Crystal structure of 2-phenyl­ethyl­amin­ium 4-nitro­phenolate monohydrate

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

doi:10.1107/S1600536814025318

. 2014 Nov 21;70(Pt 12):o1280. doi: 10.1107/S1600536814025318

Crystal structure of 2-phenylethylaminium 4-nitrophenolate monohydrate

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

PMCID: PMC4257380 PMID: 25553045

Abstract

In the title hydrated molecular salt, C₈H₁₂N⁺·C₆H₄NO₃ ⁻·H₂O, the conformation of the side chain in the cation is anti [C—C—C—N = 179.62 (12)°] and the dihedral angle between the aromatic ring and the nitro group in the anion is 3.34 (11)°. In the crystal, the components are linked by O—H⋯O and N—H⋯O hydrogen bonds, generating (10-1) sheets, which feature R ₄ ⁴(21) loops. The sheets interact by weak aromatic π–π stacking interactions [centroid–centroid distance = 3.896 (3) Å], forming a three-dimensional network.

Keywords: crystal structure, 2-phenylethylaminium, 4-nitrophenolate, hydrated salt, O—H⋯O and N—H⋯O hydrogen bonds, π–π stacking interactions

Related literature

For related structures, see: Kanagathara et al. (2012 ▶); Lejon et al. (2006 ▶); Sankar et al. (2014 ▶); Smith et al. (2003 ▶).

Experimental

Crystal data

C₈H₁₂N⁺·C₆H₄NO₃ ⁻·H₂O
M _r = 278.30
Monoclinic,
a = 30.381 (5) Å
b = 6.100 (4) Å
c = 21.357 (5) Å
β = 131.876 (5)°
V = 2947 (2) Å³
Z = 8
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
14174 measured reflections
3675 independent reflections
2748 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.124
S = 1.03
3675 reflections
200 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 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.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814025318/hb7318sup1.cif

e-70-o1280-sup1.cif^{(24KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814025318/hb7318Isup2.hkl

e-70-o1280-Isup2.hkl^{(176.6KB, hkl)}

Click here for additional data file.^{(5.5KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814025318/hb7318Isup3.cml

Click here for additional data file.^{(897.7KB, tif)}

. DOI: 10.1107/S1600536814025318/hb7318fig1.tif

The molecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms.

Click here for additional data file.^{(2.2MB, tif)}

b . DOI: 10.1107/S1600536814025318/hb7318fig2.tif

The packing of (I), viewed down b axis. Intermolecular Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

CCDC reference: 1034880

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1AO1	0.90(1)	1.81(1)	2.7108(17)	176(18)
O4H4BO1	0.84(1)	1.90(1)	2.7262(18)	173(2)
N1H1BO2ⁱ	0.90(1)	2.11(1)	2.8937(17)	145(15)
N1H1CO4ⁱⁱ	0.91(1)	1.84(1)	2.742(2)	172(18)
O4H4AO1ⁱⁱⁱ	0.83(1)	1.93(1)	2.7574(16)	175(2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors thank the SAIF, IIT, Madras, for the data collection.

supplementary crystallographic information

S1. Structural commentary

The geometric parameters of the title compound (I) (Fig.1) are comparable with the reported similar structures (Kanagathara et al., 2012; Sankar et al., 2014; Lejon et al., 2006; Smith et al., 2003). The cation is protonated at N1 atom. The dihedral angle between the two benzene rings (C1—C6) and (C9—C14) is 3.71 (11)°. In the anion, the nitro group (N2/O2/O3) is twisted at an angle of 3.34 (11)° with the benzene ring (C9—C14).

S2. Supramolecular features

In the molecular structure, weak N—H···O and O—H···O hydrogen bonds link the cation, anion and water molecule which generates S(6) graph set motif. In the crystal structure, N—H···O and O—H···O hydrogen bonds link the anions, cations and water molecules into sheets, parallel to ac plane and further theses sheets are linked by O—H···O hydrogen bonds along [0 1 0] (Table 2 & Fig. 2). The N—H···O hydrogen bonds generates R₄⁴(21) graph-set motif (Fig. 2).

The crystal structure also features weak C—H···π (Table 2) and π–π [Cg2···Cg2ⁱ distance = 3.896 (3)Å; (i) -x,2-y,-z; Cg2 is the centroid of the C9—C14 ring] interactions to form a three dimensional network.

S3. Synthesis and crystallization

2-Phenylethylamine (1.26 g) and 4-nitrophenol (1.39 g) were disssolved in methanol and colourless blocks of the title compound were grown by slow evaporation.

S4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The C-bound H atoms were positioned geometrically and refined using riding model, with C—H = 0.93 and 0.97 Å for CH_aromatic and CH₂, respectively with U_iso(H) = 1.2Ueq(C). The H atoms bound to O and N atoms were found in a difference map and refined isotropically, with U_iso(H) = 1.5Ueq(O) and distance restraints: O—H = 0.82 (1)Å and N—H = 0.88 (1)Å. The components of the anisotropic displacement parameters in the direction of the bond between C3 and C4 were restrained to be equal within an effective standard deviation of 0.001 using the DELU command in SHELXL97 (Sheldrick, 2008).