Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029637/om2136sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029637/om2136Isup2.hkl |
CCDC reference: 657752
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.002 Å
- R factor = 0.032
- wR factor = 0.080
- Data-to-parameter ratio = 10.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
Alert level G 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 27.54 From the CIF: _reflns_number_total 1571 Count of symmetry unique reflns 1581 Completeness (_total/calc) 99.37% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8 = . S
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
N-((S)-1-Phenyl-ethyl)-benzene-1,2-diamine (8.479 g, 39.9 mmol) was placed in a flask, and dissolved in HC(OEt)3 (85 ml). p-Toluenesulphonic acid (0.340 g, 1.7 mmol, 5 mol%) was added, and the solution heated at 353 K for 24 h. Removal of volatiles in vacuo gave a yellow oil, which was partitioned between aqueous Na2CO3 solution (5% w/v, 200 ml) and DCM (3 τimes 200 ml). The combined organics were dried (MgSO4), and solvent removed to yield pale yellow plates (3.323 g, 37%). Slow evaporation of a DCM solution produced colourless crystals of (I) suitable for diffraction; mp 418–420 K; [α]D -9.3 (c = 1.73, DCM); C15H14N2 requires C 81.05, H 6.35, N 12.60%; found C 81.21, H 6.38, N 12.64%.
Anomalous dispersion was negligible and Friedel pairs were merged before refinement. The S chirality at C8 was assigned based on the known chirality of the equivalent atom in the starting material. The hydrogen atoms were placed in calculated positions (C—H = 0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The –CH3 group was allowed to rotate but not to tip, to best fit the electron density.
The title compound (Fig. 1) was prepared as a possible component of a chiral catalyst. The same compound was recently reported by Rivas et al. (2002).
The geometrical parameters may be regarded as normal (Allen et al., 1987). The dihedral angle between the mean planes of the C1—C7/N1/N2 fused ring and C10—C15 ring is 81.59 (4)°. Atom C8 of the title molecule is chiral: S configuration was assigned to this atom based on the known chirality of the equivalent atom in the starting material.
The crystal packing is consolidated by a C8—H8···N2i interaction (Table 1), which links the molecules into [100] chains (Fig. 2) with a C(5) graph-set motif (Etter, 1990). There are no π-π stacking interactions, as the minimum separation of the centroids of the aromatic rings of nearby molecules is greater than 5 Å.
The synthesis of the title compound was recently reported by Rivas et al. (2002).
For related literature, see: Allen et al. (1987); Etter (1990).
Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
C15H14N2 | F(000) = 472 |
Mr = 222.28 | Dx = 1.260 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1583 reflections |
a = 6.3159 (3) Å | θ = 2.9–27.5° |
b = 8.6989 (3) Å | µ = 0.08 mm−1 |
c = 21.3277 (9) Å | T = 120 K |
V = 1171.77 (8) Å3 | Shard, colourless |
Z = 4 | 0.46 × 0.20 × 0.13 mm |
Nonius KappaCCD diffractometer | 1571 independent reflections |
Radiation source: fine-focus sealed tube | 1463 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω and φ scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −8→8 |
Tmin = 0.966, Tmax = 0.990 | k = −9→11 |
8654 measured reflections | l = −27→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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0349P)2 + 0.2819P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1571 reflections | Δρmax = 0.16 e Å−3 |
156 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.033 (6) |
C15H14N2 | V = 1171.77 (8) Å3 |
Mr = 222.28 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.3159 (3) Å | µ = 0.08 mm−1 |
b = 8.6989 (3) Å | T = 120 K |
c = 21.3277 (9) Å | 0.46 × 0.20 × 0.13 mm |
Nonius KappaCCD diffractometer | 1571 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 1463 reflections with I > 2σ(I) |
Tmin = 0.966, Tmax = 0.990 | Rint = 0.039 |
8654 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.16 e Å−3 |
1571 reflections | Δρmin = −0.17 e Å−3 |
156 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 | ||
C1 | 0.2835 (3) | 0.24132 (17) | 0.13869 (7) | 0.0194 (3) | |
C2 | 0.1813 (3) | 0.21889 (19) | 0.08162 (7) | 0.0235 (4) | |
H2 | 0.0451 | 0.2607 | 0.0735 | 0.028* | |
C3 | 0.2884 (3) | 0.13264 (19) | 0.03749 (8) | 0.0264 (4) | |
H3 | 0.2243 | 0.1150 | −0.0022 | 0.032* | |
C4 | 0.4891 (3) | 0.0703 (2) | 0.04954 (8) | 0.0270 (4) | |
H4 | 0.5580 | 0.0121 | 0.0179 | 0.032* | |
C5 | 0.5886 (3) | 0.09180 (19) | 0.10661 (8) | 0.0251 (4) | |
H5 | 0.7241 | 0.0488 | 0.1148 | 0.030* | |
C6 | 0.4826 (3) | 0.17917 (19) | 0.15197 (7) | 0.0213 (3) | |
C7 | 0.3886 (3) | 0.3043 (2) | 0.23324 (8) | 0.0229 (4) | |
H7 | 0.3884 | 0.3491 | 0.2739 | 0.027* | |
C8 | 0.0229 (3) | 0.40316 (18) | 0.19948 (7) | 0.0198 (3) | |
H8 | −0.0933 | 0.3274 | 0.1918 | 0.024* | |
C9 | −0.0023 (3) | 0.4646 (2) | 0.26587 (7) | 0.0262 (4) | |
H9A | 0.0136 | 0.3800 | 0.2959 | 0.039* | |
H9B | −0.1430 | 0.5107 | 0.2706 | 0.039* | |
H9C | 0.1063 | 0.5426 | 0.2739 | 0.039* | |
C10 | 0.0007 (3) | 0.53183 (18) | 0.15155 (7) | 0.0196 (3) | |
C11 | 0.1706 (3) | 0.62418 (19) | 0.13505 (8) | 0.0250 (4) | |
H11 | 0.3061 | 0.6053 | 0.1528 | 0.030* | |
C12 | 0.1443 (3) | 0.7442 (2) | 0.09273 (8) | 0.0285 (4) | |
H12 | 0.2619 | 0.8063 | 0.0813 | 0.034* | |
C13 | −0.0541 (3) | 0.7733 (2) | 0.06721 (8) | 0.0291 (4) | |
H13 | −0.0726 | 0.8557 | 0.0385 | 0.035* | |
C14 | −0.2241 (3) | 0.6824 (2) | 0.08370 (8) | 0.0292 (4) | |
H14 | −0.3599 | 0.7024 | 0.0663 | 0.035* | |
C15 | −0.1974 (3) | 0.5614 (2) | 0.12572 (8) | 0.0247 (4) | |
H15 | −0.3149 | 0.4988 | 0.1368 | 0.030* | |
N1 | 0.2257 (2) | 0.32261 (15) | 0.19189 (6) | 0.0193 (3) | |
N2 | 0.5455 (2) | 0.21984 (17) | 0.21242 (7) | 0.0252 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0217 (8) | 0.0153 (7) | 0.0211 (7) | −0.0007 (7) | 0.0028 (6) | 0.0023 (6) |
C2 | 0.0253 (8) | 0.0219 (8) | 0.0233 (8) | 0.0021 (7) | −0.0003 (7) | 0.0025 (6) |
C3 | 0.0366 (10) | 0.0225 (8) | 0.0200 (8) | 0.0003 (8) | 0.0017 (7) | 0.0004 (6) |
C4 | 0.0348 (10) | 0.0209 (8) | 0.0252 (8) | 0.0024 (9) | 0.0092 (8) | −0.0010 (7) |
C5 | 0.0232 (8) | 0.0205 (8) | 0.0316 (9) | 0.0024 (7) | 0.0054 (7) | 0.0033 (7) |
C6 | 0.0213 (8) | 0.0187 (7) | 0.0239 (7) | −0.0022 (7) | 0.0019 (7) | 0.0021 (6) |
C7 | 0.0234 (8) | 0.0221 (8) | 0.0232 (8) | −0.0009 (7) | −0.0032 (7) | 0.0001 (7) |
C8 | 0.0177 (7) | 0.0185 (7) | 0.0233 (8) | 0.0008 (7) | 0.0023 (6) | 0.0004 (6) |
C9 | 0.0304 (9) | 0.0251 (8) | 0.0232 (8) | 0.0040 (9) | 0.0052 (9) | −0.0001 (7) |
C10 | 0.0223 (8) | 0.0190 (7) | 0.0177 (7) | 0.0017 (7) | 0.0011 (7) | −0.0020 (6) |
C11 | 0.0232 (9) | 0.0232 (8) | 0.0285 (9) | 0.0030 (7) | 0.0012 (7) | 0.0025 (7) |
C12 | 0.0330 (10) | 0.0234 (9) | 0.0290 (9) | 0.0020 (8) | 0.0093 (8) | 0.0040 (7) |
C13 | 0.0410 (11) | 0.0255 (9) | 0.0207 (7) | 0.0108 (9) | 0.0049 (7) | 0.0027 (7) |
C14 | 0.0294 (9) | 0.0317 (9) | 0.0264 (8) | 0.0090 (9) | −0.0047 (8) | −0.0018 (7) |
C15 | 0.0231 (8) | 0.0253 (8) | 0.0257 (8) | 0.0007 (8) | −0.0004 (7) | −0.0010 (7) |
N1 | 0.0204 (7) | 0.0186 (6) | 0.0189 (6) | 0.0005 (6) | 0.0000 (5) | −0.0001 (5) |
N2 | 0.0234 (7) | 0.0254 (7) | 0.0267 (7) | 0.0013 (6) | −0.0028 (6) | −0.0004 (6) |
C1—N1 | 1.3858 (19) | C8—C10 | 1.522 (2) |
C1—C2 | 1.391 (2) | C8—H8 | 1.0000 |
C1—C6 | 1.398 (2) | C9—H9A | 0.9800 |
C2—C3 | 1.381 (2) | C9—H9B | 0.9800 |
C2—H2 | 0.9500 | C9—H9C | 0.9800 |
C3—C4 | 1.402 (3) | C10—C11 | 1.386 (2) |
C3—H3 | 0.9500 | C10—C15 | 1.391 (2) |
C4—C5 | 1.383 (3) | C11—C12 | 1.390 (2) |
C4—H4 | 0.9500 | C11—H11 | 0.9500 |
C5—C6 | 1.401 (2) | C12—C13 | 1.389 (3) |
C5—H5 | 0.9500 | C12—H12 | 0.9500 |
C6—N2 | 1.395 (2) | C13—C14 | 1.379 (3) |
C7—N2 | 1.311 (2) | C13—H13 | 0.9500 |
C7—N1 | 1.364 (2) | C14—C15 | 1.393 (2) |
C7—H7 | 0.9500 | C14—H14 | 0.9500 |
C8—N1 | 1.469 (2) | C15—H15 | 0.9500 |
C8—C9 | 1.522 (2) | ||
N1—C1—C2 | 131.74 (16) | C8—C9—H9B | 109.5 |
N1—C1—C6 | 105.56 (14) | H9A—C9—H9B | 109.5 |
C2—C1—C6 | 122.70 (15) | C8—C9—H9C | 109.5 |
C3—C2—C1 | 116.44 (16) | H9A—C9—H9C | 109.5 |
C3—C2—H2 | 121.8 | H9B—C9—H9C | 109.5 |
C1—C2—H2 | 121.8 | C11—C10—C15 | 119.24 (15) |
C2—C3—C4 | 121.88 (16) | C11—C10—C8 | 121.71 (15) |
C2—C3—H3 | 119.1 | C15—C10—C8 | 118.99 (15) |
C4—C3—H3 | 119.1 | C10—C11—C12 | 120.53 (17) |
C5—C4—C3 | 121.31 (16) | C10—C11—H11 | 119.7 |
C5—C4—H4 | 119.3 | C12—C11—H11 | 119.7 |
C3—C4—H4 | 119.3 | C13—C12—C11 | 119.92 (17) |
C4—C5—C6 | 117.67 (17) | C13—C12—H12 | 120.0 |
C4—C5—H5 | 121.2 | C11—C12—H12 | 120.0 |
C6—C5—H5 | 121.2 | C14—C13—C12 | 119.86 (16) |
N2—C6—C1 | 110.21 (14) | C14—C13—H13 | 120.1 |
N2—C6—C5 | 129.79 (16) | C12—C13—H13 | 120.1 |
C1—C6—C5 | 119.99 (16) | C13—C14—C15 | 120.20 (17) |
N2—C7—N1 | 114.61 (15) | C13—C14—H14 | 119.9 |
N2—C7—H7 | 122.7 | C15—C14—H14 | 119.9 |
N1—C7—H7 | 122.7 | C10—C15—C14 | 120.25 (17) |
N1—C8—C9 | 111.16 (14) | C10—C15—H15 | 119.9 |
N1—C8—C10 | 110.91 (13) | C14—C15—H15 | 119.9 |
C9—C8—C10 | 110.92 (13) | C7—N1—C1 | 105.73 (13) |
N1—C8—H8 | 107.9 | C7—N1—C8 | 129.94 (13) |
C9—C8—H8 | 107.9 | C1—N1—C8 | 124.27 (13) |
C10—C8—H8 | 107.9 | C7—N2—C6 | 103.88 (14) |
C8—C9—H9A | 109.5 | ||
N1—C1—C2—C3 | 178.50 (16) | C11—C12—C13—C14 | −0.4 (3) |
C6—C1—C2—C3 | −0.9 (2) | C12—C13—C14—C15 | −0.1 (3) |
C1—C2—C3—C4 | 0.3 (2) | C11—C10—C15—C14 | 0.1 (2) |
C2—C3—C4—C5 | 0.4 (3) | C8—C10—C15—C14 | 177.38 (14) |
C3—C4—C5—C6 | −0.5 (2) | C13—C14—C15—C10 | 0.3 (3) |
N1—C1—C6—N2 | 0.65 (17) | N2—C7—N1—C1 | 0.02 (19) |
C2—C1—C6—N2 | −179.85 (15) | N2—C7—N1—C8 | 177.34 (14) |
N1—C1—C6—C5 | −178.71 (14) | C2—C1—N1—C7 | −179.84 (17) |
C2—C1—C6—C5 | 0.8 (2) | C6—C1—N1—C7 | −0.40 (16) |
C4—C5—C6—N2 | −179.32 (16) | C2—C1—N1—C8 | 2.6 (3) |
C4—C5—C6—C1 | −0.1 (2) | C6—C1—N1—C8 | −177.92 (13) |
N1—C8—C10—C11 | −39.39 (19) | C9—C8—N1—C7 | −3.7 (2) |
C9—C8—C10—C11 | 84.65 (19) | C10—C8—N1—C7 | 120.19 (17) |
N1—C8—C10—C15 | 143.39 (15) | C9—C8—N1—C1 | 173.17 (14) |
C9—C8—C10—C15 | −92.57 (18) | C10—C8—N1—C1 | −62.93 (18) |
C15—C10—C11—C12 | −0.6 (2) | N1—C7—N2—C6 | 0.38 (19) |
C8—C10—C11—C12 | −177.81 (15) | C1—C6—N2—C7 | −0.63 (17) |
C10—C11—C12—C13 | 0.7 (3) | C5—C6—N2—C7 | 178.64 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···N2i | 1.00 | 2.50 | 3.422 (2) | 152 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C15H14N2 |
Mr | 222.28 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 120 |
a, b, c (Å) | 6.3159 (3), 8.6989 (3), 21.3277 (9) |
V (Å3) | 1171.77 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.46 × 0.20 × 0.13 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.966, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8654, 1571, 1463 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.081, 1.05 |
No. of reflections | 1571 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.17 |
Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···N2i | 1.00 | 2.50 | 3.422 (2) | 152 |
Symmetry code: (i) x−1, y, z. |
The title compound (Fig. 1) was prepared as a possible component of a chiral catalyst. The same compound was recently reported by Rivas et al. (2002).
The geometrical parameters may be regarded as normal (Allen et al., 1987). The dihedral angle between the mean planes of the C1—C7/N1/N2 fused ring and C10—C15 ring is 81.59 (4)°. Atom C8 of the title molecule is chiral: S configuration was assigned to this atom based on the known chirality of the equivalent atom in the starting material.
The crystal packing is consolidated by a C8—H8···N2i interaction (Table 1), which links the molecules into [100] chains (Fig. 2) with a C(5) graph-set motif (Etter, 1990). There are no π-π stacking interactions, as the minimum separation of the centroids of the aromatic rings of nearby molecules is greater than 5 Å.