; accepted 26 September 2013; online 2 October 2013)

In the title compound, C₁₂H₁₆FNO₂, the dioxane ring adopts a chair conformation with the methyl substituents and the C—N bond in equatorial orientations. Its mean plane subtends a dihedral angle of 40.17 (6)° with the benzene ring. In the crystal, weak N—H⋯F hydrogen bonds link the molecules into C(7) chains propagating in [100].

CCDC reference: 963313

Related literature

For a related structure and background to dioxanes, see: Fatima et al. (2013 ).

Experimental

Crystal data

C₁₂H₁₆FNO₂
M_r = 225.26
Monoclinic, P 2₁ /n
a = 10.4924 (10) Å
b = 10.0614 (10) Å
c = 11.0379 (11) Å
β = 90.136 (2)°
V = 1165.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.649, T_max = 0.746
10977 measured reflections
2910 independent reflections
2179 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.129
S = 1.01
2910 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯F1ⁱ	0.86	2.48	3.1556 (14)	136
Symmetry code: (i) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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

CCDC reference: 963313

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813026561/hb7138sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026561/hb7138Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813026561/hb7138Isup3.cml

checkCIF report

Comment top

As part of our ongoing studies of dioxane derivatives with possible biological activity (Fatima et al., 2013), we now describe the single-crystal structure determination of the title compound.

Molecules of the title compound, C₁₂H₁₆N₁O₂F₁, (Fig.1) are linked by intermolecular N—H···F hydrogen bonds into infinite chains propagating along 'a' axis (Fig. 2). The dioxane ring (O1/O2/C2—C5) adopts a chair conformation and the best plane through the dioxane ring makes a dihedral angle of 40.17 (6)° with the phenyl ring (C7—C12).

Related literature top

For a related structure and background to dioxanes, see: Fatima et al. (2013).

Experimental top

To 4-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 with diethylether.

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 a axis. H-atoms not involved in H-bonds have been excluded for clarity.

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

Crystal data top

C₁₂H₁₆FNO₂	F(000) = 480
M_r = 225.26	D_x = 1.284 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2910 reflections
a = 10.4924 (10) Å	θ = 2.7–28.4°
b = 10.0614 (10) Å	µ = 0.10 mm⁻¹
c = 11.0379 (11) Å	T = 293 K
β = 90.136 (2)°	Block, colourless
V = 1165.2 (2) Å³	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEXII area-detector diffractometer	2910 independent reflections
Radiation source: fine-focus sealed tube	2179 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω and ϕ scans	θ_max = 28.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→13
T_min = 0.649, T_max = 0.746	k = −13→13
10977 measured reflections	l = −14→14

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0644P)² + 0.1851P] where P = (F_o² + 2F_c²)/3
2910 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₂H₁₆FNO₂	V = 1165.2 (2) Å³
M_r = 225.26	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.4924 (10) Å	µ = 0.10 mm⁻¹
b = 10.0614 (10) Å	T = 293 K
c = 11.0379 (11) Å	0.25 × 0.20 × 0.15 mm
β = 90.136 (2)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	2910 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2179 reflections with I > 2σ(I)
T_min = 0.649, T_max = 0.746	R_int = 0.020
10977 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.01	Δρ_max = 0.15 e Å⁻³
2910 reflections	Δρ_min = −0.18 e Å⁻³
147 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
O1	0.85420 (8)	0.16432 (8)	0.95248 (8)	0.0469 (2)
O2	0.91002 (9)	0.28191 (9)	0.77911 (8)	0.0509 (2)
C3	0.91619 (12)	0.04131 (13)	0.77606 (11)	0.0491 (3)
H3A	0.8970	−0.0356	0.7263	0.059*
H3B	1.0045	0.0351	0.8018	0.059*
C5	0.82700 (12)	0.27629 (12)	0.87937 (12)	0.0482 (3)
H5	0.7386	0.2718	0.8509	0.058*
N1	0.84979 (10)	−0.06797 (11)	0.96310 (10)	0.0525 (3)
H1	0.9177	−0.1148	0.9546	0.063*
C4	0.83024 (11)	0.04228 (11)	0.88605 (11)	0.0453 (3)
H4	0.7413	0.0421	0.8587	0.054*
C2	0.89697 (13)	0.16759 (13)	0.70224 (12)	0.0514 (3)
H2	0.8111	0.1669	0.6672	0.062*
F1	0.49573 (9)	−0.21970 (11)	1.30521 (8)	0.0788 (3)
C7	0.76261 (11)	−0.10329 (11)	1.05237 (11)	0.0442 (3)
C8	0.77421 (13)	−0.22492 (13)	1.11186 (14)	0.0556 (3)
H8	0.8424	−0.2806	1.0939	0.067*
C9	0.68551 (15)	−0.26374 (15)	1.19728 (14)	0.0622 (4)
H9	0.6935	−0.3450	1.2367	0.075*
C12	0.66199 (11)	−0.02028 (12)	1.08440 (12)	0.0497 (3)
H12	0.6546	0.0628	1.0481	0.060*
C11	0.57272 (13)	−0.05951 (14)	1.16951 (12)	0.0539 (3)
H11	0.5051	−0.0041	1.1898	0.065*
C6	0.84563 (15)	0.39947 (14)	0.95358 (14)	0.0630 (4)
H6A	0.9318	0.4026	0.9830	0.095*
H6B	0.7879	0.3985	1.0209	0.095*
H6C	0.8292	0.4763	0.9044	0.095*
C10	0.58580 (13)	−0.18076 (15)	1.22298 (12)	0.0553 (3)
C1	0.99285 (17)	0.18267 (17)	0.60184 (14)	0.0693 (4)
H1A	0.9765	0.2637	0.5585	0.104*
H1B	0.9860	0.1086	0.5474	0.104*
H1C	1.0772	0.1854	0.6357	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0494 (5)	0.0386 (4)	0.0529 (5)	−0.0015 (3)	−0.0005 (4)	0.0021 (3)
O2	0.0567 (5)	0.0407 (5)	0.0551 (5)	−0.0081 (4)	−0.0008 (4)	0.0033 (4)
C3	0.0510 (7)	0.0415 (6)	0.0550 (7)	−0.0041 (5)	0.0010 (5)	−0.0027 (5)
C5	0.0448 (6)	0.0382 (6)	0.0615 (7)	0.0007 (5)	−0.0030 (5)	0.0043 (5)
N1	0.0438 (5)	0.0426 (5)	0.0712 (7)	0.0076 (4)	0.0087 (5)	0.0123 (5)
C4	0.0402 (6)	0.0372 (6)	0.0584 (7)	−0.0023 (4)	−0.0015 (5)	0.0035 (5)
C2	0.0558 (7)	0.0469 (7)	0.0514 (7)	−0.0082 (5)	−0.0057 (6)	0.0004 (5)
F1	0.0799 (6)	0.0875 (7)	0.0691 (6)	−0.0231 (5)	0.0156 (5)	0.0142 (5)
C7	0.0412 (6)	0.0360 (6)	0.0555 (7)	−0.0029 (4)	−0.0031 (5)	0.0024 (5)
C8	0.0480 (7)	0.0442 (7)	0.0747 (9)	0.0025 (5)	−0.0051 (6)	0.0114 (6)
C9	0.0643 (8)	0.0516 (7)	0.0705 (9)	−0.0076 (6)	−0.0097 (7)	0.0214 (7)
C12	0.0499 (6)	0.0372 (6)	0.0621 (7)	0.0001 (5)	0.0030 (5)	0.0039 (5)
C11	0.0503 (7)	0.0510 (7)	0.0603 (8)	−0.0029 (5)	0.0048 (6)	−0.0042 (6)
C6	0.0729 (9)	0.0416 (7)	0.0746 (9)	−0.0004 (6)	0.0029 (7)	−0.0027 (6)
C10	0.0554 (7)	0.0602 (8)	0.0502 (7)	−0.0158 (6)	0.0003 (6)	0.0050 (6)
C1	0.0872 (11)	0.0654 (9)	0.0554 (8)	−0.0120 (8)	0.0075 (8)	0.0026 (7)

Geometric parameters (Å, º) top

O1—C5	1.4145 (14)	C7—C8	1.3940 (17)
O1—C4	1.4517 (14)	C7—C12	1.3924 (17)
O2—C5	1.4111 (16)	C8—C9	1.383 (2)
O2—C2	1.4357 (15)	C8—H8	0.9300
C3—C4	1.5141 (17)	C9—C10	1.369 (2)
C3—C2	1.5226 (18)	C9—H9	0.9300
C3—H3A	0.9700	C12—C11	1.3856 (17)
C3—H3B	0.9700	C12—H12	0.9300
C5—C6	1.4981 (19)	C11—C10	1.362 (2)
C5—H5	0.9800	C11—H11	0.9300
N1—C7	1.3922 (15)	C6—H6A	0.9600
N1—C4	1.4125 (15)	C6—H6B	0.9600
N1—H1	0.8600	C6—H6C	0.9600
C4—H4	0.9800	C1—H1A	0.9600
C2—C1	1.5061 (19)	C1—H1B	0.9600
C2—H2	0.9800	C1—H1C	0.9600
F1—C10	1.3691 (15)

C5—O1—C4	110.55 (9)	C8—C7—C12	118.19 (12)
C5—O2—C2	111.92 (9)	N1—C7—C12	121.77 (11)
C4—C3—C2	110.20 (10)	C9—C8—C7	120.73 (13)
C4—C3—H3A	109.6	C9—C8—H8	119.6
C2—C3—H3A	109.6	C7—C8—H8	119.6
C4—C3—H3B	109.6	C10—C9—C8	119.02 (13)
C2—C3—H3B	109.6	C10—C9—H9	120.5
H3A—C3—H3B	108.1	C8—C9—H9	120.5
O2—C5—O1	110.80 (9)	C11—C12—C7	121.03 (12)
O2—C5—C6	108.40 (10)	C11—C12—H12	119.5
O1—C5—C6	108.73 (11)	C7—C12—H12	119.5
O2—C5—H5	109.6	C10—C11—C12	118.78 (13)
O1—C5—H5	109.6	C10—C11—H11	120.6
C6—C5—H5	109.6	C12—C11—H11	120.6
C7—N1—C4	122.13 (10)	C5—C6—H6A	109.5
C7—N1—H1	118.9	C5—C6—H6B	109.5
C4—N1—H1	118.9	H6A—C6—H6B	109.5
N1—C4—O1	109.60 (10)	C5—C6—H6C	109.5
N1—C4—C3	113.06 (10)	H6A—C6—H6C	109.5
O1—C4—C3	107.92 (9)	H6B—C6—H6C	109.5
N1—C4—H4	108.7	C11—C10—C9	122.19 (12)
O1—C4—H4	108.7	C11—C10—F1	118.33 (13)
C3—C4—H4	108.7	C9—C10—F1	119.47 (13)
O2—C2—C1	106.93 (10)	C2—C1—H1A	109.5
O2—C2—C3	109.87 (10)	C2—C1—H1B	109.5
C1—C2—C3	112.96 (12)	H1A—C1—H1B	109.5
O2—C2—H2	109.0	C2—C1—H1C	109.5
C1—C2—H2	109.0	H1A—C1—H1C	109.5
C3—C2—H2	109.0	H1B—C1—H1C	109.5
C8—C7—N1	120.04 (11)

C2—O2—C5—O1	61.43 (13)	C4—C3—C2—C1	171.55 (11)
C2—O2—C5—C6	−179.33 (10)	C4—N1—C7—C8	168.84 (12)
C4—O1—C5—O2	−64.23 (12)	C4—N1—C7—C12	−10.76 (19)
C4—O1—C5—C6	176.73 (10)	N1—C7—C8—C9	−177.40 (13)
C7—N1—C4—O1	74.98 (14)	C12—C7—C8—C9	2.2 (2)
C7—N1—C4—C3	−164.58 (11)	C7—C8—C9—C10	−0.1 (2)
C5—O1—C4—N1	−176.11 (9)	C8—C7—C12—C11	−2.58 (19)
C5—O1—C4—C3	60.37 (12)	N1—C7—C12—C11	177.03 (12)
C2—C3—C4—N1	−175.84 (10)	C7—C12—C11—C10	0.8 (2)
C2—C3—C4—O1	−54.45 (12)	C12—C11—C10—C9	1.4 (2)
C5—O2—C2—C1	−178.06 (10)	C12—C11—C10—F1	−178.74 (12)
C5—O2—C2—C3	−55.13 (13)	C8—C9—C10—C11	−1.7 (2)
C4—C3—C2—O2	52.25 (14)	C8—C9—C10—F1	178.39 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F1ⁱ	0.86	2.48	3.1556 (14)	136

Symmetry code: (i) x+1/2, −y−1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F1ⁱ	0.86	2.48	3.1556 (14)	136

Symmetry code: (i) x+1/2, −y−1/2, z−1/2.

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.

References

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