Penta­decyl­ammonium methyl sulfate

Zhang, L.; Di, Y.; Dan, W.

doi:10.1107/S1600536811011226

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1051

doi:10.1107/S1600536811011226

Open

access

Pentadecylammonium methyl sulfate

Lijun Zhang,^a Youying Di ^a ^* and Wenyan Dan ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: diyouying@126.com

(Received 28 February 2011; accepted 25 March 2011; online 7 April 2011)

In the crystal of the title compound, C₁₅H₃₄N⁺·CH₃SO₄⁻, the cations and anions are joined together via strong N—H⋯O hydrogen bonds into layers parallel to (001).

Related literature

Long-chain n-alkylammonium halides are widely used as surfactants (Aratono et al., 1998 ; Tornblom et al., 2000 ) and as models for biological membranes (Ringsdorf et al., 1988 ). For solid-solid phase transitions in n-alkylammonium chlorides, see: Terreros et al. (2000 ).

Experimental

Crystal data

C₁₅H₃₄N⁺·CH₃O₄S⁻
M_r = 339.53
Monoclinic, P 2₁ /m
a = 5.4260 (5) Å
b = 7.4981 (6) Å
c = 24.376 (2) Å
β = 93.557 (1)°
V = 989.83 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 298 K
0.31 × 0.30 × 0.28 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.946, T_max = 0.951
5243 measured reflections
1880 independent reflections
1025 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.228
S = 1.06
1880 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89	2.03	2.857 (6)	155
N1—H1B⋯O3ⁱⁱ	0.89	2.03	2.911 (3)	169
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011226/ru2002sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011226/ru2002Isup2.hkl

checkCIF report

Comment top

Long-chain n–alkylammonium halides are widely used as surfactants (Aratono et al., 1998; Tornblom et al., 2000) and as models for biological membranes (Ringsdorf et al., 1988). They exhibit polymorphism at room temperature; solid-solid phase transitions occurred in n–alkylammonium chlorides (Terreros et al., 2000). As a part of the studies on novel potential phase transition materials with the thermochemical properties such as n–alkylammonium chlorides, we report the crystal structure of the title compound (Fig. 1).

Atoms N1–C15 are coplanar in the title compound. The Space group of the title compound is P2(1)/m, however, the space group is P2(1)/c (Melanie Rademeyer,2009). The title compound has a symmetry plane, similarly, the n-pentadecylammonium bromide monohydrates has a symmetry axis. Furthermore, the S, O1, O2 and C16 are coplanar in the title compound.

The crystal packing (Fig. 2) is stabilized by one intermolecular N—H···O hydrogen bonds forming ionic pairs, and two other intramolecular N—H···O hydrogen bonds (Table 1).

Related literature top

Long-chain n-alkylammonium halides are widely used as surfactants (Aratono et al., 1998; Tornblom et al., 2000) and as models for biological membranes (Ringsdorf et al., 1988). For solid-solid phase transitions in n-alkylammonium chlorides, see: Terreros et al. (2000).

Experimental top

n–Pentadecylammonium methyl sulfate was prepared by the addition of sulfuric acid to an methanol solution of n–pentadecylamine. The mixture was heated and stirred under reflux for 6 h. Single crystals suitable for X–ray diffraction were prepared by evaporation of the resulting solutionat room temperature. Analysis, calculated for C₁₆H₃₇NSO₄ (Mr =339.53): C 56.60, H 10.98, N 4.13%; found: C 56.59, H 10.99, N 4.12%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. N—H···O interactions and intramolecular (dotted lines) in the crystal structure of the title compound. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) x + 1, y, z]

Pentadecylammonium methyl sulfate top

Crystal data top

C₁₅H₃₄N⁺·CH₃O₄S⁻	F(000) = 376
M_r = 339.53	D_x = 1.139 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 823 reflections
a = 5.4260 (5) Å	θ = 2.5–26.3°
b = 7.4981 (6) Å	µ = 0.18 mm⁻¹
c = 24.376 (2) Å	T = 298 K
β = 93.557 (1)°	Acicular, colourless
V = 989.83 (15) Å³	0.31 × 0.30 × 0.28 mm
Z = 2

Data collection top

Siemens SMART CCD area-detector diffractometer	1880 independent reflections
Radiation source: fine-focus sealed tube	1025 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 10 pixels mm^-1	θ_max = 25.0°, θ_min = 2.5°
phi and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −8→8
T_min = 0.946, T_max = 0.951	l = −26→28
5243 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.228	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1131P)²] where P = (F_o² + 2F_c²)/3
1880 reflections	(Δ/σ)_max = 0.001
130 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₅H₃₄N⁺·CH₃O₄S⁻	V = 989.83 (15) Å³
M_r = 339.53	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 5.4260 (5) Å	µ = 0.18 mm⁻¹
b = 7.4981 (6) Å	T = 298 K
c = 24.376 (2) Å	0.31 × 0.30 × 0.28 mm
β = 93.557 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	1880 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1025 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.951	R_int = 0.062
5243 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	0 restraints
wR(F²) = 0.228	H-atom parameters constrained
S = 1.06	Δρ_max = 0.43 e Å⁻³
1880 reflections	Δρ_min = −0.24 e Å⁻³
130 parameters

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
S1	0.3365 (3)	0.7500	0.07723 (6)	0.0623 (6)
O1	0.3834 (8)	0.7500	0.14136 (16)	0.0806 (13)
O2	0.0747 (8)	0.7500	0.07105 (18)	0.1042 (16)
O3	0.4507 (5)	0.5923 (3)	0.05732 (12)	0.0784 (10)
N1	1.2215 (8)	0.2500	0.03004 (18)	0.0562 (12)
H1A	1.1749	0.2500	−0.0056	0.084*
H1B	1.3113	0.3469	0.0381	0.084*
C1	0.9998 (10)	0.2500	0.0626 (2)	0.0559 (14)
H1	0.9012	0.3544	0.0527	0.067*
C2	1.0542 (10)	0.2500	0.1226 (2)	0.0582 (14)
H2	1.1521	0.3545	0.1327	0.070*
C3	0.8258 (10)	0.2500	0.1545 (2)	0.0601 (14)
H3	0.7285	0.3543	0.1437	0.072*
C4	0.8663 (11)	0.2500	0.2159 (2)	0.0702 (16)
H4	0.9641	0.3542	0.2265	0.084*
C5	0.6433 (11)	0.2500	0.2481 (2)	0.0720 (17)
H5	0.5458	0.3541	0.2374	0.086*
C6	0.6793 (13)	0.2500	0.3087 (3)	0.087 (2)
H6	0.7782	0.3539	0.3190	0.104*
C7	0.4670 (12)	0.2500	0.3429 (2)	0.0811 (19)
H7	0.3682	0.3538	0.3325	0.097*
C8	0.5000 (14)	0.2500	0.4025 (3)	0.098 (2)
H8	0.5995	0.3537	0.4127	0.117*
C9	0.2936 (12)	0.2500	0.4378 (2)	0.085 (2)
H9	0.1941	0.3538	0.4277	0.102*
C10	0.3271 (14)	0.2500	0.4972 (3)	0.101 (2)
H10	0.4269	0.3537	0.5072	0.122*
C11	0.1238 (13)	0.2500	0.5329 (3)	0.089 (2)
H11	0.0241	0.3537	0.5228	0.106*
C12	0.1563 (14)	0.2500	0.5919 (3)	0.106 (2)
H12	0.2565	0.3536	0.6018	0.127*
C13	−0.0447 (14)	0.2500	0.6282 (3)	0.092 (2)
H13	−0.1449	0.3536	0.6184	0.111*
C14	−0.0117 (16)	0.2500	0.6873 (3)	0.116 (3)
H14	0.0882	0.3537	0.6973	0.139*
C15	−0.2143 (16)	0.2500	0.7228 (3)	0.113 (3)
H15C	−0.1514	0.2500	0.7605	0.169*
H15D	−0.3134	0.3545	0.7157	0.169*
C16	0.6344 (14)	0.7500	0.1633 (3)	0.096 (2)
H16A	0.6379	0.7500	0.2028	0.144*
H16B	0.7168	0.8545	0.1510	0.144*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0630 (10)	0.0772 (11)	0.0489 (9)	0.000	0.0208 (7)	0.000
O1	0.077 (3)	0.116 (3)	0.050 (3)	0.000	0.015 (2)	0.000
O2	0.066 (3)	0.177 (5)	0.071 (3)	0.000	0.021 (2)	0.000
O3	0.096 (2)	0.0590 (16)	0.083 (2)	−0.0101 (15)	0.0296 (18)	−0.0184 (14)
N1	0.054 (3)	0.056 (3)	0.060 (3)	0.000	0.017 (2)	0.000
C1	0.052 (3)	0.063 (3)	0.054 (4)	0.000	0.017 (3)	0.000
C2	0.057 (3)	0.065 (3)	0.054 (4)	0.000	0.012 (3)	0.000
C3	0.060 (3)	0.065 (3)	0.057 (4)	0.000	0.018 (3)	0.000
C4	0.072 (4)	0.081 (4)	0.060 (4)	0.000	0.020 (3)	0.000
C5	0.074 (4)	0.087 (4)	0.056 (4)	0.000	0.023 (3)	0.000
C6	0.083 (5)	0.112 (5)	0.067 (4)	0.000	0.026 (3)	0.000
C7	0.080 (5)	0.104 (5)	0.063 (4)	0.000	0.028 (3)	0.000
C8	0.089 (5)	0.136 (6)	0.071 (5)	0.000	0.027 (4)	0.000
C9	0.082 (5)	0.111 (5)	0.064 (5)	0.000	0.027 (4)	0.000
C10	0.095 (6)	0.139 (6)	0.073 (5)	0.000	0.030 (4)	0.000
C11	0.090 (5)	0.115 (5)	0.064 (5)	0.000	0.026 (4)	0.000
C12	0.104 (6)	0.143 (7)	0.074 (5)	0.000	0.034 (4)	0.000
C13	0.100 (5)	0.116 (6)	0.064 (5)	0.000	0.029 (4)	0.000
C14	0.121 (7)	0.152 (7)	0.077 (6)	0.000	0.041 (5)	0.000
C15	0.128 (7)	0.135 (7)	0.081 (6)	0.000	0.043 (5)	0.000
C16	0.110 (6)	0.106 (5)	0.072 (5)	0.000	0.013 (4)	0.000

Geometric parameters (Å, º) top

S1—O2	1.419 (5)	C7—C8	1.453 (8)
S1—O3ⁱ	1.434 (3)	C7—H7	0.9700
S1—O3	1.434 (3)	C8—C9	1.454 (8)
S1—O1	1.568 (4)	C8—H8	0.9700
O1—C16	1.432 (8)	C9—C10	1.450 (8)
N1—C1	1.481 (6)	C9—H9	0.9700
N1—H1A	0.8900	C10—C11	1.445 (8)
N1—H1B	0.8900	C10—H10	0.9700
C1—C2	1.474 (7)	C11—C12	1.439 (9)
C1—H1	0.9700	C11—H11	0.9700
C2—C3	1.503 (7)	C12—C13	1.447 (9)
C2—H2	0.9700	C12—H12	0.9700
C3—C4	1.500 (7)	C13—C14	1.440 (8)
C3—H3	0.9700	C13—H13	0.9700
C4—C5	1.483 (7)	C14—C15	1.441 (9)
C4—H4	0.9700	C14—H14	0.9700
C5—C6	1.478 (8)	C15—H15C	0.9600
C5—H5	0.9700	C15—H15D	0.9600
C6—C7	1.462 (8)	C16—H16A	0.9600
C6—H6	0.9700	C16—H16B	0.9600

O2—S1—O3ⁱ	114.50 (15)	C8—C7—H7	107.0
O2—S1—O3	114.50 (15)	C6—C7—H7	107.1
O3ⁱ—S1—O3	111.2 (2)	C7—C8—C9	122.7 (7)
O2—S1—O1	101.8 (3)	C7—C8—H8	106.7
O3ⁱ—S1—O1	106.91 (15)	C9—C8—H8	106.6
O3—S1—O1	106.91 (15)	C10—C9—C8	122.6 (6)
C16—O1—S1	117.7 (4)	C10—C9—H9	106.7
C1—N1—H1A	109.4	C8—C9—H9	106.7
C1—N1—H1B	109.5	C11—C10—C9	123.2 (7)
H1A—N1—H1B	109.5	C11—C10—H10	106.5
C2—C1—N1	114.3 (4)	C9—C10—H10	106.5
C2—C1—H1	108.6	C12—C11—C10	123.4 (7)
N1—C1—H1	108.7	C12—C11—H11	106.5
C1—C2—C3	113.1 (4)	C10—C11—H11	106.4
C1—C2—H2	109.0	C11—C12—C13	124.2 (7)
C3—C2—H2	108.9	C11—C12—H12	106.3
C4—C3—C2	116.2 (5)	C13—C12—H12	106.3
C4—C3—H3	108.3	C14—C13—C12	124.1 (7)
C2—C3—H3	108.2	C14—C13—H13	106.3
C5—C4—C3	117.0 (5)	C12—C13—H13	106.3
C5—C4—H4	108.0	C13—C14—C15	123.2 (8)
C3—C4—H4	108.0	C13—C14—H14	106.5
C6—C5—C4	117.9 (5)	C15—C14—H14	106.5
C6—C5—H5	107.8	C14—C15—H15C	109.6
C4—C5—H5	107.8	C14—C15—H15D	109.4
C7—C6—C5	120.6 (6)	H15C—C15—H15D	109.5
C7—C6—H6	107.2	O1—C16—H16A	109.5
C5—C6—H6	107.2	O1—C16—H16B	109.5
C8—C7—C6	121.1 (6)	H16A—C16—H16B	109.5

O2—S1—O1—C16	180.000 (1)	C5—C6—C7—C8	180.000 (3)
O3ⁱ—S1—O1—C16	−59.57 (14)	C6—C7—C8—C9	180.000 (3)
O3—S1—O1—C16	59.57 (14)	C7—C8—C9—C10	180.000 (4)
N1—C1—C2—C3	180.0	C8—C9—C10—C11	180.000 (3)
C1—C2—C3—C4	180.000 (1)	C9—C10—C11—C12	180.000 (4)
C2—C3—C4—C5	180.000 (1)	C10—C11—C12—C13	180.000 (5)
C3—C4—C5—C6	180.000 (2)	C11—C12—C13—C14	180.000 (6)
C4—C5—C6—C7	180.000 (2)	C12—C13—C14—C15	180.000 (6)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱ	0.89	2.03	2.857 (6)	155
N1—H1B···O3ⁱⁱⁱ	0.89	2.03	2.911 (3)	169

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

Experimental details

Crystal data
Chemical formula	C₁₅H₃₄N⁺·CH₃O₄S⁻
M_r	339.53
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	298
a, b, c (Å)	5.4260 (5), 7.4981 (6), 24.376 (2)
β (°)	93.557 (1)
V (Å³)	989.83 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.31 × 0.30 × 0.28

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.946, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	5243, 1880, 1025
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.228, 1.06
No. of reflections	1880
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.24

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	2.03	2.857 (6)	154.7
N1—H1B···O3ⁱⁱ	0.89	2.03	2.911 (3)	168.7

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

Acknowledgements

We acknowledge the National Natural Science Foundation of China (20973089) for financial support.

References

Aratono, M., Villeneuve, M., Takiue, T., Ikeda, N. & Iyota, H. (1998). J. Colloid Interface Sci. 200, 161–171. Web of Science CrossRef CAS Google Scholar
Ringsdorf, H., Schlarb, B. & Venzmer, J. (1988). Angew. Chem. Int. Ed. Engl. 27, 113–158. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-Ray Systems, Inc., Madison, Wisconsin, USA. Google Scholar
Terreros, A., Galera-Gomez, P. J. & Lopez-Cabarcos, E. (2000). J. Therm. Anal. Calorim. 61, 341–350. Web of Science CrossRef CAS Google Scholar
Tornblom, M., Sitnikov, R. & Henriksson, U. (2000). J. Phys. Chem. B, 104, 1529–1538. Web of Science CrossRef Google Scholar