(2-Phenylethyl)­ammonium chloride

The crystal structure of the title compound, C₈H₁₂N⁺·Cl⁻, determined at 100 K, is stabilized by inter­molecular N—H...Cl hydrogen bonds. The benzene rings stack along the a axis, with a distance between the substituted C atom and the para C atom of a neighbouring molecule at (x + 1, y, z) of 3.600 (3) Å, which suggests that π–π stacking inter­actions also contribute to the stabilization.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.027
• wR factor = 0.071
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       0.07

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.52
           From the CIF: _reflns_number_total               1884
           Count of symmetry unique reflns         1204
           Completeness (_total/calc)            156.48%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       680
           Fraction of Friedel pairs measured     0.565
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

There is an interest to develop organic semiconductors that will provide more versatile field effect transistors (Jurchescu et al., 2007). This research is focused on making new organic materials that are easily processable and have good π-π stacking. We present here the crystal structure, at 100 K, of the title compound, (I), which is based on a benzene derivative with an ammonium group and chlorine counter ions (Fig 1.). The crystal structure is stabilized by hydrogen bonds that are formed by the ammonium group and three chlorine atoms (Fig 2.). In this way an intermolecular network is created. Besides, the benzene rings form stacks along the a axis. The distance between the C3···C6 (x + 1, y, z) is 3.600 (3) Å, which suggests that π-π stacking interactions also contribute to the stabilization of this crystal structure.

Related literature

Earlier reports (Touscaris, 1960; Horn et al., 1990) have found the same crystal structure for the title compound at room temperature. In addition, the crystal structure shows similar benzene stacks and hydrogen networks as the diamine equivalent of this material (Arkenbout et al., 2007).

For related literature, see: Jurchescu et al. (2007); Le Page (1987, 1988); Spek (1988).

S2. Experimental

A saturated (37%) HCl solution (5 ml, Merck) was slowly added to 2 ml of 2–Phenyl–ethylamin (Fluka, purum >99.0%), while stirring and cooling on a water bath. The resulting mixture was filtered, washed with water and dried in air. Needle like colorless crystals were obtained by recrystallization from a saturated aqueous solution via slow evaporation of the water at room temperature.

S3. Refinement

All hydrogen atoms were located in a difference Fourier map and refined with isotropic displacement parameters. C—H distances were in the range of 0.91 - 1.00 (3) Å.

Computing details

Data collection: SMART (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus; program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006) and PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures

	Fig. 1. Perspective (PLATON) drawing of the title compound. Displacement ellipsoids for non–H atoms are represented at the 50% probability level. The hydrogen atoms are shown as spheres of arbitrary raduis.
	Fig. 2. Portion of the crystal packing (DIAMOND), showing N–H···Cl hydrogen bonds shown as red dashed lines. Colour code: Cl atoms are shown in green, N atoms in blue, C atoms in black and H atoms in grey.

(2-Phenyl)ethylammonium chloride

Crystal data

C8H12N^+.Cl^−	The final unit cell was obtained from the xyz centroids of 4595 reflections after integration using the SAINT–Plus software package (Bruker, 2006). Reduced cell calculations did not indicate any higher metric lattice symmetry and examination of the finalatomic coordinates of the structure did not yield extra symmetry elements (Spek, 1988; Le Page 1987, 1988).
Mr = 157.64	Dx = 1.226 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4595 reflections
a = 4.5354 (6) Å	θ = 3.2–27.5°
b = 5.8868 (8) Å	µ = 0.37 mm^−1
c = 31.991 (4) Å	T = 100 K
V = 854.13 (19) Å^3	Block, colourless
Z = 4	0.47 × 0.34 × 0.16 mm
F(000) = 336

Data collection

Bruker Smart Apex CCD area detector diffractometer	1884 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	1818 reflections with I > 2σ(I)
Parallel mounted graphite monochromator	Rint = 0.025
Detector resolution: 66.06 pixels mm^-1	θmax = 27.5°, θmin = 3.5°
φ and ω scans	h = −5→5
Absorption correction: multi-scan SADABS (Bruker, 2006)	k = −7→7
Tmin = 0.819, Tmax = 0.942	l = −37→41
6845 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	All H-atom parameters refined
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0331P)^2 + 0.2312P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max < 0.001
1884 reflections	Δρmax = 0.24 e Å^−3
139 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Absolute structure: The absolute structure of the molecule was determined by Flack's x refinement (Flack & Bernardinelli, 1999, 2000)
Primary atom site location: heavy-atom method	Absolute structure parameter: 0.00 (7)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Ų)

	x	y	z	Uiso*/Ueq
N	1.1098 (3)	0.0830 (2)	0.21770 (4)	0.0173 (4)
C1	0.9122 (4)	0.0687 (3)	0.18056 (5)	0.0184 (4)
C2	1.0932 (4)	0.0472 (3)	0.14066 (5)	0.0214 (5)
C3	0.8947 (4)	0.0024 (3)	0.10356 (5)	0.0204 (5)
C4	0.8476 (4)	0.1680 (3)	0.07339 (6)	0.0237 (5)
C5	0.6611 (4)	0.1269 (3)	0.03975 (6)	0.0270 (5)
C6	0.5203 (4)	−0.0815 (4)	0.03607 (6)	0.0280 (5)
C7	0.5661 (4)	−0.2473 (3)	0.06602 (6)	0.0281 (6)
C8	0.7532 (4)	−0.2063 (3)	0.09954 (6)	0.0245 (5)
Cl	0.37787 (8)	0.57866 (6)	0.21042 (1)	0.0186 (1)
H1	0.790 (5)	0.198 (4)	0.1806 (6)	0.025 (5)*
H1'	0.788 (4)	−0.067 (4)	0.1851 (6)	0.025 (5)*
H2	1.228 (5)	−0.073 (4)	0.1439 (7)	0.030 (5)*
H2'	1.216 (5)	0.186 (4)	0.1373 (7)	0.041 (6)*
H4	0.935 (5)	0.306 (4)	0.0752 (6)	0.030 (6)*
H5	0.625 (5)	0.243 (4)	0.0191 (6)	0.029 (5)*
H6	0.393 (5)	−0.110 (4)	0.0129 (7)	0.039 (6)*
H7	0.478 (5)	−0.392 (4)	0.0634 (7)	0.039 (6)*
H8	0.780 (4)	−0.320 (4)	0.1206 (7)	0.027 (5)*
H9	1.232 (5)	−0.047 (4)	0.2196 (7)	0.035 (6)*
H9'	1.224 (5)	0.207 (4)	0.2161 (7)	0.032 (6)*
H9"	0.998 (5)	0.086 (4)	0.2417 (7)	0.029 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N	0.0191 (6)	0.0149 (6)	0.0180 (7)	0.0001 (7)	0.0010 (6)	−0.0006 (5)
C1	0.0177 (8)	0.0191 (7)	0.0183 (8)	0.0011 (8)	0.0005 (6)	−0.0009 (7)
C2	0.0191 (8)	0.0279 (9)	0.0172 (8)	0.0006 (8)	0.0008 (7)	−0.0002 (7)
C3	0.0181 (8)	0.0259 (8)	0.0171 (8)	0.0034 (7)	0.0043 (7)	−0.0032 (6)
C4	0.0222 (9)	0.0243 (8)	0.0247 (9)	−0.0014 (7)	0.0027 (8)	0.0005 (7)
C5	0.0265 (9)	0.0339 (10)	0.0207 (8)	0.0049 (8)	0.0010 (7)	0.0024 (7)
C6	0.0250 (8)	0.0375 (10)	0.0215 (9)	0.0045 (9)	−0.0025 (7)	−0.0094 (9)
C7	0.0284 (10)	0.0247 (9)	0.0311 (10)	−0.0016 (8)	0.0040 (8)	−0.0086 (8)
C8	0.0278 (9)	0.0240 (9)	0.0217 (9)	0.0036 (8)	0.0037 (7)	−0.0006 (8)
Cl	0.0208 (2)	0.0148 (2)	0.0201 (2)	−0.0003 (2)	0.0013 (2)	0.0003 (2)

Geometric parameters (Å, º)

N—C1	1.491 (2)	C7—C8	1.389 (3)
N—H9"	0.92 (2)	C1—H1	0.94 (2)
N—H9	0.95 (2)	C1—H1'	0.99 (2)
N—H9'	0.90 (2)	C2—H2	0.94 (2)
C1—C2	1.523 (2)	C2—H2'	1.00 (2)
C2—C3	1.513 (2)	C4—H4	0.91 (2)
C3—C8	1.392 (3)	C5—H5	0.97 (2)
C3—C4	1.388 (3)	C6—H6	0.95 (2)
C4—C5	1.390 (3)	C7—H7	0.95 (2)
C5—C6	1.388 (3)	C8—H8	0.96 (2)
C6—C7	1.383 (3)
Cl···N^i	3.1696 (13)	C8···H2^i	2.88 (2)
Cl···N^ii	3.2167 (13)	C8···H1'	2.86 (2)
Cl···N^iii	3.2692 (14)	C8···H4^xii	3.09 (2)
Cl···N^iv	3.1907 (14)	H1···Cl	3.07 (2)
Cl···H1'^v	2.91 (2)	H1'···Cl^xii	2.91 (2)
Cl···H1	3.07 (2)	H1'···C8	2.86 (2)
Cl···H9'^i	2.30 (2)	H1'···H8	2.55 (3)
Cl···H2^ii	3.03 (2)	H2···H9	2.43 (3)
Cl···H9^ii	2.32 (2)	H2···Cl^vi	3.03 (2)
Cl···H9^iii	2.95 (2)	H2···C8^vii	2.88 (2)
Cl···H9'^iii	3.06 (2)	H2'···H4	2.46 (3)
Cl···H9"^iv	2.29 (2)	H2'···H9'	2.52 (3)
N···Cl^vi	3.2167 (13)	H4···H2'	2.46 (3)
N···Cl^vii	3.1696 (13)	H4···C8^v	3.09 (2)
N···Cl^viii	3.1907 (14)	H5···C5^xiii	2.93 (2)
N···Cl^ix	3.2692 (14)	H5···H5^xiii	2.58 (3)
C2···C8^vii	3.594 (3)	H5···H5^x	2.58 (3)
C3···C6^vii	3.600 (3)	H6···C7^xiv	3.05 (2)
C3···C7^vii	3.588 (3)	H6···C6^xiv	2.93 (2)
C4···C6^vii	3.590 (3)	H7···C5^xii	3.05 (2)
C6···C4^i	3.590 (3)	H8···C1	3.05 (2)
C6···C3^i	3.600 (3)	H8···H1'	2.55 (3)
C7···C3^i	3.588 (3)	H9···Cl^vi	2.32 (2)
C8···C2^i	3.594 (3)	H9···H2	2.43 (3)
C1···H8	3.05 (2)	H9···Cl^ix	2.95 (2)
C5···H7^v	3.05 (2)	H9'···Cl^ix	3.06 (2)
C5···H5^x	2.93 (2)	H9'···H2'	2.52 (3)
C6···H6^xi	2.93 (2)	H9'···Cl^vii	2.30 (2)
C7···H6^xi	3.05 (2)	H9"···Cl^viii	2.29 (2)
H9'—N—H9"	111 (2)	C2—C1—H1	112.7 (12)
C1—N—H9'	110.4 (14)	C2—C1—H1'	111.3 (12)
C1—N—H9"	109.6 (14)	H1—C1—H1'	108.5 (18)
C1—N—H9	110.9 (14)	C1—C2—H2	108.7 (14)
H9—N—H9"	107 (2)	C1—C2—H2'	108.9 (13)
H9—N—H9'	109 (2)	C3—C2—H2	110.0 (14)
N—C1—C2	110.41 (14)	C3—C2—H2'	113.1 (13)
C1—C2—C3	110.57 (15)	H2—C2—H2'	105.4 (19)
C2—C3—C4	120.97 (16)	C3—C4—H4	121.2 (13)
C2—C3—C8	120.05 (15)	C5—C4—H4	118.2 (13)
C4—C3—C8	118.98 (16)	C4—C5—H5	120.7 (13)
C3—C4—C5	120.64 (16)	C6—C5—H5	119.4 (13)
C4—C5—C6	119.96 (17)	C5—C6—H6	120.0 (14)
C5—C6—C7	119.72 (17)	C7—C6—H6	120.3 (14)
C6—C7—C8	120.26 (17)	C6—C7—H7	120.8 (14)
C3—C8—C7	120.43 (17)	C8—C7—H7	118.9 (14)
N—C1—H1	107.9 (13)	C3—C8—H8	119.6 (13)
N—C1—H1'	105.7 (11)	C7—C8—H8	120.0 (13)
N—C1—C2—C3	172.74 (13)	C4—C3—C8—C7	−0.5 (3)
C1—C2—C3—C4	108.95 (19)	C3—C4—C5—C6	−0.1 (3)
C1—C2—C3—C8	−70.3 (2)	C4—C5—C6—C7	0.1 (3)
C2—C3—C4—C5	−178.94 (17)	C5—C6—C7—C8	−0.3 (3)
C8—C3—C4—C5	0.3 (3)	C6—C7—C8—C3	0.5 (3)
C2—C3—C8—C7	178.74 (17)

Symmetry codes: (i) x−1, y, z; (ii) x−1, y+1, z; (iii) −x+2, y+1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2; (v) x, y+1, z; (vi) x+1, y−1, z; (vii) x+1, y, z; (viii) −x+1, y−1/2, −z+1/2; (ix) −x+2, y−1/2, −z+1/2; (x) x+1/2, −y+1/2, −z; (xi) x+1/2, −y−1/2, −z; (xii) x, y−1, z; (xiii) x−1/2, −y+1/2, −z; (xiv) x−1/2, −y−1/2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H9···Cl^vi	0.95 (2)	2.32 (2)	3.2167 (13)	158 (2)
N—H9′···Cl^vii	0.90 (2)	2.30 (2)	3.1696 (13)	162 (2)
N—H9"···Cl^viii	0.92 (2)	2.29 (2)	3.1907 (14)	165 (2)

Symmetry codes: (vi) x+1, y−1, z; (vii) x+1, y, z; (viii) −x+1, y−1/2, −z+1/2.