N,N-Dibenzylmethanesulfonamide

organic compounds Acta Crystallographica Section E Orthorhombic, P21 21 21 a = 6.0948 (1) Å b = 13.4498 (4) Å c = 17.1293 (4) Å V = 1404.15 (6) Å3 Structure Reports Online ISSN 1600-5368 Z=4 Mo K radiation  = 0.23 mm
1 T = 293 (2) K 0.32  0.10  0.08 mm Data collection N,N-Dibenzylmethanesulfonamide Mrityunjoy Datta,a Alan J. Buglass,a* Chang Seop Hongb and Jeon Hak Limb a Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea, and bDepartment of Chemistry, Korea University, Seoul 136-701, Republic of Korea Correspondence e-mail: [email protected] Bruker APEXII diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.931, Tmax = 0.982 8426 measured reflections 3421 independent reflections 2694 reflections with I > 2(I) Rint = 0.025 Refinement Received 7 May 2008; accepted 19 May 2008 R[F 2 > 2(F 2)] = 0.036 wR(F 2) = 0.095 S = 1.10 3421 reflections 173 parameters H-atom parameters constrained Key indicators: single-crystal X-ray study; T = 293 K; mean (C–C) = 0.003 Å; R factor = 0.036; wR factor = 0.095; data-to-parameter ratio = 19.8. Table 1
max = 0.14 e Å
3
min =
0.29 e Å
3 Absolute structure: Flack (1983), 1428 Friedel pairs Flack parameter: 0.01 (8) Hydrogen-bond geometry (Å,  ). Molecules of the title compound, C15H17NO2S, which was synthesized from methanesulfonyl chloride and dibenzylamine, are packed in antiparallel arrays along the c axis, with the methyl group of one molecule dovetailed between the two phenyl rings of the next molecule. Along any such array, the sulfonyl O atoms protrude alternately up and down. Related literature For crystallographic literature on sulfonamides such as methanesulfonamides, see: Gowda et al. (2007). For literature on N,N-dialkylmethanesulfonamides, see: van Otterlo et al. (2004). For the synthesis, see: Banks & Hudson (1986); Stretter et al. (1969); Youn & Herrmann (1986). D—H  A i C14—H14B  O1 C7—H7B  O1 C8—H8  N1 D—H H  A D  A D—H  A 0.97 0.97 0.93 2.50 2.44 2.61 3.366 (2) 2.911 (2) 2.937 (2) 149 109 101 Symmetry code: (i) x þ 1; y; z. Data collection: APEX2 (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999). MD and AJB thank KAIST for financial support. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2454). References Banks & Hudson (1986). J. Chem. Soc. Perkin Trans 2, pp. 151–155. Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. Flack, H. D. (1983). Acta Cryst. A39, 876–881. Gowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o3084. Otterlo, W. A. L. van, Panayides, J.-L. & Fernandes, M. A. (2004). Acta Cryst. E60, o1586–o1588. Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Stretter, H., Krause, M. & Last, W.-D. (1969). Chem. Ber. 102, 3357–3363. Youn, J.-H. & Herrmann, R. (1986). Tetrahedron Lett. 27, 1493–1494. Experimental Crystal data C15H17NO2S Acta Cryst. (2008). E64, o1235 Mr = 275.36 doi:10.1107/S1600536808015055 Datta et al. o1235 supporting information supporting information Acta Cryst. (2008). E64, o1235 [doi:10.1107/S1600536808015055] N,N-Dibenzylmethanesulfonamide Mrityunjoy Datta, Alan J. Buglass, Chang Seop Hong and Jeon Hak Lim S1. Comment The title compound (I) was prepared by an established method (Stretter et al., 1969) from dibenzylamine and methanesulfonyl chloride. The last-named compound was prepared unintentionally from methyl sulfide, sulfuryl chloride and acetic acid (Youn and Herrmann, 1986), but with an excess of sulfuryl chloride (1:4:2). With the normal ratio of reactants (1:3:2), methanesulfinyl chloride is the main product. No observation of this kind was reported by the original authors, and indeed, oxidation of disulfides or sulfinyl moeities to sulfonyl moeities generally needs the use of peroxyacids or hydroperoxides. The molecular structure of (I) (Fig. 1) exhibits no unusual bond lengths or bond angles. The crystal packing of (I) (Fig. 2) shows antiparallel arrays along the c axis, with the S-methyl group occupying the space between the two benzene rings of the next molecule. Along each of these arrays, the oxygen atoms point alternately up and down, and there appears to be some stacking of benzene rings between molecules, along the a and b axes. There is no evidence of hydrogen bonding, but there are weak C14—H14···O1, C7—H7···O2 and C8—H8···N1 interactions (Table 1). S2. Experimental Methanesulfonyl chloride was prepared by the method of Youn and Herrmann, but using an excess of sulfuryl chloride (viz. methyl disulfide (0.01 mol), acetic acid (0.02 mol) and sulfuryl chloride (0.04 mol)). The title compound was prepared by the method of Stretter et al., using dibenzylamine (1.5 g, 8 mmol), methanesulfonyl chloride (458 mg, 4 mmol) and dichloromethane (30 ml). The crude product was purified by column chromatography on silica gel using dichloromethane as eluent, giving N,N-dibenzylmethanesulfonamide as white crystals (1.05 g, 96%), mp, 83–85°C. Literature mp. 84–85 oC (Banks & Hudson, 1986). Crystals were obtained by evaporation of solvent from a solution of (I) in dichoromethane/hexane (1:4). FTIR (KBr) (cm-1) 3088, 3062, 3009, 1496, 1446, 1438, 1382, 1318, 1265, 1207, 1132, 1091, 1056, 949 1 H NMR (400 MHz, CDCl3, p.p.m. with respect to TMS) 7.39–7.29 (m, 10H), 4.35 (s, 4H), 2.77 (s, 3H) 13 C NMR (100 MHz, CDCl3, p.p.m. with respect to TMS) 135.4, 128.7, 128.0, 49.8, 40.2 EIMS m/z (%) 275 (M+., 19), 196 (M+. - CH3SO2., 84), 195 (82), 184 (84), 91 (100) Anal. Calcd. for C15H17NO2S (%): C, 65.45; H, 6.18; N, 5.09; S, 11.63. Found (%): C, 65.22; H, 6.15; N, 5.03; S, 11.80. S3. Refinement H atoms were located on a difference Fourier map, positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 (1.5 for CH3) times Ueq(C). Acta Cryst. (2008). E64, o1235 sup-1 supporting information Figure 1 Molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. Acta Cryst. (2008). E64, o1235 sup-2 supporting information Figure 2 The packing of (I), viewed down the a axis. N,N-Dibenzylmethanesulfonamide Crystal data C15H17NO2S Mr = 275.36 Orthorhombic, P212121 Hall symbol: P 2ac 2ab a = 6.0948 (1) Å b = 13.4498 (4) Å c = 17.1293 (4) Å V = 1404.15 (6) Å3 Z=4 F(000) = 584 Dx = 1.303 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3097 reflections θ = 3.0–26.3° µ = 0.23 mm−1 T = 293 K Plate, white 0.32 × 0.10 × 0.08 mm Data collection Bruker APEXII diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.931, Tmax = 0.982 Acta Cryst. (2008). E64, o1235 8426 measured reflections 3421 independent reflections 2694 reflections with I > 2σ(I) Rint = 0.025 θmax = 28.3°, θmin = 1.9° h = −8→7 k = −17→15 l = −18→22 sup-3 supporting information Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.036 wR(F2) = 0.095 S = 1.10 3421 reflections 173 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0517P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 Δρmax = 0.14 e Å−3 Δρmin = −0.29 e Å−3 Absolute structure: Flack (1983), 1428 Friedel pairs Absolute structure parameter: 0.01 (8) Special details 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) C1 H1 C2 H2 C3 H3 C4 H4 C5 H5 C6 C7 H7A H7B C8 H8 C9 H9 C10 H10 C11 H11 C12 x y z Uiso*/Ueq 0.6426 (3) 0.7540 0.6736 (4) 0.8057 0.5109 (4) 0.5322 0.3181 (4) 0.2082 0.2856 (3) 0.1535 0.4471 (3) 0.4079 (3) 0.5423 0.2971 0.3166 (3) 0.2041 0.3116 (4) 0.1967 0.4744 (4) 0.4698 0.6452 (4) 0.7554 0.6529 (3) 0.26792 (15) 0.2208 0.36030 (17) 0.3754 0.43099 (17) 0.4935 0.40880 (15) 0.4566 0.31565 (14) 0.3011 0.24390 (13) 0.14042 (14) 0.1022 0.1084 0.30315 (13) 0.2963 0.38057 (14) 0.4260 0.39038 (15) 0.4422 0.32373 (16) 0.3301 0.24733 (14) 0.41616 (10) 0.4192 0.44782 (11) 0.4723 0.44367 (11) 0.4656 0.40713 (12) 0.4036 0.37533 (11) 0.3507 0.37967 (9) 0.34963 (10) 0.3542 0.3816 0.15342 (10) 0.1897 0.09996 (11) 0.1010 0.04575 (11) 0.0099 0.04415 (11) 0.0069 0.09789 (10) 0.0536 (4) 0.064* 0.0659 (6) 0.079* 0.0697 (6) 0.084* 0.0645 (6) 0.077* 0.0518 (5) 0.062* 0.0437 (4) 0.0515 (5) 0.062* 0.062* 0.0476 (4) 0.057* 0.0551 (5) 0.066* 0.0614 (5) 0.074* 0.0626 (5) 0.075* 0.0501 (4) Acta Cryst. (2008). E64, o1235 sup-4 supporting information H12 C13 C14 H14A H14B N1 S1 O1 O2 C15 H15A H15B H15C 0.7698 0.4884 (3) 0.5104 (3) 0.5184 0.6485 0.3353 (2) 0.13533 (6) −0.0312 (2) 0.0845 (2) 0.2358 (4) 0.1233 0.2779 0.3610 0.2029 0.23622 (12) 0.15067 (15) 0.0895 0.1579 0.14007 (10) 0.06492 (3) 0.07909 (13) 0.08028 (11) −0.05725 (14) −0.1038 −0.0679 −0.0665 0.0972 0.15276 (9) 0.20925 (10) 0.1793 0.2368 0.26726 (7) 0.24587 (3) 0.30334 (10) 0.16558 (8) 0.25679 (12) 0.2426 0.3101 0.2235 0.060* 0.0381 (4) 0.0508 (4) 0.061* 0.061* 0.0411 (3) 0.04857 (14) 0.0755 (4) 0.0706 (4) 0.0625 (5) 0.094* 0.094* 0.094* Atomic displacement parameters (Å2) C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 N1 S1 O1 O2 C15 U11 U22 U33 U12 U13 U23 0.0547 (10) 0.0788 (14) 0.1070 (17) 0.0838 (15) 0.0494 (9) 0.0517 (9) 0.0658 (11) 0.0486 (9) 0.0626 (12) 0.0896 (14) 0.0761 (12) 0.0519 (10) 0.0413 (7) 0.0419 (9) 0.0426 (7) 0.0398 (2) 0.0430 (7) 0.0796 (9) 0.0804 (12) 0.0613 (12) 0.0725 (15) 0.0532 (12) 0.0532 (12) 0.0554 (12) 0.0427 (10) 0.0457 (10) 0.0484 (10) 0.0447 (10) 0.0486 (12) 0.0645 (13) 0.0506 (10) 0.0378 (9) 0.0528 (11) 0.0420 (8) 0.0481 (2) 0.0847 (11) 0.0658 (9) 0.0414 (10) 0.0448 (10) 0.0466 (11) 0.0490 (12) 0.0565 (13) 0.0506 (11) 0.0368 (9) 0.0431 (10) 0.0459 (10) 0.0580 (12) 0.0459 (11) 0.0472 (11) 0.0478 (10) 0.0352 (8) 0.0577 (11) 0.0387 (7) 0.0578 (3) 0.0987 (11) 0.0665 (9) 0.0655 (13) 0.0043 (11) −0.0145 (13) −0.0108 (15) 0.0162 (12) 0.0045 (9) −0.0001 (8) 0.0025 (9) 0.0070 (8) 0.0091 (9) −0.0099 (11) −0.0042 (12) 0.0005 (10) −0.0007 (7) 0.0103 (8) 0.0012 (6) 0.00017 (19) 0.0038 (8) −0.0051 (8) −0.0019 (10) −0.0069 (9) −0.0131 (10) 0.0061 (12) 0.0131 (11) 0.0012 (8) −0.0009 (7) −0.0100 (8) 0.0010 (7) −0.0101 (9) −0.0092 (11) 0.0139 (10) 0.0077 (8) −0.0025 (6) 0.0060 (8) −0.0023 (6) −0.0094 (2) 0.0144 (7) −0.0352 (7) −0.0118 (11) 0.0037 (9) −0.0001 (10) −0.0087 (10) −0.0011 (10) 0.0007 (9) 0.0050 (8) 0.0083 (8) 0.0033 (8) 0.0042 (9) 0.0095 (9) 0.0025 (9) −0.0032 (8) −0.0018 (7) 0.0116 (9) 0.0043 (6) 0.0060 (2) 0.0118 (9) 0.0106 (7) 0.0052 (10) Geometric parameters (Å, º) C1—C2 C1—C6 C1—H1 C2—C3 C2—H2 C3—C4 C3—H3 C4—C5 C4—H4 Acta Cryst. (2008). E64, o1235 1.369 (3) 1.384 (3) 0.930 1.376 (3) 0.930 1.364 (3) 0.930 1.380 (3) 0.930 C9—H9 C10—C11 C10—H10 C11—C12 C11—H11 C12—C13 C12—H12 C13—C14 C14—N1 0.930 1.374 (3) 0.930 1.380 (3) 0.930 1.382 (2) 0.930 1.509 (2) 1.465 (2) sup-5 supporting information C5—C6 C5—H5 C6—C7 C7—N1 C7—H7A C7—H7B C8—C13 C8—C9 C8—H8 C9—C10 1.380 (2) 0.930 1.503 (3) 1.479 (2) 0.970 0.970 1.381 (2) 1.387 (3) 0.9300 1.366 (3) C14—H14A C14—H14B N1—S1 S1—O2 S1—O1 S1—C15 C15—H15A C15—H15B C15—H15C 0.970 0.970 1.6250 (14) 1.4247 (13) 1.4269 (14) 1.764 (2) 0.960 0.960 0.960 C2—C1—C6 C2—C1—H1 C6—C1—H1 C1—C2—C3 C1—C2—H2 C3—C2—H2 C4—C3—C2 C4—C3—H3 C2—C3—H3 C3—C4—C5 C3—C4—H4 C5—C4—H4 C6—C5—C4 C6—C5—H5 C4—C5—H5 C5—C6—C1 C5—C6—C7 C1—C6—C7 N1—C7—C6 N1—C7—H7A C6—C7—H7A N1—C7—H7B C6—C7—H7B H7A—C7—H7B C13—C8—C9 C13—C8—H8 C9—C8—H8 C10—C9—C8 C10—C9—H9 C8—C9—H9 C9—C10—C11 C9—C10—H10 120.7 (2) 119.7 119.7 120.5 (2) 119.8 119.8 119.6 (2) 120.2 120.2 120.2 (2) 119.9 119.9 120.7 (2) 119.6 119.6 118.34 (17) 121.06 (16) 120.50 (16) 112.15 (14) 109.2 109.2 109.2 109.2 107.9 120.04 (17) 120.0 120.0 120.37 (19) 119.8 119.8 120.07 (18) 120.0 C11—C10—H10 C10—C11—C12 C10—C11—H11 C12—C11—H11 C11—C12—C13 C11—C12—H12 C13—C12—H12 C8—C13—C12 C8—C13—C14 C12—C13—C14 N1—C14—C13 N1—C14—H14A C13—C14—H14A N1—C14—H14B C13—C14—H14B H14A—C14—H14B C14—N1—C7 C14—N1—S1 C7—N1—S1 O2—S1—O1 O2—S1—N1 O1—S1—N1 O2—S1—C15 O1—S1—C15 N1—S1—C15 S1—C15—H15A S1—C15—H15B H15A—C15—H15B S1—C15—H15C H15A—C15—H15C H15B—C15—H15C 120.0 119.9 (2) 120.1 120.1 120.61 (19) 119.7 119.7 119.02 (15) 124.00 (15) 116.98 (15) 116.36 (14) 108.2 108.2 108.2 108.2 107.4 115.38 (14) 116.99 (12) 116.21 (11) 119.46 (10) 106.89 (8) 107.15 (8) 108.24 (10) 107.36 (10) 107.16 (9) 109.5 109.5 109.5 109.5 109.5 109.5 Hydrogen-bond geometry (Å, º) D—H···A i C14—H14B···O1 Acta Cryst. (2008). E64, o1235 D—H H···A D···A D—H···A 0.97 2.50 3.366 (2) 149 sup-6 supporting information C7—H7B···O1 C8—H8···N1 0.97 0.93 2.44 2.61 2.911 (2) 2.937 (2) 109 101 Symmetry code: (i) x+1, y, z. Acta Cryst. (2008). E64, o1235 sup-7