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The crystal structure of the title compound, C14H16N2, has been determined at 180 (2) K in the non-centrosymmetric space group P212121. The structure is formed by herring-bone-packed layers within which inter- and intramolecular N—H...N hydrogen bonds can be found, forming a one-dimensional infinite chain. Intermolecular N—H...π interactions are also present.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005385/cm6032sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005385/cm6032Isup2.hkl
Contains datablock I

CCDC reference: 209946

Key indicators

  • Single-crystal X-ray study
  • T = 180 K
  • Mean [sigma](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


Yellow Alert 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

Comment top

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).

Experimental top

(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).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular unit in (I), showing the labelling scheme for all non-H atoms. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres.
[Figure 2] Fig. 2. View in detail of the N—H···N intra- and intermolecular hydrogen bonds (dashed green lines) and the N—H···π interactions (red dashed lines) between adjacent molecules of the (I). For hydrogen-bond details and symmetry code, see Table 2.
[Figure 3] Fig. 3. Perspective view along the a direction of (I). Hydrogen bonds (see Table 2) are represented as green dashed lines, while N—H···π interactions as red dashed lines.
(1R,2R)-(+)-1,2-Diphenylethylenediamine top
Crystal data top
C14H16N2Dx = 1.200 Mg m3
Mr = 212.29Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 4851 reflections
a = 5.1447 (1) Åθ = 1.0–25.0°
b = 12.3264 (4) ŵ = 0.07 mm1
c = 18.5357 (7) ÅT = 180 K
V = 1175.45 (6) Å3Block, colourless
Z = 40.23 × 0.18 × 0.12 mm
F(000) = 456
Data collection top
Nonius KappaCCD
diffractometer
1148 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.056
Thin–slice ω and ϕ scansθmax = 25.0°, θmin = 4.1°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 66
Tmin = 0.895, Tmax = 0.992k = 1214
6085 measured reflectionsl = 2122
1229 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H 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 reflectionsΔρmax = 0.14 e Å3
159 parametersΔρmin = 0.14 e Å3
6 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.038 (6)
Crystal data top
C14H16N2V = 1175.45 (6) Å3
Mr = 212.29Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.1447 (1) ŵ = 0.07 mm1
b = 12.3264 (4) ÅT = 180 K
c = 18.5357 (7) Å0.23 × 0.18 × 0.12 mm
Data collection top
Nonius KappaCCD
diffractometer
1229 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
1148 reflections with I > 2σ(I)
Tmin = 0.895, Tmax = 0.992Rint = 0.056
6085 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0356 restraints
wR(F2) = 0.082H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.14 e Å3
1229 reflectionsΔρmin = 0.14 e Å3
159 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.2012 (3)0.84363 (15)0.96358 (9)0.0359 (4)
H1A0.258 (5)0.8633 (17)1.0077 (9)0.043*
H1B0.084 (4)0.7881 (16)0.9674 (11)0.043*
N20.2509 (3)0.79800 (14)0.88188 (9)0.0343 (4)
H2A0.322 (4)0.7698 (16)0.8406 (10)0.041*
H2B0.390 (4)0.8223 (17)0.9094 (10)0.041*
C10.0608 (4)0.93146 (16)0.92840 (10)0.0308 (5)
H10.19280.98540.91160.037*
C20.1355 (4)0.99255 (16)0.97474 (10)0.0306 (5)
C30.2294 (4)0.95283 (17)1.03990 (10)0.0336 (5)
H30.16530.88601.05830.040*
C40.4163 (4)1.01012 (17)1.07833 (10)0.0378 (5)
H40.47950.98161.12260.045*
C50.5117 (5)1.10768 (18)1.05338 (11)0.0405 (5)
H50.63931.14631.08010.049*
C60.4179 (5)1.14861 (18)0.98844 (11)0.0423 (6)
H60.48221.21550.97020.051*
C70.2314 (5)1.09183 (17)0.95054 (11)0.0392 (5)
H7A0.16661.12120.90670.047*
C80.0773 (4)0.88628 (16)0.86034 (9)0.0296 (5)
H80.18510.94560.83890.036*
C90.1166 (4)0.84889 (17)0.80404 (9)0.0315 (5)
C100.1622 (4)0.74029 (18)0.78895 (11)0.0386 (5)
H100.06740.68590.81400.046*
C110.3451 (5)0.7102 (2)0.73751 (12)0.0490 (6)
H110.37440.63560.72770.059*
C120.4842 (5)0.7881 (2)0.70062 (12)0.0557 (7)
H120.61020.76710.66580.067*
C130.4399 (5)0.8958 (2)0.71430 (11)0.0515 (7)
H130.53480.94970.68880.062*
C140.2568 (5)0.92617 (19)0.76524 (10)0.0407 (5)
H140.22611.00100.77390.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0316 (10)0.0494 (11)0.0268 (8)0.0043 (9)0.0060 (7)0.0034 (8)
N20.0301 (9)0.0457 (10)0.0269 (8)0.0067 (9)0.0002 (7)0.0031 (7)
C10.0280 (11)0.0369 (11)0.0276 (10)0.0023 (9)0.0005 (8)0.0015 (8)
C20.0307 (10)0.0343 (10)0.0269 (9)0.0051 (9)0.0033 (8)0.0055 (8)
C30.0378 (11)0.0378 (11)0.0254 (9)0.0003 (10)0.0024 (9)0.0017 (8)
C40.0439 (13)0.0434 (12)0.0261 (10)0.0017 (11)0.0043 (9)0.0022 (9)
C50.0415 (12)0.0418 (12)0.0383 (11)0.0030 (11)0.0043 (9)0.0100 (10)
C60.0489 (13)0.0357 (12)0.0422 (11)0.0065 (11)0.0031 (11)0.0003 (9)
C70.0479 (13)0.0375 (11)0.0321 (10)0.0023 (11)0.0064 (10)0.0018 (9)
C80.0271 (10)0.0361 (10)0.0256 (9)0.0002 (9)0.0002 (8)0.0025 (8)
C90.0291 (10)0.0430 (12)0.0222 (9)0.0011 (10)0.0035 (8)0.0002 (8)
C100.0375 (12)0.0483 (13)0.0302 (11)0.0017 (10)0.0030 (9)0.0051 (9)
C110.0445 (13)0.0643 (15)0.0382 (12)0.0125 (13)0.0062 (11)0.0175 (11)
C120.0394 (13)0.100 (2)0.0279 (11)0.0066 (15)0.0013 (10)0.0129 (13)
C130.0438 (13)0.0838 (18)0.0269 (11)0.0110 (14)0.0048 (10)0.0049 (12)
C140.0411 (12)0.0533 (13)0.0279 (10)0.0060 (11)0.0011 (10)0.0028 (9)
Geometric parameters (Å, º) top
N1—C11.456 (3)C6—C71.380 (3)
N1—H1A0.902 (17)C6—H60.9500
N1—H1B0.916 (17)C7—H7A0.9500
N2—C81.463 (3)C8—C91.516 (3)
N2—H2A0.917 (17)C8—H81.0000
N2—H2B0.927 (18)C9—C101.387 (3)
C1—C21.524 (3)C9—C141.394 (3)
C1—C81.551 (2)C10—C111.390 (3)
C1—H11.0000C10—H100.9500
C2—C31.390 (3)C11—C121.378 (4)
C2—C71.394 (3)C11—H110.9500
C3—C41.390 (3)C12—C131.372 (4)
C3—H30.9500C12—H120.9500
C4—C51.379 (3)C13—C141.385 (3)
C4—H40.9500C13—H130.9500
C5—C61.392 (3)C14—H140.9500
C5—H50.9500
C1—N1—H1A111.6 (14)C6—C7—C2121.85 (19)
C1—N1—H1B105.3 (15)C6—C7—H7A119.1
H1A—N1—H1B110.1 (17)C2—C7—H7A119.1
C8—N2—H2A107.4 (13)N2—C8—C9111.32 (16)
C8—N2—H2B112.4 (14)N2—C8—C1108.94 (15)
H2A—N2—H2B105.8 (17)C9—C8—C1111.57 (16)
N1—C1—C2116.33 (15)N2—C8—H8108.3
N1—C1—C8108.93 (16)C9—C8—H8108.3
C2—C1—C8109.41 (16)C1—C8—H8108.3
N1—C1—H1107.3C10—C9—C14117.90 (19)
C2—C1—H1107.3C10—C9—C8122.91 (18)
C8—C1—H1107.3C14—C9—C8119.19 (18)
C3—C2—C7117.77 (19)C9—C10—C11120.7 (2)
C3—C2—C1123.08 (18)C9—C10—H10119.7
C7—C2—C1119.13 (17)C11—C10—H10119.7
C4—C3—C2120.46 (19)C12—C11—C10120.4 (2)
C4—C3—H3119.8C12—C11—H11119.8
C2—C3—H3119.8C10—C11—H11119.8
C5—C4—C3121.18 (19)C13—C12—C11119.7 (2)
C5—C4—H4119.4C13—C12—H12120.1
C3—C4—H4119.4C11—C12—H12120.1
C4—C5—C6118.9 (2)C12—C13—C14120.0 (2)
C4—C5—H5120.6C12—C13—H13120.0
C6—C5—H5120.6C14—C13—H13120.0
C7—C6—C5119.8 (2)C13—C14—C9121.2 (2)
C7—C6—H6120.1C13—C14—H14119.4
C5—C6—H6120.1C9—C14—H14119.4
N1—C1—C2—C316.3 (3)N1—C1—C8—C965.6 (2)
C8—C1—C2—C3107.6 (2)C2—C1—C8—C9166.25 (16)
N1—C1—C2—C7165.24 (18)N2—C8—C9—C1014.5 (3)
C8—C1—C2—C770.8 (2)C1—C8—C9—C10107.4 (2)
C7—C2—C3—C41.2 (3)N2—C8—C9—C14165.40 (17)
C1—C2—C3—C4177.30 (18)C1—C8—C9—C1472.7 (2)
C2—C3—C4—C50.5 (3)C14—C9—C10—C111.0 (3)
C3—C4—C5—C60.1 (3)C8—C9—C10—C11179.04 (17)
C4—C5—C6—C70.4 (3)C9—C10—C11—C120.0 (3)
C5—C6—C7—C21.1 (3)C10—C11—C12—C130.6 (3)
C3—C2—C7—C61.5 (3)C11—C12—C13—C140.3 (4)
C1—C2—C7—C6177.04 (19)C12—C13—C14—C90.7 (3)
N1—C1—C8—N257.7 (2)C10—C9—C14—C131.4 (3)
C2—C1—C8—N270.5 (2)C8—C9—C14—C13178.68 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···N20.92 (2)2.34 (2)2.832 (2)113 (2)
N2—H2B···N1i0.93 (2)2.35 (2)3.249 (2)164 (2)
Symmetry code: (i) x1, y, z.

Experimental details

Crystal data
Chemical formulaC14H16N2
Mr212.29
Crystal system, space groupOrthorhombic, P212121
Temperature (K)180
a, b, c (Å)5.1447 (1), 12.3264 (4), 18.5357 (7)
V3)1175.45 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.23 × 0.18 × 0.12
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.895, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
6085, 1229, 1148
Rint0.056
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.082, 1.09
No. of reflections1229
No. of parameters159
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
N1—C11.456 (3)C6—C71.380 (3)
N2—C81.463 (3)C8—C91.516 (3)
C1—C21.524 (3)C9—C101.387 (3)
C1—C81.551 (2)C9—C141.394 (3)
C2—C31.390 (3)C10—C111.390 (3)
C2—C71.394 (3)C11—C121.378 (4)
C3—C41.390 (3)C12—C131.372 (4)
C4—C51.379 (3)C13—C141.385 (3)
C5—C61.392 (3)
N1—C1—C2116.33 (15)N2—C8—C9111.32 (16)
N1—C1—C8108.93 (16)N2—C8—C1108.94 (15)
C2—C1—C8109.41 (16)C9—C8—C1111.57 (16)
C3—C2—C7117.77 (19)C10—C9—C14117.90 (19)
C3—C2—C1123.08 (18)C10—C9—C8122.91 (18)
C7—C2—C1119.13 (17)C14—C9—C8119.19 (18)
C4—C3—C2120.46 (19)C9—C10—C11120.7 (2)
C5—C4—C3121.18 (19)C12—C11—C10120.4 (2)
C4—C5—C6118.9 (2)C13—C12—C11119.7 (2)
C7—C6—C5119.8 (2)C12—C13—C14120.0 (2)
C6—C7—C2121.85 (19)C13—C14—C9121.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···N20.916 (17)2.34 (2)2.832 (2)113.1 (16)
N2—H2B···N1i0.927 (18)2.346 (18)3.249 (2)164.3 (17)
Symmetry code: (i) x1, y, z.
 

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