organic compounds
2,6-Dimethyl-N-(2-methylphenyl)-1,3-dioxan-4-amine
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
In the title compound, C13H19NO2, the dioxane ring adopts a chair conformation and its mean plane makes a dihedral angle of 45.36 (8)° with the phenyl ring. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with R22(12) ring motifs. These dimers are consolidated by pairs of C—H⋯O hydrogen bonds with R22(8) ring motifs.
CCDC reference: 960698
Related literature
For applications of 1,3-dioxane derivatives, see: Wang et al. (1996a,b); Yuan et al. (2005). Dioxane rings are frequently encountered in many bioactive molecules, some of which are cytotoxic agents (Aubele et al., 2005) and antimuscarinic agents (Marucci et al., 2005). For related crystal structures, see: Chuprunov et al. (1981); Thevenet et al. (2010); Fatima et al. (2013). For hydrogen-bond motifs, see: Bernstein et al. (1995).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2008); cell 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) and Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
CCDC reference: 960698
10.1107/S1600536813025294/su2643sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813025294/su2643Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813025294/su2643Isup3.cml
To 2-toulidine (1 mmol), acetaldehyde (3 mmol) was added drop wise and the mixture was stirred for ca. 4 h at 273 K. The progress of the reaction was monitored through TLC. On completion the reaction the mixture was washed with petroleum ether. The resultant mixture was dissolved in diethylether and the solvent allowed to evaporate. The solid product obtained was recrystallized with diethylether to yield block-like colourless crystals, suitable for X-ray diffraction analysis.
The NH H atom was located in a difference Fourier map and freely refined. The C bound H atoms were placed in calculated positions and refined as riding atoms: C—H = 0.93 - 0.98 Å with Uiso(H) = 1.5Ueq(C-methyl) and = 1.2Ueq(C) for other H atoms.
Data collection: APEX2 (Bruker, 2008); cell
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) and Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C13H19NO2 | F(000) = 480 |
Mr = 221.29 | Dx = 1.153 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3177 reflections |
a = 8.0209 (2) Å | θ = 2.0–28.4° |
b = 7.8762 (2) Å | µ = 0.08 mm−1 |
c = 20.4293 (5) Å | T = 293 K |
β = 99.066 (2)° | Block, colourless |
V = 1274.48 (6) Å3 | 0.30 × 0.25 × 0.20 mm |
Z = 4 |
Bruker SMART APEXII area-detector diffractometer | 3177 independent reflections |
Radiation source: fine-focus sealed tube | 2481 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω and ϕ scans | θmax = 28.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −10→10 |
Tmin = 0.692, Tmax = 0.746 | k = −10→10 |
12359 measured reflections | l = −26→27 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0553P)2 + 0.1687P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3177 reflections | Δρmax = 0.18 e Å−3 |
152 parameters | Δρmin = −0.12 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.077 (4) |
C13H19NO2 | V = 1274.48 (6) Å3 |
Mr = 221.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.0209 (2) Å | µ = 0.08 mm−1 |
b = 7.8762 (2) Å | T = 293 K |
c = 20.4293 (5) Å | 0.30 × 0.25 × 0.20 mm |
β = 99.066 (2)° |
Bruker SMART APEXII area-detector diffractometer | 3177 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2481 reflections with I > 2σ(I) |
Tmin = 0.692, Tmax = 0.746 | Rint = 0.019 |
12359 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.119 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.18 e Å−3 |
3177 reflections | Δρmin = −0.12 e Å−3 |
152 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
H1 | 0.3087 (18) | 0.4830 (19) | 0.5783 (7) | 0.067 (4)* | |
C1 | 0.31391 (18) | 0.68745 (18) | 0.35171 (7) | 0.0682 (4) | |
H1A | 0.3217 | 0.6610 | 0.3064 | 0.102* | |
H1B | 0.4212 | 0.7278 | 0.3737 | 0.102* | |
H1C | 0.2300 | 0.7738 | 0.3531 | 0.102* | |
C2 | 0.26506 (14) | 0.53043 (15) | 0.38614 (6) | 0.0509 (3) | |
H2 | 0.1570 | 0.4884 | 0.3627 | 0.061* | |
C3 | 0.24940 (13) | 0.56014 (14) | 0.45810 (5) | 0.0474 (3) | |
H3A | 0.3511 | 0.6147 | 0.4804 | 0.057* | |
H3B | 0.1550 | 0.6354 | 0.4607 | 0.057* | |
C4 | 0.22287 (12) | 0.39494 (14) | 0.49256 (5) | 0.0457 (3) | |
H4 | 0.1121 | 0.3489 | 0.4739 | 0.055* | |
C5 | 0.35637 (15) | 0.25112 (14) | 0.41290 (6) | 0.0511 (3) | |
H5 | 0.2477 | 0.2066 | 0.3910 | 0.061* | |
C6 | 0.4939 (2) | 0.12583 (18) | 0.40646 (8) | 0.0727 (4) | |
H6A | 0.4992 | 0.1072 | 0.3604 | 0.109* | |
H6B | 0.4703 | 0.0204 | 0.4267 | 0.109* | |
H6C | 0.6000 | 0.1697 | 0.4281 | 0.109* | |
C7 | 0.19069 (13) | 0.28783 (15) | 0.60341 (5) | 0.0475 (3) | |
C8 | 0.13383 (15) | 0.12993 (17) | 0.57909 (7) | 0.0570 (3) | |
H8 | 0.1240 | 0.1079 | 0.5339 | 0.068* | |
C9 | 0.09169 (17) | 0.00538 (19) | 0.62110 (8) | 0.0684 (4) | |
H9 | 0.0524 | −0.0991 | 0.6040 | 0.082* | |
C10 | 0.10746 (19) | 0.0348 (2) | 0.68794 (8) | 0.0773 (4) | |
H10 | 0.0799 | −0.0494 | 0.7163 | 0.093* | |
C11 | 0.16463 (19) | 0.1905 (2) | 0.71237 (7) | 0.0739 (4) | |
H11 | 0.1760 | 0.2096 | 0.7578 | 0.089* | |
C12 | 0.20590 (14) | 0.31981 (18) | 0.67183 (6) | 0.0573 (3) | |
C13 | 0.2628 (2) | 0.4902 (2) | 0.69976 (7) | 0.0778 (4) | |
H13A | 0.2537 | 0.4935 | 0.7460 | 0.117* | |
H13B | 0.1929 | 0.5772 | 0.6768 | 0.117* | |
H13C | 0.3781 | 0.5088 | 0.6943 | 0.117* | |
N1 | 0.22865 (13) | 0.41904 (13) | 0.56182 (5) | 0.0508 (2) | |
O1 | 0.35151 (9) | 0.27540 (10) | 0.48107 (4) | 0.0477 (2) | |
O2 | 0.39299 (10) | 0.40450 (10) | 0.38245 (4) | 0.0509 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0724 (8) | 0.0649 (8) | 0.0671 (8) | 0.0025 (7) | 0.0106 (6) | 0.0160 (6) |
C2 | 0.0435 (5) | 0.0577 (7) | 0.0495 (6) | −0.0018 (5) | 0.0009 (4) | 0.0032 (5) |
C3 | 0.0407 (5) | 0.0495 (6) | 0.0513 (6) | 0.0054 (4) | 0.0047 (4) | −0.0003 (5) |
C4 | 0.0375 (5) | 0.0529 (6) | 0.0461 (6) | −0.0011 (4) | 0.0045 (4) | −0.0026 (4) |
C5 | 0.0567 (6) | 0.0469 (6) | 0.0500 (6) | −0.0108 (5) | 0.0095 (5) | −0.0089 (5) |
C6 | 0.0930 (10) | 0.0516 (7) | 0.0778 (9) | 0.0049 (7) | 0.0270 (8) | −0.0136 (6) |
C7 | 0.0377 (5) | 0.0567 (7) | 0.0486 (6) | 0.0031 (4) | 0.0085 (4) | 0.0021 (5) |
C8 | 0.0502 (6) | 0.0623 (7) | 0.0587 (7) | −0.0030 (5) | 0.0096 (5) | 0.0005 (6) |
C9 | 0.0576 (7) | 0.0630 (8) | 0.0861 (10) | −0.0058 (6) | 0.0158 (6) | 0.0088 (7) |
C10 | 0.0706 (9) | 0.0835 (11) | 0.0808 (10) | −0.0003 (8) | 0.0211 (7) | 0.0279 (8) |
C11 | 0.0714 (8) | 0.0987 (12) | 0.0537 (7) | 0.0022 (8) | 0.0161 (6) | 0.0137 (7) |
C12 | 0.0497 (6) | 0.0738 (8) | 0.0497 (6) | 0.0029 (6) | 0.0122 (5) | −0.0002 (6) |
C13 | 0.0895 (10) | 0.0930 (11) | 0.0544 (8) | −0.0102 (9) | 0.0217 (7) | −0.0172 (7) |
N1 | 0.0514 (5) | 0.0556 (6) | 0.0455 (5) | −0.0050 (4) | 0.0079 (4) | −0.0035 (4) |
O1 | 0.0496 (4) | 0.0458 (4) | 0.0475 (4) | 0.0004 (3) | 0.0073 (3) | −0.0025 (3) |
O2 | 0.0523 (4) | 0.0504 (5) | 0.0517 (4) | −0.0042 (3) | 0.0136 (3) | −0.0022 (3) |
C1—C2 | 1.5048 (17) | C6—H6B | 0.9600 |
C1—H1A | 0.9600 | C6—H6C | 0.9600 |
C1—H1B | 0.9600 | C7—C8 | 1.3893 (17) |
C1—H1C | 0.9600 | C7—N1 | 1.4014 (15) |
C2—O2 | 1.4376 (14) | C7—C12 | 1.4065 (16) |
C2—C3 | 1.5133 (16) | C8—C9 | 1.3800 (18) |
C2—H2 | 0.9800 | C8—H8 | 0.9300 |
C3—C4 | 1.5103 (16) | C9—C10 | 1.371 (2) |
C3—H3A | 0.9700 | C9—H9 | 0.9300 |
C3—H3B | 0.9700 | C10—C11 | 1.375 (2) |
C4—N1 | 1.4212 (14) | C10—H10 | 0.9300 |
C4—O1 | 1.4431 (13) | C11—C12 | 1.386 (2) |
C4—H4 | 0.9800 | C11—H11 | 0.9300 |
C5—O2 | 1.4108 (14) | C12—C13 | 1.501 (2) |
C5—O1 | 1.4122 (13) | C13—H13A | 0.9600 |
C5—C6 | 1.5010 (18) | C13—H13B | 0.9600 |
C5—H5 | 0.9800 | C13—H13C | 0.9600 |
C6—H6A | 0.9600 | N1—H1 | 0.843 (15) |
C2—C1—H1A | 109.5 | C5—C6—H6C | 109.5 |
C2—C1—H1B | 109.5 | H6A—C6—H6C | 109.5 |
H1A—C1—H1B | 109.5 | H6B—C6—H6C | 109.5 |
C2—C1—H1C | 109.5 | C8—C7—N1 | 122.26 (10) |
H1A—C1—H1C | 109.5 | C8—C7—C12 | 119.20 (11) |
H1B—C1—H1C | 109.5 | N1—C7—C12 | 118.51 (11) |
O2—C2—C1 | 107.58 (9) | C9—C8—C7 | 120.85 (12) |
O2—C2—C3 | 109.08 (8) | C9—C8—H8 | 119.6 |
C1—C2—C3 | 113.24 (10) | C7—C8—H8 | 119.6 |
O2—C2—H2 | 109.0 | C10—C9—C8 | 120.41 (14) |
C1—C2—H2 | 109.0 | C10—C9—H9 | 119.8 |
C3—C2—H2 | 109.0 | C8—C9—H9 | 119.8 |
C4—C3—C2 | 111.04 (9) | C9—C10—C11 | 119.03 (14) |
C4—C3—H3A | 109.4 | C9—C10—H10 | 120.5 |
C2—C3—H3A | 109.4 | C11—C10—H10 | 120.5 |
C4—C3—H3B | 109.4 | C10—C11—C12 | 122.41 (14) |
C2—C3—H3B | 109.4 | C10—C11—H11 | 118.8 |
H3A—C3—H3B | 108.0 | C12—C11—H11 | 118.8 |
N1—C4—O1 | 109.70 (8) | C11—C12—C7 | 118.09 (13) |
N1—C4—C3 | 111.35 (9) | C11—C12—C13 | 121.14 (12) |
O1—C4—C3 | 109.23 (8) | C7—C12—C13 | 120.76 (12) |
N1—C4—H4 | 108.8 | C12—C13—H13A | 109.5 |
O1—C4—H4 | 108.8 | C12—C13—H13B | 109.5 |
C3—C4—H4 | 108.8 | H13A—C13—H13B | 109.5 |
O2—C5—O1 | 111.04 (9) | C12—C13—H13C | 109.5 |
O2—C5—C6 | 108.50 (10) | H13A—C13—H13C | 109.5 |
O1—C5—C6 | 108.08 (10) | H13B—C13—H13C | 109.5 |
O2—C5—H5 | 109.7 | C7—N1—C4 | 121.93 (10) |
O1—C5—H5 | 109.7 | C7—N1—H1 | 115.0 (10) |
C6—C5—H5 | 109.7 | C4—N1—H1 | 112.4 (10) |
C5—C6—H6A | 109.5 | C5—O1—C4 | 112.35 (8) |
C5—C6—H6B | 109.5 | C5—O2—C2 | 111.57 (8) |
H6A—C6—H6B | 109.5 | ||
O2—C2—C3—C4 | −52.82 (11) | N1—C7—C12—C13 | −0.45 (17) |
C1—C2—C3—C4 | −172.57 (9) | C8—C7—N1—C4 | −4.57 (16) |
C2—C3—C4—N1 | 172.86 (8) | C12—C7—N1—C4 | 177.47 (10) |
C2—C3—C4—O1 | 51.55 (11) | O1—C4—N1—C7 | −65.48 (12) |
N1—C7—C8—C9 | −177.63 (11) | C3—C4—N1—C7 | 173.48 (9) |
C12—C7—C8—C9 | 0.31 (17) | O2—C5—O1—C4 | 60.92 (11) |
C7—C8—C9—C10 | −0.9 (2) | C6—C5—O1—C4 | 179.82 (9) |
C8—C9—C10—C11 | 0.5 (2) | N1—C4—O1—C5 | −177.70 (9) |
C9—C10—C11—C12 | 0.5 (2) | C3—C4—O1—C5 | −55.39 (11) |
C10—C11—C12—C7 | −1.0 (2) | O1—C5—O2—C2 | −61.96 (11) |
C10—C11—C12—C13 | 178.05 (14) | C6—C5—O2—C2 | 179.40 (9) |
C8—C7—C12—C11 | 0.63 (17) | C1—C2—O2—C5 | −179.23 (9) |
N1—C7—C12—C11 | 178.65 (11) | C3—C2—O2—C5 | 57.58 (11) |
C8—C7—C12—C13 | −178.47 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.843 (15) | 2.559 (15) | 3.3688 (13) | 161.3 (13) |
C3—H3A···O1i | 0.97 | 2.54 | 3.4950 (13) | 167 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.843 (15) | 2.559 (15) | 3.3688 (13) | 161.3 (13) |
C3—H3A···O1i | 0.97 | 2.54 | 3.4950 (13) | 167 |
Symmetry code: (i) −x+1, −y+1, −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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1,3-dioxane derivatives have applications in the pharmaceutical (Wang et al., 1996b) and cosmetics industry (Wang et al., 1996a; Yuan et al., 2005). Dioxane rings are frequently encountered in many bioactive molecules, some of which are cytotoxic agents (Aubele et al., 2005) and antimuscarinic agents (Marucci et al., 2005). In view of the excellent biological and pharmacological applications of this class of compounds, we have undertaken the synthesis of the title compound and report herein on its crystal structure.
In the title molecule, Fig. 1, the dioxane ring (O1/O2/C2—C5) adopts a chair conformation and its mean plane makes a dihedral angle of 45.36 (8)° with the phenyl ring (C7—C12).
In the crystal, molecules are linked by a pair of N-H···O hydrogen bonds forming inversion dimers with an R22(12) ring motif (Bernstein et al., 1995). These dimers are consolidated by a pair of C-H···O hydrogen bonds with an R22(8) ring motif (Table 1 and Fig. 2).