Diiso­propyl­ammonium benzene­sulfonate

Seye, D.; Diop, C.A.K.; Diop, L.; Geiger, D.K.

doi:10.1107/S2414314618008763

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 6| June 2018| x180876

https://doi.org/10.1107/S2414314618008763

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Diisopropylammonium benzenesulfonate

Dame Seye,^a Cheikh Abdoul Khadir Diop,^a ^* Libasse Diop ^a and David K. Geiger ^b

^aLaboratoire de Chimie Minerale et Analytique, Département de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, and ^bDepartment of Chemistry, SUNY-College at Geneseo, Geneseo, NY 14454
^*Correspondence e-mail: dlibasse@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 11 May 2018; accepted 14 June 2018; online 26 June 2018)

In the anion of the title molecular salt, C₆H₁₆N⁺·C₆H₅O₃S⁻, the O atoms of the sulfonate group is rotationally disordered over two sets of sites in a a 0.711 (9):0.289 (9) ratio. The extended structure displays N—H⋯O hydrogen bonds between the cation and anion, which results in infinite chains propagating parallel to [010]. The chains are linked by weak C—H⋯O interactions, yielding a two-dimensional network.

Keywords: crystal structure; hydrogen bonds; layered structure.

CCDC reference: 1849402

Structure description

Ammonium salts of phenylsulfonic acid have been reported by several groups (Lee et al., 2015 ; Skořepová et al., 2017 ; Karak et al., 2017 ). We have now reacted phenylsulfonic acid with diisopropylamine, which yielded crystals of the title molecular salt.

The asymmetric unit is comprised of one diisopropylammonium cation and one phenyl sulfonate anion (Fig. 1): the oxygen atoms of the sulfonate group are rotationally disordered over two orientations in a 0.711 (9):0.289 (9) ratio. The C—C and C—N bonds in the cation are similar to those reported previously for diisopropylammonium-containing compounds (Sarr et al., 2012 ; Lin et al., 2017 ).

Figure 1
View of the title molecular salt showing anisotropic displacement parameters for non-H atoms drawn at the 30% probability level. Only the major disorder component of the sulfonate group is shown.

In the extended structure, the cations and anions are linked via N—H⋯O hydrogen bonds (Table 1) giving rise to [010] chains. These chains are in turn linked through weak C—H⋯O interactions, leading to a layered structure (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86 (2)	2.06 (2)	2.893 (4)	165.0 (19)
N1—H1A⋯O1Aⁱ	0.86 (2)	1.85 (2)	2.684 (6)	163 (2)
N1—H1B⋯O2	0.91 (2)	1.90 (3)	2.782 (4)	162 (2)
N1—H1B⋯O2A	0.91 (2)	2.05 (3)	2.946 (9)	167 (2)
C8—H8A⋯O2	0.98	2.45	3.246 (5)	138
C9—H9A⋯O1ⁱ	0.98	2.54	3.313 (4)	136
C11—H11B⋯O3ⁱⁱ	0.98	2.57	3.493 (4)	157
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+1, -z+2.

Figure 2
Partial packing diagram showing the hydrogen-bonding interactions. Only H atoms involved in the intermolecular interactions are shown. Symmetry codes: (a) −x + 1, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (b) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (c) −x + 1, y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ .

Synthesis and crystallization

Phenylsulfonic acid (5.0 g; 3.0 mmol) was reacted wirh diisopropylamine (3.0 g; 3.0 mmol) in ethanol (50 ml). Slow solvent evaporation at room temperature yielded colourless blocks of the title compound after a weak.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. During the early stages of the refinement, rotational disorder of the oxygen atoms of the sulfonate group was detected. The disorder was modelled using two sets of sites, which refined to occupancies of 0.711 (9):0.289 (9).

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₁₆N⁺·C₆H₅O₃S⁻
M_r	259.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	11.7370 (13), 8.8719 (8), 14.3722 (16)
β (°)	106.616 (3)
V (Å³)	1434.1 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.22
Crystal size (mm)	0.60 × 0.45 × 0.35

Data collection
Diffractometer	Bruker X2S Benchtop
Absorption correction	Multi-scan (SADABS; Bruker, 2016)
T_min, T_max	0.38, 0.93
No. of measured, independent and observed [I > 2σ(I)] reflections	11569, 2910, 2104
R_int	0.106
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.152, 1.05
No. of reflections	2910
No. of parameters	195
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.34
Computer programs: APEX2 and SAINT (Bruker, 2013 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009 ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1849402

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618008763/hb4233sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618008763/hb4233Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618008763/hb4233Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Diisopropylammonium bis(propan-2-yl)azanium top

Crystal data top

C₆H₁₆N⁺·C₆H₅O₃S⁻	F(000) = 560
M_r = 259.36	D_x = 1.201 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.7370 (13) Å	Cell parameters from 4767 reflections
b = 8.8719 (8) Å	θ = 2.7–25.1°
c = 14.3722 (16) Å	µ = 0.22 mm⁻¹
β = 106.616 (3)°	T = 200 K
V = 1434.1 (3) Å³	Block, colorless
Z = 4	0.60 × 0.45 × 0.35 mm

Data collection top

Bruker X2S Benchtop diffractometer	2910 independent reflections
Radiation source: sealed microfocus tube	2104 reflections with I > 2σ(I)
Detector resolution: 8.3330 pixels mm^-1	R_int = 0.106
ω scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −14→14
T_min = 0.38, T_max = 0.93	k = −10→10
11569 measured reflections	l = −17→17

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.050	w = 1/[σ²(F_o²) + (0.0486P)² + 0.288P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.152	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.26 e Å⁻³
2910 reflections	Δρ_min = −0.34 e Å⁻³
195 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015)
3 restraints	Extinction coefficient: 0.0085 (18)
Primary atom site location: structure-invariant direct methods

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. All hydrogen atoms were observed in difference Fourier maps. The H atoms were refined using a riding model with C—H distances of 0.98 Å for the methyl carbon atoms and 0.95 Å for the phenyl carbon atoms. The methyl C—H hydrogen atom isotropic displacement parameters were set using the approximation U_iso(H) = 1.5U_eq(C) and the phenyl hydrogen-atom isotropic displacement parameters were set using the approximation U_iso(H) = 1.2U_eq(C). The hydrogen atoms bonded to the nitrogen atom were refined freely, including isotropic displacement parameters.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.71911 (5)	0.49488 (6)	0.84523 (4)	0.0597 (2)
O1	0.7417 (3)	0.6492 (3)	0.8574 (3)	0.0749 (12)	0.711 (9)
O2	0.6149 (3)	0.4620 (6)	0.7613 (3)	0.0911 (15)	0.711 (9)
O3	0.7116 (4)	0.4164 (4)	0.9309 (3)	0.0989 (19)	0.711 (9)
O1A	0.6956 (12)	0.6349 (8)	0.7859 (11)	0.102 (4)	0.289 (9)
O2A	0.6285 (6)	0.3979 (7)	0.8244 (11)	0.087 (4)	0.289 (9)
O3A	0.7621 (8)	0.5452 (19)	0.9473 (6)	0.131 (7)	0.289 (9)
N1	0.37129 (18)	0.4253 (2)	0.72964 (14)	0.0541 (5)
H1A	0.3478 (19)	0.335 (3)	0.7122 (14)	0.059 (6)*
H1B	0.452 (2)	0.422 (3)	0.7500 (16)	0.071 (7)*
C1	0.84060 (18)	0.4120 (2)	0.81419 (16)	0.0532 (5)
C2	0.8331 (2)	0.3820 (3)	0.71892 (19)	0.0742 (7)
H2	0.7635	0.4086	0.669	0.089*
C3	0.9270 (3)	0.3130 (4)	0.6959 (3)	0.1026 (10)
H3	0.9213	0.2918	0.6299	0.123*
C4	1.0259 (3)	0.2755 (4)	0.7654 (3)	0.1098 (12)
H4	1.0894	0.227	0.7485	0.132*
C5	1.0359 (2)	0.3064 (4)	0.8596 (3)	0.1040 (11)
H5	1.107	0.2812	0.9084	0.125*
C6	0.9420 (2)	0.3753 (3)	0.8858 (2)	0.0769 (7)
H6	0.9485	0.3963	0.952	0.092*
C7	0.3239 (3)	0.5281 (2)	0.64440 (17)	0.0660 (7)
H7	0.3422	0.6346	0.6664	0.079*
C8	0.3885 (3)	0.4913 (3)	0.5695 (2)	0.1053 (11)
H8A	0.4745	0.4962	0.5999	0.158*
H8B	0.3659	0.5643	0.5162	0.158*
H8C	0.3667	0.3896	0.544	0.158*
C9	0.1911 (3)	0.5110 (4)	0.6045 (2)	0.0968 (10)
H9A	0.1719	0.4063	0.5843	0.145*
H9B	0.1618	0.5778	0.5484	0.145*
H9C	0.1532	0.5378	0.6548	0.145*
C10	0.3368 (2)	0.4608 (3)	0.82055 (16)	0.0628 (6)
H10	0.2486	0.4748	0.8028	0.075*
C11	0.3956 (3)	0.6040 (3)	0.86640 (18)	0.0797 (8)
H11A	0.4819	0.5894	0.8886	0.119*
H11B	0.3666	0.6301	0.9219	0.119*
H11C	0.3766	0.6857	0.8186	0.119*
C12	0.3702 (3)	0.3269 (3)	0.8884 (2)	0.0883 (8)
H12A	0.4564	0.3115	0.906	0.132*
H12B	0.3297	0.2366	0.8559	0.132*
H12C	0.3461	0.3462	0.9473	0.132*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0560 (4)	0.0497 (4)	0.0838 (4)	0.0034 (2)	0.0366 (3)	−0.0044 (2)
O1	0.0762 (18)	0.0450 (13)	0.106 (3)	0.0086 (11)	0.0297 (18)	−0.0087 (14)
O2	0.0475 (15)	0.110 (3)	0.119 (3)	−0.0055 (16)	0.0300 (18)	−0.035 (2)
O3	0.134 (4)	0.082 (2)	0.118 (3)	0.024 (2)	0.095 (3)	0.022 (2)
O1A	0.140 (9)	0.042 (4)	0.149 (10)	0.042 (5)	0.082 (8)	0.031 (5)
O2A	0.048 (4)	0.046 (4)	0.177 (13)	−0.001 (3)	0.050 (6)	−0.011 (5)
O3A	0.098 (6)	0.224 (18)	0.075 (5)	0.015 (7)	0.031 (4)	−0.046 (7)
N1	0.0545 (11)	0.0392 (10)	0.0768 (12)	0.0004 (9)	0.0318 (9)	0.0019 (8)
C1	0.0482 (11)	0.0393 (10)	0.0803 (13)	−0.0035 (8)	0.0318 (10)	0.0005 (9)
C2	0.0680 (15)	0.0794 (16)	0.0849 (16)	0.0017 (13)	0.0374 (13)	−0.0044 (13)
C3	0.107 (2)	0.104 (2)	0.127 (3)	0.001 (2)	0.081 (2)	−0.0199 (19)
C4	0.090 (2)	0.082 (2)	0.189 (4)	0.0177 (17)	0.090 (3)	0.007 (2)
C5	0.0518 (15)	0.097 (2)	0.165 (3)	0.0134 (15)	0.0345 (19)	0.028 (2)
C6	0.0588 (14)	0.0732 (15)	0.0996 (18)	0.0020 (12)	0.0241 (14)	0.0064 (13)
C7	0.102 (2)	0.0376 (10)	0.0683 (14)	0.0005 (11)	0.0403 (14)	0.0031 (9)
C8	0.154 (3)	0.098 (2)	0.086 (2)	−0.014 (2)	0.069 (2)	−0.0031 (15)
C9	0.098 (2)	0.099 (2)	0.0853 (19)	0.0297 (17)	0.0137 (18)	0.0179 (15)
C10	0.0497 (12)	0.0769 (14)	0.0711 (13)	0.0092 (11)	0.0319 (11)	0.0153 (11)
C11	0.093 (2)	0.0788 (16)	0.0755 (16)	0.0141 (14)	0.0369 (14)	−0.0058 (12)
C12	0.0853 (18)	0.0942 (19)	0.0882 (17)	0.0015 (16)	0.0293 (15)	0.0330 (15)

Geometric parameters (Å, º) top

S1—O2A	1.334 (6)	C5—H5	0.95
S1—O1	1.396 (3)	C6—H6	0.95
S1—O3	1.439 (3)	C7—C9	1.507 (4)
S1—O3A	1.478 (7)	C7—C8	1.519 (3)
S1—O2	1.481 (3)	C7—H7	1.0
S1—O1A	1.487 (7)	C8—H8A	0.98
S1—C1	1.771 (2)	C8—H8B	0.98
N1—C7	1.501 (3)	C8—H8C	0.98
N1—C10	1.508 (3)	C9—H9A	0.98
N1—H1A	0.86 (2)	C9—H9B	0.98
N1—H1B	0.91 (2)	C9—H9C	0.98
C1—C6	1.372 (3)	C10—C11	1.504 (3)
C1—C2	1.373 (3)	C10—C12	1.516 (3)
C2—C3	1.381 (4)	C10—H10	1.0
C2—H2	0.95	C11—H11A	0.98
C3—C4	1.339 (5)	C11—H11B	0.98
C3—H3	0.95	C11—H11C	0.98
C4—C5	1.354 (5)	C12—H12A	0.98
C4—H4	0.95	C12—H12B	0.98
C5—C6	1.403 (4)	C12—H12C	0.98

O1—S1—O3	115.1 (2)	N1—C7—C9	110.5 (2)
O2A—S1—O3A	116.2 (6)	N1—C7—C8	107.7 (2)
O1—S1—O2	112.2 (2)	C9—C7—C8	112.3 (2)
O3—S1—O2	111.3 (2)	N1—C7—H7	108.7
O2A—S1—O1A	113.9 (6)	C9—C7—H7	108.7
O3A—S1—O1A	105.8 (6)	C8—C7—H7	108.7
O2A—S1—C1	108.8 (3)	C7—C8—H8A	109.5
O1—S1—C1	107.50 (14)	C7—C8—H8B	109.5
O3—S1—C1	105.38 (14)	H8A—C8—H8B	109.5
O3A—S1—C1	107.7 (4)	C7—C8—H8C	109.5
O2—S1—C1	104.49 (14)	H8A—C8—H8C	109.5
O1A—S1—C1	103.5 (3)	H8B—C8—H8C	109.5
C7—N1—C10	116.82 (17)	C7—C9—H9A	109.5
C7—N1—H1A	108.3 (14)	C7—C9—H9B	109.5
C10—N1—H1A	107.7 (14)	H9A—C9—H9B	109.5
C7—N1—H1B	112.8 (15)	C7—C9—H9C	109.5
C10—N1—H1B	104.0 (15)	H9A—C9—H9C	109.5
H1A—N1—H1B	107 (2)	H9B—C9—H9C	109.5
C6—C1—C2	119.8 (2)	C11—C10—N1	110.68 (18)
C6—C1—S1	119.83 (19)	C11—C10—C12	112.2 (2)
C2—C1—S1	120.32 (18)	N1—C10—C12	108.0 (2)
C1—C2—C3	119.8 (3)	C11—C10—H10	108.6
C1—C2—H2	120.1	N1—C10—H10	108.6
C3—C2—H2	120.1	C12—C10—H10	108.6
C4—C3—C2	120.8 (3)	C10—C11—H11A	109.5
C4—C3—H3	119.6	C10—C11—H11B	109.5
C2—C3—H3	119.6	H11A—C11—H11B	109.5
C3—C4—C5	120.3 (3)	C10—C11—H11C	109.5
C3—C4—H4	119.9	H11A—C11—H11C	109.5
C5—C4—H4	119.9	H11B—C11—H11C	109.5
C4—C5—C6	120.5 (3)	C10—C12—H12A	109.5
C4—C5—H5	119.8	C10—C12—H12B	109.5
C6—C5—H5	119.8	H12A—C12—H12B	109.5
C1—C6—C5	118.8 (3)	C10—C12—H12C	109.5
C1—C6—H6	120.6	H12A—C12—H12C	109.5
C5—C6—H6	120.6	H12B—C12—H12C	109.5

O2A—S1—C1—C6	−112.9 (7)	C6—C1—C2—C3	1.0 (4)
O1—S1—C1—C6	82.8 (3)	S1—C1—C2—C3	−178.0 (2)
O3—S1—C1—C6	−40.4 (3)	C1—C2—C3—C4	−0.3 (5)
O3A—S1—C1—C6	13.9 (7)	C2—C3—C4—C5	−0.7 (5)
O2—S1—C1—C6	−157.8 (3)	C3—C4—C5—C6	1.2 (5)
O1A—S1—C1—C6	125.6 (7)	C2—C1—C6—C5	−0.5 (4)
O2A—S1—C1—C2	66.0 (7)	S1—C1—C6—C5	178.4 (2)
O1—S1—C1—C2	−98.3 (3)	C4—C5—C6—C1	−0.6 (4)
O3—S1—C1—C2	138.5 (3)	C10—N1—C7—C9	−68.0 (3)
O3A—S1—C1—C2	−167.2 (7)	C10—N1—C7—C8	168.9 (2)
O2—S1—C1—C2	21.1 (3)	C7—N1—C10—C11	−69.1 (3)
O1A—S1—C1—C2	−55.4 (7)	C7—N1—C10—C12	167.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86 (2)	2.06 (2)	2.893 (4)	165.0 (19)
N1—H1A···O1Aⁱ	0.86 (2)	1.85 (2)	2.684 (6)	163 (2)
N1—H1B···O2	0.91 (2)	1.90 (3)	2.782 (4)	162 (2)
N1—H1B···O2A	0.91 (2)	2.05 (3)	2.946 (9)	167 (2)
C8—H8A···O2	0.98	2.45	3.246 (5)	138
C9—H9A···O1ⁱ	0.98	2.54	3.313 (4)	136
C11—H11B···O3ⁱⁱ	0.98	2.57	3.493 (4)	157
C7—H7···O2Aⁱⁱⁱ	1.0	2.36	3.336 (8)	166
C12—H12B···O1Aⁱ	0.98	2.17	2.944 (11)	135
C12—H12C···O3Aⁱⁱ	0.98	2.44	3.371 (8)	159

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) −x+1, y+1/2, −z+3/2.

Funding information

The authors acknowledge Cheikh Anta Diop University, Dakar, Senegal, for support and the US Department of Education via a Congressionally directed grant (grant No. P116Z100020) for the X-ray diffractometer.

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