From an aqueous solution of racemic 2,3-dibromosuccinic acid and (R)-1-phenylethanamine, crystals of the title compound, C8H12N+·0.5C4H2Br2O42−·0.5C4H4Br2O4·H2O, were obtained in almost quantitative yield. The structure contains both enantiomers of the starting material, dibromosuccinic acid. The S,S enantiomer is present as a dianion and the R,R enantiomer as the neutral acid; both of these components lie on twofold rotation axes. The structure features a complex two-dimensional network of hydrogen bonds.
Supporting information
CCDC reference: 605204
Key indicators
- Single-crystal X-ray study
- T = 299 K
- Mean (C-C) = 0.013 Å
- R factor = 0.059
- wR factor = 0.120
- Data-to-parameter ratio = 20.2
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry ..... 90 PerFit
PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry ..... 90 PerFit
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C10
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C2
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 13
PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. Br2 .. 3.59 Ang.
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su .. 0.03
Alert level G
REFLT03_ALERT_4_G 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.
From the CIF: _diffrn_reflns_theta_max 27.51
From the CIF: _reflns_number_total 3652
Count of symmetry unique reflns 2130
Completeness (_total/calc) 171.46%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1522
Fraction of Friedel pairs measured 0.715
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
6 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2003); data reduction: EVALCCD (Duisenberg, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: maXus (Mackay et al., 1999).
(
R)-1-Phenylethanaminium–(
S,
S)-2,3-dibromosuccinate–
(
R,
R)-2,3-dibromosuccinic acid–water (2/1/1/2)
top
Crystal data top
C8H12N+·0.5C4H2Br2O42−·0.5C4H4Br2O4·H2O | F(000) = 824 |
Mr = 415.07 | Dx = 1.705 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 39 reflections |
a = 12.609 (2) Å | θ = 8.0–20.2° |
b = 13.235 (3) Å | µ = 5.03 mm−1 |
c = 9.689 (2) Å | T = 299 K |
V = 1616.8 (6) Å3 | Fragment, colourless |
Z = 4 | 0.40 × 0.30 × 0.14 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2529 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.075 |
φ and ω scans | θmax = 27.5°, θmin = 4.5° |
Absorption correction: numerical (HABITUS; Herrendorf & Bärnighausen, 1997) | h = −16→15 |
Tmin = 0.265, Tmax = 0.759 | k = −16→17 |
12294 measured reflections | l = −11→12 |
3652 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.059 | w = 1/[σ2(Fo2) + (0.0061P)2 + 4.8215P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.120 | (Δ/σ)max < 0.001 |
S = 1.21 | Δρmax = 0.65 e Å−3 |
3652 reflections | Δρmin = −0.60 e Å−3 |
181 parameters | Absolute structure: Flack (1983), 1550 Friedel pairs |
0 restraints | Absolute structure parameter: 0.00 (3) |
Primary atom site location: structure-invariant direct methods | |
Special details top
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 | x | y | z | Uiso*/Ueq | |
Br1 | 0.13275 (8) | 0.46912 (9) | 0.39939 (7) | 0.0718 (3) | |
O3 | 0.1973 (4) | −0.0311 (4) | 0.1058 (5) | 0.0488 (15) | |
H3 | 0.2391 | −0.0029 | 0.0338 | 0.059* | |
O4 | 0.0908 (4) | 0.1007 (4) | 0.0783 (6) | 0.0485 (14) | |
C3 | 0.1185 (6) | 0.0227 (5) | 0.1366 (6) | 0.0310 (15) | |
C4 | 0.0567 (5) | −0.0154 (6) | 0.2623 (6) | 0.0338 (16) | |
H4 | 0.0612 | −0.0893 | 0.2662 | 0.041* | |
O1 | 0.1979 (4) | 0.5360 (4) | 0.0837 (5) | 0.0462 (13) | |
C1 | 0.1186 (6) | 0.4810 (5) | 0.1150 (6) | 0.0316 (14) | |
O2 | 0.0919 (4) | 0.4059 (4) | 0.0548 (6) | 0.0461 (14) | |
C2 | 0.0560 (5) | 0.5188 (6) | 0.2401 (6) | 0.0319 (16) | |
H2 | 0.0688 | 0.5918 | 0.2358 | 0.038* | |
N1 | 0.2072 (4) | 0.2464 (5) | 0.9049 (5) | 0.0393 (12) | |
H1A | 0.2724 | 0.2510 | 0.8980 | 0.047* | |
H1B | 0.1816 | 0.3129 | 0.9384 | 0.047* | |
H1C | 0.1816 | 0.2088 | 0.9684 | 0.047* | |
C11 | 0.1695 (5) | 0.2197 (5) | 0.7626 (8) | 0.0377 (17) | |
H11 | 0.1841 | 0.1479 | 0.7475 | 0.045* | |
C10 | 0.0511 (5) | 0.2345 (6) | 0.7540 (7) | 0.0395 (17) | |
C9 | 0.0066 (9) | 0.3289 (7) | 0.7463 (11) | 0.066 (3) | |
H9 | 0.0495 | 0.3861 | 0.7482 | 0.079* | |
C5 | −0.0126 (8) | 0.1520 (7) | 0.7563 (11) | 0.064 (3) | |
H5 | 0.0173 | 0.0878 | 0.7598 | 0.077* | |
C8 | −0.1032 (10) | 0.3392 (10) | 0.7368 (12) | 0.084 (4) | |
H8 | −0.1333 | 0.4029 | 0.7272 | 0.100* | |
C6 | −0.1231 (10) | 0.1628 (10) | 0.7534 (12) | 0.088 (4) | |
H6 | −0.1746 | 0.1013 | 0.7617 | 0.105* | |
C7 | −0.1653 (7) | 0.2561 (13) | 0.7407 (11) | 0.088 (3) | |
H7 | −0.2385 | 0.2633 | 0.7342 | 0.106* | |
C12 | 0.2329 (6) | 0.2793 (7) | 0.6574 (9) | 0.057 (2) | |
H12A | 0.2181 | 0.2540 | 0.5666 | 0.069* | |
H12B | 0.3072 | 0.2721 | 0.6767 | 0.069* | |
H12C | 0.2136 | 0.3493 | 0.6624 | 0.069* | |
O5 | 0.0685 (3) | 0.7490 (5) | 0.0978 (5) | 0.0528 (12) | |
H5A | 0.0275 | 0.8026 | 0.0911 | 0.063* | |
H5B | 0.0278 | 0.7009 | 0.0712 | 0.063* | |
Br2 | 0.12994 (8) | 0.04180 (8) | 0.42145 (7) | 0.0578 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0415 (5) | 0.1352 (10) | 0.0386 (4) | 0.0213 (7) | −0.0113 (4) | 0.0044 (5) |
O3 | 0.041 (3) | 0.050 (3) | 0.056 (3) | 0.023 (3) | 0.024 (2) | 0.020 (3) |
O4 | 0.038 (3) | 0.049 (3) | 0.059 (3) | 0.014 (2) | 0.014 (3) | 0.020 (3) |
C3 | 0.026 (4) | 0.038 (4) | 0.029 (3) | −0.005 (3) | −0.001 (3) | 0.007 (3) |
C4 | 0.027 (3) | 0.043 (4) | 0.031 (3) | −0.006 (3) | −0.001 (3) | 0.002 (3) |
O1 | 0.035 (3) | 0.046 (3) | 0.057 (3) | −0.006 (2) | 0.016 (2) | −0.015 (3) |
C1 | 0.024 (3) | 0.038 (4) | 0.033 (3) | 0.005 (3) | −0.004 (3) | −0.007 (3) |
O2 | 0.039 (3) | 0.044 (3) | 0.055 (3) | −0.010 (2) | 0.015 (3) | −0.015 (3) |
C2 | 0.025 (3) | 0.044 (4) | 0.026 (3) | 0.000 (3) | −0.002 (2) | −0.003 (3) |
N1 | 0.034 (2) | 0.045 (3) | 0.039 (3) | 0.002 (3) | −0.004 (2) | −0.002 (3) |
C11 | 0.043 (4) | 0.026 (4) | 0.045 (4) | 0.003 (3) | −0.005 (3) | −0.003 (3) |
C10 | 0.044 (4) | 0.038 (5) | 0.036 (4) | 0.000 (4) | −0.005 (3) | 0.001 (4) |
C9 | 0.057 (6) | 0.055 (6) | 0.086 (7) | 0.000 (5) | −0.006 (6) | 0.015 (6) |
C5 | 0.053 (6) | 0.052 (5) | 0.086 (7) | −0.015 (4) | −0.013 (5) | −0.003 (5) |
C8 | 0.077 (9) | 0.093 (9) | 0.081 (7) | 0.029 (7) | −0.015 (7) | 0.016 (7) |
C6 | 0.056 (7) | 0.107 (9) | 0.101 (8) | −0.041 (7) | 0.001 (7) | −0.014 (7) |
C7 | 0.050 (5) | 0.129 (10) | 0.085 (7) | 0.017 (9) | −0.017 (5) | 0.009 (10) |
C12 | 0.058 (5) | 0.068 (7) | 0.046 (5) | −0.008 (4) | 0.001 (4) | 0.012 (4) |
O5 | 0.038 (2) | 0.040 (2) | 0.080 (4) | 0.004 (3) | −0.017 (2) | −0.004 (4) |
Br2 | 0.0392 (4) | 0.0955 (7) | 0.0389 (4) | −0.0126 (5) | −0.0101 (3) | −0.0114 (4) |
Geometric parameters (Å, º) top
C1—C2 | 1.530 (9) | C11—C12 | 1.516 (10) |
C1—O1 | 1.273 (9) | C11—H11 | 0.9800 |
C1—O2 | 1.201 (8) | C10—C5 | 1.356 (11) |
C2—C2i | 1.497 (13) | C10—C9 | 1.372 (12) |
C2—H2 | 0.9817 | C9—C8 | 1.393 (15) |
C2—Br1 | 1.936 (6) | C9—H9 | 0.9300 |
C3—O3 | 1.258 (8) | C5—C6 | 1.401 (17) |
C3—O4 | 1.229 (8) | C5—H5 | 0.9300 |
C3—C4 | 1.531 (8) | C8—C7 | 1.351 (16) |
O3—H3 | 0.9517 | C8—H8 | 0.9300 |
C4—C4ii | 1.487 (13) | C6—C7 | 1.350 (16) |
C4—Br2 | 1.950 (7) | C6—H6 | 1.0437 |
C4—H4 | 0.9800 | C7—H7 | 0.9300 |
N1—C11 | 1.500 (8) | C12—H12A | 0.9601 |
N1—H1A | 0.8265 | C12—H12B | 0.9600 |
N1—H1B | 0.9934 | C12—H12C | 0.9600 |
N1—H1C | 0.8541 | O5—H5A | 0.8801 |
C11—C10 | 1.508 (9) | O5—H5B | 0.8569 |
| | | |
C3—O3—H3 | 112.9 | N1—C11—H11 | 107.8 |
O4—C3—O3 | 126.3 (6) | C10—C11—H11 | 107.7 |
O4—C3—C4 | 119.9 (6) | C12—C11—H11 | 107.8 |
O3—C3—C4 | 113.8 (6) | C5—C10—C9 | 119.5 (7) |
C4ii—C4—C3 | 113.5 (5) | C5—C10—C11 | 118.8 (8) |
C4ii—C4—Br2 | 110.4 (4) | C9—C10—C11 | 121.7 (8) |
C3—C4—Br2 | 105.1 (4) | C10—C9—C8 | 119.9 (10) |
C4ii—C4—H4 | 109.3 | C10—C9—H9 | 120.1 |
C3—C4—H4 | 109.3 | C8—C9—H9 | 120.0 |
Br2—C4—H4 | 109.3 | C10—C5—C6 | 120.5 (10) |
O2—C1—O1 | 125.3 (7) | C10—C5—H5 | 119.8 |
O2—C1—C2 | 120.7 (6) | C6—C5—H5 | 119.8 |
O1—C1—C2 | 114.0 (6) | C7—C8—C9 | 119.7 (10) |
C2i—C2—C1 | 112.2 (5) | C7—C8—H8 | 120.3 |
C2i—C2—Br1 | 111.0 (4) | C9—C8—H8 | 120.0 |
C1—C2—Br1 | 105.2 (4) | C7—C6—C5 | 119.1 (10) |
C2i—C2—H2 | 118.8 | C7—C6—H6 | 118.4 |
C1—C2—H2 | 101.7 | C5—C6—H6 | 122.5 |
Br1—C2—H2 | 106.6 | C6—C7—C8 | 121.2 (9) |
C11—N1—H1A | 105.0 | C6—C7—H7 | 119.4 |
C11—N1—H1B | 113.9 | C8—C7—H7 | 119.3 |
H1A—N1—H1B | 106.5 | C11—C12—H12A | 109.4 |
C11—N1—H1C | 113.9 | C11—C12—H12B | 109.4 |
H1A—N1—H1C | 118.6 | H12A—C12—H12B | 109.5 |
H1B—N1—H1C | 99.1 | C11—C12—H12C | 109.6 |
N1—C11—C10 | 109.5 (6) | H12A—C12—H12C | 109.5 |
N1—C11—C12 | 109.1 (6) | H12B—C12—H12C | 109.5 |
C10—C11—C12 | 114.7 (6) | H5A—O5—H5B | 102.9 |
Symmetry codes: (i) −x, −y+1, z; (ii) −x, −y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1iii | 0.95 | 1.48 | 2.431 (6) | 177 |
N1—H1A···O5iv | 0.83 | 2.01 | 2.828 (6) | 172 |
N1—H1B···O2v | 0.99 | 2.02 | 2.947 (8) | 155 |
N1—H1C···O4v | 0.85 | 2.12 | 2.948 (8) | 164 |
O5—H5A···O4i | 0.88 | 1.97 | 2.833 (8) | 167 |
O5—H5B···O2i | 0.86 | 2.07 | 2.910 (8) | 165 |
Symmetry codes: (i) −x, −y+1, z; (iii) −x+1/2, y−1/2, −z; (iv) −x+1/2, y−1/2, −z+1; (v) x, y, z+1. |