d-Phenyl­glycinium bromide

Parthasarathy, M.; Arun Kumar, K.; Gopalakrishnan, R.

doi:10.1107/S1600536813004807

organic compounds

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Volume 69| Part 4| April 2013| Page o470

doi:10.1107/S1600536813004807

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D-Phenylglycinium bromide

Mohanadoss Parthasarathy,^a Kannan Arun Kumar ^b and Rengasamy Gopalakrishnan ^a ^*

^aCrystal Research Laboratory, Department of Physics, Anna University, Chennai 600 025, India, and ^bDepartment of Chemistry, Loyola College (Autonomous), Chennai 600 034, India
^*Correspondence e-mail: krgkrishnan@annauniv.edu

(Received 30 January 2013; accepted 19 February 2013; online 2 March 2013)

In the crystal of the title salt, C₈H₁₀NO₂⁺·Br⁻, the bromide anions and the phenylglycinium cations are linked through N—H⋯Br, O—H⋯Br and C—H⋯O hydrogen bonds, generating sheets lying parallel to (001).

Related literature

For a similar compound with a different halogen anion, see: Ravichandran et al. (1998 ). For related structures and background, see: Srinivasan et al. (2001 ); Bouchouit et al. (2004 ); Ramaswamy et al. (2001 ); Bouacida et al. (2006 ); Thomsen et al. (1994 ). For biological importance, see: Satyam et al. (1996 ); Jayasinghe et al. (1994 ); Chun et al. (2010 ); Thomas & West (2011 ).

Experimental

Crystal data

C₈H₁₀NO₂⁺·Br⁻
M_r = 232.08
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.5240 (5) Å
b = 7.4735 (5) Å
c = 23.1229 (18) Å
V = 954.60 (13) Å³
Z = 4
Mo Kα radiation
μ = 4.27 mm⁻¹
T = 295 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.317, T_max = 0.415
5824 measured reflections
2170 independent reflections
2003 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.046
S = 1.03
2170 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 )
Flack parameter: 0.011 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Br1ⁱ	0.89	2.54	3.3586 (17)	154
N1—H1C⋯Br1ⁱⁱ	0.89	2.57	3.429 (2)	163
N1—H1A⋯Br1	0.89	2.45	3.3166 (18)	164
O1—H1D⋯Br1ⁱⁱⁱ	0.82	2.39	3.2027 (17)	171
C7—H7⋯O2^iv	0.98	2.59	3.527 (3)	159
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x-1, y, z; (iii) x-1, y-1, z; (iv) x+1, y, z.

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813004807/pk2465sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813004807/pk2465Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813004807/pk2465Isup3.cml

checkCIF report

Comment top

D-Phenylglycine is an important constituent in the production of semisynthetic penicillins and cephalosporins. Recently the usages of some phenylglycine derivatives in the synthesis of antitumor drugs and other pharmacological applications have been found to be increasing (Satyam et al., 1996; Jayasinghe et al., 1994). Phenylglycine has been reported as a delivery tool for improving l-dopa absorption (Chun et al., 2010) and also found to have anti-inflammatory activity (Thomas et al., 2011). The torsion angle N1-C7-C8-O1, which indicates the relative orientation of the carboxyl group and the amino N atom, is 15.5 (3)° and close to the corresponding value of 18.9°(5) reported for D-Phenylglycine Hydrochloride (Ravichandran et al., 1998). The orientation of the phenyl ring as described by the torsion angle C5—C6—C7—N1 is 130.05 (3)°. The intermolecular interaction between the molecular ions are primarly decided by hydrogen bonding. The hydrogen bonds N1—H1A···Br1, N1—H1B···Br1ⁱ [Symmetry code: (i) -x+1, y-1/2, -z+3/2], N1—H1C···Br1ⁱⁱ [Symmetry code: (ii) x-1, y, z] and O1—H1D···Br1ⁱⁱⁱ [Symmetry code: (iii) x-1, y-1, z] and C7—H7···O2^iv [Symmetry code: (iv) x-1, y-1, z] hydrogen bond interconnects the molecular ions to form an extensive two-dimensional molecular sheet parallel to (001) plane. Parallel stacking of these sheets along [0 0 1] direction constitute the molecular packing of the crystal.

Related literature top

For a similar compound with different halogen see: Ravichandran et al. (1998). For related structures and background see: Srinivasan et al. (2001); Bouchouit et al. (2004); Ramaswamy et al. (2001); Bouacida et al. (2006); Thomsen et al.(1994). For biological importance see: Satyam et al. (1996); Jayasinghe et al. (1994); Chun et al. (2010); Thomas et al. (2011).

Experimental top

The title compound (I), was prepared by mixing a 1:1 ratio of D-Phenylglycine and hydrobromic acid in water solvent. The suitable single-crystal of the compound was selected for X-ray analysis from the above solution by slow evaporation method.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Displacement ellipsoid plot of the molecular structure drawn at the 40% probability level.
	Fig. 2. Part of the crystal structure showing the two dimensional anionic-cationic (0 0 1) sheet formed through N—H···Br, O—H···Br and C—H···O interactions viewed down c axis.

D-Phenylglycinium bromide top

Crystal data top

C₈H₁₀NO₂⁺·Br⁻	F(000) = 464
M_r = 232.08	D_x = 1.615 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3239 reflections
a = 5.5240 (5) Å	θ = 2.6–28.8°
b = 7.4735 (5) Å	µ = 4.27 mm⁻¹
c = 23.1229 (18) Å	T = 295 K
V = 954.60 (13) Å³	Block, colourless
Z = 4	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2170 independent reflections
Radiation source: fine-focus sealed tube	2003 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω and ϕ scan	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −6→7
T_min = 0.317, T_max = 0.415	k = −9→5
5824 measured reflections	l = −28→30

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²)]
wR(F²) = 0.046	(Δ/σ)_max = 0.003
S = 1.03	Δρ_max = 0.25 e Å⁻³
2170 reflections	Δρ_min = −0.29 e Å⁻³
114 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0530 (13)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.011 (8)

Crystal data top

C₈H₁₀NO₂⁺·Br⁻	V = 954.60 (13) Å³
M_r = 232.08	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.5240 (5) Å	µ = 4.27 mm⁻¹
b = 7.4735 (5) Å	T = 295 K
c = 23.1229 (18) Å	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2170 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2003 reflections with I > 2σ(I)
T_min = 0.317, T_max = 0.415	R_int = 0.022
5824 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.046	Δρ_max = 0.25 e Å⁻³
S = 1.03	Δρ_min = −0.29 e Å⁻³
2170 reflections	Absolute structure: Flack (1983)
114 parameters	Absolute structure parameter: 0.011 (8)
0 restraints

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	U_iso*/U_eq
C1	0.1060 (5)	0.5444 (3)	0.56980 (9)	0.0370 (5)
H1	−0.0251	0.5884	0.5906	0.044*
C2	0.1209 (5)	0.5734 (3)	0.51081 (9)	0.0418 (6)
H2	−0.0006	0.6372	0.4921	0.050*
C3	0.3119 (5)	0.5092 (3)	0.47991 (9)	0.0424 (6)
H3	0.3196	0.5290	0.4402	0.051*
C4	0.4922 (5)	0.4160 (3)	0.50678 (9)	0.0443 (6)
H4	0.6229	0.3734	0.4855	0.053*
C5	0.4804 (4)	0.3849 (3)	0.56595 (9)	0.0355 (5)
H5	0.6024	0.3204	0.5842	0.043*
C6	0.2866 (4)	0.4500 (2)	0.59770 (7)	0.0264 (4)
C7	0.2695 (4)	0.4057 (2)	0.66152 (7)	0.0282 (5)
H7	0.4217	0.3499	0.6738	0.034*
C8	0.0650 (4)	0.2773 (3)	0.67328 (8)	0.0311 (5)
N1	0.2266 (4)	0.5687 (2)	0.69772 (6)	0.0345 (4)
H1A	0.3369	0.6514	0.6892	0.063 (8)*
H1B	0.2379	0.5399	0.7350	0.063 (8)*
H1C	0.0794	0.6117	0.6905	0.047 (7)*
O1	0.1199 (4)	0.1163 (2)	0.65347 (8)	0.0561 (5)
H1D	0.0051	0.0486	0.6586	0.084*
O2	−0.1206 (3)	0.3164 (2)	0.69632 (6)	0.0441 (4)
Br1	0.71415 (4)	0.82278 (3)	0.681529 (8)	0.03843 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0381 (14)	0.0388 (11)	0.0339 (11)	0.0062 (12)	0.0048 (10)	−0.0032 (10)
C2	0.0552 (17)	0.0342 (12)	0.0360 (12)	0.0066 (11)	−0.0030 (11)	0.0072 (10)
C3	0.0638 (18)	0.0364 (12)	0.0270 (10)	−0.0101 (13)	0.0087 (11)	0.0010 (9)
C4	0.0417 (16)	0.0496 (14)	0.0415 (14)	−0.0021 (12)	0.0170 (11)	−0.0082 (11)
C5	0.0277 (13)	0.0429 (12)	0.0360 (12)	0.0004 (11)	0.0035 (9)	−0.0027 (10)
C6	0.0261 (11)	0.0258 (9)	0.0273 (9)	−0.0062 (10)	0.0011 (9)	−0.0013 (7)
C7	0.0261 (13)	0.0316 (10)	0.0269 (9)	−0.0034 (10)	0.0012 (8)	0.0002 (7)
C8	0.0352 (14)	0.0323 (11)	0.0258 (11)	−0.0071 (10)	−0.0018 (9)	0.0014 (8)
N1	0.0377 (13)	0.0396 (9)	0.0262 (9)	−0.0137 (10)	0.0029 (8)	−0.0036 (7)
O1	0.0634 (15)	0.0333 (8)	0.0715 (12)	−0.0161 (9)	0.0238 (10)	−0.0057 (8)
O2	0.0328 (9)	0.0448 (9)	0.0547 (9)	−0.0106 (9)	0.0085 (7)	−0.0021 (8)
Br1	0.04061 (14)	0.03701 (12)	0.03766 (12)	−0.01269 (10)	0.00446 (10)	−0.00279 (9)

Geometric parameters (Å, º) top

C1—C6	1.382 (3)	C6—C7	1.515 (2)
C1—C2	1.383 (3)	C7—N1	1.497 (2)
C1—H1	0.9300	C7—C8	1.507 (3)
C2—C3	1.361 (3)	C7—H7	0.9800
C2—H2	0.9300	C8—O2	1.192 (3)
C3—C4	1.365 (3)	C8—O1	1.323 (3)
C3—H3	0.9300	N1—H1A	0.8900
C4—C5	1.389 (3)	N1—H1B	0.8900
C4—H4	0.9300	N1—H1C	0.8900
C5—C6	1.386 (3)	O1—H1D	0.8200
C5—H5	0.9300

C6—C1—C2	119.8 (2)	C5—C6—C7	119.15 (19)
C6—C1—H1	120.1	N1—C7—C8	107.37 (17)
C2—C1—H1	120.1	N1—C7—C6	112.12 (15)
C3—C2—C1	120.6 (2)	C8—C7—C6	111.19 (16)
C3—C2—H2	119.7	N1—C7—H7	108.7
C1—C2—H2	119.7	C8—C7—H7	108.7
C2—C3—C4	120.4 (2)	C6—C7—H7	108.7
C2—C3—H3	119.8	O2—C8—O1	125.1 (2)
C4—C3—H3	119.8	O2—C8—C7	124.73 (19)
C3—C4—C5	120.0 (2)	O1—C8—C7	110.16 (19)
C3—C4—H4	120.0	C7—N1—H1A	109.5
C5—C4—H4	120.0	C7—N1—H1B	109.5
C6—C5—C4	119.9 (2)	H1A—N1—H1B	109.5
C6—C5—H5	120.0	C7—N1—H1C	109.5
C4—C5—H5	120.0	H1A—N1—H1C	109.5
C1—C6—C5	119.30 (19)	H1B—N1—H1C	109.5
C1—C6—C7	121.4 (2)	C8—O1—H1D	109.5

C6—C1—C2—C3	0.2 (4)	C1—C6—C7—N1	−54.0 (3)
C1—C2—C3—C4	−0.3 (4)	C5—C6—C7—N1	130.1 (2)
C2—C3—C4—C5	0.5 (4)	C1—C6—C7—C8	66.2 (2)
C3—C4—C5—C6	−0.6 (3)	C5—C6—C7—C8	−109.7 (2)
C2—C1—C6—C5	−0.2 (3)	N1—C7—C8—O2	15.6 (3)
C2—C1—C6—C7	−176.2 (2)	C6—C7—C8—O2	−107.4 (2)
C4—C5—C6—C1	0.5 (3)	N1—C7—C8—O1	−165.48 (17)
C4—C5—C6—C7	176.5 (2)	C6—C7—C8—O1	71.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Br1ⁱ	0.89	2.54	3.3586 (17)	154
N1—H1C···Br1ⁱⁱ	0.89	2.57	3.429 (2)	163
N1—H1A···Br1	0.89	2.45	3.3166 (18)	164
O1—H1D···Br1ⁱⁱⁱ	0.82	2.39	3.2027 (17)	171
C7—H7···O2^iv	0.98	2.59	3.527 (3)	159

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1, y, z; (iii) x−1, y−1, z; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₈H₁₀NO₂⁺·Br⁻
M_r	232.08
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	5.5240 (5), 7.4735 (5), 23.1229 (18)
V (Å³)	954.60 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.27
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.317, 0.415
No. of measured, independent and observed [I > 2σ(I)] reflections	5824, 2170, 2003
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.046, 1.03
No. of reflections	2170
No. of parameters	114
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.29
Absolute structure	Flack (1983)
Absolute structure parameter	0.011 (8)

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Br1ⁱ	0.89	2.54	3.3586 (17)	154.0
N1—H1C···Br1ⁱⁱ	0.89	2.57	3.429 (2)	162.6
N1—H1A···Br1	0.89	2.45	3.3166 (18)	163.9
O1—H1D···Br1ⁱⁱⁱ	0.82	2.39	3.2027 (17)	171.1
C7—H7···O2^iv	0.98	2.59	3.527 (3)	159.3

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1, y, z; (iii) x−1, y−1, z; (iv) x+1, y, z.

Acknowledgements

The authors are grateful to Professor K. Sivakumar, Department of Physics, Anna University, Chennai-25, for fruitful scientific discussions. The authors are thankful to the SAIF, IIT Madras, Chennai-36, India, for the X-ray data collection.

References

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