(1R,2R)/(1S,2S)-1,2-Bis(2-hydroxy­phenyl)­ethyl­enediammonium dibromide monohydrate

In the cation of the title compound, C₁₄H₁₈N₂O₂²⁺·2Br⁻·H₂O, the two H atoms attached to the two sp³-hybridized C atoms are in an anti orientation with respect to each other and the dihedral angle between the two benzene rings is 49.5 (2)°. The crystal structure is stabilized by O—H...Br and N—H...Br hydrogen bonds. The solvent O atom is disordered equally over three positions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• H-atom completeness 91%
• Disorder in solvent or counterion
• R factor = 0.052
• wR factor = 0.153
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR) is > 1.50
            Tmin and Tmax reported:      0.465     0.855
            Tmin and Tmax expected:      0.264     0.876
            RR =      1.803
            Please check that your absorption correction is appropriate.
PLAT060_ALERT_3_B Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.82

Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.110
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.02
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      25.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2C    ..  BR1     ..       2.95 Ang.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C14 H20 Br2 N2 O3
            Atom count from the _atom_site data:  C14 H18 Br2 N2 O3.004
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C14 H20 Br2 N2 O3
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         56.00     56.00    0.00
           H         80.00     72.00    8.00
           Br         8.00      8.00    0.00
           N          8.00      8.00    0.00
           O         12.00     12.00    0.00
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT793_ALERT_1_G Check the Absolute Configuration of C1     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          S

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   7 ALERT level G = General alerts; check

   9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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.

Related literature

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).

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = 1.2U_eq(C,N) or U_iso(H) = 1.5U_eq(C_methyl 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.

Computing details

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.

Figures

Fig. 1. The molecular structure with displacement ellipsoids drawn at the 30% probability level. The disordered water solvent molecule is not shown.

(1R,2R)/(1S,2S)-1,2- Bis(2-hydroxyphenyl)ethylenediammonium dibromide monohydrate

Crystal data

C14H18N2O2^2+·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) Å^3	0.36 × 0.26 × 0.03 mm
Z = 4

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.0794P)^2] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0034 (10)

Special details

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 (Ų)

	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

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Br2^i	0.82	2.43	3.217 (4)	160
O2—H2···Br2^ii	0.82	2.42	3.194 (4)	157
N1—H1B···Br2^iii	0.89	2.43	3.314 (5)	170
N1—H1C···Br1	0.89	2.72	3.517 (5)	150
N1—H1D···Br1^ii	0.89	2.46	3.285 (5)	155
N2—H2B···Br2	0.89	2.45	3.330 (5)	168
N2—H2C···Br1^ii	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.