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

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

doi:10.1107/S1600536813025750

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page o1579

doi:10.1107/S1600536813025750

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N-(4-Bromophenyl)-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 10 September 2013; accepted 17 September 2013; online 21 September 2013)

In the title compound, C₁₂H₁₆BrNO₂, the dioxane ring adopts a chair conformation and its mean plane makes a dihedral angle of 60.63 (12)° with the 4-bromophenyl ring. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R₂²(8) ring motif. These dimers are consolidated by pairs of C—H⋯O hydrogen bonds with an R₂²(16) ring motif. Adjacent dimers are connected via C—H⋯O hydrogen bonds, forming infinite chains propagating along the c-axis direction.

CCDC reference: 961593

Related literature

For biological properties of dioxanes and applications of 1,3-dioxane derivatives, see: Aubele et al. (2005 ); Marucci et al. (2005 ); Wang et al. (1996a ,b ); Yuan et al. (2005 ). For related crystal structures, see: Chuprunov et al. (1981 ); Thevenet et al. (2010 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₂H₁₆BrNO₂
M_r = 286.17
Monoclinic, P 2₁ /c
a = 9.9367 (5) Å
b = 13.5660 (6) Å
c = 10.3206 (5) Å
β = 115.543 (3)°
V = 1255.25 (10) Å³
Z = 4
Mo Kα radiation
μ = 3.26 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 = 0.310, T_max = 0.746
11981 measured reflections
3119 independent reflections
1819 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.092
S = 1.01
3119 reflections
150 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.82 (2)	2.66 (2)	3.465 (2)	168 (2)
C8—H8⋯O2ⁱ	0.93	2.51	3.352 (3)	150
C9—H9⋯O2ⁱⁱ	0.93	2.65	3.557 (3)	165
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y, z+1.

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: 961593

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813025750/su2646sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813025750/su2646Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813025750/su2646Isup3.cml

checkCIF report

Comment top

Dioxane rings are frequently encountered as structural motifs in many bioactive molecules such as cytotoxic agents (Aubele et al., 2005) and antimuscarinic agents (Marucci et al., 2005). 1,3-dioxane derivatives have applications in fine medicinal chemistry in the pharmaceutical (Wang et al., 1996a) and cosmetic industries (Wang et al., 1996b; Yuan et al., 2005). In view of the excellent biological and pharmacological applications of this class of compounds, we report herein on the synthesis and crystal structure of the title compound.

In the title compound, Fig 1, the dioxane ring (O1/O2/C2—C5) adopts a chair conformation and its mean plane makes a dihedral angle of 60.63 (12)° with the benzene ring (C7—C12).

In the crystal, molecules are linked by a pair of N—H···O hydrogen bonds forming inversion dimers with an R₂²(8) ring motif (Bernstein et al., 1995). These dimers are consolidated by a pair of C—H···O hydrogen bonds with an R₂²(16) ring motif. Adjacent dimers are connected via C—H···O hydrogen bonds forming infinite chains propagating along the c axis (see Table 1 and Fig. 2 for details).

Related literature top

For biological properties of dioxanes and applications of 1,3-dioxane derivatives, see: Aubele et al. (2005); Marucci et al. (2005); Wang et al. (1996a,b); Yuan et al. (2005). For related crystal structures, see: Chuprunov et al. (1981); Thevenet et al. (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

To 4-bromoaniline (1 mmol), acetaldehyde (3 mmol) was added drop wise and stirred for about 4 h at 273 K. The progress of the reaction was monitored through TLC. On completion of the reaction the mixture was washed with petroleum ether. The resultant product was dissolved in diethylether and allowed to evaporate. Block-like colourless crystals of the title compound were obtained by recrystallization 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 molecule, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the a axis. The hydrogen bonds are shown as dashed lines (see Table 1 fro details; H atoms not involved in hydrogen bonding have been omitted for clarity).

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

Crystal data top

C₁₂H₁₆BrNO₂	F(000) = 584
M_r = 286.17	D_x = 1.514 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3119 reflections
a = 9.9367 (5) Å	θ = 2.3–28.4°
b = 13.5660 (6) Å	µ = 3.26 mm⁻¹
c = 10.3206 (5) Å	T = 293 K
β = 115.543 (3)°	Block, colourless
V = 1255.25 (10) Å³	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEXII area-detector diffractometer	3119 independent reflections
Radiation source: fine-focus sealed tube	1819 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω and ϕ scans	θ_max = 28.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→13
T_min = 0.310, T_max = 0.746	k = −18→15
11981 measured reflections	l = −13→13

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0432P)² + 0.0602P] where P = (F_o² + 2F_c²)/3
3119 reflections	(Δ/σ)_max = 0.001
150 parameters	Δρ_max = 0.45 e Å⁻³
1 restraint	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₂H₁₆BrNO₂	V = 1255.25 (10) Å³
M_r = 286.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.9367 (5) Å	µ = 3.26 mm⁻¹
b = 13.5660 (6) Å	T = 293 K
c = 10.3206 (5) Å	0.25 × 0.20 × 0.15 mm
β = 115.543 (3)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	3119 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1819 reflections with I > 2σ(I)
T_min = 0.310, T_max = 0.746	R_int = 0.032
11981 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.45 e Å⁻³
3119 reflections	Δρ_min = −0.38 e Å⁻³
150 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
Br1	1.07805 (3)	0.63232 (2)	1.22087 (3)	0.07742 (15)
O1	0.70096 (17)	0.52265 (9)	0.47016 (15)	0.0474 (4)
O2	0.61959 (17)	0.53559 (10)	0.22317 (15)	0.0488 (4)
N1	0.6108 (2)	0.62162 (13)	0.6010 (2)	0.0502 (5)
H1	0.531 (2)	0.5954 (17)	0.588 (3)	0.060*
C1	0.4240 (3)	0.64080 (17)	0.0718 (3)	0.0640 (7)
H1A	0.4566	0.6270	−0.0014	0.096*
H1B	0.3852	0.7067	0.0598	0.096*
H1C	0.3475	0.5949	0.0642	0.096*
C2	0.5537 (3)	0.63121 (15)	0.2171 (2)	0.0497 (6)
H2	0.6276	0.6818	0.2260	0.060*
C3	0.5121 (3)	0.64209 (15)	0.3411 (3)	0.0504 (6)
H3A	0.4781	0.7088	0.3433	0.060*
H3B	0.4311	0.5973	0.3282	0.060*
C4	0.6445 (3)	0.61968 (14)	0.4810 (2)	0.0461 (5)
H4	0.7225	0.6685	0.4960	0.055*
C5	0.7436 (3)	0.51969 (17)	0.3564 (2)	0.0522 (6)
H5	0.8196	0.5701	0.3714	0.063*
C6	0.8065 (3)	0.4193 (2)	0.3537 (3)	0.0756 (8)
H6A	0.8360	0.4162	0.2766	0.113*
H6B	0.7320	0.3701	0.3394	0.113*
H6C	0.8917	0.4075	0.4432	0.113*
C7	0.7211 (3)	0.62384 (13)	0.7422 (2)	0.0433 (5)
C8	0.6828 (3)	0.60493 (15)	0.8537 (3)	0.0501 (6)
H8	0.5844	0.5896	0.8328	0.060*
C9	0.7872 (3)	0.60831 (15)	0.9954 (3)	0.0545 (6)
H9	0.7594	0.5944	1.0687	0.065*
C10	0.9320 (3)	0.63231 (14)	1.0272 (3)	0.0504 (6)
C11	0.9719 (3)	0.65323 (19)	0.9185 (3)	0.0622 (7)
H11	1.0698	0.6707	0.9402	0.075*
C12	0.8674 (3)	0.64851 (18)	0.7771 (3)	0.0586 (6)
H12	0.8960	0.6622	0.7042	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0657 (2)	0.1039 (3)	0.05105 (18)	0.01315 (15)	0.01413 (14)	−0.00249 (14)
O1	0.0466 (10)	0.0523 (8)	0.0450 (8)	0.0057 (7)	0.0215 (7)	0.0021 (7)
O2	0.0433 (9)	0.0577 (9)	0.0437 (9)	−0.0010 (7)	0.0170 (7)	−0.0041 (7)
N1	0.0444 (12)	0.0600 (12)	0.0494 (11)	−0.0045 (9)	0.0232 (10)	−0.0055 (9)
C1	0.0644 (18)	0.0693 (16)	0.0515 (15)	0.0022 (13)	0.0185 (13)	0.0100 (12)
C2	0.0489 (15)	0.0482 (13)	0.0496 (13)	−0.0078 (10)	0.0189 (12)	0.0034 (10)
C3	0.0513 (15)	0.0458 (12)	0.0521 (14)	0.0051 (11)	0.0205 (12)	0.0013 (10)
C4	0.0472 (14)	0.0483 (12)	0.0449 (12)	−0.0050 (10)	0.0218 (11)	−0.0036 (10)
C5	0.0410 (14)	0.0714 (15)	0.0454 (13)	−0.0020 (11)	0.0199 (11)	−0.0053 (11)
C6	0.067 (2)	0.0956 (19)	0.0612 (17)	0.0282 (16)	0.0250 (15)	−0.0049 (15)
C7	0.0451 (14)	0.0386 (11)	0.0480 (12)	0.0019 (10)	0.0219 (11)	−0.0023 (9)
C8	0.0457 (15)	0.0546 (12)	0.0556 (14)	−0.0051 (11)	0.0273 (12)	−0.0005 (11)
C9	0.0614 (18)	0.0605 (14)	0.0499 (13)	0.0015 (12)	0.0319 (13)	0.0046 (11)
C10	0.0494 (15)	0.0528 (13)	0.0471 (13)	0.0079 (11)	0.0190 (11)	−0.0007 (10)
C11	0.0418 (15)	0.0861 (17)	0.0596 (16)	−0.0025 (12)	0.0226 (13)	−0.0010 (13)
C12	0.0468 (15)	0.0854 (17)	0.0514 (15)	−0.0032 (13)	0.0284 (12)	0.0014 (12)

Geometric parameters (Å, º) top

Br1—C10	1.898 (2)	C4—H4	0.9800
O1—C5	1.410 (2)	C5—C6	1.504 (3)
O1—C4	1.454 (2)	C5—H5	0.9800
O2—C5	1.412 (3)	C6—H6A	0.9600
O2—C2	1.442 (2)	C6—H6B	0.9600
N1—C7	1.396 (3)	C6—H6C	0.9600
N1—C4	1.416 (3)	C7—C12	1.379 (3)
N1—H1	0.824 (16)	C7—C8	1.383 (3)
C1—C2	1.503 (3)	C8—C9	1.382 (3)
C1—H1A	0.9600	C8—H8	0.9300
C1—H1B	0.9600	C9—C10	1.369 (4)
C1—H1C	0.9600	C9—H9	0.9300
C2—C3	1.513 (3)	C10—C11	1.371 (3)
C2—H2	0.9800	C11—C12	1.381 (4)
C3—C4	1.507 (3)	C11—H11	0.9300
C3—H3A	0.9700	C12—H12	0.9300
C3—H3B	0.9700

C5—O1—C4	110.76 (15)	O1—C5—C6	108.55 (19)
C5—O2—C2	111.66 (16)	O2—C5—C6	108.37 (19)
C7—N1—C4	122.5 (2)	O1—C5—H5	109.7
C7—N1—H1	116.7 (18)	O2—C5—H5	109.7
C4—N1—H1	114.8 (18)	C6—C5—H5	109.7
C2—C1—H1A	109.5	C5—C6—H6A	109.5
C2—C1—H1B	109.5	C5—C6—H6B	109.5
H1A—C1—H1B	109.5	H6A—C6—H6B	109.5
C2—C1—H1C	109.5	C5—C6—H6C	109.5
H1A—C1—H1C	109.5	H6A—C6—H6C	109.5
H1B—C1—H1C	109.5	H6B—C6—H6C	109.5
O2—C2—C1	107.42 (17)	C12—C7—C8	117.7 (2)
O2—C2—C3	109.59 (17)	C12—C7—N1	122.8 (2)
C1—C2—C3	114.0 (2)	C8—C7—N1	119.4 (2)
O2—C2—H2	108.6	C9—C8—C7	121.6 (2)
C1—C2—H2	108.6	C9—C8—H8	119.2
C3—C2—H2	108.6	C7—C8—H8	119.2
C4—C3—C2	110.3 (2)	C10—C9—C8	119.6 (2)
C4—C3—H3A	109.6	C10—C9—H9	120.2
C2—C3—H3A	109.6	C8—C9—H9	120.2
C4—C3—H3B	109.6	C9—C10—C11	119.9 (2)
C2—C3—H3B	109.6	C9—C10—Br1	119.97 (18)
H3A—C3—H3B	108.1	C11—C10—Br1	120.13 (19)
N1—C4—O1	109.21 (16)	C10—C11—C12	120.3 (2)
N1—C4—C3	113.3 (2)	C10—C11—H11	119.9
O1—C4—C3	108.37 (17)	C12—C11—H11	119.9
N1—C4—H4	108.6	C7—C12—C11	121.0 (2)
O1—C4—H4	108.6	C7—C12—H12	119.5
C3—C4—H4	108.6	C11—C12—H12	119.5
O1—C5—O2	110.92 (17)

C5—O2—C2—C1	179.79 (18)	C2—O2—C5—C6	−179.48 (18)
C5—O2—C2—C3	−55.9 (2)	C4—N1—C7—C12	16.4 (3)
O2—C2—C3—C4	53.0 (2)	C4—N1—C7—C8	−166.52 (18)
C1—C2—C3—C4	173.36 (17)	C12—C7—C8—C9	−1.4 (3)
C7—N1—C4—O1	73.0 (2)	N1—C7—C8—C9	−178.59 (18)
C7—N1—C4—C3	−166.05 (17)	C7—C8—C9—C10	1.0 (3)
C5—O1—C4—N1	−176.72 (18)	C8—C9—C10—C11	0.3 (3)
C5—O1—C4—C3	59.4 (2)	C8—C9—C10—Br1	−177.60 (15)
C2—C3—C4—N1	−175.78 (17)	C9—C10—C11—C12	−1.1 (4)
C2—C3—C4—O1	−54.4 (2)	Br1—C10—C11—C12	176.77 (18)
C4—O1—C5—O2	−63.2 (2)	C8—C7—C12—C11	0.6 (3)
C4—O1—C5—C6	177.81 (19)	N1—C7—C12—C11	177.6 (2)
C2—O2—C5—O1	61.5 (2)	C10—C11—C12—C7	0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.82 (2)	2.66 (2)	3.465 (2)	168 (2)
C8—H8···O2ⁱ	0.93	2.51	3.352 (3)	150
C9—H9···O2ⁱⁱ	0.93	2.65	3.557 (3)	165

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.824 (16)	2.655 (16)	3.465 (2)	168 (2)
C8—H8···O2ⁱ	0.93	2.51	3.352 (3)	150
C9—H9···O2ⁱⁱ	0.93	2.65	3.557 (3)	165

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

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 facilities. ZF also thanks the UGC for a meritorious fellowship.

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