Tris(diisopropyl­ammonium) hydrogensulfate sulfate

Mohammadnezhad, G.S.; Amini, M.M.; Khavasi, H.R.; Ng, S.W.

doi:10.1107/S160053680802237X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1564

doi:10.1107/S160053680802237X

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Tris(diisopropylammonium) hydrogensulfate sulfate

Gholamhossein Sh. Mohammadnezhad,^a Mostafa M. Amini,^a Hamid Reza Khavasi ^a and Seik Weng Ng ^b ^*

^aDepartment of Chemistry, Shahid Beheshti University, Tehran, Iran, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 10 July 2008; accepted 16 July 2008; online 23 July 2008)

The cations and anions of the title salt, 3C₆H₁₆N⁺·HSO₄⁻·SO₄²⁻, are linked by N—H⋯O and O—H⋯O hydrogen bonds into a three-dimensional network. The hydrogensulfate ion, with a single S—O(H) bond of 1.563 (2) Å, forms a short O—H⋯O hydrogen bond [O⋯O = 2.609 (2) Å] to the sulfate ion. The hydrogensulfate ion accepts two hydrogen bonds from two cations, whereas the sulfate ion, as an acceptor, binds to four cations. The sulfate ion is disordered approximately equally over two sites related by rotation around one of the O—S bonds.

Related literature

For the crystal structures of other hydrogensulfate–sulfate salts, see: Anderson et al. (2006 ); Banerjee & Murugavel (2004 ); Kang et al. (2005 ); Novozhilova et al. (1987 ); Sridhar et al. (2001 ); Warden et al. (2004 ). For the synthesis of ammonium sulfates, see: Jordanovska et al. (2000 ).

Experimental

Crystal data

3C₆H₁₆N⁺·HSO₄⁻·SO₄²⁻
M_r = 499.72
Monoclinic, P 2₁ /c
a = 8.6178 (6) Å
b = 16.741 (1) Å
c = 19.819 (1) Å
β = 101.973 (5)°
V = 2797.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 (2) K
0.40 × 0.30 × 0.25 mm

Data collection

Stoe IPDSII imaging plate diffractometer
Absorption correction: analytical (X-SHAPE; Stoe & Cie, 2003 ) T_min = 0.91, T_max = 0.94
16154 measured reflections
6311 independent reflections
4905 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.122
S = 1.06
6311 reflections
336 parameters
94 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7⋯O4	0.86 (1)	1.76 (1)	2.609 (2)	174 (4)
N1—H1N1⋯O1	0.86 (1)	1.76 (1)	2.585 (5)	159 (3)
N1—H1N2⋯O6ⁱ	0.85 (1)	2.02 (1)	2.874 (2)	176 (3)
N2—H2N2⋯O4	0.85 (1)	2.10 (1)	2.929 (2)	166 (2)
N2—H2N1⋯O2ⁱⁱ	0.85 (1)	1.85 (1)	2.695 (6)	179 (3)
N2—H2N1⋯O2′ⁱⁱ	0.85 (1)	2.02 (2)	2.855 (8)	166 (3)
N3—H3N1⋯O3	0.86 (1)	1.89 (1)	2.738 (8)	174 (2)
N3—H3N1⋯O3′	0.86 (1)	1.88 (1)	2.711 (7)	162 (2)
N3—H3N2⋯O5ⁱⁱⁱ	0.86 (1)	2.00 (1)	2.819 (2)	159 (2)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) x+1, y, z.

Data collection: X-RED (Stoe & Cie, 2001 ); cell refinement: X-AREA (Stoe & Cie, 2005 ); data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680802237X/gk2158sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680802237X/gk2158Isup2.hkl

checkCIF report

Comment top

Disubstituted ammonium sulfates are used in the synthesis of double salts with other metal sulfates (Jordanovska et al., 2000). The reaction of diisopropylamine with sulfuric acid yielded the expected compound as a double sulfate with diisopropylammonium hydrogensulfate ( Fig. 1). A small number of such double salts are known (Anderson et al., 2006; Banerjee & Murugavel, 2004; Kang et al., 2005; Novozhilova et al., 1987; Sridhar et al., 2001; Warden et al., 2004). In the title compound, the cations and anions are linked by N–H···O and O–H···O hydrogen bonds into three-dimensional network structure. The sulfate ion is disordered over two sites in an "umbrella" type of disorder (only three of the four oxygen atoms are disordered).

Related literature top

For the crystal structures of other hydrogensulfate–sulfate salts, see: Anderson et al. (2006); Banerjee & Murugavel (2004); Kang et al. (2005); Novozhilova et al. (1987); Sridhar et al. (2001); Warden et al. (2004). For the synthesis of ammonium sulfates, see: Jordanovska et al. (2000).

Experimental top

Following the method of Jordanovska et al. (2000), diisopropylamine (1 ml, 7.1 mmol) was dissolved in chloroform (10 ml) and concentrated sulfuric acid was added dropwise at 273 K until a white precipitate was formed. The precipitate was collected and recrystallized from water.

Computing details top

Data collection: X-RED (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of [(C₆H₁₆N)₃]₃ [HSO4] [SO4]; displacement ellipsoids are drawn at the 50% probablity level and H atoms are drawn as spheres of arbitrary radii. Disorder in the sulfate ion is shown.

Tris(diisopropylammonium) hydrogensulfate sulfate top

Crystal data top

3C₆H₁₆N⁺·HSO₄⁻·SO₄²⁻	F(000) = 1096
M_r = 499.72	D_x = 1.187 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4365 reflections
a = 8.6178 (6) Å	θ = 2.4–27.5°
b = 16.741 (1) Å	µ = 0.23 mm⁻¹
c = 19.819 (1) Å	T = 295 K
β = 101.973 (5)°	Block, colorless
V = 2797.2 (3) Å³	0.40 × 0.30 × 0.25 mm
Z = 4

Data collection top

Stoe IPDS-II imaging plate diffractometer	6311 independent reflections
Radiation source: medium-focus sealed tube	4905 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Rotation method scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: analytical (X-SHAPE; Stoe & Cie, 2003)	h = −11→11
T_min = 0.91, T_max = 0.94	k = −21→21
16154 measured reflections	l = −25→15

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.054P)² + 0.953P] where P = (F_o² + 2F_c²)/3
6311 reflections	(Δ/σ)_max = 0.001
336 parameters	Δρ_max = 0.26 e Å⁻³
94 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

3C₆H₁₆N⁺·HSO₄⁻·SO₄²⁻	V = 2797.2 (3) Å³
M_r = 499.72	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6178 (6) Å	µ = 0.23 mm⁻¹
b = 16.741 (1) Å	T = 295 K
c = 19.819 (1) Å	0.40 × 0.30 × 0.25 mm
β = 101.973 (5)°

Data collection top

Stoe IPDS-II imaging plate diffractometer	6311 independent reflections
Absorption correction: analytical (X-SHAPE; Stoe & Cie, 2003)	4905 reflections with I > 2σ(I)
T_min = 0.91, T_max = 0.94	R_int = 0.035
16154 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	94 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.26 e Å⁻³
6311 reflections	Δρ_min = −0.23 e Å⁻³
336 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.69023 (5)	0.61641 (3)	0.59691 (2)	0.03414 (13)
S2	0.50949 (5)	0.60829 (3)	0.81272 (3)	0.03843 (14)
O1	0.6113 (17)	0.6922 (6)	0.5791 (8)	0.093 (4)	0.49 (3)
O2	0.6440 (16)	0.5588 (7)	0.5417 (4)	0.068 (3)	0.49 (3)
O3	0.8606 (6)	0.6263 (9)	0.6126 (4)	0.072 (3)	0.49 (3)
O4	0.63401 (18)	0.58408 (10)	0.65737 (8)	0.0505 (4)
O1'	0.5800 (8)	0.6754 (5)	0.5608 (5)	0.082 (3)	0.51 (3)
O2'	0.6958 (17)	0.5496 (4)	0.5505 (4)	0.065 (2)	0.51 (3)
O3'	0.8453 (7)	0.6519 (7)	0.6185 (4)	0.068 (2)	0.51 (3)
O5	0.36497 (17)	0.57133 (11)	0.77530 (9)	0.0522 (4)
O6	0.4807 (2)	0.66251 (12)	0.86590 (9)	0.0640 (5)
O7	0.5682 (2)	0.66486 (10)	0.76049 (10)	0.0562 (4)
H7	0.584 (4)	0.640 (2)	0.7247 (12)	0.099 (12)*
O8	0.63320 (19)	0.55114 (12)	0.83566 (10)	0.0625 (5)
N1	0.6123 (2)	0.82382 (11)	0.51105 (9)	0.0410 (4)
H1n1	0.604 (3)	0.7752 (8)	0.5238 (13)	0.046 (6)*
H1n2	0.577 (3)	0.8265 (16)	0.4676 (6)	0.057 (7)*
N2	0.4034 (2)	0.46240 (11)	0.59581 (9)	0.0378 (4)
H2n1	0.390 (3)	0.4557 (16)	0.5525 (6)	0.059 (8)*
H2n2	0.480 (2)	0.4947 (12)	0.6089 (13)	0.049 (7)*
N3	1.0587 (2)	0.63815 (11)	0.73947 (9)	0.0379 (4)
H3n1	1.003 (2)	0.6345 (14)	0.6985 (7)	0.047 (7)*
H3n2	1.1482 (17)	0.6160 (13)	0.7392 (13)	0.044 (6)*
C1	0.8175 (4)	0.92758 (18)	0.50748 (18)	0.0813 (9)
H1A	0.7674	0.9628	0.5347	0.122*
H1B	0.7749	0.9369	0.4594	0.122*
H1C	0.9297	0.9374	0.5172	0.122*
C2	0.7866 (3)	0.84177 (15)	0.52506 (12)	0.0518 (6)
H2	0.8301	0.8333	0.5743	0.062*
C3	0.8635 (3)	0.78284 (19)	0.48440 (18)	0.0711 (8)
H3A	0.8421	0.7294	0.4975	0.107*
H3B	0.9761	0.7916	0.4938	0.107*
H3C	0.8213	0.7900	0.4360	0.107*
C4	0.5666 (5)	0.8766 (2)	0.62260 (17)	0.0905 (11)
H4A	0.6716	0.8988	0.6330	0.136*
H4B	0.5689	0.8234	0.6408	0.136*
H4C	0.4970	0.9091	0.6431	0.136*
C5	0.5075 (3)	0.87439 (16)	0.54560 (14)	0.0609 (7)
H5	0.5067	0.9290	0.5277	0.073*
C6	0.3412 (4)	0.8405 (3)	0.5257 (2)	0.0934 (12)
H6A	0.3080	0.8401	0.4763	0.140*
H6B	0.2698	0.8729	0.5451	0.140*
H6C	0.3404	0.7869	0.5429	0.140*
C7	0.4706 (4)	0.38395 (19)	0.70440 (14)	0.0758 (9)
H7A	0.3691	0.3969	0.7143	0.114*
H7B	0.5470	0.4233	0.7248	0.114*
H7C	0.5035	0.3323	0.7231	0.114*
C8	0.4583 (3)	0.38282 (13)	0.62715 (12)	0.0459 (5)
H8	0.3798	0.3424	0.6072	0.055*
C9	0.6128 (3)	0.36272 (16)	0.60696 (15)	0.0620 (7)
H9A	0.5979	0.3624	0.5576	0.093*
H9B	0.6479	0.3110	0.6247	0.093*
H9C	0.6911	0.4020	0.6257	0.093*
C10	0.1143 (3)	0.44046 (19)	0.58522 (16)	0.0659 (7)
H10A	0.1346	0.3909	0.6098	0.099*
H10B	0.1027	0.4309	0.5367	0.099*
H10C	0.0185	0.4637	0.5939	0.099*
C11	0.2517 (3)	0.49718 (14)	0.60939 (12)	0.0461 (5)
H11	0.2637	0.5058	0.6591	0.055*
C12	0.2265 (3)	0.57729 (16)	0.57311 (16)	0.0597 (6)
H12A	0.3155	0.6114	0.5903	0.090*
H12B	0.1316	0.6015	0.5817	0.090*
H12C	0.2166	0.5697	0.5244	0.090*
C13	0.9325 (4)	0.76767 (18)	0.7572 (2)	0.0849 (10)
H13A	0.8896	0.7448	0.7938	0.127*
H13B	0.8580	0.7612	0.7142	0.127*
H13C	0.9526	0.8235	0.7660	0.127*
C14	1.0867 (3)	0.72570 (14)	0.75319 (14)	0.0547 (6)
H14	1.1609	0.7320	0.7976	0.066*
C15	1.1633 (4)	0.75867 (18)	0.69695 (19)	0.0760 (9)
H15A	1.2604	0.7306	0.6970	0.114*
H15B	1.1854	0.8144	0.7051	0.114*
H15C	1.0926	0.7519	0.6530	0.114*
C16	1.0647 (3)	0.5999 (2)	0.86078 (14)	0.0712 (8)
H16A	1.0666	0.6552	0.8738	0.107*
H16B	1.1714	0.5808	0.8655	0.107*
H16C	1.0113	0.5694	0.8901	0.107*
C17	0.9777 (2)	0.59106 (15)	0.78665 (13)	0.0476 (5)
H17	0.8696	0.6116	0.7824	0.057*
C18	0.9683 (3)	0.50527 (16)	0.76210 (19)	0.0720 (8)
H18A	0.9115	0.5029	0.7150	0.108*
H18B	0.9139	0.4738	0.7904	0.108*
H18C	1.0735	0.4847	0.7653	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0348 (2)	0.0397 (3)	0.0275 (2)	−0.00589 (19)	0.00538 (17)	0.00145 (19)
S2	0.0328 (2)	0.0516 (3)	0.0309 (2)	0.0025 (2)	0.00650 (18)	−0.0062 (2)
O1	0.102 (6)	0.046 (3)	0.155 (7)	0.025 (4)	0.081 (5)	0.045 (4)
O2	0.077 (5)	0.100 (5)	0.028 (2)	−0.031 (4)	0.011 (3)	−0.018 (3)
O3	0.029 (2)	0.140 (8)	0.046 (3)	−0.017 (3)	0.0059 (19)	−0.009 (4)
O4	0.0605 (9)	0.0598 (10)	0.0357 (8)	−0.0112 (8)	0.0203 (7)	−0.0017 (7)
O1'	0.050 (3)	0.056 (3)	0.127 (5)	−0.015 (3)	−0.011 (4)	0.045 (3)
O2'	0.100 (6)	0.051 (3)	0.044 (3)	0.002 (3)	0.014 (3)	−0.011 (2)
O3'	0.057 (3)	0.096 (5)	0.045 (3)	−0.040 (3)	−0.008 (2)	0.025 (3)
O5	0.0340 (7)	0.0676 (11)	0.0536 (10)	−0.0023 (7)	0.0058 (6)	−0.0119 (8)
O6	0.0698 (11)	0.0832 (13)	0.0400 (9)	0.0056 (10)	0.0138 (8)	−0.0220 (9)
O7	0.0715 (11)	0.0512 (10)	0.0520 (10)	−0.0055 (8)	0.0265 (9)	−0.0041 (8)
O8	0.0450 (9)	0.0744 (12)	0.0647 (12)	0.0125 (8)	0.0037 (8)	0.0073 (9)
N1	0.0502 (10)	0.0411 (10)	0.0312 (9)	−0.0023 (8)	0.0068 (7)	0.0063 (7)
N2	0.0391 (9)	0.0437 (10)	0.0297 (9)	−0.0076 (7)	0.0046 (7)	0.0014 (7)
N3	0.0317 (8)	0.0428 (9)	0.0365 (9)	0.0022 (7)	0.0010 (7)	−0.0008 (7)
C1	0.099 (2)	0.0678 (19)	0.076 (2)	−0.0386 (17)	0.0171 (17)	−0.0039 (16)
C2	0.0525 (12)	0.0613 (14)	0.0389 (12)	−0.0140 (11)	0.0031 (9)	0.0054 (10)
C3	0.0594 (15)	0.0784 (19)	0.083 (2)	−0.0034 (14)	0.0311 (14)	0.0107 (16)
C4	0.120 (3)	0.101 (3)	0.0549 (18)	0.025 (2)	0.0283 (18)	−0.0156 (17)
C5	0.0791 (18)	0.0545 (14)	0.0517 (15)	0.0212 (13)	0.0196 (12)	0.0102 (11)
C6	0.0603 (17)	0.137 (3)	0.087 (2)	0.031 (2)	0.0243 (16)	0.030 (2)
C7	0.114 (2)	0.0731 (19)	0.0387 (14)	0.0098 (17)	0.0132 (14)	0.0174 (13)
C8	0.0604 (13)	0.0373 (11)	0.0375 (11)	−0.0082 (10)	0.0044 (9)	0.0023 (9)
C9	0.0673 (16)	0.0542 (14)	0.0614 (16)	0.0126 (12)	0.0063 (13)	0.0080 (12)
C10	0.0451 (13)	0.0831 (19)	0.0718 (19)	−0.0161 (13)	0.0175 (12)	−0.0057 (15)
C11	0.0446 (11)	0.0612 (14)	0.0337 (11)	−0.0034 (10)	0.0109 (9)	−0.0096 (10)
C12	0.0482 (13)	0.0610 (15)	0.0682 (17)	0.0057 (11)	0.0081 (11)	−0.0031 (13)
C13	0.088 (2)	0.0484 (15)	0.122 (3)	0.0157 (15)	0.030 (2)	−0.0075 (17)
C14	0.0540 (13)	0.0440 (12)	0.0603 (15)	−0.0026 (10)	−0.0017 (11)	−0.0095 (11)
C15	0.0704 (18)	0.0574 (17)	0.098 (2)	−0.0149 (14)	0.0111 (16)	0.0124 (16)
C16	0.0617 (15)	0.109 (2)	0.0455 (14)	0.0151 (15)	0.0178 (12)	0.0147 (15)
C17	0.0341 (10)	0.0587 (13)	0.0511 (13)	0.0062 (9)	0.0114 (9)	0.0079 (10)
C18	0.0656 (17)	0.0508 (15)	0.100 (3)	−0.0043 (13)	0.0192 (16)	0.0134 (15)

Geometric parameters (Å, º) top

S1—O3	1.445 (4)	C6—H6A	0.9600
S1—O3'	1.444 (4)	C6—H6B	0.9600
S1—O1	1.448 (4)	C6—H6C	0.9600
S1—O2	1.450 (5)	C7—C8	1.513 (3)
S1—O1'	1.452 (4)	C7—H7A	0.9600
S1—O2'	1.456 (4)	C7—H7B	0.9600
S1—O4	1.4848 (15)	C7—H7C	0.9600
S2—O8	1.4344 (17)	C8—C9	1.506 (4)
S2—O5	1.4494 (16)	C8—H8	0.9800
S2—O6	1.4508 (17)	C9—H9A	0.9600
S2—O7	1.5627 (18)	C9—H9B	0.9600
O7—H7	0.856 (10)	C9—H9C	0.9600
N1—C5	1.502 (3)	C10—C11	1.516 (3)
N1—C2	1.500 (3)	C10—H10A	0.9600
N1—H1n1	0.860 (10)	C10—H10B	0.9600
N1—H1n2	0.854 (10)	C10—H10C	0.9600
N2—C8	1.504 (3)	C11—C12	1.516 (4)
N2—C11	1.506 (3)	C11—H11	0.9800
N2—H2n1	0.849 (10)	C12—H12A	0.9600
N2—H2n2	0.851 (10)	C12—H12B	0.9600
N3—C17	1.501 (3)	C12—H12C	0.9600
N3—C14	1.501 (3)	C13—C14	1.519 (4)
N3—H3n1	0.856 (10)	C13—H13A	0.9600
N3—H3n2	0.857 (10)	C13—H13B	0.9600
C1—C2	1.515 (4)	C13—H13C	0.9600
C1—H1A	0.9600	C14—C15	1.513 (4)
C1—H1B	0.9600	C14—H14	0.9800
C1—H1C	0.9600	C15—H15A	0.9600
C2—C3	1.511 (4)	C15—H15B	0.9600
C2—H2	0.9800	C15—H15C	0.9600
C3—H3A	0.9600	C16—C17	1.512 (4)
C3—H3B	0.9600	C16—H16A	0.9600
C3—H3C	0.9600	C16—H16B	0.9600
C4—C5	1.506 (4)	C16—H16C	0.9600
C4—H4A	0.9600	C17—C18	1.513 (4)
C4—H4B	0.9600	C17—H17	0.9800
C4—H4C	0.9600	C18—H18A	0.9600
C5—C6	1.516 (5)	C18—H18B	0.9600
C5—H5	0.9800	C18—H18C	0.9600

O3—S1—O1	110.9 (4)	C8—C7—H7A	109.5
O3—S1—O2	110.3 (4)	C8—C7—H7B	109.5
O1—S1—O2	110.9 (4)	H7A—C7—H7B	109.5
O3'—S1—O1'	109.7 (4)	C8—C7—H7C	109.5
O3'—S1—O2'	110.7 (4)	H7A—C7—H7C	109.5
O1'—S1—O2'	108.3 (4)	H7B—C7—H7C	109.5
O3—S1—O4	110.8 (4)	C9—C8—N2	107.92 (19)
O3'—S1—O4	110.3 (3)	C9—C8—C7	113.1 (2)
O1—S1—O4	107.5 (3)	N2—C8—C7	110.9 (2)
O2—S1—O4	106.4 (3)	C9—C8—H8	108.3
O1'—S1—O4	110.9 (3)	N2—C8—H8	108.3
O2'—S1—O4	106.8 (3)	C7—C8—H8	108.3
O8—S2—O5	112.37 (11)	C8—C9—H9A	109.5
O8—S2—O6	114.51 (11)	C8—C9—H9B	109.5
O5—S2—O6	112.38 (10)	H9A—C9—H9B	109.5
O8—S2—O7	107.02 (11)	C8—C9—H9C	109.5
O5—S2—O7	106.37 (10)	H9A—C9—H9C	109.5
O6—S2—O7	103.28 (11)	H9B—C9—H9C	109.5
S2—O7—H7	112 (3)	C11—C10—H10A	109.5
C5—N1—C2	118.4 (2)	C11—C10—H10B	109.5
C5—N1—H1n1	107.6 (17)	H10A—C10—H10B	109.5
C2—N1—H1n1	106.2 (16)	C11—C10—H10C	109.5
C5—N1—H1n2	107.9 (18)	H10A—C10—H10C	109.5
C2—N1—H1n2	108.1 (18)	H10B—C10—H10C	109.5
H1n1—N1—H1n2	108 (2)	N2—C11—C10	110.6 (2)
C8—N2—C11	118.61 (18)	N2—C11—C12	107.53 (19)
C8—N2—H2n1	105.4 (18)	C10—C11—C12	112.3 (2)
C11—N2—H2n1	106.8 (18)	N2—C11—H11	108.8
C8—N2—H2n2	106.2 (17)	C10—C11—H11	108.8
C11—N2—H2n2	110.3 (17)	C12—C11—H11	108.8
H2n1—N2—H2n2	109 (3)	C11—C12—H12A	109.5
C17—N3—C14	118.56 (19)	C11—C12—H12B	109.5
C17—N3—H3n1	108.2 (17)	H12A—C12—H12B	109.5
C14—N3—H3n1	106.2 (16)	C11—C12—H12C	109.5
C17—N3—H3n2	108.2 (17)	H12A—C12—H12C	109.5
C14—N3—H3n2	108.2 (16)	H12B—C12—H12C	109.5
H3n1—N3—H3n2	107 (2)	C14—C13—H13A	109.5
C2—C1—H1A	109.5	C14—C13—H13B	109.5
C2—C1—H1B	109.5	H13A—C13—H13B	109.5
H1A—C1—H1B	109.5	C14—C13—H13C	109.5
C2—C1—H1C	109.5	H13A—C13—H13C	109.5
H1A—C1—H1C	109.5	H13B—C13—H13C	109.5
H1B—C1—H1C	109.5	N3—C14—C15	107.5 (2)
N1—C2—C3	107.7 (2)	N3—C14—C13	110.6 (2)
N1—C2—C1	111.4 (2)	C15—C14—C13	112.9 (3)
C3—C2—C1	112.3 (2)	N3—C14—H14	108.6
N1—C2—H2	108.5	C15—C14—H14	108.6
C3—C2—H2	108.5	C13—C14—H14	108.6
C1—C2—H2	108.5	C14—C15—H15A	109.5
C2—C3—H3A	109.5	C14—C15—H15B	109.5
C2—C3—H3B	109.5	H15A—C15—H15B	109.5
H3A—C3—H3B	109.5	C14—C15—H15C	109.5
C2—C3—H3C	109.5	H15A—C15—H15C	109.5
H3A—C3—H3C	109.5	H15B—C15—H15C	109.5
H3B—C3—H3C	109.5	C17—C16—H16A	109.5
C5—C4—H4A	109.5	C17—C16—H16B	109.5
C5—C4—H4B	109.5	H16A—C16—H16B	109.5
H4A—C4—H4B	109.5	C17—C16—H16C	109.5
C5—C4—H4C	109.5	H16A—C16—H16C	109.5
H4A—C4—H4C	109.5	H16B—C16—H16C	109.5
H4B—C4—H4C	109.5	N3—C17—C16	110.7 (2)
N1—C5—C4	111.5 (2)	N3—C17—C18	107.4 (2)
N1—C5—C6	107.2 (2)	C16—C17—C18	112.8 (2)
C4—C5—C6	112.1 (3)	N3—C17—H17	108.6
N1—C5—H5	108.6	C16—C17—H17	108.6
C4—C5—H5	108.6	C18—C17—H17	108.6
C6—C5—H5	108.6	C17—C18—H18A	109.5
C5—C6—H6A	109.5	C17—C18—H18B	109.5
C5—C6—H6B	109.5	H18A—C18—H18B	109.5
H6A—C6—H6B	109.5	C17—C18—H18C	109.5
C5—C6—H6C	109.5	H18A—C18—H18C	109.5
H6A—C6—H6C	109.5	H18B—C18—H18C	109.5
H6B—C6—H6C	109.5

C5—N1—C2—C3	−180.0 (2)	C8—N2—C11—C10	−58.1 (3)
C5—N1—C2—C1	−56.5 (3)	C8—N2—C11—C12	179.04 (18)
C2—N1—C5—C4	−53.9 (3)	C17—N3—C14—C15	−177.8 (2)
C2—N1—C5—C6	−176.9 (2)	C17—N3—C14—C13	−54.1 (3)
C11—N2—C8—C9	−178.90 (19)	C14—N3—C17—C16	−55.2 (3)
C11—N2—C8—C7	−54.6 (3)	C14—N3—C17—C18	−178.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4	0.86 (1)	1.76 (1)	2.609 (2)	174 (4)
N1—H1N1···O1	0.86 (1)	1.76 (1)	2.585 (5)	159 (3)
N1—H1N2···O6ⁱ	0.85 (1)	2.02 (1)	2.874 (2)	176 (3)
N2—H2N2···O4	0.85 (1)	2.10 (1)	2.929 (2)	166 (2)
N2—H2N1···O2ⁱⁱ	0.85 (1)	1.85 (1)	2.695 (6)	179 (3)
N2—H2N1···O2′ⁱⁱ	0.85 (1)	2.02 (2)	2.855 (8)	166 (3)
N3—H3N1···O3	0.86 (1)	1.89 (1)	2.738 (8)	174 (2)
N3—H3N1···O3′	0.86 (1)	1.88 (1)	2.711 (7)	162 (2)
N3—H3N2···O5ⁱⁱⁱ	0.86 (1)	2.00 (1)	2.819 (2)	159 (2)

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

Experimental details

Crystal data
Chemical formula	3C₆H₁₆N⁺·HSO₄⁻·SO₄²⁻
M_r	499.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	8.6178 (6), 16.741 (1), 19.819 (1)
β (°)	101.973 (5)
V (Å³)	2797.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.40 × 0.30 × 0.25

Data collection
Diffractometer	Stoe IPDS-II imaging plate diffractometer
Absorption correction	Analytical (X-SHAPE; Stoe & Cie, 2003)
T_min, T_max	0.91, 0.94
No. of measured, independent and observed [I > 2σ(I)] reflections	16154, 6311, 4905
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.122, 1.06
No. of reflections	6311
No. of parameters	336
No. of restraints	94
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.23

Computer programs: X-RED (Stoe & Cie, 2001), X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4	0.86 (1)	1.76 (1)	2.609 (2)	174 (4)
N1—H1N1···O1	0.86 (1)	1.76 (1)	2.585 (5)	159 (3)
N1—H1N2···O6ⁱ	0.85 (1)	2.02 (1)	2.874 (2)	176 (3)
N2—H2N2···O4	0.85 (1)	2.10 (1)	2.929 (2)	166 (2)
N2—H2N1···O2ⁱⁱ	0.85 (1)	1.85 (1)	2.695 (6)	179 (3)
N2—H2N1···O2'ⁱⁱ	0.85 (1)	2.02 (2)	2.855 (8)	166 (3)
N3—H3N1···O3	0.86 (1)	1.89 (1)	2.738 (8)	174 (2)
N3—H3N1···O3'	0.86 (1)	1.88 (1)	2.711 (7)	162 (2)
N3—H3N2···O5ⁱⁱⁱ	0.86 (1)	2.00 (1)	2.819 (2)	159 (2)

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

Acknowledgements

The authors thank Shahid Beheshti University and the University of Malaya for supporting this study.

References

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