Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005385/cm6032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005385/cm6032Isup2.hkl |
CCDC reference: 209946
Key indicators
- Single-crystal X-ray study
- T = 180 K
- Mean (C-C) = 0.003 Å
- R factor = 0.035
- wR factor = 0.082
- Data-to-parameter ratio = 7.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N(1) - H(1A) ? PLAT_420 Alert C D-H Without Acceptor N(2) - H(2A) ? General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 24.99 From the CIF: _reflns_number_total 1229 Count of symmetry unique reflns 1235 Completeness (_total/calc) 99.51% 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 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.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
(1R,2R)-(+)-1,2-Diphenylethylenediamine was purchased from Aldrich (99.99% purity) and used without further purification. Crystals suitable for X-ray diffraction analysis were obtained by recrystallization from methanol. 1H NMR (CD3OD): δ 3.95 (s, 1H), 7.05–7.22 (m, 5H). 13C NMR (CD3OD): δ 64.2 (CH), 128.5, 128.8, 129.5, 144.2 (Ph).
H atoms bound to C atoms were placed in calculated positions and allowed to ride during subsequent refinement, with Uiso(H) = 1.2Ueq(C). The NH2 H atoms were located from difference Fourier maps and refined successfully. A total of 801 Friedel pairs were merged and not used as independent data. The corresponding Flack (1983) parameter was found to be meaningless and was omitted.
Data collection: COLLECT (Nonius 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare at al., 1994); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C14H16N2 | Dx = 1.200 Mg m−3 |
Mr = 212.29 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 4851 reflections |
a = 5.1447 (1) Å | θ = 1.0–25.0° |
b = 12.3264 (4) Å | µ = 0.07 mm−1 |
c = 18.5357 (7) Å | T = 180 K |
V = 1175.45 (6) Å3 | Block, colourless |
Z = 4 | 0.23 × 0.18 × 0.12 mm |
F(000) = 456 |
Nonius KappaCCD diffractometer | 1148 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.056 |
Thin–slice ω and ϕ scans | θmax = 25.0°, θmin = 4.1° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −6→6 |
Tmin = 0.895, Tmax = 0.992 | k = −12→14 |
6085 measured reflections | l = −21→22 |
1229 independent reflections |
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)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0337P)2 + 0.2099P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
1229 reflections | Δρmax = 0.14 e Å−3 |
159 parameters | Δρmin = −0.14 e Å−3 |
6 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.038 (6) |
C14H16N2 | V = 1175.45 (6) Å3 |
Mr = 212.29 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.1447 (1) Å | µ = 0.07 mm−1 |
b = 12.3264 (4) Å | T = 180 K |
c = 18.5357 (7) Å | 0.23 × 0.18 × 0.12 mm |
Nonius KappaCCD diffractometer | 1229 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1148 reflections with I > 2σ(I) |
Tmin = 0.895, Tmax = 0.992 | Rint = 0.056 |
6085 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 6 restraints |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.14 e Å−3 |
1229 reflections | Δρmin = −0.14 e Å−3 |
159 parameters |
Experimental. The –NH2 hydrogen atoms were located and refined successfully. |
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 | ||
N1 | 0.2012 (3) | 0.84363 (15) | 0.96358 (9) | 0.0359 (4) | |
H1A | 0.258 (5) | 0.8633 (17) | 1.0077 (9) | 0.043* | |
H1B | 0.084 (4) | 0.7881 (16) | 0.9674 (11) | 0.043* | |
N2 | −0.2509 (3) | 0.79800 (14) | 0.88188 (9) | 0.0343 (4) | |
H2A | −0.322 (4) | 0.7698 (16) | 0.8406 (10) | 0.041* | |
H2B | −0.390 (4) | 0.8223 (17) | 0.9094 (10) | 0.041* | |
C1 | 0.0608 (4) | 0.93146 (16) | 0.92840 (10) | 0.0308 (5) | |
H1 | 0.1928 | 0.9854 | 0.9116 | 0.037* | |
C2 | −0.1355 (4) | 0.99255 (16) | 0.97474 (10) | 0.0306 (5) | |
C3 | −0.2294 (4) | 0.95283 (17) | 1.03990 (10) | 0.0336 (5) | |
H3 | −0.1653 | 0.8860 | 1.0583 | 0.040* | |
C4 | −0.4163 (4) | 1.01012 (17) | 1.07833 (10) | 0.0378 (5) | |
H4 | −0.4795 | 0.9816 | 1.1226 | 0.045* | |
C5 | −0.5117 (5) | 1.10768 (18) | 1.05338 (11) | 0.0405 (5) | |
H5 | −0.6393 | 1.1463 | 1.0801 | 0.049* | |
C6 | −0.4179 (5) | 1.14861 (18) | 0.98844 (11) | 0.0423 (6) | |
H6 | −0.4822 | 1.2155 | 0.9702 | 0.051* | |
C7 | −0.2314 (5) | 1.09183 (17) | 0.95054 (11) | 0.0392 (5) | |
H7A | −0.1666 | 1.1212 | 0.9067 | 0.047* | |
C8 | −0.0773 (4) | 0.88628 (16) | 0.86034 (9) | 0.0296 (5) | |
H8 | −0.1851 | 0.9456 | 0.8389 | 0.036* | |
C9 | 0.1166 (4) | 0.84889 (17) | 0.80404 (9) | 0.0315 (5) | |
C10 | 0.1622 (4) | 0.74029 (18) | 0.78895 (11) | 0.0386 (5) | |
H10 | 0.0674 | 0.6859 | 0.8140 | 0.046* | |
C11 | 0.3451 (5) | 0.7102 (2) | 0.73751 (12) | 0.0490 (6) | |
H11 | 0.3744 | 0.6356 | 0.7277 | 0.059* | |
C12 | 0.4842 (5) | 0.7881 (2) | 0.70062 (12) | 0.0557 (7) | |
H12 | 0.6102 | 0.7671 | 0.6658 | 0.067* | |
C13 | 0.4399 (5) | 0.8958 (2) | 0.71430 (11) | 0.0515 (7) | |
H13 | 0.5348 | 0.9497 | 0.6888 | 0.062* | |
C14 | 0.2568 (5) | 0.92617 (19) | 0.76524 (10) | 0.0407 (5) | |
H14 | 0.2261 | 1.0010 | 0.7739 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0316 (10) | 0.0494 (11) | 0.0268 (8) | 0.0043 (9) | −0.0060 (7) | −0.0034 (8) |
N2 | 0.0301 (9) | 0.0457 (10) | 0.0269 (8) | −0.0067 (9) | 0.0002 (7) | −0.0031 (7) |
C1 | 0.0280 (11) | 0.0369 (11) | 0.0276 (10) | −0.0023 (9) | 0.0005 (8) | −0.0015 (8) |
C2 | 0.0307 (10) | 0.0343 (10) | 0.0269 (9) | −0.0051 (9) | −0.0033 (8) | −0.0055 (8) |
C3 | 0.0378 (11) | 0.0378 (11) | 0.0254 (9) | 0.0003 (10) | −0.0024 (9) | −0.0017 (8) |
C4 | 0.0439 (13) | 0.0434 (12) | 0.0261 (10) | −0.0017 (11) | 0.0043 (9) | −0.0022 (9) |
C5 | 0.0415 (12) | 0.0418 (12) | 0.0383 (11) | 0.0030 (11) | 0.0043 (9) | −0.0100 (10) |
C6 | 0.0489 (13) | 0.0357 (12) | 0.0422 (11) | 0.0065 (11) | 0.0031 (11) | −0.0003 (9) |
C7 | 0.0479 (13) | 0.0375 (11) | 0.0321 (10) | −0.0023 (11) | 0.0064 (10) | 0.0018 (9) |
C8 | 0.0271 (10) | 0.0361 (10) | 0.0256 (9) | 0.0002 (9) | −0.0002 (8) | 0.0025 (8) |
C9 | 0.0291 (10) | 0.0430 (12) | 0.0222 (9) | −0.0011 (10) | −0.0035 (8) | 0.0002 (8) |
C10 | 0.0375 (12) | 0.0483 (13) | 0.0302 (11) | 0.0017 (10) | −0.0030 (9) | −0.0051 (9) |
C11 | 0.0445 (13) | 0.0643 (15) | 0.0382 (12) | 0.0125 (13) | −0.0062 (11) | −0.0175 (11) |
C12 | 0.0394 (13) | 0.100 (2) | 0.0279 (11) | 0.0066 (15) | 0.0013 (10) | −0.0129 (13) |
C13 | 0.0438 (13) | 0.0838 (18) | 0.0269 (11) | −0.0110 (14) | 0.0048 (10) | 0.0049 (12) |
C14 | 0.0411 (12) | 0.0533 (13) | 0.0279 (10) | −0.0060 (11) | 0.0011 (10) | 0.0028 (9) |
N1—C1 | 1.456 (3) | C6—C7 | 1.380 (3) |
N1—H1A | 0.902 (17) | C6—H6 | 0.9500 |
N1—H1B | 0.916 (17) | C7—H7A | 0.9500 |
N2—C8 | 1.463 (3) | C8—C9 | 1.516 (3) |
N2—H2A | 0.917 (17) | C8—H8 | 1.0000 |
N2—H2B | 0.927 (18) | C9—C10 | 1.387 (3) |
C1—C2 | 1.524 (3) | C9—C14 | 1.394 (3) |
C1—C8 | 1.551 (2) | C10—C11 | 1.390 (3) |
C1—H1 | 1.0000 | C10—H10 | 0.9500 |
C2—C3 | 1.390 (3) | C11—C12 | 1.378 (4) |
C2—C7 | 1.394 (3) | C11—H11 | 0.9500 |
C3—C4 | 1.390 (3) | C12—C13 | 1.372 (4) |
C3—H3 | 0.9500 | C12—H12 | 0.9500 |
C4—C5 | 1.379 (3) | C13—C14 | 1.385 (3) |
C4—H4 | 0.9500 | C13—H13 | 0.9500 |
C5—C6 | 1.392 (3) | C14—H14 | 0.9500 |
C5—H5 | 0.9500 | ||
C1—N1—H1A | 111.6 (14) | C6—C7—C2 | 121.85 (19) |
C1—N1—H1B | 105.3 (15) | C6—C7—H7A | 119.1 |
H1A—N1—H1B | 110.1 (17) | C2—C7—H7A | 119.1 |
C8—N2—H2A | 107.4 (13) | N2—C8—C9 | 111.32 (16) |
C8—N2—H2B | 112.4 (14) | N2—C8—C1 | 108.94 (15) |
H2A—N2—H2B | 105.8 (17) | C9—C8—C1 | 111.57 (16) |
N1—C1—C2 | 116.33 (15) | N2—C8—H8 | 108.3 |
N1—C1—C8 | 108.93 (16) | C9—C8—H8 | 108.3 |
C2—C1—C8 | 109.41 (16) | C1—C8—H8 | 108.3 |
N1—C1—H1 | 107.3 | C10—C9—C14 | 117.90 (19) |
C2—C1—H1 | 107.3 | C10—C9—C8 | 122.91 (18) |
C8—C1—H1 | 107.3 | C14—C9—C8 | 119.19 (18) |
C3—C2—C7 | 117.77 (19) | C9—C10—C11 | 120.7 (2) |
C3—C2—C1 | 123.08 (18) | C9—C10—H10 | 119.7 |
C7—C2—C1 | 119.13 (17) | C11—C10—H10 | 119.7 |
C4—C3—C2 | 120.46 (19) | C12—C11—C10 | 120.4 (2) |
C4—C3—H3 | 119.8 | C12—C11—H11 | 119.8 |
C2—C3—H3 | 119.8 | C10—C11—H11 | 119.8 |
C5—C4—C3 | 121.18 (19) | C13—C12—C11 | 119.7 (2) |
C5—C4—H4 | 119.4 | C13—C12—H12 | 120.1 |
C3—C4—H4 | 119.4 | C11—C12—H12 | 120.1 |
C4—C5—C6 | 118.9 (2) | C12—C13—C14 | 120.0 (2) |
C4—C5—H5 | 120.6 | C12—C13—H13 | 120.0 |
C6—C5—H5 | 120.6 | C14—C13—H13 | 120.0 |
C7—C6—C5 | 119.8 (2) | C13—C14—C9 | 121.2 (2) |
C7—C6—H6 | 120.1 | C13—C14—H14 | 119.4 |
C5—C6—H6 | 120.1 | C9—C14—H14 | 119.4 |
N1—C1—C2—C3 | −16.3 (3) | N1—C1—C8—C9 | −65.6 (2) |
C8—C1—C2—C3 | 107.6 (2) | C2—C1—C8—C9 | 166.25 (16) |
N1—C1—C2—C7 | 165.24 (18) | N2—C8—C9—C10 | −14.5 (3) |
C8—C1—C2—C7 | −70.8 (2) | C1—C8—C9—C10 | 107.4 (2) |
C7—C2—C3—C4 | 1.2 (3) | N2—C8—C9—C14 | 165.40 (17) |
C1—C2—C3—C4 | −177.30 (18) | C1—C8—C9—C14 | −72.7 (2) |
C2—C3—C4—C5 | −0.5 (3) | C14—C9—C10—C11 | 1.0 (3) |
C3—C4—C5—C6 | 0.1 (3) | C8—C9—C10—C11 | −179.04 (17) |
C4—C5—C6—C7 | −0.4 (3) | C9—C10—C11—C12 | 0.0 (3) |
C5—C6—C7—C2 | 1.1 (3) | C10—C11—C12—C13 | −0.6 (3) |
C3—C2—C7—C6 | −1.5 (3) | C11—C12—C13—C14 | 0.3 (4) |
C1—C2—C7—C6 | 177.04 (19) | C12—C13—C14—C9 | 0.7 (3) |
N1—C1—C8—N2 | 57.7 (2) | C10—C9—C14—C13 | −1.4 (3) |
C2—C1—C8—N2 | −70.5 (2) | C8—C9—C14—C13 | 178.68 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N2 | 0.92 (2) | 2.34 (2) | 2.832 (2) | 113 (2) |
N2—H2B···N1i | 0.93 (2) | 2.35 (2) | 3.249 (2) | 164 (2) |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C14H16N2 |
Mr | 212.29 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 180 |
a, b, c (Å) | 5.1447 (1), 12.3264 (4), 18.5357 (7) |
V (Å3) | 1175.45 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.23 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.895, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6085, 1229, 1148 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.082, 1.09 |
No. of reflections | 1229 |
No. of parameters | 159 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.14, −0.14 |
Computer programs: COLLECT (Nonius 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SIR92 (Altomare at al., 1994), SHELXTL (Bruker, 2001), SHELXTL.
N1—C1 | 1.456 (3) | C6—C7 | 1.380 (3) |
N2—C8 | 1.463 (3) | C8—C9 | 1.516 (3) |
C1—C2 | 1.524 (3) | C9—C10 | 1.387 (3) |
C1—C8 | 1.551 (2) | C9—C14 | 1.394 (3) |
C2—C3 | 1.390 (3) | C10—C11 | 1.390 (3) |
C2—C7 | 1.394 (3) | C11—C12 | 1.378 (4) |
C3—C4 | 1.390 (3) | C12—C13 | 1.372 (4) |
C4—C5 | 1.379 (3) | C13—C14 | 1.385 (3) |
C5—C6 | 1.392 (3) | ||
N1—C1—C2 | 116.33 (15) | N2—C8—C9 | 111.32 (16) |
N1—C1—C8 | 108.93 (16) | N2—C8—C1 | 108.94 (15) |
C2—C1—C8 | 109.41 (16) | C9—C8—C1 | 111.57 (16) |
C3—C2—C7 | 117.77 (19) | C10—C9—C14 | 117.90 (19) |
C3—C2—C1 | 123.08 (18) | C10—C9—C8 | 122.91 (18) |
C7—C2—C1 | 119.13 (17) | C14—C9—C8 | 119.19 (18) |
C4—C3—C2 | 120.46 (19) | C9—C10—C11 | 120.7 (2) |
C5—C4—C3 | 121.18 (19) | C12—C11—C10 | 120.4 (2) |
C4—C5—C6 | 118.9 (2) | C13—C12—C11 | 119.7 (2) |
C7—C6—C5 | 119.8 (2) | C12—C13—C14 | 120.0 (2) |
C6—C7—C2 | 121.85 (19) | C13—C14—C9 | 121.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N2 | 0.916 (17) | 2.34 (2) | 2.832 (2) | 113.1 (16) |
N2—H2B···N1i | 0.927 (18) | 2.346 (18) | 3.249 (2) | 164.3 (17) |
Symmetry code: (i) x−1, y, z. |
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As part of our study devoted to the synthesis and characterization of novel chiral catalysts, we came across (1R,2R)-(+)-1,2-diphenylethylenediamine, (I), a bidentate chiral amine capable of forming chelates with d-transition metal cations (Jones et al., 2003; Rouzaud et al., 2003). Here, we report the crystal structure, determined at 180 (2) K, of this chiral compound.
Compound (I) crystallizes in the orthorhombic chiral space group P212121, with one whole molecule in the asymmetric unit (Fig. 1). Adjacent molecules of (I) are linked by a combination of inter- and intramolecular N—H···N hydrogen bonds (Table 2 and Fig. 2), forming a one-dimensional infinite chain which runs along the a direction (Fig. 3). Further intermolecular N—H···π interactions are also evident in the crystal structure [H2A···Cgi = 2.61 (4) Å and N2—H2A···Cgi = 138 (4)°, where Cg is the centroid of the C9–C14 ring; symmetry code: (i) x − 1, y, z] (Fig. 2). Although one could expect to find a similar interaction between atom N1 and the neighbouring C2–C7 ring, the spatial arrangement of the molecules does not allow it. Individual molecules of (I) are stacked in a herring-bone manner, forming layers which pack in an ABAB fashion along the b direction (Fig. 3).