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access3,5-Dinitrobenzyl methanesulfonate
aChemistry Department, The University of Auckland, Private Bag 92019, Auckland, New Zealand
*Correspondence e-mail: g.clark@auckland.ac.nz
The title compound, C8H8N2O7S, an intermediate in the synthesis of N,N-bis(2-hydroxyethyl)-3,5-dinitroaniline, exists as a discrete molecule; the nitro groups are twisted with respect to the aromatic system [dihedral angles = 17.0 (1) and 26.3 (1)°].
Related literature
For the utility of benzyl methanesulfonates in synthesis, see: Barker et al. (2008![[Barker, D., Lehmann, A. L., Mai, A., Khan, G. S. & Ng, E. (2008). Tetrahedron Lett. 49, 1660-1664.]](../../../../../../logos/arrows/e_arr.gif "Barker, D., Lehmann, A. L., Mai, A., Khan, G. S. & Ng, E. (2008). Tetrahedron Lett. 49, 1660-1664.")
); Bretonniere et al. (2004); Oh et al. (2004); Schirok et al. (2005). For the incorporation of N,N-bis(2-hydroxyethyl)benzylamines in macromolecular metal complexes, see: Crans & Boukhobza (1998); Koizumi et al. (2005, 2007).
![[Scheme 1]](ng2470scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Bruker, 1995); cell SAINT (Bruker, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536808020850/ng2470sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808020850/ng2470Isup2.hkl
To a solution of 3,5-dinitrobenzyl alcohol (1.5 g, 7.57 mmol) and triethylamine (1.58 ml, 11.35 mmol) in dry THF (15 ml) at 0°C, under an atmosphere of nitrogen, was added dropwise a solution of methanesulfonyl chloride (0.88 ml, 11.35 mmol) in dry THF (5 ml) and the resulting solution stirred at room temperature for 3 h. The solvent was removed in vacuo and the residue diluted with ethyl acetate (150 ml), washed with brine (50 ml), dried (MgSO4) and the solvent removed in vacuo to afford the title compound (2 g, 96%) as a yellow solid which was recrystallized from ethyl acetate to give yellow crystals (m.p. 356–357 K) suitable for X-ray crystallography. IR νmax (NaCl)/cm-1 3399, 1627, 1541, 1458, 1344. 1H NMR (400 MHz, CDCl3, δ, p.p.m.) 3.15 (3H, s, CH3), 5.40 (2H, s, CH2O), 8.60 (2H, br s, Ar—H), 9.05 (1H, br s, Ar—H). δC (100 MHz, CDCl3, δ, p.p.m.) 38.6 (CH3, CH3), 67.4 (CH2, CH2O), 119.5 (CH, Ar—C), 128.2 (CH, Ar—C), 138.6 (CH, Ar—C), 149.1 (quat., Ar—C). MS m/z (EI) 276 (M+, 1%), 197 (100), 181 (42), 134 (20). HRMS (EI) Found M+ 276.00489, C8H8N2O7S requires 276.00522.
Hydrogen atoms were placed in calculated positions and refined using the riding model [C—H 0.93–0.97 Å), with Uiso(H) = 1.2 or 1.5 times Ueq(C).
Data collection: SMART (Bruker, 1995); cell SAINT (Bruker, 1995); data reduction: SAINT (Bruker, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./ng2470fig1thm.gif) | Fig. 1. : Structure showing 50% probability displacement ellipsoids for non-hydrogen atoms and hydrogen atoms as arbitary spheres (Burnett & Johnson, 1996). |
| C8H8N2O7S | F(000) = 568 |
| Mr = 276.22 | Dx = 1.659 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 4665 reflections |
| a = 9.3549 (5) Å | θ = 2.3–26.4° |
| b = 8.7552 (5) Å | µ = 0.32 mm−1 |
| c = 14.1526 (8) Å | T = 89 K |
| β = 107.430 (1)° | Rod, yellow |
| V = 1105.91 (11) Å3 | 0.32 × 0.14 × 0.14 mm |
| Z = 4 |
| Bruker SMART diffractometer | 2233 independent reflections |
| Radiation source: fine-focus sealed tube | 1959 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.019 |
| ω scans | θmax = 26.4°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −9→11 |
| Tmin = 0.799, Tmax = 0.971 | k = −10→9 |
| 6374 measured reflections | l = −17→8 |
| 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.088 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0465P)2 + 0.6248P] where P = (Fo2 + 2Fc2)/3 |
| 2233 reflections | (Δ/σ)max = 0.001 |
| 163 parameters | Δρmax = 0.28 e Å−3 |
| 0 restraints | Δρmin = −0.49 e Å−3 |
| C8H8N2O7S | V = 1105.91 (11) Å3 |
| Mr = 276.22 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 9.3549 (5) Å | µ = 0.32 mm−1 |
| b = 8.7552 (5) Å | T = 89 K |
| c = 14.1526 (8) Å | 0.32 × 0.14 × 0.14 mm |
| β = 107.430 (1)° |
| Bruker SMART diffractometer | 2233 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 1959 reflections with I > 2σ(I) |
| Tmin = 0.799, Tmax = 0.971 | Rint = 0.019 |
| 6374 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
| wR(F2) = 0.088 | H-atom parameters constrained |
| S = 1.06 | Δρmax = 0.28 e Å−3 |
| 2233 reflections | Δρmin = −0.49 e Å−3 |
| 163 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 | ||
| S | 0.28908 (4) | 0.49088 (4) | 0.39904 (3) | 0.01554 (13) | |
| O1 | 0.79782 (14) | 0.02166 (15) | 0.65112 (9) | 0.0229 (3) | |
| O2 | 0.75778 (13) | −0.16192 (14) | 0.74420 (9) | 0.0199 (3) | |
| O3 | 0.23786 (14) | −0.34566 (14) | 0.65950 (9) | 0.0230 (3) | |
| O4 | 0.06497 (14) | −0.21217 (16) | 0.55662 (12) | 0.0343 (4) | |
| O5 | 0.31800 (13) | 0.32888 (13) | 0.45017 (8) | 0.0171 (3) | |
| O6 | 0.31513 (15) | 0.60687 (14) | 0.47320 (9) | 0.0259 (3) | |
| O7 | 0.37522 (14) | 0.49312 (14) | 0.33100 (9) | 0.0223 (3) | |
| N1 | 0.71506 (16) | −0.05791 (16) | 0.68364 (10) | 0.0166 (3) | |
| N2 | 0.19482 (16) | −0.23139 (16) | 0.60944 (11) | 0.0191 (3) | |
| C1 | 0.35300 (19) | 0.15179 (18) | 0.58246 (11) | 0.0149 (3) | |
| C2 | 0.50631 (18) | 0.11998 (19) | 0.61537 (11) | 0.0155 (3) | |
| H2A | 0.5761 | 0.1957 | 0.6155 | 0.019* | |
| C3 | 0.55267 (18) | −0.02626 (19) | 0.64782 (12) | 0.0148 (3) | |
| C4 | 0.45474 (18) | −0.14488 (18) | 0.64856 (11) | 0.0148 (3) | |
| H4A | 0.4880 | −0.2418 | 0.6720 | 0.018* | |
| C5 | 0.30408 (18) | −0.10912 (18) | 0.61204 (11) | 0.0150 (3) | |
| C6 | 0.25038 (19) | 0.03509 (19) | 0.57931 (12) | 0.0154 (3) | |
| H6A | 0.1479 | 0.0536 | 0.5557 | 0.019* | |
| C7 | 0.29970 (19) | 0.31110 (18) | 0.54971 (12) | 0.0163 (3) | |
| H7A | 0.1955 | 0.3235 | 0.5470 | 0.020* | |
| H7B | 0.3593 | 0.3862 | 0.5951 | 0.020* | |
| C8 | 0.0984 (2) | 0.4858 (2) | 0.33155 (17) | 0.0319 (5) | |
| H8A | 0.0702 | 0.5810 | 0.2974 | 0.048* | |
| H8B | 0.0399 | 0.4696 | 0.3760 | 0.048* | |
| H8C | 0.0807 | 0.4040 | 0.2843 | 0.048* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S | 0.0168 (2) | 0.0125 (2) | 0.0157 (2) | −0.00083 (14) | 0.00236 (16) | 0.00293 (14) |
| O1 | 0.0180 (6) | 0.0286 (7) | 0.0219 (7) | −0.0040 (5) | 0.0057 (5) | 0.0021 (5) |
| O2 | 0.0211 (6) | 0.0168 (6) | 0.0175 (6) | 0.0029 (5) | −0.0006 (5) | 0.0006 (5) |
| O3 | 0.0241 (7) | 0.0172 (6) | 0.0263 (7) | −0.0011 (5) | 0.0057 (5) | 0.0086 (5) |
| O4 | 0.0164 (7) | 0.0248 (7) | 0.0529 (9) | −0.0036 (5) | −0.0030 (6) | 0.0140 (7) |
| O5 | 0.0237 (6) | 0.0143 (6) | 0.0134 (6) | 0.0010 (5) | 0.0055 (5) | 0.0022 (4) |
| O6 | 0.0421 (8) | 0.0133 (6) | 0.0230 (6) | −0.0022 (5) | 0.0105 (6) | 0.0000 (5) |
| O7 | 0.0250 (7) | 0.0227 (7) | 0.0200 (6) | −0.0002 (5) | 0.0079 (5) | 0.0053 (5) |
| N1 | 0.0176 (7) | 0.0164 (7) | 0.0138 (6) | −0.0001 (6) | 0.0018 (6) | −0.0035 (6) |
| N2 | 0.0189 (7) | 0.0149 (7) | 0.0227 (7) | −0.0007 (6) | 0.0052 (6) | 0.0035 (6) |
| C1 | 0.0207 (8) | 0.0135 (8) | 0.0100 (7) | 0.0010 (6) | 0.0038 (6) | 0.0006 (6) |
| C2 | 0.0190 (8) | 0.0147 (8) | 0.0126 (7) | −0.0022 (6) | 0.0044 (6) | −0.0009 (6) |
| C3 | 0.0155 (8) | 0.0178 (8) | 0.0099 (7) | 0.0001 (6) | 0.0018 (6) | −0.0016 (6) |
| C4 | 0.0200 (8) | 0.0132 (8) | 0.0101 (7) | 0.0020 (6) | 0.0030 (6) | 0.0000 (6) |
| C5 | 0.0185 (8) | 0.0140 (8) | 0.0124 (7) | −0.0028 (6) | 0.0046 (6) | −0.0004 (6) |
| C6 | 0.0171 (8) | 0.0163 (8) | 0.0120 (7) | 0.0010 (6) | 0.0031 (6) | 0.0005 (6) |
| C7 | 0.0216 (8) | 0.0136 (8) | 0.0136 (8) | −0.0003 (6) | 0.0053 (6) | 0.0009 (6) |
| C8 | 0.0177 (9) | 0.0331 (11) | 0.0390 (12) | 0.0005 (8) | −0.0002 (8) | 0.0141 (9) |
| S—O6 | 1.4279 (13) | C1—C7 | 1.507 (2) |
| S—O7 | 1.4290 (13) | C2—C3 | 1.385 (2) |
| S—O5 | 1.5783 (12) | C2—H2A | 0.9300 |
| S—C8 | 1.7538 (19) | C3—C4 | 1.387 (2) |
| O1—N1 | 1.2289 (19) | C4—C5 | 1.384 (2) |
| O2—N1 | 1.2322 (18) | C4—H4A | 0.9300 |
| O3—N2 | 1.2223 (18) | C5—C6 | 1.386 (2) |
| O4—N2 | 1.2323 (19) | C6—H6A | 0.9300 |
| O5—C7 | 1.4773 (19) | C7—H7A | 0.9700 |
| N1—C3 | 1.476 (2) | C7—H7B | 0.9700 |
| N2—C5 | 1.473 (2) | C8—H8A | 0.9600 |
| C1—C6 | 1.394 (2) | C8—H8B | 0.9600 |
| C1—C2 | 1.397 (2) | C8—H8C | 0.9600 |
| O6—S—O7 | 118.62 (8) | C5—C4—C3 | 115.40 (15) |
| O6—S—O5 | 109.52 (7) | C5—C4—H4A | 122.3 |
| O7—S—O5 | 105.51 (7) | C3—C4—H4A | 122.3 |
| O6—S—C8 | 109.88 (10) | C4—C5—C6 | 123.88 (15) |
| O7—S—C8 | 108.68 (9) | C4—C5—N2 | 117.80 (14) |
| O5—S—C8 | 103.51 (8) | C6—C5—N2 | 118.32 (14) |
| C7—O5—S | 118.62 (10) | C5—C6—C1 | 118.68 (15) |
| O1—N1—O2 | 124.75 (14) | C5—C6—H6A | 120.7 |
| O1—N1—C3 | 117.64 (13) | C1—C6—H6A | 120.7 |
| O2—N1—C3 | 117.61 (14) | O5—C7—C1 | 105.58 (13) |
| O3—N2—O4 | 123.85 (14) | O5—C7—H7A | 110.6 |
| O3—N2—C5 | 118.35 (13) | C1—C7—H7A | 110.6 |
| O4—N2—C5 | 117.80 (14) | O5—C7—H7B | 110.6 |
| C6—C1—C2 | 119.55 (15) | C1—C7—H7B | 110.6 |
| C6—C1—C7 | 120.50 (15) | H7A—C7—H7B | 108.8 |
| C2—C1—C7 | 119.95 (15) | S—C8—H8A | 109.5 |
| C3—C2—C1 | 118.88 (15) | S—C8—H8B | 109.5 |
| C3—C2—H2A | 120.6 | H8A—C8—H8B | 109.5 |
| C1—C2—H2A | 120.6 | S—C8—H8C | 109.5 |
| C2—C3—C4 | 123.55 (15) | H8A—C8—H8C | 109.5 |
| C2—C3—N1 | 118.36 (14) | H8B—C8—H8C | 109.5 |
| C4—C3—N1 | 118.09 (14) |
Experimental details
| Crystal data | |
| Chemical formula | C8H8N2O7S |
| Mr | 276.22 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 89 |
| a, b, c (Å) | 9.3549 (5), 8.7552 (5), 14.1526 (8) |
| β (°) | 107.430 (1) |
| V (Å3) | 1105.91 (11) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.32 |
| Crystal size (mm) | 0.32 × 0.14 × 0.14 |
| Data collection | |
| Diffractometer | Bruker SMART diffractometer |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
| Tmin, Tmax | 0.799, 0.971 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6374, 2233, 1959 |
| Rint | 0.019 |
| (sin θ/λ)max (Å−1) | 0.625 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.088, 1.06 |
| No. of reflections | 2233 |
| No. of parameters | 163 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.28, −0.49 |
Computer programs: SMART (Bruker, 1995), SAINT (Bruker, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors acknowledge financial support from the Higher Education Commission of Pakistan and the University of Auckland, New Zealand.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Benzylic methansulfonates are readily prepared from benzylic alcohols and are often more easily prepared and more stable than the corresponding benzylic halide (Barker et al., 2008). In particular benzylic methanesulfonates are useful for the preparation of N,N-bis(2-hydroxyethyl)benzylamines, which are nitrogen mustard precursors. The dual functionality of the two free hydroxyl groups along with a basic nitrogen have also seen N,N-bis(2-hydroxyethyl)benzylamines used in synthesis of numerous metal complexes including those containing vanadium (Crans & Boukhobza, 1998), manganese (Koizumi et al., 2005, 2007) and iron (Koizumi et al., 2005). There are no hydrogen bonding or π - π interactions in the crystal. The closest intermolecular contacts are O3 ··· N1 of 2.83 Å, and a pair of O ··· O 3.32 Å contacts between sulfonate oxygen atoms.