2 Phenyl­ethyl­ammonium bromide

organic papers

Acta Cryst.(2007). E63, o221–o223 doi:10.1107/S1600536806051488 Melanie Rademeyer _C

8H12N+Br

o221

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

2-Phenylethylammonium bromide

Melanie Rademeyer

School of Chemistry, University of KwaZulu-Natal, Pietermaritzburg Campus, Private Bag X01, Scottsville 3209, South Africa

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 295 K

Mean(C–C) = 0.005 A˚ Rfactor = 0.032 wRfactor = 0.059

Data-to-parameter ratio = 32.5

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 7 November 2006 Accepted 28 November 2006

#2007 International Union of Crystallography All rights reserved

2-Phenylethylammonium bromide, C8H12N +

Br, adopts a layered structure consisting of alternating hydrophilic and hydrophobic regions. The ammonium groups and bromide anions interact through N+—H Br hydrogen bonds, forming transoid one-dimensional ladders, which are further linked by electrostatic N+ Br interactions into two-dimensional sheets.

Comment

The crystal structure of 2-phenylethylammonium bromide, (I) (Fig. 1), was determined as part of an ongoing study of the structural characteristics and hydrogen-bonding interactions of organic salts consisting of arylammonium cations and halide anions. The unit-cell parameters of (I) have been reported previously by Tsoucaris (1961), but fractional coordinates were not given in that report. The crystal structure of the analogous chloride salt has also been described previously (Tsoucaris, 1961; Hornet al., 1990), and (I) is isostructural to it. Compared to the unit-cell parameters of the chloride salt [a

= 4.603 (1) A˚ , b= 5.906 (1) A˚ , c= 32.360 (1) A˚ ; Horn et al., 1990], the bparameter in (I) is slightly elongated and the c

parameter is slightly shortened. As expected, the unit-cell volume of (I) is larger than that of the chloride salt [880 (1) A˚3].

The crystal structure of (I) consists of layers lying parallel to theabplane, with alternating hydrophobic regions (containing the ammonium groups and bromide anions) and hydrophilic regions (containing the rest of the organic cations) (Fig. 2). In the organic cation, the ethylammonium chain is close to a fully extended all-transconformation, with the N1—C1—C2—C3 torsion angle equal to 173.6 (2)_{. The benzene rings pack in a}

non-interdigitated fashion, with the ring plane forming a dihedral angle of 55.68 (7)to theabplane. In this region, the shortest centroid-to-centroid distance between benzene rings is 5.590 (2) A˚ .

charge-assisted hydrogen bonds to three different bromide anions, with N+ Brdistances ranging from 3.3186 (19) A˚ to 3.370 (2) A˚ . These interactions define atransoid one-dimen-sional hydrogen-bonded ladder (Fig. 2). A fourth, longer N+ Brcontact [N1 Br1i= 3.459 (2) A˚ ; symmetry code: (i)

1 + x, y, z] links these hydrogen-bonded ladders into corrugated two-dimensional sheets (Fig. 3). A similar sheet structure has been reported for ethylammonium bromide (Jellinek, 1958; Bond, 2005). In both that structure and (I), adjacent sheets are stacked in a parallel offset fashion, with Br N+ Brangles close to 90_.

Experimental

2-Phenylethylammonium bromide was synthesized by dropwise addition of HBr (8.2 ml, 72.9 mmol, 48%, Fluka) to a solution of 2-phenylethylamine (5.3 ml, 42.2 mmol, Aldrich, 99%) in chloroform (30 ml). The resulting precipitate was filtered off. The crystal used for this structure determination was crystallized from an aqueous solu-tion of 2-phenylethylammonium bromide (0.500 g, 2.47 mmol) and

CoBr2(Aldrich, 99%, 0.271 g, 1.24 mmol) (2:1 molar ratio), open to the atmosphere, at room temperature over a period of eight weeks.

Crystal data

C8H12N+Br

Mr= 202.10

Orthorhombic,P212121

a= 4.6871 (4) A˚

b= 6.1419 (4) A˚

c= 32.047 (2) A˚

V= 922.56 (12) A˚3

Z= 4

Dx= 1.455 Mg m

3

MoKradiation

= 4.39 mm1

T= 295 (2) K Block, colourless 0.300.200.20 mm

Data collection

Oxford Diffraction Excalibur2 CCD diffractometer

!scans

Absorption correction: multi-scan (Blessing, 1995)

Tmin= 0.340,Tmax= 0.419

9448 measured reflections 2958 independent reflections 2063 reflections withI> 2(I)

Rint= 0.027 max= 32.0

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.032

wR(F2_{) = 0.059}

S= 1.06 2958 reflections 91 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0257P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.003

max= 0.46 e A˚

3

min=0.86 e A˚

3

Absolute structure: Flack (1983), 1047 Friedel pairs

Flack parameter: 0.029 (15)

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N1—H1A Br1 0.89 2.49 3.360 (2) 166 N1—H1B Br1i

0.89 2.46 3.3186 (19) 162 N1—H1C Br1ii

0.89 2.51 3.370 (2) 163

Symmetry codes: (i)xþ1;y1 2;zþ

3

2; (ii)xþ1;yþ 1 2;zþ

3 2.

organic papers

o222

Melanie Rademeyer _C

[image:2.610.315.563.67.288.2]

8H12N+Br Acta Cryst.(2007). E63, o221–o223

Figure 1

[image:2.610.99.240.74.302.2]

The molecular structure of (I), showing displacement ellipsoids at the 50% probability level for non-H atoms.

Figure 2

View of (I) down theaaxis, showing layers lying parallel to theabplane and N+—H Brhydrogen bonds (blue dotted lines) forming extended one-dimensional ladders.

Figure 3

View of (I) down thecaxis, showing a single two-dimensional sheet in the

[image:2.610.59.279.349.458.2]

H atoms were placed in calculated positions, with methylene C—H = 0.97 A˚ , aromatic C—H = 0.93 A˚, and N—H = 0.89 A˚, and were refined using a riding model, withUiso(H) = 1.2Ueq(C) or 1.5Ueq(N). Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED(Oxford Diffraction, 2006); data reduc-tion:CrysAlis RED; program(s) used to solve structure:SHELXS97

(Sheldrick, 1997); program(s) used to refine structure:SHELXL97

(Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows

(Farrugia, 1997) andMercury(Brunoet al., 2002); software used to prepare material for publication:PLATON(Spek, 2003) andWinGX

(Farrugia, 1999).

This work was funded by the University of KwaZulu-Natal Research Office, and the National Research Foundation (GUN:2054350).

References

Blessing, R. H. (1995).Acta Cryst.A51, 33–38. Bond, A. D. (2005).Cryst. Growth Des.5, 755–771.

Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002).Acta Cryst.B58, 389–397.

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838. Flack, H. D. (1983).Acta Cryst.A39, 876–881.

Horn, E., Tiekink, E. R. T., Jones, G. P., Naiola, B. P. & Paleg, L. G. (1990).Acta Cryst.C46, 1575–1576.

Jellinek, F. (1958).Acta Cryst.11, 626–631.

Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171.29.9. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13. Tsoucaris, G. (1961).Acta Cryst.14, 909–914.

organic papers

Acta Cryst.(2007). E63, o221–o223 Melanie Rademeyer _C

supporting information

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Acta Cryst. (2007). E63, o221–o223

supporting information

Acta Cryst. (2007). E63, o221–o223 [https://doi.org/10.1107/S1600536806051488]

2-Phenylethylammonium bromide

Melanie Rademeyer

2-Phenylethylammonium bromide

Crystal data

C8H12N+_·Br− Mr = 202.10

Orthorhombic, P212121

Hall symbol: P 2ac 2ab

a = 4.6871 (4) Å

b = 6.1419 (4) Å

c = 32.047 (2) Å

V = 922.56 (12) Å3

Z = 4

F(000) = 408

Dx = 1.455 Mg m−3

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 4396 reflections

θ = 3.8–32.0°

µ = 4.39 mm−1

T = 295 K

Block, colourless 0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Excalibur2 CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω–2θ scans

Absorption correction: multi-scan (Blessing, 1995)

Tmin = 0.340, Tmax = 0.419

9448 measured reflections 2958 independent reflections 2063 reflections with I > 2σ(I) Rint = 0.027

θmax = 32.0°, θmin = 3.8°

h = −6→6

k = −8→7

l = −46→45

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.032} wR(F2_{) = 0.059}

S = 1.06

2958 reflections 91 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0257P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.003

Δρmax = 0.46 e Å−3 Δρmin = −0.86 e Å−3

Absolute structure: Flack (1983), 1047 Friedel pairs

Absolute structure parameter: 0.029 (15)

Special details

supporting information

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Acta Cryst. (2007). E63, o221–o223

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Br1 0.88110 (6) 0.45078 (4) 0.792497 (8) 0.04480 (8)

N1 0.3964 (4) 0.4462 (3) 0.71525 (6) 0.0421 (4)

H1A 0.4992 0.4364 0.7385 0.063*

H1B 0.2841 0.3300 0.7130 0.063*

H1C 0.2897 0.5660 0.7162 0.063*

C1 0.5899 (5) 0.4568 (4) 0.67874 (7) 0.0419 (5)

H1D 0.7084 0.3274 0.6781 0.050*

H1E 0.7143 0.5822 0.6815 0.050*

C2 0.4263 (5) 0.4736 (5) 0.63826 (8) 0.0510 (7)

H2A 0.3185 0.3408 0.6339 0.061*

H2B 0.2920 0.5935 0.6400 0.061*

C3 0.6239 (6) 0.5098 (4) 0.60187 (8) 0.0475 (6)

C4 0.7563 (7) 0.7084 (6) 0.59673 (10) 0.0640 (9)

H4 0.7208 0.8207 0.6155 0.077*

C5 0.9434 (8) 0.7414 (6) 0.56346 (12) 0.0784 (11)

H5 1.0339 0.8751 0.5602 0.094*

C6 0.9932 (8) 0.5778 (8) 0.53580 (12) 0.0832 (12)

H6 1.1163 0.6008 0.5135 0.100*

C7 0.8653 (10) 0.3822 (7) 0.54052 (11) 0.0827 (10)

H7 0.9010 0.2710 0.5215 0.099*

C8 0.6804 (7) 0.3472 (6) 0.57376 (11) 0.0666 (9)

H8 0.5939 0.2120 0.5770 0.080*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Br1 0.04897 (14) 0.03200 (11) 0.05344 (14) 0.00065 (13) −0.00575 (15) 0.00154 (12)

N1 0.0466 (11) 0.0324 (9) 0.0473 (11) 0.0006 (14) −0.0066 (11) 0.0005 (9)

C1 0.0348 (13) 0.0423 (11) 0.0488 (13) 0.0021 (15) −0.0048 (12) 0.0031 (12)

C2 0.0418 (16) 0.0590 (16) 0.0520 (15) 0.0045 (14) −0.0028 (12) −0.0030 (13)

C3 0.0442 (13) 0.0514 (18) 0.0468 (14) 0.0051 (15) −0.0129 (14) 0.0027 (10)

C4 0.073 (2) 0.0584 (19) 0.061 (2) 0.0075 (16) −0.0054 (17) 0.0090 (16)

C5 0.074 (3) 0.075 (2) 0.086 (3) −0.006 (2) −0.010 (2) 0.030 (2)

C6 0.074 (2) 0.115 (3) 0.061 (2) 0.013 (2) 0.0072 (17) 0.022 (3)

C7 0.086 (3) 0.102 (3) 0.060 (2) 0.015 (3) 0.013 (2) −0.0136 (18)

supporting information

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Acta Cryst. (2007). E63, o221–o223 Geometric parameters (Å, º)

N1—C1 1.482 (3) C2—H2B 0.970

N1—H1A 0.890 C8—C7 1.390 (5)

N1—H1B 0.890 C8—H8 0.930

N1—H1C 0.890 C5—C6 1.360 (5)

C1—C2 1.511 (3) C5—C4 1.396 (5)

C1—H1D 0.970 C5—H5 0.930

C1—H1E 0.970 C6—C7 1.351 (6)

C3—C8 1.370 (4) C6—H6 0.930

C3—C4 1.379 (4) C4—H4 0.930

C3—C2 1.506 (4) C7—H7 0.930

C2—H2A 0.970

C1—N1—H1A 109.5 C3—C2—H2B 109.4

C1—N1—H1B 109.5 C1—C2—H2B 109.4

H1A—N1—H1B 109.5 H2A—C2—H2B 108.0

C1—N1—H1C 109.5 C3—C8—C7 120.8 (4)

H1A—N1—H1C 109.5 C3—C8—H8 119.6

H1B—N1—H1C 109.5 C7—C8—H8 119.6

N1—C1—C2 111.73 (19) C6—C5—C4 119.9 (4)

N1—C1—H1D 109.3 C6—C5—H5 120.0

C2—C1—H1D 109.3 C4—C5—H5 120.0

N1—C1—H1E 109.3 C7—C6—C5 120.5 (4)

C2—C1—H1E 109.3 C7—C6—H6 119.7

H1D—C1—H1E 107.9 C5—C6—H6 119.7

C8—C3—C4 118.6 (3) C3—C4—C5 120.2 (3)

C8—C3—C2 121.4 (3) C3—C4—H4 119.9

C4—C3—C2 120.0 (3) C5—C4—H4 119.9

C3—C2—C1 111.3 (2) C6—C7—C8 120.0 (3)

C3—C2—H2A 109.4 C6—C7—H7 120.0

C1—C2—H2A 109.4 C8—C7—H7 120.0

C8—C3—C2—C1 106.6 (3) C8—C3—C4—C5 0.0 (4)

C4—C3—C2—C1 −72.2 (3) C2—C3—C4—C5 178.9 (3)

N1—C1—C2—C3 173.6 (2) C6—C5—C4—C3 0.6 (5)

C4—C3—C8—C7 −0.6 (5) C5—C6—C7—C8 0.2 (6)

C2—C3—C8—C7 −179.4 (3) C3—C8—C7—C6 0.4 (6)

C4—C5—C6—C7 −0.8 (6)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H1A···Br1 0.89 2.49 3.360 (2) 166

N1—H1B···Br1i _{0.89 2.46 3.3186 (19) 162}

N1—H1C···Br1ii _{0.89 2.51 3.370 (2) 163}