Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803011681/cf6256sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803011681/cf6256Isup2.hkl |
CCDC reference: 217436
Key indicators
- Single-crystal X-ray study
- T = 180 K
- Mean (C-C) = 0.002 Å
- R factor = 0.036
- wR factor = 0.100
- Data-to-parameter ratio = 9.8
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(1) - H(1B) ? General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.49 From the CIF: _reflns_number_total 1635 Count of symmetry unique reflns 1092 Completeness (_total/calc) 149.73% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 543 Fraction of Friedel pairs measured 0.497 Are heavy atom types Z>Si present no ALERT: MoKa measured Friedel data cannot be used to determine absolute structure in a light-atom study EXCEPT under VERY special conditions. It is preferred that Friedel data is merged in such cases.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
(R)-(+)-2,2'-Diamino-1,1'-binaphthyl was purchased from Aldrich (99.5% purity) and used without further purification. Crystals suitable for X-Ray diffraction analysis were obtained by recrystallization from methanol.
All 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 in difference Fourier maps and refined independently. A total of 574 Friedel pairs have been 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 et al., 1994); program(s) used to refine structure: SHELXTL (Bruker 2001); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C20H16N2 | Dx = 1.268 Mg m−3 |
Mr = 284.35 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P43212 | Cell parameters from 4522 reflections |
Hall symbol: P 4nw 2abw | θ = 1.0–27.5° |
a = 7.0388 (2) Å | µ = 0.08 mm−1 |
c = 30.0684 (8) Å | T = 180 K |
V = 1489.73 (7) Å3 | Block, colourless |
Z = 4 | 0.46 × 0.46 × 0.23 mm |
F(000) = 600 |
Nonius KappaCCD diffractometer | 1455 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Thin–slice ω and ϕ scans | θmax = 27.5°, θmin = 3.5° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −9→9 |
Tmin = 0.944, Tmax = 0.983 | k = −6→9 |
4236 measured reflections | l = −39→39 |
1635 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0563P)2 + 0.37P] where P = (Fo2 + 2Fc2)/3 |
1061 reflections | (Δ/σ)max < 0.001 |
108 parameters | Δρmax = 0.17 e Å−3 |
2 restraints | Δρmin = −0.19 e Å−3 |
C20H16N2 | Z = 4 |
Mr = 284.35 | Mo Kα radiation |
Tetragonal, P43212 | µ = 0.08 mm−1 |
a = 7.0388 (2) Å | T = 180 K |
c = 30.0684 (8) Å | 0.46 × 0.46 × 0.23 mm |
V = 1489.73 (7) Å3 |
Nonius KappaCCD diffractometer | 1635 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1455 reflections with I > 2σ(I) |
Tmin = 0.944, Tmax = 0.983 | Rint = 0.029 |
4236 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 2 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.17 e Å−3 |
1061 reflections | Δρmin = −0.19 e Å−3 |
108 parameters |
Experimental. Friedel equivalents merged for refinement. H-atom from –NH2 group have been located in difference Fourier maps. The N–H distance has been restrained to be 0.88 (1) A. |
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 | 0.4707 (3) | 0.1703 (2) | −0.05183 (5) | 0.0366 (4) | |
H1A | 0.368 (2) | 0.239 (3) | −0.0574 (8) | 0.053 (7)* | |
H1B | 0.457 (4) | 0.0482 (16) | −0.0579 (8) | 0.067 (8)* | |
C1 | 0.5529 (2) | 0.2117 (2) | −0.01137 (5) | 0.0257 (4) | |
C2 | 0.6753 (3) | 0.0735 (2) | 0.00785 (6) | 0.0319 (4) | |
H2 | 0.6970 | −0.0427 | −0.0074 | 0.038* | |
C3 | 0.7617 (2) | 0.1046 (3) | 0.04747 (6) | 0.0303 (4) | |
H3 | 0.8408 | 0.0090 | 0.0599 | 0.036* | |
C4 | 0.7352 (2) | 0.2782 (2) | 0.07047 (5) | 0.0239 (4) | |
C5 | 0.8226 (2) | 0.3122 (3) | 0.11225 (6) | 0.0291 (4) | |
H5 | 0.8995 | 0.2163 | 0.1253 | 0.035* | |
C6 | 0.7980 (3) | 0.4804 (3) | 0.13397 (6) | 0.0335 (4) | |
H6 | 0.8563 | 0.5006 | 0.1621 | 0.040* | |
C7 | 0.6859 (3) | 0.6244 (3) | 0.11468 (6) | 0.0328 (4) | |
H7 | 0.6703 | 0.7421 | 0.1297 | 0.039* | |
C8 | 0.5989 (2) | 0.5963 (2) | 0.07429 (5) | 0.0260 (4) | |
H8 | 0.5244 | 0.6952 | 0.0617 | 0.031* | |
C9 | 0.6186 (2) | 0.4215 (2) | 0.05104 (5) | 0.0210 (3) | |
C10 | 0.5244 (2) | 0.3859 (2) | 0.00963 (5) | 0.0212 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0516 (11) | 0.0268 (8) | 0.0314 (8) | 0.0000 (8) | −0.0124 (8) | −0.0075 (7) |
C1 | 0.0293 (9) | 0.0236 (8) | 0.0243 (8) | −0.0021 (7) | −0.0017 (7) | 0.0004 (6) |
C2 | 0.0396 (10) | 0.0226 (8) | 0.0335 (8) | 0.0059 (8) | 0.0008 (8) | −0.0021 (7) |
C3 | 0.0290 (9) | 0.0280 (9) | 0.0339 (9) | 0.0064 (7) | −0.0016 (8) | 0.0076 (8) |
C4 | 0.0194 (7) | 0.0292 (8) | 0.0231 (8) | −0.0022 (6) | 0.0005 (6) | 0.0066 (7) |
C5 | 0.0221 (8) | 0.0402 (9) | 0.0248 (8) | −0.0036 (8) | −0.0024 (7) | 0.0101 (7) |
C6 | 0.0311 (9) | 0.0475 (11) | 0.0218 (8) | −0.0093 (9) | −0.0052 (7) | 0.0026 (8) |
C7 | 0.0377 (10) | 0.0344 (9) | 0.0264 (8) | −0.0074 (8) | −0.0003 (8) | −0.0066 (8) |
C8 | 0.0278 (8) | 0.0257 (8) | 0.0245 (8) | −0.0020 (7) | −0.0001 (7) | 0.0002 (7) |
C9 | 0.0193 (7) | 0.0238 (8) | 0.0198 (7) | −0.0035 (6) | 0.0015 (6) | 0.0033 (6) |
C10 | 0.0218 (7) | 0.0219 (8) | 0.0200 (7) | −0.0011 (6) | 0.0003 (6) | 0.0028 (6) |
N1—C1 | 1.378 (2) | C5—C6 | 1.363 (3) |
N1—H1A | 0.884 (10) | C5—H5 | 0.950 |
N1—H1B | 0.884 (10) | C6—C7 | 1.409 (3) |
C1—C10 | 1.393 (2) | C6—H6 | 0.950 |
C1—C2 | 1.423 (2) | C7—C8 | 1.374 (2) |
C2—C3 | 1.355 (2) | C7—H7 | 0.950 |
C2—H2 | 0.950 | C8—C9 | 1.422 (2) |
C3—C4 | 1.417 (2) | C8—H8 | 0.950 |
C3—H3 | 0.950 | C9—C10 | 1.433 (2) |
C4—C5 | 1.419 (2) | C10—C10i | 1.496 (3) |
C4—C9 | 1.426 (2) | ||
C1—N1—H1A | 113.1 (15) | C4—C5—H5 | 119.5 |
C1—N1—H1B | 115.7 (16) | C5—C6—C7 | 119.91 (16) |
H1A—N1—H1B | 114 (2) | C5—C6—H6 | 120.0 |
N1—C1—C10 | 121.72 (15) | C7—C6—H6 | 120.0 |
N1—C1—C2 | 117.93 (15) | C8—C7—C6 | 120.63 (17) |
C10—C1—C2 | 120.30 (15) | C8—C7—H7 | 119.7 |
C3—C2—C1 | 121.25 (16) | C6—C7—H7 | 119.7 |
C3—C2—H2 | 119.4 | C7—C8—C9 | 121.05 (17) |
C1—C2—H2 | 119.4 | C7—C8—H8 | 119.5 |
C2—C3—C4 | 120.61 (16) | C9—C8—H8 | 119.5 |
C2—C3—H3 | 119.7 | C8—C9—C4 | 117.82 (14) |
C4—C3—H3 | 119.7 | C8—C9—C10 | 122.26 (14) |
C3—C4—C5 | 121.36 (16) | C4—C9—C10 | 119.91 (15) |
C3—C4—C9 | 119.09 (15) | C1—C10—C9 | 118.79 (14) |
C5—C4—C9 | 119.55 (16) | C1—C10—C10i | 119.46 (14) |
C6—C5—C4 | 121.02 (16) | C9—C10—C10i | 121.58 (15) |
C6—C5—H5 | 119.5 | ||
N1—C1—C2—C3 | 179.76 (17) | C3—C4—C9—C8 | −178.28 (14) |
C10—C1—C2—C3 | 2.3 (3) | C5—C4—C9—C8 | 1.6 (2) |
C1—C2—C3—C4 | −1.3 (3) | C3—C4—C9—C10 | 2.4 (2) |
C2—C3—C4—C5 | 179.19 (17) | C5—C4—C9—C10 | −177.80 (14) |
C2—C3—C4—C9 | −1.0 (2) | N1—C1—C10—C9 | −178.22 (15) |
C3—C4—C5—C6 | 179.34 (16) | C2—C1—C10—C9 | −0.8 (2) |
C9—C4—C5—C6 | −0.5 (2) | N1—C1—C10—C10i | 6.4 (2) |
C4—C5—C6—C7 | −0.7 (3) | C2—C1—C10—C10i | −176.20 (14) |
C5—C6—C7—C8 | 0.8 (3) | C8—C9—C10—C1 | 179.22 (14) |
C6—C7—C8—C9 | 0.3 (3) | C4—C9—C10—C1 | −1.5 (2) |
C7—C8—C9—C4 | −1.5 (2) | C8—C9—C10—C10i | −5.5 (2) |
C7—C8—C9—C10 | 177.85 (15) | C4—C9—C10—C10i | 173.83 (12) |
Symmetry code: (i) y, x, −z. |
Experimental details
Crystal data | |
Chemical formula | C20H16N2 |
Mr | 284.35 |
Crystal system, space group | Tetragonal, P43212 |
Temperature (K) | 180 |
a, c (Å) | 7.0388 (2), 30.0684 (8) |
V (Å3) | 1489.73 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.46 × 0.46 × 0.23 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.944, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4236, 1635, 1455 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.100, 1.02 |
No. of reflections | 1061 |
No. of parameters | 108 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.19 |
Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK, SIR92 (Altomare et al., 1994), SHELXTL (Bruker 2001), SHELXTL.
N1—C1 | 1.378 (2) | C5—C6 | 1.363 (3) |
C1—C10 | 1.393 (2) | C6—C7 | 1.409 (3) |
C1—C2 | 1.423 (2) | C7—C8 | 1.374 (2) |
C2—C3 | 1.355 (2) | C8—C9 | 1.422 (2) |
C3—C4 | 1.417 (2) | C9—C10 | 1.433 (2) |
C4—C5 | 1.419 (2) | C10—C10i | 1.496 (3) |
C4—C9 | 1.426 (2) | ||
N1—C1—C10 | 121.72 (15) | C5—C6—C7 | 119.91 (16) |
N1—C1—C2 | 117.93 (15) | C8—C7—C6 | 120.63 (17) |
C10—C1—C2 | 120.30 (15) | C7—C8—C9 | 121.05 (17) |
C3—C2—C1 | 121.25 (16) | C8—C9—C4 | 117.82 (14) |
C2—C3—C4 | 120.61 (16) | C8—C9—C10 | 122.26 (14) |
C3—C4—C5 | 121.36 (16) | C4—C9—C10 | 119.91 (15) |
C3—C4—C9 | 119.09 (15) | C1—C10—C9 | 118.79 (14) |
C5—C4—C9 | 119.55 (16) | C1—C10—C10i | 119.46 (14) |
C6—C5—C4 | 121.02 (16) | C9—C10—C10i | 121.58 (15) |
Symmetry code: (i) y, x, −z. |
We have been focusing our research on the use of amines which can lead to the synthesis of chiral metal complexes with applications, for example, as catalysts in asymmetric hydrogenation processes (Jones et al., 2003a,b,c; Raynor et al., 2000). As part of our study, we came across (R)-2,2'-diamino-1,1'-binaphthyl, (I), an interesting bidentate chiral amine capable of forming chelates with transition metal centres (Mikami, Aikawa & Yusa, 2002; Mikami & Aikawa, 2002; Jones et al., 2003a). Gridunova et al. (1982) have investigated the structure of racemic 2,2'-diamino-1,1'-binaphthyl. Here we report the crystal structure, determined at 180 (2) K, of the pure R form.
Compound (I) crystallizes in the tetragonal chiral space group P43212, with the origin located at 2112 and the asymmetric unit containing only half of the molecular unit (Fig. 1). Adjacent molecules of (I) are linked by a combination of intermolecular N—H···π and C—H···π interactions [H1B···Cgi = 2.60 (3) Å and N1—H1B···Cgi = 166 (3)°, H5···Cgii = 2.68 Å and C5—H5···Cgii = 159°, where Cg is the centroid of the C4–C9 aromatic ring; symmetry codes: (i) y, −1 + x, −z; (ii) 1/2 + x, 1/2 − y, 1/4 − z] (see Fig. 2). Although one could expect to find a similar N—H···π interaction between the N1—H1A bond and a neighbouring aromatic ring, the spatial arrangement of the molecules does not allow it. Individual molecules of (I) are arranged in the c direction in a way that leads to a herring-bone packing manner (Fig. 3).