Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040810/lw2027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040810/lw2027Isup2.hkl |
CCDC reference: 660360
The title compound was prepared according to a literature procedure (Gust & Schönenberger, 1993). Crystals suitable for X-ray diffraction were grown as colorless plates by slow diffusion of ethanol to a solution of the title compound in water over a period of 2 weeks. 1H NMR (300 MHz, DMSO-d6): 10.29 (s, 2H of OH); 8.50 (br s, 6H of NH3); 7.09 (m, 4H of ArH); 6.80 (d, 3J = 8.1 Hz, 2H of ArH); 6.68 (t, 3J = 7.5 Hz, 2H of ArH); 5.19 (s, 2H of C*H).
All hydrogen atoms were placed in calculated positions with C—H = 0.93 to 0.98 Å, N—H = 0.89 Å and O—H = 0.82 Å. They were included in the refinement in the riding-motion approximation with Uiso(H) = 1.2Ueq(C,N) or Uiso(H) = 1.5Ueq(Cmethyl and O). A difference Fourier map revealed three peaks close to each other which were interpreted as a disordered O atom from a solvent H2O molecule. This disordered water molecule was included in the refinement as three one third occupancy O atoms but the H atoms were not located or included. These H atoms are however included in the molecular formula.
Chiral vicinal diamines are found in a wide variety of stereoselective catalysts (Lucet et al., 1998). We have shown that the title compound is very useful for making many chiral vicinal diamines in enantiomerically pure form by diaza-Cope rearrangement reaction (Kim, Kim, Alhakimi et al., 2005; Kim, Kim, Lough et al., 2005; Kim et al., 2006). The crystal structure reveals that the two hydrogen atoms attached to the two sp3 hybridized carbon are in an anti orientation with respect to each other while the two phenol groups and the two ammonium groups are in gauche orientations. Diimines formed between the title compound and aryl aldehydes also form the same conformer and are ideally pre-organized for the diaza-Cope rearrangement reaction. In contrast, in the structure of the meso-1,2-(2-hydroxyphenyl)-ethylenediamine (Bryant et al., 2002) the hydrogen atoms, the phenols and the ammonium groups are all in anti orientations.
For background information, see: Kim, Kim, Alhakimi et al. (2005); Kim, Kim, Lough et al. (2005); Kim et al. (2006). For other related literature, see: Bryant et al. (2002); Gust & Schönenberger (1993); Lucet et al. (1998).
Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure with displacement ellipsoids drawn at the 30% probability level. The disordered water solvent molecule is not shown. |
C14H18N2O22+·2Br−·H2O | F(000) = 848 |
Mr = 424.14 | Dx = 1.534 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 30763 reflections |
a = 5.4499 (5) Å | θ = 2.6–25.0° |
b = 16.883 (2) Å | µ = 4.43 mm−1 |
c = 20.042 (2) Å | T = 293 K |
β = 95.321 (8)° | Plate, colourless |
V = 1836.1 (3) Å3 | 0.36 × 0.26 × 0.03 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 3233 independent reflections |
Radiation source: fine-focus sealed tube | 2162 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.110 |
Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 2.6° |
φ scans, and ω scans with κ offsets | h = −6→6 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −17→20 |
Tmin = 0.465, Tmax = 0.855 | l = −23→23 |
10004 measured 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)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.0794P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3233 reflections | Δρmax = 0.57 e Å−3 |
211 parameters | Δρmin = −0.45 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Sheldrick, 2001), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0034 (10) |
C14H18N2O22+·2Br−·H2O | V = 1836.1 (3) Å3 |
Mr = 424.14 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.4499 (5) Å | µ = 4.43 mm−1 |
b = 16.883 (2) Å | T = 293 K |
c = 20.042 (2) Å | 0.36 × 0.26 × 0.03 mm |
β = 95.321 (8)° |
Nonius KappaCCD diffractometer | 3233 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 2162 reflections with I > 2σ(I) |
Tmin = 0.465, Tmax = 0.855 | Rint = 0.110 |
10004 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.57 e Å−3 |
3233 reflections | Δρmin = −0.45 e Å−3 |
211 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 | Occ. (<1) | |
Br1 | −0.02139 (12) | 0.20389 (4) | 0.14353 (3) | 0.0609 (3) | |
Br2 | 0.22244 (12) | −0.09688 (4) | 0.17880 (4) | 0.0618 (3) | |
O1 | 0.1756 (8) | 0.2625 (3) | 0.3199 (2) | 0.0627 (12) | |
H1 | 0.0814 | 0.2971 | 0.3308 | 0.094* | |
O2 | 0.8556 (8) | 0.0179 (3) | 0.2481 (2) | 0.0656 (12) | |
H2 | 0.9143 | −0.0205 | 0.2302 | 0.098* | |
N1 | 0.5375 (9) | 0.2472 (3) | 0.2386 (2) | 0.0503 (12) | |
H1B | 0.5854 | 0.2928 | 0.2580 | 0.075* | |
H1C | 0.3762 | 0.2489 | 0.2266 | 0.075* | |
H1D | 0.6181 | 0.2395 | 0.2025 | 0.075* | |
N2 | 0.4404 (10) | 0.0871 (3) | 0.1949 (2) | 0.0537 (13) | |
H2B | 0.4033 | 0.0362 | 0.1882 | 0.081* | |
H2C | 0.5906 | 0.0965 | 0.1827 | 0.081* | |
H2D | 0.3312 | 0.1169 | 0.1706 | 0.081* | |
C1 | 0.5929 (10) | 0.1802 (3) | 0.2873 (3) | 0.0453 (13) | |
H1A | 0.7665 | 0.1655 | 0.2862 | 0.054* | |
C2 | 0.4339 (10) | 0.1066 (3) | 0.2677 (3) | 0.0457 (13) | |
H2A | 0.2631 | 0.1191 | 0.2753 | 0.055* | |
C3 | 0.5552 (10) | 0.2058 (3) | 0.3577 (3) | 0.0472 (14) | |
C4 | 0.3491 (11) | 0.2476 (4) | 0.3722 (3) | 0.0542 (15) | |
C5 | 0.3219 (13) | 0.2731 (4) | 0.4373 (3) | 0.0628 (17) | |
H5A | 0.1841 | 0.3022 | 0.4463 | 0.075* | |
C6 | 0.5030 (15) | 0.2544 (5) | 0.4885 (3) | 0.073 (2) | |
H6A | 0.4854 | 0.2713 | 0.5320 | 0.087* | |
C7 | 0.7045 (15) | 0.2121 (4) | 0.4758 (4) | 0.070 (2) | |
H7A | 0.8232 | 0.1994 | 0.5105 | 0.084* | |
C8 | 0.7338 (13) | 0.1876 (4) | 0.4108 (3) | 0.0604 (17) | |
H8A | 0.8730 | 0.1588 | 0.4022 | 0.072* | |
C9 | 0.5135 (11) | 0.0366 (3) | 0.3109 (3) | 0.0471 (14) | |
C10 | 0.3794 (12) | 0.0146 (4) | 0.3634 (3) | 0.0611 (17) | |
H10A | 0.2408 | 0.0436 | 0.3722 | 0.073* | |
C11 | 0.4512 (15) | −0.0507 (5) | 0.4033 (4) | 0.082 (2) | |
H11A | 0.3621 | −0.0646 | 0.4389 | 0.098* | |
C12 | 0.6536 (15) | −0.0946 (5) | 0.3899 (5) | 0.082 (2) | |
H12A | 0.6986 | −0.1388 | 0.4159 | 0.098* | |
C13 | 0.7897 (13) | −0.0735 (4) | 0.3383 (4) | 0.070 (2) | |
H13A | 0.9262 | −0.1035 | 0.3295 | 0.084* | |
C14 | 0.7238 (10) | −0.0074 (4) | 0.2993 (3) | 0.0536 (15) | |
O1W | 0.480 (6) | 0.0574 (12) | 0.0596 (8) | 0.124 (9) | 0.333 |
O2W | 0.330 (6) | 0.0251 (11) | 0.0205 (9) | 0.127 (10) | 0.333 |
O3W | 0.645 (4) | 0.0134 (14) | 0.0410 (9) | 0.115 (7) | 0.333 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0569 (4) | 0.0658 (5) | 0.0593 (4) | 0.0077 (3) | 0.0020 (3) | 0.0038 (3) |
Br2 | 0.0619 (4) | 0.0403 (4) | 0.0838 (5) | 0.0006 (3) | 0.0100 (3) | −0.0018 (3) |
O1 | 0.056 (3) | 0.063 (3) | 0.069 (3) | 0.013 (2) | −0.001 (2) | −0.011 (2) |
O2 | 0.064 (3) | 0.050 (3) | 0.086 (3) | 0.015 (2) | 0.024 (2) | 0.008 (2) |
N1 | 0.053 (3) | 0.040 (3) | 0.058 (3) | −0.004 (2) | 0.008 (2) | 0.005 (2) |
N2 | 0.063 (3) | 0.044 (3) | 0.053 (3) | 0.004 (2) | 0.001 (2) | −0.002 (2) |
C1 | 0.043 (3) | 0.041 (3) | 0.051 (3) | 0.000 (2) | 0.000 (3) | 0.004 (3) |
C2 | 0.043 (3) | 0.037 (3) | 0.058 (3) | −0.001 (2) | 0.010 (3) | −0.003 (3) |
C3 | 0.045 (3) | 0.043 (3) | 0.054 (3) | −0.007 (3) | 0.005 (3) | 0.000 (3) |
C4 | 0.050 (3) | 0.048 (3) | 0.065 (4) | 0.000 (3) | 0.005 (3) | −0.003 (3) |
C5 | 0.067 (4) | 0.058 (4) | 0.064 (4) | −0.006 (3) | 0.014 (4) | −0.014 (3) |
C6 | 0.090 (5) | 0.076 (5) | 0.054 (4) | −0.015 (4) | 0.014 (4) | −0.012 (4) |
C7 | 0.084 (5) | 0.068 (5) | 0.056 (4) | −0.015 (4) | −0.010 (4) | 0.007 (3) |
C8 | 0.059 (4) | 0.053 (4) | 0.068 (4) | −0.009 (3) | −0.003 (3) | 0.004 (3) |
C9 | 0.051 (3) | 0.037 (3) | 0.054 (3) | −0.003 (3) | 0.006 (3) | 0.000 (3) |
C10 | 0.060 (4) | 0.055 (4) | 0.069 (4) | −0.006 (3) | 0.015 (3) | 0.010 (3) |
C11 | 0.080 (5) | 0.080 (6) | 0.088 (5) | −0.008 (4) | 0.021 (4) | 0.028 (5) |
C12 | 0.072 (5) | 0.071 (5) | 0.100 (6) | −0.002 (4) | −0.003 (4) | 0.030 (5) |
C13 | 0.065 (4) | 0.046 (4) | 0.099 (6) | 0.004 (3) | 0.005 (4) | 0.011 (4) |
C14 | 0.043 (3) | 0.041 (3) | 0.076 (4) | −0.004 (3) | 0.003 (3) | 0.002 (3) |
O1W | 0.26 (3) | 0.074 (12) | 0.039 (9) | −0.018 (17) | 0.047 (14) | −0.006 (8) |
O2W | 0.27 (3) | 0.059 (11) | 0.056 (11) | −0.026 (15) | 0.030 (14) | 0.003 (9) |
O3W | 0.132 (17) | 0.135 (18) | 0.073 (12) | 0.030 (14) | −0.009 (12) | −0.042 (12) |
O1—C4 | 1.368 (7) | C4—C5 | 1.394 (9) |
O1—H1 | 0.8200 | C5—C6 | 1.393 (10) |
O2—C14 | 1.374 (7) | C5—H5A | 0.9300 |
O2—H2 | 0.8200 | C6—C7 | 1.354 (11) |
N1—C1 | 1.507 (7) | C6—H6A | 0.9300 |
N1—H1B | 0.8900 | C7—C8 | 1.390 (10) |
N1—H1C | 0.8900 | C7—H7A | 0.9300 |
N1—H1D | 0.8900 | C8—H8A | 0.9300 |
N2—C2 | 1.500 (7) | C9—C10 | 1.386 (9) |
N2—H2B | 0.8900 | C9—C14 | 1.403 (8) |
N2—H2C | 0.8900 | C10—C11 | 1.396 (10) |
N2—H2D | 0.8900 | C10—H10A | 0.9300 |
C1—C3 | 1.508 (8) | C11—C12 | 1.376 (11) |
C1—C2 | 1.544 (8) | C11—H11A | 0.9300 |
C1—H1A | 0.9800 | C12—C13 | 1.374 (11) |
C2—C9 | 1.506 (8) | C12—H12A | 0.9300 |
C2—H2A | 0.9800 | C13—C14 | 1.391 (9) |
C3—C4 | 1.380 (8) | C13—H13A | 0.9300 |
C3—C8 | 1.407 (8) | ||
C4—O1—H1 | 109.5 | C3—C4—C5 | 120.9 (6) |
C14—O2—H2 | 109.5 | C6—C5—C4 | 119.4 (7) |
C1—N1—H1B | 109.5 | C6—C5—H5A | 120.3 |
C1—N1—H1C | 109.5 | C4—C5—H5A | 120.3 |
H1B—N1—H1C | 109.5 | C7—C6—C5 | 120.7 (7) |
C1—N1—H1D | 109.5 | C7—C6—H6A | 119.6 |
H1B—N1—H1D | 109.5 | C5—C6—H6A | 119.6 |
H1C—N1—H1D | 109.5 | C6—C7—C8 | 120.0 (7) |
C2—N2—H2B | 109.5 | C6—C7—H7A | 120.0 |
C2—N2—H2C | 109.5 | C8—C7—H7A | 120.0 |
H2B—N2—H2C | 109.5 | C7—C8—C3 | 120.7 (7) |
C2—N2—H2D | 109.5 | C7—C8—H8A | 119.6 |
H2B—N2—H2D | 109.5 | C3—C8—H8A | 119.6 |
H2C—N2—H2D | 109.5 | C10—C9—C14 | 118.7 (6) |
N1—C1—C3 | 110.8 (5) | C10—C9—C2 | 120.2 (5) |
N1—C1—C2 | 111.4 (4) | C14—C9—C2 | 121.1 (5) |
C3—C1—C2 | 110.3 (5) | C9—C10—C11 | 120.4 (7) |
N1—C1—H1A | 108.1 | C9—C10—H10A | 119.8 |
C3—C1—H1A | 108.1 | C11—C10—H10A | 119.8 |
C2—C1—H1A | 108.1 | C12—C11—C10 | 120.1 (8) |
N2—C2—C9 | 110.8 (4) | C12—C11—H11A | 120.0 |
N2—C2—C1 | 111.2 (5) | C10—C11—H11A | 120.0 |
C9—C2—C1 | 111.1 (5) | C13—C12—C11 | 120.4 (7) |
N2—C2—H2A | 107.9 | C13—C12—H12A | 119.8 |
C9—C2—H2A | 107.9 | C11—C12—H12A | 119.8 |
C1—C2—H2A | 107.9 | C12—C13—C14 | 120.1 (7) |
C4—C3—C8 | 118.2 (6) | C12—C13—H13A | 120.0 |
C4—C3—C1 | 121.8 (5) | C14—C13—H13A | 120.0 |
C8—C3—C1 | 119.9 (5) | O2—C14—C13 | 122.9 (6) |
O1—C4—C3 | 116.8 (6) | O2—C14—C9 | 116.8 (5) |
O1—C4—C5 | 122.2 (6) | C13—C14—C9 | 120.3 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Br2i | 0.82 | 2.43 | 3.217 (4) | 160 |
O2—H2···Br2ii | 0.82 | 2.42 | 3.194 (4) | 157 |
N1—H1B···Br2iii | 0.89 | 2.43 | 3.314 (5) | 170 |
N1—H1C···Br1 | 0.89 | 2.72 | 3.517 (5) | 150 |
N1—H1D···Br1ii | 0.89 | 2.46 | 3.285 (5) | 155 |
N2—H2B···Br2 | 0.89 | 2.45 | 3.330 (5) | 168 |
N2—H2C···Br1ii | 0.89 | 2.95 | 3.757 (5) | 152 |
N2—H2D···Br1 | 0.89 | 2.44 | 3.287 (5) | 159 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H18N2O22+·2Br−·H2O |
Mr | 424.14 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 5.4499 (5), 16.883 (2), 20.042 (2) |
β (°) | 95.321 (8) |
V (Å3) | 1836.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.43 |
Crystal size (mm) | 0.36 × 0.26 × 0.03 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.465, 0.855 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10004, 3233, 2162 |
Rint | 0.110 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.153, 1.03 |
No. of reflections | 3233 |
No. of parameters | 211 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.45 |
Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2001), PLATON (Spek, 2003), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Br2i | 0.82 | 2.43 | 3.217 (4) | 160.2 |
O2—H2···Br2ii | 0.82 | 2.42 | 3.194 (4) | 157.1 |
N1—H1B···Br2iii | 0.89 | 2.43 | 3.314 (5) | 169.5 |
N1—H1C···Br1 | 0.89 | 2.72 | 3.517 (5) | 150.4 |
N1—H1D···Br1ii | 0.89 | 2.46 | 3.285 (5) | 154.5 |
N2—H2B···Br2 | 0.89 | 2.45 | 3.330 (5) | 168.4 |
N2—H2C···Br1ii | 0.89 | 2.95 | 3.757 (5) | 152.1 |
N2—H2D···Br1 | 0.89 | 2.44 | 3.287 (5) | 159.3 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z+1/2. |
Chiral vicinal diamines are found in a wide variety of stereoselective catalysts (Lucet et al., 1998). We have shown that the title compound is very useful for making many chiral vicinal diamines in enantiomerically pure form by diaza-Cope rearrangement reaction (Kim, Kim, Alhakimi et al., 2005; Kim, Kim, Lough et al., 2005; Kim et al., 2006). The crystal structure reveals that the two hydrogen atoms attached to the two sp3 hybridized carbon are in an anti orientation with respect to each other while the two phenol groups and the two ammonium groups are in gauche orientations. Diimines formed between the title compound and aryl aldehydes also form the same conformer and are ideally pre-organized for the diaza-Cope rearrangement reaction. In contrast, in the structure of the meso-1,2-(2-hydroxyphenyl)-ethylenediamine (Bryant et al., 2002) the hydrogen atoms, the phenols and the ammonium groups are all in anti orientations.