Crystal structure of 2-phenyl­ethanaminium 3-carb­oxy­prop-2-enoate

N Swarna Sowmya; S Sampathkrishnan; R Akilan; G Chakkaravarthi; R Mohan Kumar

doi:10.1107/S2056989015014292

. 2015 Aug 6;71(Pt 9):o641–o642. doi: 10.1107/S2056989015014292

Crystal structure of 2-phenylethanaminium 3-carboxyprop-2-enoate

N Swarna Sowmya ^a, S Sampathkrishnan ^a, R Akilan ^b, G Chakkaravarthi ^c,^*, R Mohan Kumar ^d,^*

PMCID: PMC4555434 PMID: 26396880

Abstract

The title molecular salt, C₈H₁₂N⁺·C₄H₃O₄ ⁻, crystallized with two independent cations and anions in the asymmetric unit. The ethanaminium side chains of the cations exhibit anti conformations [C—C—C—N torsion angles = 176.5 (3) and −179.4 (3)°]. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds connect adjacent anions and cations, and , O—H⋯O hydrogen bonds connect adjacent anions, generating sheets parallel to (001).

Keywords: crystal structure, molecular salt, aminium, 3-carboxyprop-2-enoate, hydrogen bonding

Related literature

For the crystal structures of related compounds, see: Ambalatharasu et al. (2014 ▸); Lejon et al. (2006 ▸); Smith et al. (2003 ▸).

Experimental

Crystal data

C₈H₁₂N⁺·C₄H₃O₄ ⁻
M _r = 237.25
Triclinic,
a = 9.2940 (5) Å
b = 10.8010 (7) Å
c = 12.7470 (8) Å
α = 81.773 (4)°
β = 88.907 (5)°
γ = 87.396 (4)°
V = 1265.02 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.26 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T _min = 0.976, T _max = 0.982
29606 measured reflections
5579 independent reflections
3453 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.199
S = 1.04
5579 reflections
309 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: SAINT (Bruker, 2004 ▸); data reduction: SAINT; 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: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015014292/su5183sup1.cif

e-71-0o641-sup1.cif^{(31.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014292/su5183Isup2.hkl

e-71-0o641-Isup2.hkl^{(267.6KB, hkl)}

Click here for additional data file.^{(4.6KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015014292/su5183Isup3.cml

Click here for additional data file.^{(1MB, tif)}

. DOI: 10.1107/S2056989015014292/su5183fig1.tif

The molecular structure of the title salt, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.^{(1.5MB, tif)}

b . DOI: 10.1107/S2056989015014292/su5183fig2.tif

The crystal packing of the title salt viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 1) and C-bound H atoms have been omitted for clarity.

CCDC reference: 1415628

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1CO4	0.89	1.92	2.805(3)	177
N1H1AO8ⁱ	0.89	2.00	2.863(3)	163
N1H1BO1ⁱⁱ	0.89	2.38	2.992(2)	126
N1H1BO5ⁱⁱⁱ	0.89	2.20	2.961(3)	143
N2H2AO1^iv	0.89	1.92	2.814(3)	177
N2H2CO6^iv	0.89	1.99	2.863(3)	167
N2H2BO7^v	0.89	2.23	2.974(3)	141
N2H2BO4^vi	0.89	2.38	2.992(2)	126
O2H2DO5^vii	0.82	1.65	2.470(2)	176
O7H7O3^viii	0.82	1.68	2.494(2)	174
C7H7AO8ⁱ	0.97	2.58	3.349(4)	136

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Acknowledgments

The authors wish to acknowledge the SAIF, IIT Madras, for the data collection.

supplementary crystallographic information

S1. Comment

The molecular structure of the title molecular salt is illustrated in Fig. 1. The geometric parameters are comparable with those reported for similar structures (Ambalatharasu et al., 2014; Lejon et al., 2006; Smith et al., 2003). The asymmetric unit consists of two independent 2-phenylethanaminium cations and 3-carboxyprop-2-enoate anions. The cations are protonated at amine-N atoms, and in the cations the side chains exhibit anti-conformations [C1—C7—C8—N1 = 176.5 (3) ° and C9—C15—C16—N2 = 179.4 (3) °]. The dihedral angle between the aromatic rings, (C1—C6) and (C9—C14), is 34.0 (3)Å.

In the crystal, the molecular structure is stabilized by a medium-strength intramolecular cation-anion N—H···O hydrogen bond (Table 1 and Fig. 2). Adjacent anions and cations are linked by further N—H···O and O—H···O hydrogen bonds into infinite two-dimensional networks parallel to the ab plane (Table 1 and Fig. 2). There are also weak C—H···O hydrogen bonds within the sheets (Table 1).

S2. Synthesis and crystallization

The title slat was synthesized by mixing 2-phenylethylamine (1.26 g) and fumaric acid (1.16 g) in methanol-water (1:1) and the single crystals suitable for X-ray diffraction were grown by slow evaporation.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All the H atoms were positioned geometrically and refined using a riding model: O—H = 0.82 Å, N—H = 0.89 Å, C—H = 0.93 - 0.97 Å with U_iso(H) = 1.5U_eq(O,N) for OH and NH₃ H atoms and 1.2U_eq(C) for other H atoms. The bond distances C1—C6, C3—C4 and C5—C6 were restrained to 1.390 (1) Å.