Tri­benzyl­ammonium chloride

Single crystals of the title salt, C₂₁H₂₁NH⁺·Cl⁻, were isolated as a side product from the reaction involving [(C₆H₅CH₂)₃NH]₂[HPO₄] and Sn(CH₃)₃Cl in ethanol. Both the cation and the anion are situated on a threefold rotation axis. The central N atom in the cation has a slightly distorted tetra­hedral environment, with angles ranging from 107.7 to 111.16 (10)°. In the crystal, the tri­benzyl­ammonium cations and chloride anions are linked through N—H⋯Cl and C—H⋯Cl hydrogen bonds, leading to the formation of infinite chains along [001]. The crystal studied was a merohedral twin.

Related literature

For related crystal structures containing the tri­benzyl­ammonium cation, see: Kozhomuratova et al. (2007); Jarvinen et al. (1988); Guo et al. (2010); Zeng et al. (1994); Faza­eli et al. (2010); Guan et al. (2013); Yousefi et al. (2007); Gueye et al. (2012); Traore et al. (2013). For details of the treatment of intensity data from a twinned crystal, see: Spek (2009).

Experimental

Crystal data

• C₂₁H₂₂N⁺·Cl⁻

• M_r = 323.85

• Trigonal, R 3

• a = 15.3833 (8) Å

• c = 6.7051 (3) Å

• V = 1374.15 (18) ų

• Z = 3

• Mo Kα radiation

• μ = 0.21 mm⁻¹

• T = 115 K

• 0.47 × 0.27 × 0.12 mm

Data collection

• Nonius KappaCCD diffractometer

• Absorption correction: multi-scan (Blessing, 1995) T_min = 0.923, T_max = 0.963

• 1884 measured reflections

• 1047 independent reflections

• 1045 reflections with I > 2σ(I)

• R_int = 0.016

Refinement

• R[F² > 2σ(F²)] = 0.021

• wR(F²) = 0.052

• S = 1.10

• 1047 reflections

• 71 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.12 e Å⁻³

• Δρ_min = −0.11 e Å⁻³

• Absolute structure: Flack parameter determined using 348 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2012)

• Absolute structure parameter: 0.01 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H⋯Cl^i	1.00	2.00	3.004 (2)	180
C1—H1B⋯Cl	0.99	2.70	3.5470 (18)	144
C3—H3⋯Cl^i	0.95	3.06	3.683 (2)	125
Symmetry code: (i) x, y, z-1.

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; 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: WinGX (Farrugia, 2012).

Supporting information

S1. Comment

Tribenzylammonium cations are often used to stabilize metal complex-anions such as [(C₆H₅CH₂)₃NH·C₆H₅CH₂NH₂][CuCl₄] (Zeng et al., 1994), (Bz₃NH)₃[Mo₆OCl₁₃] and (Bz₃NH)₂[Mo₆Cl₁₄]·2CH₃CN (Bz is benzyl; Kozhomuratova et al., 2007), [(C₆H₅CH₂)₃NH][AuCl₄] (Fazaeli et al., 2010), 2[C₂₁H₂₂N⁺]·[MCl₆]^2- (M = Se, Re, Te) (Guo et al., 2010), 2[C₂₁H₂₂N⁺]·[CoCl₄]^2- and 2[C₂₁H₂₂N⁺]·[CuCl₄]^2- (Guan et al., 2013). In the course of our ongoing studies on organotin(IV) chemistry, we serendipitously isolated the title salt, tribenzylammonium chloride C₂₁H₂₁NH⁺·Cl^-, from the reaction of [(C₆H₅CH₂)₃NH]₂[HPO₄] with Sn(CH₃)₃Cl. Together with C₂₁H₂₁NH⁺·Cl^-, we suggest the formation of the tin(IV) compound, [(C₆H₅CH₂)₃NH][HPO₄SnMe₃]. Howver, we were not successful to isolate single crystals of this compound so far.

The asymmetric unit of tribenzylammonium chloride consists of one third of a (C₆H₅CH₂)₃NH⁺ cation and an Cl^- anion (Fig. 1). The cationic molecule is completed by the symmetry operation associated with a threefold rotation axis. The N—C bond length within the cation [N–C1 1.5145 (17)] is nearly identical to that observed in tris(tribenzylammonium) hexachloridoplatinate(IV) chloride (Yousefi et al., 2007), in tribenzylammonium l,l,l,l,2,2,2,3,3,3-decacarbonyl-2,3-m-hydrido-2,3-m-sulfonyl-triangulo-triosmium (Jarvinen et al., 1988), or in dibenzylazanium (oxalato-_k²O,O')triphenylstannate(IV) (Gueye et al., 2012). The C–N–C angles [C1–N–C1ⁱⁱ 111.16 (10)°] indicate a slight angular distortion in the tetrahedral environment.

In the crystal, the chloride anion is linked to the tribenzylammonium cation via N—H···Cl hydrogen bonding (Table 1). In addition and from a supramolecular point of view, the chloride anions are also in intermolecular weak interaction with three methylinic protons of the benzyl groups of neighboring cations (Table 1). The observed distances are in the range of those reported in literature for such interactions, for example in [(C₆H₅CH₂Ph₃P]⁺[SnPh₃Cl₂]^- (Traore et al., 2013). The combination of N—H···Cl and C—H···Cl hydrogen bonding interactions leads to the formation of infinite chains along [001] (Fig. 2).

Related literature

For related crystal structures containing the tribenzylammonium cation, see: Kozhomuratova et al. (2007); Jarvinen et al. (1988); Guo et al. (2010); Zeng et al. (1994); Fazaeli et al. (2010); Guan et al. (2013); Yousefi et al. (2007); Gueye et al. (2012); Traore et al. (2013). For details of the treatment of intensity data from a twinned crystal, see: Spek (2009).

S2. Experimental

All chemicals were purchased from Sigma-Aldrich and were used without further purification. Crystals of the title compound were obtained by reacting [(C₆H₅CH₂)₃NH]₂[HPO₄] (0.300 g, 0.446 mmol), previously synthesized from phosphoric acid (98%_wt) and tribenzylamine, with Sn(CH₃)₃Cl (0.088 g, 0.446 mmol) in 15 ml of ethanol (98% purity). The mixture was stirred for around two hours at room temperature. Colorless crystals were obtained after one week by slow solvent evaporation.

S3. Refinement

The H atoms,on carbon and nitrogen atoms were placed at calculated positions using a riding model with C—H = 0.95 Å (aromatic), or 0.99 Å (methylene) or N—H = 1.00 Å (amine) with U_iso(H) = 1.2U_eq(C or N). Intensity data revealed twinning by merohedry. The twin law was found by using TwinRotMat implemented in PLATON (Spek, 2009). The use of the twin law (-h-k, k, -l) and a refined twin component ratio of 0.93:0.07 reduced the reliability factor R (I>2σ(I)) from 0.042 to 0.021. The three reflections (-1 2 0; 1 1 0; -1 1 1) were affected by the beam stop and were omitted from the refinement.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); 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: WinGX (Farrugia, 2012).

Figures

	Fig. 1. The molecular structure of the title compound with atom labeling. Displacement ellipsoids are draw at the 30% probability level. [Symmetry codes: (i) -x + y+1, -x + 1, z; (ii) -y + 1, x-y, z.]
	Fig. 2. The crystal packing of the title compound showing a chain-like arrangement along [001] through N—H···Cl and C—H···Cl interactions (dashed orange lines; H atoms not involved in hydrogen bonding were omitted for clarity). Colour code: C dark grey, H light grey, N blue, Cl green.

Tribenzylazanium chloride

Crystal data

C21H22N^+·Cl^−	Dx = 1.174 Mg m^−3
Mr = 323.85	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 2745 reflections
Hall symbol: R 3	θ = 1.0–27.5°
a = 15.3833 (8) Å	µ = 0.21 mm^−1
c = 6.7051 (3) Å	T = 115 K
V = 1374.15 (18) Å^3	Prism, colourless
Z = 3	0.47 × 0.27 × 0.12 mm
F(000) = 516

Data collection

Nonius KappaCCD diffractometer	1047 independent reflections
Radiation source: X-ray tube, Siemens KFF Mo 2K-180	1045 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 512 x 512 pixels mm^-1	θmax = 27.5°, θmin = 3.4°
ϕ and ω scans	h = −18→17
Absorption correction: multi-scan (Blessing, 1995)	k = −19→10
Tmin = 0.923, Tmax = 0.963	l = −8→6
1884 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.021	w = 1/[σ^2(Fo^2) + 0.8302P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.052	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.12 e Å^−3
1047 reflections	Δρmin = −0.11 e Å^−3
71 parameters	Absolute structure: Flack parameter determined using 348 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2012)
1 restraint	Absolute structure parameter: 0.01 (4)
Primary atom site location: iterative

Special details

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. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl	0.6667	0.3333	0.80013 (9)	0.02215 (17)
N	0.6667	0.3333	0.2481 (3)	0.0146 (5)
H	0.6667	0.3333	0.0990	0.018*
C1	0.56631 (12)	0.31837 (13)	0.3169 (3)	0.0168 (3)
H1A	0.5122	0.2574	0.2520	0.020*
H1B	0.5604	0.3064	0.4626	0.020*
C2	0.55016 (13)	0.40504 (12)	0.2725 (3)	0.0176 (4)
C3	0.51543 (14)	0.41462 (15)	0.0861 (3)	0.0231 (4)
H3	0.5043	0.3676	−0.0165	0.028*
C4	0.49715 (17)	0.49308 (17)	0.0510 (3)	0.0313 (5)
H4	0.4731	0.4991	−0.0757	0.038*
C5	0.51373 (16)	0.56246 (15)	0.1988 (4)	0.0332 (5)
H5	0.5011	0.6159	0.1738	0.040*
C6	0.54881 (15)	0.55355 (16)	0.3832 (4)	0.0313 (5)
H6	0.5613	0.6016	0.4844	0.038*
C7	0.56583 (14)	0.47482 (14)	0.4207 (3)	0.0234 (4)
H7	0.5884	0.4683	0.5487	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0273 (2)	0.0273 (2)	0.0118 (3)	0.01366 (12)	0.000	0.000
N	0.0156 (6)	0.0156 (6)	0.0128 (13)	0.0078 (3)	0.000	0.000
C1	0.0151 (7)	0.0189 (8)	0.0162 (8)	0.0084 (7)	0.0009 (7)	0.0013 (7)
C2	0.0139 (8)	0.0187 (8)	0.0202 (9)	0.0080 (7)	0.0013 (6)	−0.0002 (7)
C3	0.0240 (9)	0.0268 (9)	0.0220 (10)	0.0155 (8)	−0.0003 (7)	0.0000 (7)
C4	0.0317 (11)	0.0362 (11)	0.0349 (10)	0.0237 (9)	0.0028 (9)	0.0099 (10)
C5	0.0268 (10)	0.0240 (10)	0.0558 (15)	0.0178 (8)	0.0105 (10)	0.0066 (10)
C6	0.0227 (9)	0.0242 (9)	0.0478 (14)	0.0123 (8)	0.0087 (9)	−0.0072 (9)
C7	0.0186 (9)	0.0258 (10)	0.0254 (10)	0.0108 (8)	0.0014 (7)	−0.0053 (8)

Geometric parameters (Å, º)

N—H	1.0000	C3—H3	0.9500
N—C1^i	1.5145 (17)	C3—C4	1.389 (3)
N—C1^ii	1.5145 (17)	C4—H4	0.9500
N—C1	1.5145 (17)	C4—C5	1.384 (3)
C1—H1A	0.9900	C5—H5	0.9500
C1—H1B	0.9900	C5—C6	1.383 (3)
C1—C2	1.503 (2)	C6—H6	0.9500
C2—C3	1.396 (3)	C6—C7	1.384 (3)
C2—C7	1.392 (2)	C7—H7	0.9500
C1^ii—N—H	107.7	C2—C3—H3	120.1
C1^i—N—H	107.7	C4—C3—C2	119.86 (19)
C1—N—H	107.7	C4—C3—H3	120.1
C1^ii—N—C1^i	111.16 (10)	C3—C4—H4	119.7
C1^i—N—C1	111.16 (10)	C5—C4—C3	120.6 (2)
C1^ii—N—C1	111.16 (10)	C5—C4—H4	119.7
N—C1—H1A	108.7	C4—C5—H5	120.2
N—C1—H1B	108.7	C6—C5—C4	119.63 (19)
H1A—C1—H1B	107.6	C6—C5—H5	120.2
C2—C1—N	114.39 (13)	C5—C6—H6	119.9
C2—C1—H1A	108.7	C5—C6—C7	120.2 (2)
C2—C1—H1B	108.7	C7—C6—H6	119.9
C3—C2—C1	120.83 (16)	C2—C7—H7	119.7
C7—C2—C1	120.07 (16)	C6—C7—C2	120.62 (19)
C7—C2—C3	119.04 (17)	C6—C7—H7	119.7
N—C1—C2—C3	83.7 (2)	C2—C3—C4—C5	0.5 (3)
N—C1—C2—C7	−99.0 (2)	C3—C2—C7—C6	−1.0 (3)
C1^ii—N—C1—C2	174.09 (11)	C3—C4—C5—C6	0.0 (3)
C1^i—N—C1—C2	49.7 (2)	C4—C5—C6—C7	−1.0 (3)
C1—C2—C3—C4	177.39 (18)	C5—C6—C7—C2	1.5 (3)
C1—C2—C7—C6	−178.38 (17)	C7—C2—C3—C4	0.1 (3)

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, x−y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H···Cl^iii	1.00	2.00	3.004 (2)	180
C1—H1B···Cl	0.99	2.70	3.5470 (18)	144
C3—H3···Cl^iii	0.95	3.06	3.683 (2)	125

Symmetry code: (iii) x, y, z−1.