organic compounds
Bis(2-bromoethyl)ammonium bromide
aSchool of Chemistry, Molecular Sciences Institute, University of the Witwatersrand, Private Bag 3, Wits 2050, Johannesburg, South Africa
*Correspondence e-mail: alvaro.desousa@wits.ac.za
The title salt, C4H10Br2N+·Br−, crystallizes with four cations and four anions in the In the crystal, the bis(2-bromoethyl)ammonium cations and bromide anions are linked into chains by N—H⋯Br hydrogen bonds describing a binary C21(4) motif along [010]. Each of these chains is formed by a unique cation and anion pair. The ammonium cations occur in the less preferred anti conformation, characterized by different NCCBr torsion angles. Adjacent chains are linked by weak C—H⋯Br interactions, forming a three-dimensional network. The crystal studied was a pseudo-merohedral twin with twin ratio 0.640 (2):0.360 (2).
Related literature
For structures of related 2-haloethylammonium salts, see: Bojan et al. (2008); Briggs et al. (2004); Fischer et al. (1994); Kane et al. (1992); Kumar et al. (1998). For graph-set analysis, see: Bernstein et al. (1995). For the preparation of N-bis(2-bromoethylamine) hydrobromide, see: Pettit et al. (1964).
Experimental
Crystal data
|
|
Data collection: APEX2 (Bruker, 2005); cell APEX2 (Bruker, 2005); data reduction: SAINT-NT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON.
Supporting information
https://doi.org/10.1107/S1600536812033417/lr2074sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812033417/lr2074Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812033417/lr2074Isup3.cml
N-Bis(2-bromoethylamine) hydrobromide was prepared as reported by Pettit et al. (1964). Diethanolamine (12 g, 0.114 mol) was added, with cooling, to 100 mL of 48% HBr. The reaction vessel was fitted with a Vigreaux column and Dean-Stark apparatus and the solution heated collecting approximately 70 mL of water through azeotropic distillation. The remaining HBr was removed under reduced pressure to yield viscous orange oil that crystallized upon cooling.
1H(D2O, 300 MHz) 3.342 (4H, t, CH2NH), 3.992 (4H, t,CH2Br).
Crystals of the title compound seem to be inherently pseudo-merohedrally twinned as several recrystallizations led to twinned crystals. The pseudo-merohedral twin is approximately described by the
[-1.00 0.00 0.00 0.00 -1.00 0.00 1.00 0.00 1.00]. Hydrogen atoms were visible in the difference map and those bonded to carbon atoms were positioned geometrically and allowed for as riding atoms with C—H = 0.99 Å (CH2) and N—H = 0.92 Å (NH2). The coordinates of hydrogen atoms involved in hydrogen bonding were refined freely. During the refinements the Uiso(H) values were set at 1.2Ueq of the parent atom.Conformational analysis of 2-fluoroethylammonium hydrochloride compounds indicate gauche relationships between C—F and C—N bonds are inevitably preferred (Briggs et al., 2004). Stabilization of related syn conformers is attributed to weak stereoelectronic
and/or favourable intramolecular F···H—N+ hydrogen bonding interactions. Syn conformers exhibiting gauche relationships have also been observed in metal complexes (Kumar et al., 1998) and adducts (Kane et al., 1992) of these compounds. However, the anti conformation has been observed in the solid state for a N-alkylated derivative (Bojan et al., 2008) and in 2-chloroethylammonium hydrochloride (Fischer et al., 1994). The latter structure shows pairs of anti bis(2-chloroethyl)ammonium cations are linked via N—H···Cl hydrogen bonds to a syn cation to form chains along (1 0 0). In the solid state structure of the title compound (I), only anti conformations of bis(2-bromoethyl) ammonium cations (Figure 1) are observed, that are characterised by different NCCBr torsion angles (Table 1). Discreet intermolecular N—H···Br hydrogen bonding interactions (Table 2) mimic N-H···Cl interactions of 2-haloethylammonium compounds (Briggs et al., 2004, Fischer et al., 1994), and link cations into staggered chains along the b-axis, to define a binary C21(4) motif (Bernstein et al., 1995). Weak van der Waals C—H···Br interactions link 2-bromoethylammonium cations into layers parallel to the ac plane. The structure is also stabilized by several Br···Br interactions, the shortest being between Br3 and Br8 [3.559 (4) Å], and between Br2 and Br7 [3.594 (5) Å].For structures of related 2-haloethylammonium salts, see: Bojan et al. (2008); Briggs et al. (2004); Fischer et al. (1994); Kane et al. (1992); Kumar et al. (1998). For graph-set analysis, see: Bernstein et al. (1995). For the preparation of N-bis(2-bromoethylamine) hydrobromide, see: Pettit et al. (1964).
Data collection: APEX2 (Bruker, 2005); cell
APEX2 (Bruker, 2005); data reduction: SAINT-NT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).Fig. 1. The asymmetric unit of (1). Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. Chains along [010] arising from intermolecular N—H···Br hydrogen bonds. [symmetry codes: (i) -x+1, y+1/2,-z+1; (ii) x,y+1,z; (iii) -x+2, y-1/2,-z+1; (iv) -x+2, y+1/2, -z+1; (v) -x+1,y-1/2,-z; (vi) -x+1, y+1/2,-z; (vii) -x+2,y-1/2, -z; (viii) -x+2, y+1/2,-z] | |
Fig. 3. Weak C—H···Br interactions linking chains into a three-dimensional network parallel to (101). |
C4H10Br2N+·Br− | F(000) = 1168 |
Mr = 311.86 | Dx = 2.294 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1740 reflections |
a = 15.8861 (13) Å | θ = 2.7–28.0° |
b = 7.4891 (6) Å | µ = 13.32 mm−1 |
c = 17.1018 (18) Å | T = 173 K |
β = 117.450 (5)° | Needle, colourless |
V = 1805.6 (3) Å3 | 0.59 × 0.08 × 0.02 mm |
Z = 8 |
Bruker APEXII CCD area-detector diffractometer | 6819 independent reflections |
Radiation source: fine-focus sealed tube | 4058 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.143 |
phi and ω scans | θmax = 27.0°, θmin = 1.3° |
Absorption correction: integration [face indexed absorption corrections carried out with XPREP (Bruker, 2005)] | h = −19→20 |
Tmin = 0.083, Tmax = 0.552 | k = −9→9 |
10233 measured reflections | l = −21→8 |
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)] = 0.107 | H-atom parameters constrained |
wR(F2) = 0.285 | w = 1/[σ2(Fo2) + (0.1648P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
6819 reflections | Δρmax = 2.13 e Å−3 |
290 parameters | Δρmin = −2.01 e Å−3 |
85 restraints | Absolute structure: Flack (1983), 2573 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.15 (12) |
C4H10Br2N+·Br− | V = 1805.6 (3) Å3 |
Mr = 311.86 | Z = 8 |
Monoclinic, P21 | Mo Kα radiation |
a = 15.8861 (13) Å | µ = 13.32 mm−1 |
b = 7.4891 (6) Å | T = 173 K |
c = 17.1018 (18) Å | 0.59 × 0.08 × 0.02 mm |
β = 117.450 (5)° |
Bruker APEXII CCD area-detector diffractometer | 6819 independent reflections |
Absorption correction: integration [face indexed absorption corrections carried out with XPREP (Bruker, 2005)] | 4058 reflections with I > 2σ(I) |
Tmin = 0.083, Tmax = 0.552 | Rint = 0.143 |
10233 measured reflections |
R[F2 > 2σ(F2)] = 0.107 | H-atom parameters constrained |
wR(F2) = 0.285 | Δρmax = 2.13 e Å−3 |
S = 0.98 | Δρmin = −2.01 e Å−3 |
6819 reflections | Absolute structure: Flack (1983), 2573 Friedel pairs |
290 parameters | Absolute structure parameter: 0.15 (12) |
85 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
C1 | 0.890 (2) | 0.595 (5) | 0.623 (2) | 0.032 (8) | |
H1C | 0.8598 | 0.4761 | 0.6060 | 0.038* | |
H1D | 0.8621 | 0.6552 | 0.6580 | 0.038* | |
C2 | 0.868 (2) | 0.699 (5) | 0.5452 (19) | 0.023 (7) | |
H2C | 0.9002 | 0.8161 | 0.5628 | 0.028* | |
H2D | 0.7989 | 0.7205 | 0.5133 | 0.028* | |
C3 | 0.842 (3) | 0.666 (5) | 0.388 (2) | 0.032 (8) | |
H3C | 0.7739 | 0.6447 | 0.3672 | 0.038* | |
H3D | 0.8522 | 0.7949 | 0.3824 | 0.038* | |
C4 | 0.877 (3) | 0.559 (5) | 0.334 (2) | 0.038 (10) | |
H4C | 0.8756 | 0.4302 | 0.3461 | 0.046* | |
H4D | 0.9425 | 0.5935 | 0.3487 | 0.046* | |
N1 | 0.8992 (19) | 0.607 (4) | 0.4843 (16) | 0.024 (6) | |
H1A | 0.8926 | 0.4855 | 0.4877 | 0.029* | |
H1B | 0.9624 | 0.6305 | 0.5030 | 0.029* | |
Br1 | 1.0262 (4) | 0.5657 (7) | 0.6975 (3) | 0.0567 (14) | |
Br2 | 0.7909 (3) | 0.6111 (6) | 0.2100 (2) | 0.0343 (9) | |
C5 | 0.635 (2) | 0.016 (4) | 0.6613 (18) | 0.024 (7) | |
H5A | 0.6675 | −0.0672 | 0.6393 | 0.028* | |
H5B | 0.5687 | −0.0248 | 0.6399 | 0.028* | |
C6 | 0.636 (2) | 0.202 (4) | 0.6290 (19) | 0.024 (7) | |
H6A | 0.7028 | 0.2446 | 0.6549 | 0.029* | |
H6B | 0.6010 | 0.2825 | 0.6493 | 0.029* | |
C7 | 0.649 (3) | 0.109 (6) | 0.492 (2) | 0.041 (9) | |
H7A | 0.7174 | 0.1302 | 0.5296 | 0.049* | |
H7B | 0.6366 | −0.0201 | 0.4924 | 0.049* | |
C8 | 0.623 (2) | 0.165 (4) | 0.4031 (18) | 0.027 (7) | |
H8A | 0.6652 | 0.1042 | 0.3834 | 0.033* | |
H8B | 0.6350 | 0.2953 | 0.4036 | 0.033* | |
N2 | 0.5926 (19) | 0.211 (4) | 0.5289 (15) | 0.027 (7) | |
H2A | 0.5321 | 0.1649 | 0.5050 | 0.032* | |
H2B | 0.5880 | 0.3284 | 0.5119 | 0.032* | |
Br5 | 0.4962 (3) | 0.1204 (6) | 0.3201 (2) | 0.0408 (9) | |
Br6 | 0.7005 (3) | 0.0235 (6) | 0.7903 (2) | 0.0346 (9) | |
C9 | 0.273 (2) | 0.611 (5) | −0.1351 (19) | 0.029 (7) | |
H9A | 0.2123 | 0.6703 | −0.1729 | 0.034* | |
H9B | 0.2592 | 0.4882 | −0.1235 | 0.034* | |
C10 | 0.321 (2) | 0.710 (5) | −0.048 (2) | 0.039 (9) | |
H10A | 0.3297 | 0.8364 | −0.0594 | 0.047* | |
H10B | 0.2788 | 0.7064 | −0.0197 | 0.047* | |
C11 | 0.455 (3) | 0.690 (5) | 0.106 (2) | 0.034 (9) | |
H11A | 0.4765 | 0.8159 | 0.1101 | 0.040* | |
H11B | 0.4065 | 0.6839 | 0.1261 | 0.040* | |
C12 | 0.538 (3) | 0.574 (6) | 0.163 (2) | 0.046 (11) | |
H12A | 0.5926 | 0.5979 | 0.1510 | 0.055* | |
H12B | 0.5207 | 0.4463 | 0.1507 | 0.055* | |
N3 | 0.4142 (18) | 0.629 (4) | 0.0114 (15) | 0.023 (6) | |
H3A | 0.4564 | 0.6549 | −0.0098 | 0.028* | |
H3B | 0.4074 | 0.5064 | 0.0101 | 0.028* | |
Br8 | 0.5708 (3) | 0.6336 (6) | 0.2858 (2) | 0.0334 (9) | |
Br9 | 0.3459 (3) | 0.5968 (8) | −0.1998 (3) | 0.0546 (13) | |
C13 | 0.769 (3) | 0.542 (5) | −0.121 (2) | 0.037 (9) | |
H13A | 0.7071 | 0.6012 | −0.1541 | 0.045* | |
H13B | 0.7583 | 0.4202 | −0.1056 | 0.045* | |
C14 | 0.830 (2) | 0.647 (5) | −0.037 (2) | 0.031 (8) | |
H14A | 0.8405 | 0.7689 | −0.0532 | 0.037* | |
H14B | 0.7944 | 0.6584 | −0.0024 | 0.037* | |
C15 | 0.966 (3) | 0.625 (5) | 0.111 (2) | 0.035 (8) | |
H15A | 0.9812 | 0.7533 | 0.1129 | 0.042* | |
H15B | 0.9195 | 0.6104 | 0.1342 | 0.042* | |
C16 | 1.051 (3) | 0.525 (5) | 0.165 (2) | 0.038 (9) | |
H16A | 1.1015 | 0.5575 | 0.1491 | 0.046* | |
H16B | 1.0382 | 0.3959 | 0.1546 | 0.046* | |
N4 | 0.9227 (19) | 0.561 (4) | 0.0182 (16) | 0.026 (6) | |
H4A | 0.9634 | 0.5856 | −0.0051 | 0.031* | |
H4B | 0.9147 | 0.4394 | 0.0172 | 0.031* | |
Br11 | 1.0931 (3) | 0.5783 (5) | 0.2892 (2) | 0.0327 (10) | |
Br12 | 0.8319 (3) | 0.5275 (7) | −0.1957 (3) | 0.0483 (11) | |
Br3 | 0.6231 (2) | 0.6258 (6) | 0.5118 (2) | 0.0284 (8) | |
Br4 | 0.8830 (2) | 0.1738 (4) | 0.4877 (2) | 0.0282 (9) | |
Br7 | 0.3904 (2) | 0.1919 (5) | 0.0112 (2) | 0.0289 (9) | |
Br10 | 0.8945 (2) | 0.1288 (5) | 0.0195 (2) | 0.0284 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.033 (9) | 0.032 (9) | 0.032 (9) | 0.000 (5) | 0.017 (6) | −0.001 (5) |
C2 | 0.024 (8) | 0.021 (8) | 0.023 (8) | 0.003 (5) | 0.009 (5) | −0.002 (5) |
C3 | 0.030 (9) | 0.033 (10) | 0.033 (9) | 0.000 (5) | 0.015 (6) | 0.000 (5) |
C4 | 0.039 (11) | 0.038 (11) | 0.036 (10) | 0.000 (5) | 0.017 (6) | 0.000 (5) |
N1 | 0.032 (15) | 0.014 (13) | 0.034 (13) | −0.009 (12) | 0.022 (13) | −0.002 (13) |
Br1 | 0.042 (3) | 0.070 (4) | 0.044 (2) | −0.009 (2) | 0.008 (2) | 0.005 (2) |
Br2 | 0.0287 (19) | 0.041 (2) | 0.0319 (18) | 0.000 (2) | 0.0127 (16) | 0.005 (2) |
C5 | 0.025 (8) | 0.026 (8) | 0.022 (8) | 0.000 (5) | 0.013 (5) | 0.001 (5) |
C6 | 0.024 (8) | 0.025 (8) | 0.026 (8) | 0.001 (5) | 0.013 (5) | 0.001 (5) |
C7 | 0.042 (10) | 0.040 (10) | 0.041 (10) | 0.001 (5) | 0.020 (6) | −0.002 (5) |
C8 | 0.025 (8) | 0.029 (9) | 0.028 (8) | −0.001 (5) | 0.013 (5) | 0.000 (5) |
N2 | 0.032 (17) | 0.012 (12) | 0.019 (12) | −0.006 (12) | −0.003 (12) | −0.003 (11) |
Br5 | 0.034 (2) | 0.037 (2) | 0.049 (2) | 0.004 (2) | 0.0167 (18) | −0.005 (2) |
Br6 | 0.032 (2) | 0.040 (2) | 0.0327 (19) | 0.0076 (17) | 0.0154 (17) | 0.0036 (17) |
C9 | 0.026 (8) | 0.027 (8) | 0.031 (8) | −0.001 (5) | 0.011 (5) | −0.001 (5) |
C10 | 0.012 (17) | 0.04 (2) | 0.06 (2) | 0.003 (16) | 0.008 (17) | −0.005 (19) |
C11 | 0.05 (3) | 0.017 (15) | 0.05 (2) | −0.006 (16) | 0.04 (2) | 0.001 (16) |
C12 | 0.045 (11) | 0.047 (12) | 0.045 (11) | 0.002 (5) | 0.022 (7) | −0.002 (5) |
N3 | 0.023 (7) | 0.022 (7) | 0.024 (7) | −0.001 (5) | 0.011 (5) | −0.002 (5) |
Br8 | 0.0307 (19) | 0.037 (2) | 0.0353 (18) | −0.0017 (19) | 0.0178 (16) | −0.0001 (19) |
Br9 | 0.055 (3) | 0.070 (3) | 0.039 (2) | −0.010 (3) | 0.022 (2) | −0.006 (2) |
C13 | 0.037 (10) | 0.037 (10) | 0.037 (10) | 0.000 (5) | 0.016 (6) | 0.003 (5) |
C14 | 0.027 (18) | 0.022 (18) | 0.032 (17) | 0.002 (15) | 0.003 (15) | −0.011 (15) |
C15 | 0.034 (9) | 0.034 (9) | 0.035 (9) | 0.003 (5) | 0.014 (6) | −0.002 (5) |
C16 | 0.036 (10) | 0.038 (10) | 0.038 (10) | 0.004 (5) | 0.016 (6) | −0.003 (5) |
N4 | 0.023 (14) | 0.032 (16) | 0.019 (12) | −0.017 (12) | 0.007 (12) | −0.005 (11) |
Br11 | 0.026 (2) | 0.041 (2) | 0.0324 (19) | −0.0030 (17) | 0.0152 (17) | 0.0005 (16) |
Br12 | 0.054 (3) | 0.054 (3) | 0.041 (2) | −0.018 (2) | 0.025 (2) | −0.009 (2) |
Br3 | 0.0292 (18) | 0.0185 (18) | 0.0437 (18) | −0.0031 (16) | 0.0221 (15) | −0.0011 (17) |
Br4 | 0.0198 (17) | 0.023 (2) | 0.047 (2) | 0.0011 (13) | 0.0193 (16) | 0.0033 (15) |
Br7 | 0.0259 (19) | 0.0210 (19) | 0.046 (2) | −0.0032 (14) | 0.0216 (17) | −0.0019 (15) |
Br10 | 0.0318 (19) | 0.0171 (17) | 0.0480 (19) | −0.0017 (16) | 0.0284 (17) | 0.0005 (17) |
C1—C2 | 1.44 (5) | C9—C10 | 1.51 (5) |
C1—Br1 | 1.96 (3) | C9—Br9 | 1.93 (3) |
C1—H1C | 0.9900 | C9—H9A | 0.9900 |
C1—H1D | 0.9900 | C9—H9B | 0.9900 |
C2—N1 | 1.51 (4) | C10—N3 | 1.49 (4) |
C2—H2C | 0.9900 | C10—H10A | 0.9900 |
C2—H2D | 0.9900 | C10—H10B | 0.9900 |
C3—C4 | 1.50 (5) | C11—C12 | 1.50 (5) |
C3—N1 | 1.53 (4) | C11—N3 | 1.51 (4) |
C3—H3C | 0.9900 | C11—H11A | 0.9900 |
C3—H3D | 0.9900 | C11—H11B | 0.9900 |
C4—Br2 | 1.96 (3) | C12—Br8 | 1.97 (4) |
C4—H4C | 0.9900 | C12—H12A | 0.9900 |
C4—H4D | 0.9900 | C12—H12B | 0.9900 |
N1—H1A | 0.9200 | N3—H3A | 0.9200 |
N1—H1B | 0.9200 | N3—H3B | 0.9200 |
C5—C6 | 1.50 (4) | C13—C14 | 1.53 (5) |
C5—Br6 | 1.96 (3) | C13—Br12 | 1.94 (4) |
C5—H5A | 0.9900 | C13—H13A | 0.9900 |
C5—H5B | 0.9900 | C13—H13B | 0.9900 |
C6—N2 | 1.52 (4) | C14—N4 | 1.48 (4) |
C6—H6A | 0.9900 | C14—H14A | 0.9900 |
C6—H6B | 0.9900 | C14—H14B | 0.9900 |
C7—C8 | 1.44 (5) | C15—C16 | 1.45 (5) |
C7—N2 | 1.51 (5) | C15—N4 | 1.49 (4) |
C7—H7A | 0.9900 | C15—H15A | 0.9900 |
C7—H7B | 0.9900 | C15—H15B | 0.9900 |
C8—Br5 | 1.89 (3) | C16—Br11 | 1.95 (3) |
C8—H8A | 0.9900 | C16—H16A | 0.9900 |
C8—H8B | 0.9900 | C16—H16B | 0.9900 |
N2—H2A | 0.9200 | N4—H4A | 0.9200 |
N2—H2B | 0.9200 | N4—H4B | 0.9200 |
C2—C1—Br1 | 112 (2) | C10—C9—Br9 | 116 (2) |
C2—C1—H1C | 109.2 | C10—C9—H9A | 108.4 |
Br1—C1—H1C | 109.2 | Br9—C9—H9A | 108.4 |
C2—C1—H1D | 109.2 | C10—C9—H9B | 108.4 |
Br1—C1—H1D | 109.2 | Br9—C9—H9B | 108.4 |
H1C—C1—H1D | 107.9 | H9A—C9—H9B | 107.4 |
C1—C2—N1 | 112 (3) | N3—C10—C9 | 111 (3) |
C1—C2—H2C | 109.1 | N3—C10—H10A | 109.4 |
N1—C2—H2C | 109.1 | C9—C10—H10A | 109.4 |
C1—C2—H2D | 109.1 | N3—C10—H10B | 109.4 |
N1—C2—H2D | 109.1 | C9—C10—H10B | 109.4 |
H2C—C2—H2D | 107.8 | H10A—C10—H10B | 108.0 |
C4—C3—N1 | 108 (3) | C12—C11—N3 | 110 (3) |
C4—C3—H3C | 110.1 | C12—C11—H11A | 109.8 |
N1—C3—H3C | 110.1 | N3—C11—H11A | 109.8 |
C4—C3—H3D | 110.1 | C12—C11—H11B | 109.8 |
N1—C3—H3D | 110.1 | N3—C11—H11B | 109.8 |
H3C—C3—H3D | 108.4 | H11A—C11—H11B | 108.2 |
C3—C4—Br2 | 107 (2) | C11—C12—Br8 | 106 (3) |
C3—C4—H4C | 110.3 | C11—C12—H12A | 110.5 |
Br2—C4—H4C | 110.3 | Br8—C12—H12A | 110.5 |
C3—C4—H4D | 110.3 | C11—C12—H12B | 110.5 |
Br2—C4—H4D | 110.3 | Br8—C12—H12B | 110.5 |
H4C—C4—H4D | 108.6 | H12A—C12—H12B | 108.6 |
C2—N1—C3 | 113 (3) | C10—N3—C11 | 114 (3) |
C2—N1—H1A | 108.9 | C10—N3—H3A | 108.7 |
C3—N1—H1A | 108.9 | C11—N3—H3A | 108.7 |
C2—N1—H1B | 108.9 | C10—N3—H3B | 108.7 |
C3—N1—H1B | 108.9 | C11—N3—H3B | 108.7 |
H1A—N1—H1B | 107.8 | H3A—N3—H3B | 107.6 |
C6—C5—Br6 | 107 (2) | C14—C13—Br12 | 111 (3) |
C6—C5—H5A | 110.2 | C14—C13—H13A | 109.4 |
Br6—C5—H5A | 110.2 | Br12—C13—H13A | 109.4 |
C6—C5—H5B | 110.2 | C14—C13—H13B | 109.4 |
Br6—C5—H5B | 110.2 | Br12—C13—H13B | 109.4 |
H5A—C5—H5B | 108.5 | H13A—C13—H13B | 108.0 |
C5—C6—N2 | 112 (3) | N4—C14—C13 | 113 (3) |
C5—C6—H6A | 109.2 | N4—C14—H14A | 109.1 |
N2—C6—H6A | 109.2 | C13—C14—H14A | 109.1 |
C5—C6—H6B | 109.2 | N4—C14—H14B | 109.1 |
N2—C6—H6B | 109.2 | C13—C14—H14B | 109.1 |
H6A—C6—H6B | 107.9 | H14A—C14—H14B | 107.8 |
C8—C7—N2 | 111 (3) | C16—C15—N4 | 111 (3) |
C8—C7—H7A | 109.4 | C16—C15—H15A | 109.5 |
N2—C7—H7A | 109.4 | N4—C15—H15A | 109.5 |
C8—C7—H7B | 109.4 | C16—C15—H15B | 109.5 |
N2—C7—H7B | 109.4 | N4—C15—H15B | 109.5 |
H7A—C7—H7B | 108.0 | H15A—C15—H15B | 108.1 |
C7—C8—Br5 | 115 (2) | C15—C16—Br11 | 110 (3) |
C7—C8—H8A | 108.5 | C15—C16—H16A | 109.6 |
Br5—C8—H8A | 108.5 | Br11—C16—H16A | 109.6 |
C7—C8—H8B | 108.5 | C15—C16—H16B | 109.6 |
Br5—C8—H8B | 108.5 | Br11—C16—H16B | 109.6 |
H8A—C8—H8B | 107.5 | H16A—C16—H16B | 108.1 |
C7—N2—C6 | 113 (3) | C14—N4—C15 | 112 (3) |
C7—N2—H2A | 108.9 | C14—N4—H4A | 109.2 |
C6—N2—H2A | 108.9 | C15—N4—H4A | 109.2 |
C7—N2—H2B | 108.9 | C14—N4—H4B | 109.2 |
C6—N2—H2B | 108.9 | C15—N4—H4B | 109.2 |
H2A—N2—H2B | 107.7 | H4A—N4—H4B | 107.9 |
Br1—C1—C2—N1 | 65 (3) | Br9—C9—C10—N3 | −57 (4) |
N1—C3—C4—Br2 | 172 (2) | N3—C11—C12—Br8 | −169 (2) |
C1—C2—N1—C3 | 155 (3) | C9—C10—N3—C11 | −167 (3) |
C4—C3—N1—C2 | −177 (3) | C12—C11—N3—C10 | 168 (3) |
Br6—C5—C6—N2 | 176 (2) | Br12—C13—C14—N4 | −62 (3) |
N2—C7—C8—Br5 | −63 (4) | N4—C15—C16—Br11 | −169 (2) |
C8—C7—N2—C6 | −162 (3) | C13—C14—N4—C15 | −160 (3) |
C5—C6—N2—C7 | −66 (4) | C16—C15—N4—C14 | 174 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br4 | 0.92 | 2.34 | 3.26 (3) | 175 |
N1—H1B···Br4i | 0.92 | 2.41 | 3.31 (3) | 165 |
N2—H2B···Br3 | 0.92 | 2.30 | 3.18 (3) | 161 |
N2—H2A···Br3ii | 0.92 | 2.37 | 3.23 (3) | 157 |
N3—H3B···Br7 | 0.92 | 2.37 | 3.29 (3) | 178 |
N3—H3A···Br7iii | 0.92 | 2.46 | 3.33 (3) | 159 |
N4—H4B···Br10 | 0.92 | 2.35 | 3.27 (3) | 178 |
N4—H4A···Br10iv | 0.92 | 2.40 | 3.29 (3) | 162 |
C1—H1D···Br12v | 1.00 | 2.92 | 3.66 (3) | 131 |
C2—H2C···Br4vi | 0.99 | 2.93 | 3.73 (4) | 138 |
C2—H2D···Br3 | 0.99 | 2.87 | 3.70 (4) | 143 |
C3—H3C···Br8 | 0.98 | 2.87 | 3.84 (5) | 170 |
C7—H7B···Br3vii | 0.99 | 2.69 | 3.68 (5) | 173 |
C9—H9A···Br1viii | 0.99 | 2.87 | 3.65 (3) | 137 |
C10—H10A···Br7vi | 0.99 | 2.90 | 3.77 (4) | 148 |
C10—H10B···Br10iii | 0.99 | 2.82 | 3.72 (4) | 153 |
C12—H12A···Br2 | 1.00 | 2.83 | 3.73 (5) | 150 |
C14—H14A···Br10vi | 0.99 | 2.93 | 3.75 (4) | 142 |
C14—H14B···Br7iii | 0.99 | 2.88 | 3.74 (4) | 145 |
C15—H15B···Br2 | 0.99 | 2.88 | 3.87 (5) | 173 |
C16—H16A···Br6i | 0.99 | 2.83 | 3.66 (5) | 141 |
Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z; (iv) −x+2, y+1/2, −z; (v) x, y, z+1; (vi) x, y+1, z; (vii) x, y−1, z; (viii) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C4H10Br2N+·Br− |
Mr | 311.86 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 173 |
a, b, c (Å) | 15.8861 (13), 7.4891 (6), 17.1018 (18) |
β (°) | 117.450 (5) |
V (Å3) | 1805.6 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 13.32 |
Crystal size (mm) | 0.59 × 0.08 × 0.02 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Integration [face indexed absorption corrections carried out with XPREP (Bruker, 2005)] |
Tmin, Tmax | 0.083, 0.552 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10233, 6819, 4058 |
Rint | 0.143 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.107, 0.285, 0.98 |
No. of reflections | 6819 |
No. of parameters | 290 |
No. of restraints | 85 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.13, −2.01 |
Absolute structure | Flack (1983), 2573 Friedel pairs |
Absolute structure parameter | 0.15 (12) |
Computer programs: APEX2 (Bruker, 2005), SAINT-NT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Br1—C1—C2—N1 | 65 (3) | Br9—C9—C10—N3 | −57 (4) |
N1—C3—C4—Br2 | 172 (2) | N3—C11—C12—Br8 | −169 (2) |
Br6—C5—C6—N2 | 176 (2) | Br12—C13—C14—N4 | −62 (3) |
N2—C7—C8—Br5 | −63 (4) | N4—C15—C16—Br11 | −169 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br4 | 0.92 | 2.34 | 3.26 (3) | 174.6 |
N1—H1B···Br4i | 0.92 | 2.41 | 3.31 (3) | 164.9 |
N2—H2B···Br3 | 0.92 | 2.30 | 3.18 (3) | 161.0 |
N2—H2A···Br3ii | 0.92 | 2.37 | 3.23 (3) | 156.5 |
N3—H3B···Br7 | 0.92 | 2.37 | 3.29 (3) | 178.2 |
N3—H3A···Br7iii | 0.92 | 2.46 | 3.33 (3) | 158.9 |
N4—H4B···Br10 | 0.92 | 2.35 | 3.27 (3) | 178.0 |
N4—H4A···Br10iv | 0.92 | 2.40 | 3.29 (3) | 162.0 |
C1—H1D···Br12v | 1.00 | 2.92 | 3.66 (3) | 131 |
C2—H2C···Br4vi | 0.99 | 2.93 | 3.73 (4) | 138 |
C2—H2D···Br3 | 0.99 | 2.87 | 3.70 (4) | 143 |
C3—H3C···Br8 | 0.98 | 2.87 | 3.84 (5) | 170 |
C7—H7B···Br3vii | 0.99 | 2.69 | 3.68 (5) | 173 |
C9—H9A···Br1viii | 0.99 | 2.87 | 3.65 (3) | 137 |
C10—H10A···Br7vi | 0.99 | 2.90 | 3.77 (4) | 148 |
C10—H10B···Br10iii | 0.99 | 2.82 | 3.72 (4) | 153 |
C12—H12A···Br2 | 1.00 | 2.83 | 3.73 (5) | 150 |
C14—H14A···Br10vi | 0.99 | 2.93 | 3.75 (4) | 142 |
C14—H14B···Br7iii | 0.99 | 2.88 | 3.74 (4) | 145 |
C15—H15B···Br2 | 0.99 | 2.88 | 3.87 (5) | 173 |
C16—H16A···Br6i | 0.99 | 2.83 | 3.66 (5) | 141 |
Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z; (iv) −x+2, y+1/2, −z; (v) x, y, z+1; (vi) x, y+1, z; (vii) x, y−1, z; (viii) x−1, y, z−1. |
Acknowledgements
This work was supported by the National Research Foundation (South Africa).
References
Bernstein, J., Davis, R. E., Shinoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bojan, R. V., Varga, R. A. & Silvestru, C. (2008). Acta Cryst. E64, o86. Web of Science CSD CrossRef IUCr Journals Google Scholar
Briggs, C. R. S., Allen, M. J., O'Hagan, D., Tozer, D. J., Slawin, A. M. Z., Goeta, A. E. & Howard, J. A. K. (2004). Org. Biomol. Chem. 2, 732–740. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (2005). APEX2 and SAINT-NT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Fischer, A., Neda, I., Jones, P. G. & Schmutzler, R. (1994). Phosphorus Sulfur Silicon Relat. Elem. 91, 103–127. CrossRef CAS Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kane, C. J., Long, R., Pettit, W. E., Breneman, G. L. & Pettit, G. R. (1992). Acta Cryst. C48, 1490–1491. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Kumar, J. S., Singh, A. K., Yang, J. & Drake, J. E. (1998). J. Coord. Chem. 44, 217–223. Web of Science CrossRef CAS Google Scholar
Pettit, G. R., Chamberland, M. R., Blonda, D. S. & Vickers, M. A. (1964). Can. J. Chem. 42, 1699–1706. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Conformational analysis of 2-fluoroethylammonium hydrochloride compounds indicate gauche relationships between C—F and C—N bonds are inevitably preferred (Briggs et al., 2004). Stabilization of related syn conformers is attributed to weak stereoelectronic gauche effect and/or favourable intramolecular F···H—N+ hydrogen bonding interactions. Syn conformers exhibiting gauche relationships have also been observed in metal complexes (Kumar et al., 1998) and adducts (Kane et al., 1992) of these compounds. However, the anti conformation has been observed in the solid state for a N-alkylated derivative (Bojan et al., 2008) and in 2-chloroethylammonium hydrochloride (Fischer et al., 1994). The latter structure shows pairs of anti bis(2-chloroethyl)ammonium cations are linked via N—H···Cl hydrogen bonds to a syn cation to form chains along (1 0 0). In the solid state structure of the title compound (I), only anti conformations of bis(2-bromoethyl) ammonium cations (Figure 1) are observed, that are characterised by different NCCBr torsion angles (Table 1). Discreet intermolecular N—H···Br hydrogen bonding interactions (Table 2) mimic N-H···Cl interactions of 2-haloethylammonium compounds (Briggs et al., 2004, Fischer et al., 1994), and link cations into staggered chains along the b-axis, to define a binary C21(4) motif (Bernstein et al., 1995). Weak van der Waals C—H···Br interactions link 2-bromoethylammonium cations into layers parallel to the ac plane. The structure is also stabilized by several Br···Br interactions, the shortest being between Br3 and Br8 [3.559 (4) Å], and between Br2 and Br7 [3.594 (5) Å].