The chiral title compound, C
16H
24N
2O
3S, has been synthesized as a ligand for the asymmetric transfer hydrogenation process. The compound forms a layered structure with molecules bonded in sheets
via intermolecular N—H
O hydrogen bonds.
Supporting information
CCDC reference: 643093
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.007 Å
- R factor = 0.060
- wR factor = 0.183
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found
Alert level B
RINTA01_ALERT_3_B The value of Rint is greater than 0.15
Rint given 0.151
PLAT020_ALERT_3_B The value of Rint is greater than 0.10 ......... 0.15
PLAT063_ALERT_3_B Crystal Probably too Large for Beam Size ....... 1.00 mm
Alert level C
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.72 Ratio
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C3
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C5
PLAT318_ALERT_2_C Check Hybridisation of N1 in Main Residue . ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1' .. S1 .. 2.92 Ang.
Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
From the CIF: _diffrn_reflns_theta_max 27.72
From the CIF: _reflns_number_total 3483
From the CIF: _diffrn_reflns_limit_ max hkl 9. 12. 30.
From the CIF: _diffrn_reflns_limit_ min hkl -9. -12. -30.
TEST1: Expected hkl limits for theta max
Calculated maximum hkl 9. 12. 32.
Calculated minimum hkl -9. -12. -32.
REFLT03_ALERT_4_G 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.
From the CIF: _diffrn_reflns_theta_max 27.72
From the CIF: _reflns_number_total 3483
Count of symmetry unique reflns 2231
Completeness (_total/calc) 156.12%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1252
Fraction of Friedel pairs measured 0.561
Are heavy atom types Z>Si present yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1 = . S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2 = . R
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4 = . R
0 ALERT level A = In general: serious problem
3 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
5 ALERT level G = General alerts; check
4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
5 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 2001); software used to prepare material for publication: SHELXL97.
N-(2-Aminophenyl)-1-[(1
S,2
R)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]hept- 1-yl]methanesulfonamide
top
Crystal data top
C16H24N2O3S | F(000) = 696 |
Mr = 324.43 | Dx = 1.316 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 56 reflections |
a = 6.9780 (14) Å | θ = 5.5–10.4° |
b = 9.5840 (19) Å | µ = 0.21 mm−1 |
c = 24.478 (5) Å | T = 295 K |
V = 1637.0 (6) Å3 | Paralellepiped, colourless |
Z = 4 | 1.0 × 0.6 × 0.4 mm |
Data collection top
Kuma KM-4 κ-axis diffractometer | Rint = 0.151 |
Radiation source: fine-focus sealed tube | θmax = 27.7°, θmin = 1.7° |
Graphite monochromator | h = −9→9 |
separate ω–2θ scans for individual reflections | k = −12→12 |
4055 measured reflections | l = −30→30 |
3483 independent reflections | 3 standard reflections every 200 reflections |
2482 reflections with I > 2σ(I) | intensity decay: 0.5% |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.060 | w = 1/[σ2(Fo2) + (0.1164P)2 + 0.6351P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.183 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.69 e Å−3 |
3483 reflections | Δρmin = −0.46 e Å−3 |
206 parameters | Extinction correction: mixed |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (14) |
Secondary atom site location: difference Fourier map | |
Special details top
Experimental. The crystal taken for the data collection exceeded dimensions of an uniformity
area of the X-ray beam. Cutting the crystal would, however, disintegrate the
crystal during the cutting procedure, and other crystals in the batch were too
tiny for a measurement. |
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 | Uiso*/Ueq | |
S1 | 0.55230 (12) | 0.09221 (9) | 0.78541 (4) | 0.0354 (2) | |
O1 | 0.5398 (8) | 0.2390 (3) | 0.91663 (16) | 0.0742 (12) | |
H1' | 0.5588 | 0.2612 | 0.8847 | 0.12 (3)* | |
O2 | 0.4092 (4) | 0.1862 (3) | 0.80638 (13) | 0.0492 (8) | |
O3 | 0.4922 (5) | −0.0431 (3) | 0.76673 (13) | 0.0524 (8) | |
N1 | 0.6493 (5) | 0.1735 (3) | 0.73478 (14) | 0.0408 (8) | |
H1 | 0.6136 | 0.2576 | 0.7279 | 0.16 (4)* | |
N2 | 1.0406 (7) | 0.2478 (4) | 0.74437 (19) | 0.0602 (10) | |
H2B | 1.1599 | 0.2686 | 0.7478 | 0.08 (2)* | |
H2A | 0.9558 | 0.2919 | 0.7631 | 0.063 (16)* | |
C1 | 0.6664 (6) | 0.0048 (3) | 0.88845 (16) | 0.0351 (8) | |
C2 | 0.5160 (7) | 0.0891 (5) | 0.9202 (2) | 0.0576 (11) | |
H2 | 0.3872 | 0.0631 | 0.9079 | 0.069* | |
C3 | 0.5454 (11) | 0.0421 (7) | 0.9798 (2) | 0.0834 (19) | |
H3A | 0.5925 | 0.1182 | 1.0022 | 0.100* | |
H3B | 0.4271 | 0.0069 | 0.9954 | 0.100* | |
C4 | 0.6935 (7) | −0.0726 (5) | 0.9747 (2) | 0.0569 (12) | |
H4 | 0.7559 | −0.0977 | 1.0092 | 0.068* | |
C5 | 0.5978 (9) | −0.1958 (6) | 0.9451 (3) | 0.0711 (16) | |
H5A | 0.4724 | −0.2156 | 0.9603 | 0.069 (17)* | |
H5B | 0.6764 | −0.2791 | 0.9472 | 0.11 (3)* | |
C6 | 0.5820 (7) | −0.1430 (4) | 0.8856 (2) | 0.0496 (10) | |
H6A | 0.6552 | −0.2015 | 0.8609 | 0.060* | |
H6B | 0.4495 | −0.1408 | 0.8736 | 0.060* | |
C7 | 0.8314 (7) | −0.0159 (4) | 0.93076 (18) | 0.0436 (10) | |
C8 | 0.9857 (7) | −0.1193 (5) | 0.9132 (2) | 0.0595 (13) | |
H8A | 0.9266 | −0.2052 | 0.9021 | 0.089* | |
H8B | 1.0707 | −0.1367 | 0.9433 | 0.089* | |
H8C | 1.0569 | −0.0811 | 0.8832 | 0.089* | |
C9 | 0.9336 (9) | 0.1181 (5) | 0.9477 (3) | 0.0699 (16) | |
H9A | 1.0448 | 0.0953 | 0.9690 | 0.105* | |
H9B | 0.8483 | 0.1746 | 0.9691 | 0.105* | |
H9C | 0.9719 | 0.1688 | 0.9157 | 0.105* | |
C10 | 0.7346 (5) | 0.0682 (4) | 0.83507 (17) | 0.0360 (8) | |
H10A | 0.8330 | 0.0084 | 0.8197 | 0.043* | |
H10B | 0.7929 | 0.1579 | 0.8428 | 0.043* | |
C11 | 0.7919 (5) | 0.1112 (4) | 0.70105 (16) | 0.0379 (8) | |
C12 | 0.9856 (6) | 0.1441 (4) | 0.70897 (19) | 0.0423 (9) | |
C13 | 1.1195 (7) | 0.0718 (5) | 0.6785 (2) | 0.0501 (11) | |
H13 | 1.2492 | 0.0888 | 0.6842 | 0.060* | |
C14 | 1.0652 (8) | −0.0246 (4) | 0.6400 (2) | 0.0538 (11) | |
H14 | 1.1583 | −0.0715 | 0.6199 | 0.065* | |
C15 | 0.8758 (8) | −0.0522 (5) | 0.6308 (2) | 0.0610 (14) | |
H15 | 0.8398 | −0.1158 | 0.6041 | 0.073* | |
C16 | 0.7385 (7) | 0.0149 (4) | 0.66157 (19) | 0.0473 (10) | |
H16 | 0.6094 | −0.0044 | 0.6558 | 0.057* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0410 (4) | 0.0230 (4) | 0.0420 (5) | 0.0005 (4) | 0.0004 (4) | 0.0010 (4) |
O1 | 0.124 (3) | 0.0391 (17) | 0.060 (2) | 0.035 (2) | 0.000 (2) | −0.0106 (16) |
O2 | 0.0442 (16) | 0.0475 (16) | 0.0559 (18) | 0.0152 (12) | 0.0065 (13) | 0.0012 (14) |
O3 | 0.074 (2) | 0.0284 (13) | 0.0547 (19) | −0.0209 (13) | −0.0073 (15) | −0.0014 (12) |
N1 | 0.0588 (19) | 0.0196 (14) | 0.0440 (19) | 0.0078 (14) | 0.0068 (16) | 0.0080 (13) |
N2 | 0.053 (2) | 0.053 (2) | 0.074 (3) | −0.0096 (19) | −0.003 (2) | −0.017 (2) |
C1 | 0.0450 (19) | 0.0225 (15) | 0.038 (2) | 0.0007 (14) | −0.0022 (17) | 0.0020 (15) |
C2 | 0.070 (3) | 0.045 (2) | 0.058 (3) | 0.018 (2) | 0.007 (2) | 0.003 (2) |
C3 | 0.107 (5) | 0.088 (4) | 0.055 (3) | 0.046 (4) | 0.022 (3) | 0.013 (3) |
C4 | 0.069 (3) | 0.053 (3) | 0.048 (3) | 0.009 (2) | 0.002 (2) | 0.017 (2) |
C5 | 0.085 (4) | 0.054 (3) | 0.075 (4) | −0.016 (3) | 0.006 (3) | 0.027 (3) |
C6 | 0.060 (3) | 0.0304 (17) | 0.059 (3) | −0.0054 (18) | −0.001 (2) | 0.0080 (18) |
C7 | 0.053 (2) | 0.0297 (18) | 0.048 (2) | 0.0051 (17) | −0.007 (2) | −0.0009 (17) |
C8 | 0.058 (3) | 0.049 (3) | 0.071 (3) | 0.017 (2) | −0.008 (2) | 0.006 (2) |
C9 | 0.089 (4) | 0.037 (2) | 0.083 (4) | −0.005 (2) | −0.039 (3) | −0.002 (2) |
C10 | 0.0373 (17) | 0.0264 (17) | 0.044 (2) | −0.0011 (13) | −0.0007 (15) | 0.0019 (15) |
C11 | 0.049 (2) | 0.0200 (15) | 0.045 (2) | 0.0018 (14) | 0.0023 (16) | 0.0034 (15) |
C12 | 0.053 (2) | 0.0270 (15) | 0.047 (2) | 0.0029 (15) | −0.0014 (18) | 0.0050 (16) |
C13 | 0.052 (2) | 0.041 (2) | 0.057 (3) | 0.0047 (18) | 0.009 (2) | 0.015 (2) |
C14 | 0.067 (3) | 0.033 (2) | 0.062 (3) | 0.005 (2) | 0.019 (2) | 0.0021 (19) |
C15 | 0.076 (3) | 0.036 (2) | 0.071 (3) | −0.004 (2) | 0.018 (3) | −0.016 (2) |
C16 | 0.058 (2) | 0.038 (2) | 0.045 (2) | −0.0065 (19) | 0.003 (2) | −0.0034 (18) |
Geometric parameters (Å, º) top
S1—O3 | 1.437 (3) | C5—H5A | 0.9700 |
S1—O2 | 1.439 (3) | C5—H5B | 0.9700 |
S1—N1 | 1.613 (3) | C6—H6A | 0.9700 |
S1—C10 | 1.774 (4) | C6—H6B | 0.9700 |
O1—C2 | 1.449 (6) | C7—C8 | 1.525 (6) |
O1—H1' | 0.8200 | C7—C9 | 1.527 (6) |
N1—C11 | 1.424 (5) | C8—H8A | 0.9600 |
N1—H1 | 0.8600 | C8—H8B | 0.9600 |
N2—C12 | 1.373 (6) | C8—H8C | 0.9600 |
N2—H2B | 0.8600 | C9—H9A | 0.9600 |
N2—H2A | 0.8600 | C9—H9B | 0.9600 |
C1—C10 | 1.518 (5) | C9—H9C | 0.9600 |
C1—C6 | 1.535 (5) | C10—H10A | 0.9700 |
C1—C2 | 1.535 (6) | C10—H10B | 0.9700 |
C1—C7 | 1.561 (6) | C11—C16 | 1.387 (6) |
C2—C3 | 1.540 (7) | C11—C12 | 1.401 (5) |
C2—H2 | 0.9800 | C12—C13 | 1.382 (6) |
C3—C4 | 1.514 (7) | C13—C14 | 1.373 (7) |
C3—H3A | 0.9700 | C13—H13 | 0.9300 |
C3—H3B | 0.9700 | C14—C15 | 1.367 (8) |
C4—C5 | 1.538 (8) | C14—H14 | 0.9300 |
C4—C7 | 1.542 (7) | C15—C16 | 1.377 (7) |
C4—H4 | 0.9800 | C15—H15 | 0.9300 |
C5—C6 | 1.546 (8) | C16—H16 | 0.9300 |
| | | |
O3—S1—O2 | 118.4 (2) | C1—C6—H6B | 111.1 |
O3—S1—N1 | 108.29 (19) | C5—C6—H6B | 111.1 |
O2—S1—N1 | 105.24 (18) | H6A—C6—H6B | 109.0 |
O3—S1—C10 | 108.05 (18) | C8—C7—C9 | 107.1 (4) |
O2—S1—C10 | 109.53 (19) | C8—C7—C4 | 114.1 (4) |
N1—S1—C10 | 106.75 (18) | C9—C7—C4 | 113.5 (4) |
C2—O1—H1' | 109.5 | C8—C7—C1 | 114.6 (4) |
C11—N1—S1 | 122.4 (2) | C9—C7—C1 | 114.7 (3) |
C11—N1—H1 | 118.8 | C4—C7—C1 | 92.7 (3) |
S1—N1—H1 | 118.8 | C7—C8—H8A | 109.5 |
C12—N2—H2B | 120.0 | C7—C8—H8B | 109.5 |
C12—N2—H2A | 120.0 | H8A—C8—H8B | 109.5 |
H2B—N2—H2A | 120.0 | C7—C8—H8C | 109.5 |
C10—C1—C6 | 116.8 (3) | H8A—C8—H8C | 109.5 |
C10—C1—C2 | 116.1 (3) | H8B—C8—H8C | 109.5 |
C6—C1—C2 | 104.3 (4) | C7—C9—H9A | 109.5 |
C10—C1—C7 | 113.0 (3) | C7—C9—H9B | 109.5 |
C6—C1—C7 | 101.3 (3) | H9A—C9—H9B | 109.5 |
C2—C1—C7 | 103.6 (3) | C7—C9—H9C | 109.5 |
O1—C2—C1 | 114.4 (4) | H9A—C9—H9C | 109.5 |
O1—C2—C3 | 109.4 (5) | H9B—C9—H9C | 109.5 |
C1—C2—C3 | 103.5 (4) | C1—C10—S1 | 114.6 (3) |
O1—C2—H2 | 109.8 | C1—C10—H10A | 108.6 |
C1—C2—H2 | 109.8 | S1—C10—H10A | 108.6 |
C3—C2—H2 | 109.8 | C1—C10—H10B | 108.6 |
C4—C3—C2 | 103.0 (4) | S1—C10—H10B | 108.6 |
C4—C3—H3A | 111.2 | H10A—C10—H10B | 107.6 |
C2—C3—H3A | 111.2 | C16—C11—C12 | 120.3 (4) |
C4—C3—H3B | 111.2 | C16—C11—N1 | 119.7 (4) |
C2—C3—H3B | 111.2 | C12—C11—N1 | 120.0 (4) |
H3A—C3—H3B | 109.1 | N2—C12—C13 | 121.0 (4) |
C3—C4—C5 | 107.4 (5) | N2—C12—C11 | 121.3 (4) |
C3—C4—C7 | 103.1 (4) | C13—C12—C11 | 117.7 (4) |
C5—C4—C7 | 102.3 (4) | C14—C13—C12 | 121.4 (4) |
C3—C4—H4 | 114.2 | C14—C13—H13 | 119.3 |
C5—C4—H4 | 114.2 | C12—C13—H13 | 119.3 |
C7—C4—H4 | 114.2 | C15—C14—C13 | 120.6 (4) |
C4—C5—C6 | 102.9 (4) | C15—C14—H14 | 119.7 |
C4—C5—H5A | 111.2 | C13—C14—H14 | 119.7 |
C6—C5—H5A | 111.2 | C14—C15—C16 | 119.5 (5) |
C4—C5—H5B | 111.2 | C14—C15—H15 | 120.2 |
C6—C5—H5B | 111.2 | C16—C15—H15 | 120.2 |
H5A—C5—H5B | 109.1 | C15—C16—C11 | 120.3 (5) |
C1—C6—C5 | 103.4 (4) | C15—C16—H16 | 119.9 |
C1—C6—H6A | 111.1 | C11—C16—H16 | 119.9 |
C5—C6—H6A | 111.1 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1′···O2 | 0.82 | 2.30 | 2.893 (5) | 130 |
O1—H1′···S1 | 0.82 | 2.92 | 3.508 (4) | 130 |
N1—H1···O3i | 0.86 | 2.05 | 2.890 (4) | 165 |
N2—H2B···O2ii | 0.86 | 2.39 | 3.044 (6) | 133 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1, y, z. |