Bis(di­cyclo­hexyl­ammonium) sulfate dihydrate

Ndoye, D.; Sow, M.M.; Diop, L.

doi:10.1107/S1600536814000968

organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Page o237

doi:10.1107/S1600536814000968

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Bis(dicyclohexylammonium) sulfate dihydrate

Daouda Ndoye,^a ^* Mouhamadou M. Sow ^a and Libasse Diop ^a

^aLaboratoire de Chimie Minerale et Analytique (LACHIMIA), Departement de Chimie, Faculte des Sciences et Techniques, Universite Cheikh Anta Diop, Dakar, Senegal
^*Correspondence e-mail: ndoyedeve@yahoo.fr

(Received 3 January 2014; accepted 14 January 2014; online 5 February 2014)

In the title dihydrate salt, 2C₁₂H₂₄N⁺·SO₄²⁻·2H₂O, the cation possesses twofold rotational symmetry, with the N atom situated on the twofold axis. The sulfate anion has fourfold roto-inversion symmetry, with the S atom located on the -4 axis. In the crystal, the components are linked via ammonium–sulfate N—H⋯O and water–sulfate O—H⋯O hydrogen bonds, forming a three-dimensional network.

CCDC reference: 981528

Related literature

For the structure of triammonium hydrogen disulfate, see: Suzuki & Makita (1978 ). For various sulfate complexes, see: Hathaway (1973 ); Diassé-Sarr et al. (1997 ); Diallo et al. (2010 ); Diop et al. (2012 ).

Experimental

Crystal data

2C₁₂H₂₄N⁺·SO₄²⁻·2H₂O
M_r = 496.74
Tetragonal, $[I \overline 42d ]$
a = 12.437 (3) Å
c = 17.290 (4) Å
V = 2674.4 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 K
0.48 × 0.44 × 0.37 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
9860 measured reflections
1191 independent reflections
1131 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.075
S = 1.16
1191 reflections
84 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.12 e Å⁻³
Absolute structure: Flack (1983 ); 514 Friedel pairs
Absolute structure parameter: 0.04 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1	0.929 (18)	1.919 (19)	2.8468 (17)	176.6 (16)
O1W—H1W⋯O1	0.93 (4)	2.12 (4)	3.020 (2)	163 (3)

Data collection: locally modified CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: SET4 (de Boer & Duisenberg, 1984 ); data reduction: HELENA (Spek, 1997 ); 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 and PLATON.

Supporting information

CCDC reference: 981528

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814000968/pk2513sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814000968/pk2513Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814000968/pk2513Isup3.cml

checkCIF report

Comment top

A number of sulfato complexes have been synthesized and characterized in order to study the behaviour of the sulfate anion as a ligand (Hathaway, 1973). The triammonium hydrogen disulfate salt has been prepared by the reaction of ammonia with sulfuric acid (Suzuki & Makita, 1978). In our laboratory, previous work on the behaviour of the sulfate ion has been studied especially in relation to tin(IV) complexes (Diassé-Sarr et al., 1997; Diallo et al., 2010; Diop et al., 2012). In the present work, we prepared the title salt by the reaction of aminoiminomethanesulfonic acid and dicyclohexylamine, and we describe herein its crystal structure.

The molecular structure of the title salt is illustrated in Fig. 1. The dicyclohexylammonium cation possesses two-fold rotational symmetry, with atom N1 situated on the two-fold axis. The sulfate cation has fourfold rotary inversion symmetry with atom S1 located on the 4.

In the crystal, the various units are linked via N—H···O(sulfate) and O—H(water)···O(sulfate) hydrogen bonds forming a three-dimensional network (Table 1 and Fig. 2).

Related literature top

For the structure of triammonium hydrogen disulfate, see: Suzuki & Makita (1978). For various sulfate complexes, see: Hathaway (1973); Diassé-Sarr et al. (1997); Diallo et al. (2010); Diop et al. (2012).

Experimental top

The title compound was obtained by reacting aminoiminomethanesulfonic acid with dicyclohexylamine in a 1:1 molar ratio in water. The solution was heated for 2 h, stirred for ca 8 h and then filtered. The filtrate was allowed to evaporation in a drying cupboard at 333 K, and yielded colourless block-like crystals of the title salt suitable for an X-ray diffraction analysis.

Computing details top

Data collection: locally modified CAD-4 Software (Enraf–Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. A view of the molecular structure of the title salt, with atom labelling. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title salt. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

Bis(dicyclohexylammonium) sulfate dihydrate top

Crystal data top

2C₁₂H₂₄N⁺·SO₄²⁻·2H₂O	D_x = 1.234 Mg m⁻³
M_r = 496.74	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42d	Cell parameters from 5803 reflections
Hall symbol: I -4 2bw	θ = 3.3–25.0°
a = 12.437 (3) Å	µ = 0.16 mm⁻¹
c = 17.290 (4) Å	T = 293 K
V = 2674.4 (11) Å³	Prism, colourless
Z = 4	0.48 × 0.44 × 0.37 mm
F(000) = 1096

Data collection top

Bruker APEXII CCD area-detector diffractometer	1131 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.019
Graphite monochromator	θ_max = 25.0°, θ_min = 2.0°
ω scans	h = −14→14
9860 measured reflections	k = −14→14
1191 independent reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0427P)² + 0.6142P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max = 0.001
1191 reflections	Δρ_max = 0.16 e Å⁻³
84 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints	Absolute structure: Flack (1983); 514 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (10)

Crystal data top

2C₁₂H₂₄N⁺·SO₄²⁻·2H₂O	Z = 4
M_r = 496.74	Mo Kα radiation
Tetragonal, I42d	µ = 0.16 mm⁻¹
a = 12.437 (3) Å	T = 293 K
c = 17.290 (4) Å	0.48 × 0.44 × 0.37 mm
V = 2674.4 (11) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	1131 reflections with I > 2σ(I)
9860 measured reflections	R_int = 0.019
1191 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	Δρ_max = 0.16 e Å⁻³
S = 1.16	Δρ_min = −0.12 e Å⁻³
1191 reflections	Absolute structure: Flack (1983); 514 Friedel pairs
84 parameters	Absolute structure parameter: 0.04 (10)
0 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.10093 (14)	0.25000	0.12500	0.0327 (5)
C1	0.08284 (13)	0.36633 (14)	0.01210 (9)	0.0436 (5)
C2	0.14068 (15)	0.43411 (15)	−0.04852 (10)	0.0503 (6)
C3	0.21449 (14)	0.51624 (14)	−0.01157 (10)	0.0492 (5)
C4	0.29313 (14)	0.46346 (14)	0.04327 (11)	0.0493 (5)
C5	0.23596 (13)	0.39552 (13)	0.10417 (9)	0.0414 (5)
C6	0.16348 (12)	0.31304 (12)	0.06577 (8)	0.0330 (4)
S1	0.00000	0.00000	0.00000	0.0307 (1)
O1	−0.02822 (9)	0.09357 (10)	0.04872 (7)	0.0507 (4)
O1W	−0.1807 (2)	0.25000	0.12500	0.1049 (13)
H1A	0.03480	0.41170	0.04200	0.0520*
H1N	0.0568 (15)	0.2011 (15)	0.0997 (10)	0.045 (5)*
H2A	0.18250	0.38740	−0.08190	0.0600*
H2B	0.08790	0.47090	−0.08030	0.0600*
H3A	0.25390	0.55400	−0.05160	0.0590*
H3B	0.17180	0.56860	0.01650	0.0590*
H4A	0.33540	0.51850	0.06880	0.0590*
H4B	0.34190	0.41820	0.01400	0.0590*
H5A	0.28880	0.35910	0.13600	0.0500*
H5B	0.19330	0.44170	0.13740	0.0500*
H6	0.20800	0.26330	0.03570	0.0400*
H21B	0.03990	0.31170	−0.01340	0.0520*
H1W	−0.143 (3)	0.203 (3)	0.093 (2)	0.1570*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0290 (9)	0.0315 (9)	0.0377 (9)	0.0000	0.0000	−0.0034 (8)
C1	0.0397 (8)	0.0456 (9)	0.0454 (9)	−0.0032 (7)	−0.0098 (7)	0.0033 (7)
C2	0.0534 (11)	0.0556 (11)	0.0419 (8)	−0.0025 (8)	−0.0062 (8)	0.0093 (8)
C3	0.0541 (10)	0.0414 (9)	0.0520 (9)	−0.0032 (7)	0.0021 (8)	0.0081 (8)
C4	0.0415 (9)	0.0496 (10)	0.0567 (9)	−0.0107 (7)	−0.0021 (8)	0.0092 (8)
C5	0.0369 (8)	0.0453 (9)	0.0419 (8)	−0.0076 (7)	−0.0062 (7)	0.0042 (7)
C6	0.0322 (7)	0.0320 (7)	0.0348 (7)	0.0015 (6)	0.0011 (6)	−0.0006 (6)
S1	0.0294 (2)	0.0294 (2)	0.0332 (3)	0.0000	0.0000	0.0000
O1	0.0526 (8)	0.0448 (7)	0.0546 (6)	−0.0044 (5)	0.0049 (5)	−0.0205 (6)
O1W	0.0498 (14)	0.109 (2)	0.156 (3)	0.0000	0.0000	−0.003 (2)

Geometric parameters (Å, º) top

S1—O1ⁱ	1.4789 (13)	C4—C5	1.526 (2)
S1—O1ⁱⁱ	1.4789 (13)	C5—C6	1.518 (2)
S1—O1ⁱⁱⁱ	1.4789 (13)	C1—H21B	0.9700
S1—O1	1.4789 (13)	C1—H1A	0.9700
O1W—H1W^iv	0.93 (4)	C2—H2B	0.9700
O1W—H1W	0.93 (4)	C2—H2A	0.9700
N1—C6^iv	1.5062 (17)	C3—H3A	0.9700
N1—C6	1.5062 (17)	C3—H3B	0.9700
N1—H1N	0.929 (18)	C4—H4A	0.9700
N1—H1N^iv	0.929 (18)	C4—H4B	0.9700
C1—C6	1.519 (2)	C5—H5B	0.9700
C1—C2	1.525 (2)	C5—H5A	0.9700
C2—C3	1.515 (3)	C6—H6	0.9800
C3—C4	1.512 (3)

O1ⁱ—S1—O1ⁱⁱⁱ	110.56 (7)	C6—C1—H1A	110.00
O1ⁱⁱ—S1—O1ⁱⁱⁱ	108.93 (6)	C1—C2—H2A	109.00
O1—S1—O1ⁱⁱ	110.56 (7)	C1—C2—H2B	109.00
O1—S1—O1ⁱⁱⁱ	108.93 (6)	C3—C2—H2A	109.00
O1—S1—O1ⁱ	108.93 (6)	C3—C2—H2B	109.00
O1ⁱ—S1—O1ⁱⁱ	108.93 (6)	H2A—C2—H2B	108.00
H1W—O1W—H1W^iv	120 (3)	C2—C3—H3A	109.00
C6—N1—C6^iv	117.81 (14)	C2—C3—H3B	109.00
C6—N1—H1N^iv	106.5 (11)	C4—C3—H3A	109.00
C6—N1—H1N	109.0 (11)	C4—C3—H3B	109.00
C6^iv—N1—H1N	106.5 (11)	H3A—C3—H3B	108.00
H1N—N1—H1N^iv	107.6 (16)	H4A—C4—H4B	108.00
C6^iv—N1—H1N^iv	109.0 (11)	C3—C4—H4A	109.00
C2—C1—C6	110.46 (13)	C3—C4—H4B	109.00
C1—C2—C3	111.64 (14)	C5—C4—H4A	109.00
C2—C3—C4	111.33 (15)	C5—C4—H4B	109.00
C3—C4—C5	111.82 (14)	C4—C5—H5A	110.00
C4—C5—C6	110.43 (13)	C4—C5—H5B	110.00
N1—C6—C5	111.16 (11)	C6—C5—H5A	110.00
C1—C6—C5	111.37 (13)	C6—C5—H5B	110.00
N1—C6—C1	107.55 (12)	H5A—C5—H5B	108.00
H1A—C1—H21B	108.00	N1—C6—H6	109.00
C6—C1—H21B	110.00	C1—C6—H6	109.00
C2—C1—H1A	110.00	C5—C6—H6	109.00
C2—C1—H21B	110.00

C6^iv—N1—C6—C1	178.50 (10)	C1—C2—C3—C4	54.74 (19)
C6^iv—N1—C6—C5	−59.34 (14)	C2—C3—C4—C5	−54.68 (19)
C6—C1—C2—C3	−55.56 (19)	C3—C4—C5—C6	55.35 (18)
C2—C1—C6—N1	178.63 (12)	C4—C5—C6—N1	−176.33 (12)
C2—C1—C6—C5	56.60 (17)	C4—C5—C6—C1	−56.41 (17)

Symmetry codes: (i) y, −x, −z; (ii) −x, −y, z; (iii) −y, x, −z; (iv) x, −y+1/2, −z+1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.929 (18)	1.919 (19)	2.8468 (17)	176.6 (16)
O1W—H1W···O1	0.93 (4)	2.12 (4)	3.020 (2)	163 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.929 (18)	1.919 (19)	2.8468 (17)	176.6 (16)
O1W—H1W···O1	0.93 (4)	2.12 (4)	3.020 (2)	163 (3)

Acknowledgements

We are grateful to Professor H. Stoeckli-Evans, University of Neuchâtel, for useful discussions while preparing this submission and to Professor Y. F. Diop, Laboratorio de Quimica Organica (QO2), Departamento de Quimica Organica, Facultad de Quimica, Universidad de Vigo, for performing the X-ray diffraction analysis.

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