Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013824/ob6062sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013824/ob6062Isup2.hkl |
CCDC reference: 172222
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.007 Å
- R factor = 0.057
- wR factor = 0.162
- Data-to-parameter ratio = 18.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 74.90 From the CIF: _reflns_number_total 2484 Count of symmetry unique reflns 1451 Completeness (_total/calc) 171.19% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1033 Fraction of Friedel pairs measured 0.712 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
The synthesis of (I) has been described by Armstrong & Lowry (1902) and more recently by Davis et al. (1992). Crystals of (I) were grown by slow cooling of a toluene/2,2,5-trimethylpentane solution.
H atoms were placed in calculated positions with C—H bond distances in the range 0.96—0.98 Å and thereafter treated as riding. A torsional parameter was refined for methyl groups. Uiso = 1.2Ueq of the attached atom (1.5 for methyl groups).
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: maXus (Mackay et al., 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. View of the title compound showing the numbering scheme and ellipsoids at the 30% probability level. |
C10H14BrNO2S | F(000) = 592 |
Mr = 292.19 | Dx = 1.606 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 7.2643 (4) Å | θ = 11.3–34.0° |
b = 10.6393 (6) Å | µ = 6.11 mm−1 |
c = 15.6331 (13) Å | T = 296 K |
V = 1208.24 (14) Å3 | Fragment, colorless |
Z = 4 | 0.23 × 0.22 × 0.15 mm |
Enraf-Nonius CAD-4 diffractometer | 2348 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.057 |
Graphite monochromator | θmax = 74.9°, θmin = 5.0° |
θ/2θ scans | h = 0→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −13→13 |
Tmin = 0.267, Tmax = 0.399 | l = −19→19 |
5380 measured reflections | 3 standard reflections every 120 min |
2484 independent reflections | intensity decay: 9.0% |
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)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.162 | w = 1/[σ2(Fo2) + (0.0977P)2 + 0.6776P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max < 0.001 |
2484 reflections | Δρmax = 0.89 e Å−3 |
138 parameters | Δρmin = −0.81 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1033 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (4) |
C10H14BrNO2S | V = 1208.24 (14) Å3 |
Mr = 292.19 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 7.2643 (4) Å | µ = 6.11 mm−1 |
b = 10.6393 (6) Å | T = 296 K |
c = 15.6331 (13) Å | 0.23 × 0.22 × 0.15 mm |
Enraf-Nonius CAD-4 diffractometer | 2348 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.057 |
Tmin = 0.267, Tmax = 0.399 | 3 standard reflections every 120 min |
5380 measured reflections | intensity decay: 9.0% |
2484 independent reflections |
R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.162 | Δρmax = 0.89 e Å−3 |
S = 1.15 | Δρmin = −0.81 e Å−3 |
2484 reflections | Absolute structure: Flack (1983), 1033 Friedel pairs |
138 parameters | Absolute structure parameter: 0.02 (4) |
0 restraints |
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 | ||
Br | 0.59132 (12) | 0.63333 (8) | 0.01579 (5) | 0.1019 (3) | |
S | 0.53225 (19) | 0.45051 (10) | 0.30589 (7) | 0.0622 (3) | |
O1 | 0.6825 (7) | 0.3659 (4) | 0.2999 (3) | 0.0865 (12) | |
O2 | 0.5099 (10) | 0.5173 (5) | 0.3830 (3) | 0.1043 (17) | |
N | 0.5533 (5) | 0.5566 (3) | 0.2262 (2) | 0.0523 (8) | |
C1 | 0.3829 (7) | 0.5989 (4) | 0.0899 (3) | 0.0557 (10) | |
H1 | 0.3270 | 0.6792 | 0.1064 | 0.067* | |
C2 | 0.4345 (5) | 0.5295 (3) | 0.1694 (2) | 0.0462 (8) | |
C3 | 0.3080 (6) | 0.4175 (4) | 0.1775 (3) | 0.0559 (10) | |
C4 | 0.3776 (9) | 0.3256 (4) | 0.1077 (4) | 0.0745 (15) | |
H4A | 0.5101 | 0.3151 | 0.1108 | 0.089* | |
H4B | 0.3193 | 0.2439 | 0.1131 | 0.089* | |
C5 | 0.3207 (12) | 0.3906 (5) | 0.0238 (4) | 0.0860 (18) | |
H5A | 0.4272 | 0.4062 | −0.0121 | 0.103* | |
H5B | 0.2332 | 0.3397 | −0.0077 | 0.103* | |
C6 | 0.2327 (8) | 0.5144 (4) | 0.0527 (3) | 0.0667 (13) | |
H6 | 0.1540 | 0.5548 | 0.0098 | 0.080* | |
C7 | 0.3199 (8) | 0.3770 (5) | 0.2696 (4) | 0.0685 (12) | |
H7A | 0.3266 | 0.2862 | 0.2744 | 0.082* | |
H7B | 0.2150 | 0.4071 | 0.3021 | 0.082* | |
C8 | 0.1301 (6) | 0.4733 (4) | 0.1372 (4) | 0.0654 (12) | |
C9 | 0.0480 (7) | 0.5805 (5) | 0.1894 (5) | 0.0823 (17) | |
H9A | −0.0494 | 0.6195 | 0.1575 | 0.123* | |
H9B | 0.1419 | 0.6415 | 0.2015 | 0.123* | |
H9C | −0.0001 | 0.5480 | 0.2422 | 0.123* | |
C10 | −0.0240 (10) | 0.3749 (6) | 0.1239 (6) | 0.105 (3) | |
H10A | 0.0293 | 0.2969 | 0.1056 | 0.157* | |
H10B | −0.1084 | 0.4045 | 0.0812 | 0.157* | |
H10C | −0.0886 | 0.3623 | 0.1768 | 0.157* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.1102 (6) | 0.1140 (6) | 0.0815 (5) | 0.0030 (4) | 0.0237 (4) | 0.0414 (4) |
S | 0.0850 (7) | 0.0506 (5) | 0.0511 (5) | −0.0087 (5) | −0.0022 (5) | 0.0113 (4) |
O1 | 0.086 (2) | 0.072 (2) | 0.101 (3) | 0.006 (2) | −0.017 (2) | 0.030 (2) |
O2 | 0.169 (5) | 0.092 (3) | 0.0521 (19) | −0.031 (3) | 0.011 (3) | −0.0027 (19) |
N | 0.0623 (19) | 0.0404 (14) | 0.0540 (18) | −0.0051 (15) | 0.0009 (15) | 0.0081 (13) |
C1 | 0.066 (2) | 0.0450 (18) | 0.057 (2) | 0.0077 (17) | −0.0018 (19) | 0.0058 (17) |
C2 | 0.0517 (18) | 0.0362 (14) | 0.0507 (19) | 0.0042 (15) | 0.0037 (16) | 0.0020 (14) |
C3 | 0.060 (2) | 0.0390 (18) | 0.069 (3) | −0.0045 (17) | −0.001 (2) | −0.0031 (17) |
C4 | 0.088 (3) | 0.043 (2) | 0.093 (4) | 0.014 (2) | −0.006 (3) | −0.015 (2) |
C5 | 0.126 (5) | 0.055 (3) | 0.077 (3) | 0.014 (3) | −0.009 (3) | −0.027 (3) |
C6 | 0.085 (3) | 0.050 (2) | 0.065 (3) | 0.015 (2) | −0.022 (2) | −0.014 (2) |
C7 | 0.078 (3) | 0.049 (2) | 0.078 (3) | −0.011 (2) | 0.012 (3) | 0.014 (2) |
C8 | 0.055 (2) | 0.0415 (18) | 0.100 (4) | −0.0058 (17) | −0.009 (2) | −0.014 (2) |
C9 | 0.055 (2) | 0.063 (3) | 0.129 (5) | 0.006 (2) | 0.004 (3) | −0.024 (3) |
C10 | 0.076 (3) | 0.079 (4) | 0.159 (7) | −0.020 (3) | −0.029 (4) | −0.022 (4) |
Br—C1 | 1.941 (5) | C5—C6 | 1.532 (7) |
S—O2 | 1.408 (5) | C5—H5A | 0.9700 |
S—O1 | 1.418 (5) | C5—H5B | 0.9700 |
S—N | 1.687 (3) | C6—C8 | 1.578 (9) |
S—C7 | 1.820 (6) | C6—H6 | 0.9800 |
N—C2 | 1.271 (6) | C7—H7A | 0.9700 |
C1—C2 | 1.494 (6) | C7—H7B | 0.9700 |
C1—C6 | 1.529 (7) | C8—C9 | 1.524 (7) |
C1—H1 | 0.9800 | C8—C10 | 1.547 (7) |
C2—C3 | 1.510 (5) | C9—H9A | 0.9600 |
C3—C7 | 1.505 (7) | C9—H9B | 0.9600 |
C3—C4 | 1.550 (7) | C9—H9C | 0.9600 |
C3—C8 | 1.556 (7) | C10—H10A | 0.9600 |
C4—C5 | 1.539 (9) | C10—H10B | 0.9600 |
C4—H4A | 0.9700 | C10—H10C | 0.9600 |
C4—H4B | 0.9700 | ||
O2—S—O1 | 117.7 (4) | C4—C5—H5B | 110.9 |
O2—S—N | 107.7 (2) | H5A—C5—H5B | 108.9 |
O1—S—N | 107.8 (2) | C1—C6—C5 | 108.6 (5) |
O2—S—C7 | 112.7 (4) | C1—C6—C8 | 100.5 (4) |
O1—S—C7 | 111.1 (2) | C5—C6—C8 | 101.8 (4) |
N—S—C7 | 97.7 (2) | C1—C6—H6 | 114.8 |
C2—N—S | 107.6 (3) | C5—C6—H6 | 114.8 |
C2—C1—C6 | 101.8 (4) | C8—C6—H6 | 114.8 |
C2—C1—Br | 113.2 (3) | C3—C7—S | 102.9 (3) |
C6—C1—Br | 116.1 (3) | C3—C7—H7A | 111.2 |
C2—C1—H1 | 108.4 | S—C7—H7A | 111.2 |
C6—C1—H1 | 108.4 | C3—C7—H7B | 111.2 |
Br—C1—H1 | 108.4 | S—C7—H7B | 111.2 |
N—C2—C1 | 129.7 (4) | H7A—C7—H7B | 109.1 |
N—C2—C3 | 122.2 (4) | C9—C8—C10 | 107.2 (5) |
C1—C2—C3 | 107.9 (4) | C9—C8—C3 | 113.2 (5) |
C7—C3—C2 | 105.7 (4) | C10—C8—C3 | 113.4 (4) |
C7—C3—C4 | 118.4 (4) | C9—C8—C6 | 115.2 (4) |
C2—C3—C4 | 103.9 (4) | C10—C8—C6 | 114.7 (6) |
C7—C3—C8 | 123.0 (5) | C3—C8—C6 | 93.0 (4) |
C2—C3—C8 | 99.8 (3) | C8—C9—H9A | 109.5 |
C4—C3—C8 | 103.1 (4) | C8—C9—H9B | 109.5 |
C5—C4—C3 | 103.2 (4) | H9A—C9—H9B | 109.5 |
C5—C4—H4A | 111.1 | C8—C9—H9C | 109.5 |
C3—C4—H4A | 111.1 | H9A—C9—H9C | 109.5 |
C5—C4—H4B | 111.1 | H9B—C9—H9C | 109.5 |
C3—C4—H4B | 111.1 | C8—C10—H10A | 109.5 |
H4A—C4—H4B | 109.1 | C8—C10—H10B | 109.5 |
C6—C5—C4 | 104.4 (4) | H10A—C10—H10B | 109.5 |
C6—C5—H5A | 110.9 | C8—C10—H10C | 109.5 |
C4—C5—H5A | 110.9 | H10A—C10—H10C | 109.5 |
C6—C5—H5B | 110.9 | H10B—C10—H10C | 109.5 |
O2—S—N—C2 | −126.6 (4) | C4—C5—C6—C1 | 68.9 (6) |
O1—S—N—C2 | 105.3 (3) | C4—C5—C6—C8 | −36.5 (6) |
C7—S—N—C2 | −9.8 (3) | C2—C3—C7—S | −18.6 (4) |
S—N—C2—C1 | 173.9 (3) | C4—C3—C7—S | 97.2 (4) |
S—N—C2—C3 | −1.6 (5) | C8—C3—C7—S | −131.8 (4) |
C6—C1—C2—N | −179.8 (4) | O2—S—C7—C3 | 130.3 (4) |
Br—C1—C2—N | 54.8 (5) | O1—S—C7—C3 | −95.2 (4) |
C6—C1—C2—C3 | −3.7 (4) | N—S—C7—C3 | 17.4 (3) |
Br—C1—C2—C3 | −129.1 (3) | C7—C3—C8—C9 | 50.5 (6) |
N—C2—C3—C7 | 14.9 (5) | C2—C3—C8—C9 | −65.6 (5) |
C1—C2—C3—C7 | −161.5 (4) | C4—C3—C8—C9 | −172.5 (5) |
N—C2—C3—C4 | −110.4 (5) | C7—C3—C8—C10 | −71.8 (7) |
C1—C2—C3—C4 | 73.2 (4) | C2—C3—C8—C10 | 172.1 (5) |
N—C2—C3—C8 | 143.4 (4) | C4—C3—C8—C10 | 65.2 (7) |
C1—C2—C3—C8 | −33.0 (5) | C7—C3—C8—C6 | 169.6 (4) |
C7—C3—C4—C5 | 172.9 (5) | C2—C3—C8—C6 | 53.5 (4) |
C2—C3—C4—C5 | −70.3 (5) | C4—C3—C8—C6 | −53.4 (4) |
C8—C3—C4—C5 | 33.4 (5) | C1—C6—C8—C9 | 60.2 (5) |
C3—C4—C5—C6 | 2.3 (7) | C5—C6—C8—C9 | 172.0 (5) |
C2—C1—C6—C5 | −67.8 (5) | C1—C6—C8—C10 | −174.7 (4) |
Br—C1—C6—C5 | 55.6 (5) | C5—C6—C8—C10 | −62.9 (6) |
C2—C1—C6—C8 | 38.6 (4) | C1—C6—C8—C3 | −57.2 (4) |
Br—C1—C6—C8 | 162.0 (3) | C5—C6—C8—C3 | 54.6 (5) |
Experimental details
Crystal data | |
Chemical formula | C10H14BrNO2S |
Mr | 292.19 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 296 |
a, b, c (Å) | 7.2643 (4), 10.6393 (6), 15.6331 (13) |
V (Å3) | 1208.24 (14) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 6.11 |
Crystal size (mm) | 0.23 × 0.22 × 0.15 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.267, 0.399 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5380, 2484, 2348 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.162, 1.15 |
No. of reflections | 2484 |
No. of parameters | 138 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.89, −0.81 |
Absolute structure | Flack (1983), 1033 Friedel pairs |
Absolute structure parameter | 0.02 (4) |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, maXus (Mackay et al., 1999), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
Br—C1 | 1.941 (5) | S—N | 1.687 (3) |
S—O2 | 1.408 (5) | S—C7 | 1.820 (6) |
S—O1 | 1.418 (5) | N—C2 | 1.271 (6) |
O2—S—O1 | 117.7 (4) | O1—S—C7 | 111.1 (2) |
O2—S—N | 107.7 (2) | N—S—C7 | 97.7 (2) |
O1—S—N | 107.8 (2) | C2—N—S | 107.6 (3) |
O2—S—C7 | 112.7 (4) | C3—C8—C6 | 93.0 (4) |
C7—S—N—C2 | −9.8 (3) | N—C2—C3—C7 | 14.9 (5) |
S—N—C2—C3 | −1.6 (5) | C2—C3—C7—S | −18.6 (4) |
Br—C1—C2—N | 54.8 (5) | N—S—C7—C3 | 17.4 (3) |
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The title compound, (I), was described approximately 100 years ago by Armstrong & Lowry (1902). They correctly determined that its crystals are orthorhombic and obtained axial ratios within less than 0.1% of our values well before the discovery of X-ray diffraction. Their paper contains a beautiful drawing of a crystal and an extensive table of interfacial angles.
The structure of (I) is found to be identical to that of 3-ethylthiocamphorylsulfonimine (Barkley et al., 1995), except for the endo-Br substituent instead of SCH2CH3 at the same position. These two compounds have the same space group and very similar cell dimensions. The crystal structure of (+)-camphorylsulfonylimine, which is unsubstituted and has the opposite absolute configuration, has also been reported (Chakraborty et al., 1997). The title compound is one of three for which ab initio crystal structure predictions were recently carried out in blind tests (Motherwell et al., 2001).