Tris(cis-2-hy-droxy-cyclo-hexane-1,3,5-tri-aminium) hydrogen sulfate octa-chloride dihydrate.

The 2-hy-droxy-cyclo-hexane-1,3,5-triaminium (= H(3)L(3+)) cation of the title compound, 3C(6)H(18)N(3)O(3+)·8Cl(-)·HSO(4) (-)·2H(2)O, exhibits a cyclo-hexane chair with three equatorial ammonium groups and one axial hy-droxy group in an all-cis configuration. The hydrogen sulfate anion and two water mol-ecules lie on or in proximity to a threefold axis and are disordered. The crystal structure features N-H⋯Cl and O-H⋯Cl hydrogen bonds. Three C(3)-symmetric motifs can be identified in the structure: (i) Two chloride ions (on the C(3)-axis) together with three H(3)L(3+) cations constitute an [(H(3)L)(3)Cl(2)](7+) cage. (ii) The lipophilic C(6)H(6)-sides of three H(3)L(3+) cations, which are oriented directly towards the C(3)-axis, generate a lipophilic void. The void is filled with the disordered water mol-ecules and with the disordered part of the hydrogen sulfate ion. The hydrogen atoms of these disordered moieties were not located. (iii) Three H(3)L(3+) cations together with one HSO(4) (-) and three Cl(-) counter-ions form an [(HSO(4))(H(3)L)(3)Cl(3)](5+) cage. Looking along the C(3)-axis, these three motifs are arranged in the order (cage 1)⋯(lipophilic void)⋯(cage 2). The crystal studied was found to be a racemic twin.

Related literature

The synthesis of a sulfate salt of H3 L 3+ as well as metal complex formation of L has been reported by Merten et al. (2012 ▶). For the synthesis of a diastereomeric form of L, see: Castellanos et al. (1980 ▶). The hydrogen-bonding ability of axial versus equatorial hy­droxy groups is discussed by Bonnet et al. (2005 ▶), and further examples in related structures are provided by Neis, Merten & Hegetschweiler (2012 ▶) and Neis, Merten, Altenhofer & Hegetschweiler (2012 ▶). Puckering parameters have been calculated according to Cremer & Pople (1975 ▶). For the treatment of hydrogen atoms in SHELXL, see: Müller et al. (2006 ▶).

Experimental

Crystal data

3C6H18N3O3+·8Cl−·HSO4 −·2H2O

M = 861.40

Trigonal,

a = 12.6549 (18) Å

c = 43.616 (9) Å

V = 6049.2 (17) Å3

Z = 6

Mo Kα radiation

μ = 0.66 mm−1

T = 200 K

0.48 × 0.40 × 0.32 mm

Data collection

Stoe IPDS image plate diffractometer

14259 measured reflections

2518 independent reflections

2442 reflections with I > 2σ(I)

R int = 0.075

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.101

S = 1.07

2518 reflections

169 parameters

11 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.75 e Å−3

Δρmin = −0.32 e Å−3

Absolute structure: Flack (1983 ▶), 1255 Friedel pairs

Flack parameter: 0.41 (7)

Data collection: Stoe IPDS Software (Stoe & Cie, 1997 ▶); cell refinement: Stoe IPDS Software; data reduction: Stoe IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812022374/nk2161sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812022374/nk2161Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

3C6H18N3O3+·8Cl−·HSO4−·2H2O	Dx = 1.419 Mg m−3
Mr = 861.40	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 5824 reflections
a = 12.6549 (18) Å	θ = 3.3–38.0°
c = 43.616 (9) Å	µ = 0.66 mm−1
V = 6049.2 (17) Å3	T = 200 K
Z = 6	Prism, colourless
F(000) = 2724	0.48 × 0.40 × 0.32 mm

Stoe IPDS image plate diffractometer	2442 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.075
Graphite monochromator	θmax = 25.5°, θmin = 2.6°
phi scans	h = −14→15
14259 measured reflections	k = −15→15
2518 independent reflections	l = −52→52

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101	w = 1/[σ2(Fo2) + (0.0782P)2 + 1.7412P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
2518 reflections	Δρmax = 0.75 e Å−3
169 parameters	Δρmin = −0.32 e Å−3
11 restraints	Absolute structure: Flack (1983), 1255 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.41 (7)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.25081 (6)	0.28514 (6)	0.523148 (15)	0.02924 (18)
C1	0.2004 (2)	0.3248 (2)	0.40899 (6)	0.0217 (5)
H1	0.2232	0.4124	0.4110	0.026*
N1	0.0651 (2)	0.2485 (2)	0.40665 (6)	0.0260 (5)
H11N	0.049 (4)	0.172 (2)	0.4029 (10)	0.039*
H12N	0.033 (3)	0.264 (4)	0.4234 (7)	0.039*
H13N	0.037 (4)	0.269 (4)	0.3907 (7)	0.039*
C2	0.2434 (2)	0.2867 (2)	0.43791 (6)	0.0201 (5)
H2	0.2079	0.3027	0.4566	0.024*
O2	0.20562 (18)	0.16022 (19)	0.43620 (4)	0.0257 (4)
H2O	0.153 (3)	0.111 (3)	0.4479 (8)	0.039*
C3	0.3833 (2)	0.3621 (3)	0.43928 (6)	0.0221 (5)
H3	0.4084	0.4501	0.4418	0.027*
N3	0.4276 (2)	0.3228 (3)	0.46641 (5)	0.0272 (5)
H31N	0.382 (3)	0.321 (4)	0.4818 (7)	0.041*
H32N	0.418 (4)	0.248 (2)	0.4636 (9)	0.041*
H33N	0.5097 (18)	0.365 (3)	0.4673 (10)	0.041*
C4	0.4447 (2)	0.3482 (3)	0.41051 (6)	0.0232 (5)
H4A	0.5343	0.4014	0.4121	0.028*
H4B	0.4262	0.2627	0.4086	0.028*
C5	0.3974 (3)	0.3838 (2)	0.38230 (6)	0.0224 (5)
H5	0.4231	0.4723	0.3836	0.027*
N5	0.4537 (2)	0.3630 (2)	0.35426 (5)	0.0255 (5)
H51N	0.5342 (18)	0.413 (3)	0.3532 (9)	0.038*
H52N	0.424 (4)	0.373 (4)	0.3361 (6)	0.038*
H53N	0.438 (4)	0.287 (2)	0.3530 (9)	0.038*
C6	0.2583 (2)	0.3090 (3)	0.37982 (6)	0.0214 (5)
H6A	0.2323	0.2218	0.3769	0.026*
H6B	0.2308	0.3365	0.3618	0.026*
S1	0.6667	0.3333	0.51658 (4)	0.0494 (4)
O11	0.6667	0.3333	0.48521 (12)	0.0487 (11)
O12	0.5574 (4)	0.3375 (4)	0.52786 (9)	0.0796 (11)
Cl2	0.65819 (7)	0.61189 (6)	0.460229 (16)	0.03246 (19)
Cl3	0.0000	0.0000	0.48180 (3)	0.0243 (3)
Cl4	0.3333	0.6667	0.53799 (3)	0.0309 (3)
O1W	0.3333	0.6667	0.4283 (5)	0.113 (6)*	0.502 (13)
O2W	0.2408 (13)	0.5251 (14)	0.4717 (3)	0.127 (5)*	0.498 (13)

	U11	U22	U33	U12	U13	U23
Cl1	0.0288 (3)	0.0305 (3)	0.0258 (3)	0.0128 (3)	−0.0011 (3)	−0.0080 (3)
C1	0.0228 (13)	0.0266 (13)	0.0200 (12)	0.0155 (11)	−0.0017 (10)	−0.0011 (10)
N1	0.0236 (12)	0.0382 (13)	0.0228 (12)	0.0205 (11)	0.0001 (10)	0.0006 (10)
C2	0.0195 (12)	0.0250 (13)	0.0157 (12)	0.0111 (11)	−0.0007 (9)	−0.0012 (9)
O2	0.0232 (10)	0.0249 (10)	0.0256 (10)	0.0094 (8)	0.0020 (8)	0.0070 (8)
C3	0.0224 (13)	0.0241 (13)	0.0164 (12)	0.0090 (11)	−0.0022 (10)	−0.0020 (10)
N3	0.0227 (12)	0.0378 (14)	0.0165 (12)	0.0117 (11)	−0.0040 (9)	0.0008 (10)
C4	0.0165 (12)	0.0293 (14)	0.0211 (14)	0.0096 (12)	0.0013 (10)	0.0035 (11)
C5	0.0253 (13)	0.0216 (12)	0.0184 (12)	0.0103 (11)	0.0051 (10)	0.0041 (10)
N5	0.0250 (12)	0.0334 (13)	0.0171 (11)	0.0139 (10)	0.0029 (9)	0.0042 (10)
C6	0.0213 (12)	0.0262 (13)	0.0167 (12)	0.0119 (11)	0.0011 (9)	0.0039 (10)
S1	0.0587 (6)	0.0587 (6)	0.0308 (7)	0.0294 (3)	0.000	0.000
O11	0.0493 (17)	0.0493 (17)	0.047 (3)	0.0246 (8)	0.000	0.000
O12	0.073 (2)	0.085 (3)	0.090 (2)	0.046 (2)	0.041 (2)	0.003 (2)
Cl2	0.0304 (4)	0.0296 (3)	0.0231 (3)	0.0044 (3)	−0.0005 (3)	0.0005 (3)
Cl3	0.0252 (3)	0.0252 (3)	0.0225 (5)	0.01259 (17)	0.000	0.000
Cl4	0.0292 (4)	0.0292 (4)	0.0343 (6)	0.01459 (19)	0.000	0.000

C1—N1	1.490 (3)	N3—H33N	0.901 (19)
C1—C6	1.530 (4)	C4—C5	1.531 (4)
C1—C2	1.543 (4)	C4—H4A	0.9900
C1—H1	1.0000	C4—H4B	0.9900
N1—H11N	0.896 (19)	C5—N5	1.504 (4)
N1—H12N	0.904 (19)	C5—C6	1.529 (4)
N1—H13N	0.875 (19)	C5—H5	1.0000
C2—O2	1.425 (3)	N5—H51N	0.893 (19)
C2—C3	1.536 (4)	N5—H52N	0.912 (19)
C2—H2	1.0000	N5—H53N	0.881 (19)
O2—H2O	0.823 (19)	C6—H6A	0.9900
C3—N3	1.497 (3)	C6—H6B	0.9900
C3—C4	1.531 (4)	S1—O11	1.368 (5)
C3—H3	1.0000	S1—O12i	1.493 (3)
N3—H31N	0.876 (19)	S1—O12ii	1.493 (3)
N3—H32N	0.901 (19)	S1—O12	1.493 (3)
N1—C1—C6	109.2 (2)	C5—C4—C3	109.2 (2)
N1—C1—C2	108.9 (2)	C5—C4—H4A	109.8
C6—C1—C2	111.8 (2)	C3—C4—H4A	109.8
N1—C1—H1	108.9	C5—C4—H4B	109.8
C6—C1—H1	108.9	C3—C4—H4B	109.8
C2—C1—H1	108.9	H4A—C4—H4B	108.3
C1—N1—H11N	106 (3)	N5—C5—C6	109.5 (2)
C1—N1—H12N	108 (3)	N5—C5—C4	108.2 (2)
H11N—N1—H12N	119 (4)	C6—C5—C4	111.9 (2)
C1—N1—H13N	112 (3)	N5—C5—H5	109.1
H11N—N1—H13N	105 (4)	C6—C5—H5	109.1
H12N—N1—H13N	107 (4)	C4—C5—H5	109.1
O2—C2—C3	109.6 (2)	C5—N5—H51N	113 (3)
O2—C2—C1	109.6 (2)	C5—N5—H52N	114 (3)
C3—C2—C1	108.3 (2)	H51N—N5—H52N	105 (4)
O2—C2—H2	109.8	C5—N5—H53N	112 (3)
C3—C2—H2	109.8	H51N—N5—H53N	109 (4)
C1—C2—H2	109.8	H52N—N5—H53N	103 (4)
C2—O2—H2O	121 (3)	C5—C6—C1	109.8 (2)
N3—C3—C4	108.3 (2)	C5—C6—H6A	109.7
N3—C3—C2	109.3 (2)	C1—C6—H6A	109.7
C4—C3—C2	112.9 (2)	C5—C6—H6B	109.7
N3—C3—H3	108.7	C1—C6—H6B	109.7
C4—C3—H3	108.7	H6A—C6—H6B	108.2
C2—C3—H3	108.7	O11—S1—O12i	109.24 (18)
C3—N3—H31N	105 (3)	O11—S1—O12ii	109.24 (19)
C3—N3—H32N	111 (3)	O12i—S1—O12ii	109.70 (18)
H31N—N3—H32N	110 (4)	O11—S1—O12	109.24 (18)
C3—N3—H33N	110 (3)	O12i—S1—O12	109.70 (18)
H31N—N3—H33N	122 (4)	O12ii—S1—O12	109.70 (18)
H32N—N3—H33N	98 (4)
N1—C1—C2—O2	58.1 (3)	N3—C3—C4—C5	178.1 (2)
C6—C1—C2—O2	−62.7 (3)	C2—C3—C4—C5	56.8 (3)
N1—C1—C2—C3	177.6 (2)	C3—C4—C5—N5	−177.0 (2)
C6—C1—C2—C3	56.8 (3)	C3—C4—C5—C6	−56.3 (3)
O2—C2—C3—N3	−58.0 (3)	N5—C5—C6—C1	177.2 (2)
C1—C2—C3—N3	−177.5 (2)	C4—C5—C6—C1	57.2 (3)
O2—C2—C3—C4	62.7 (3)	N1—C1—C6—C5	−178.3 (2)
C1—C2—C3—C4	−56.8 (3)	C2—C1—C6—C5	−57.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···Cl4iii	0.90 (2)	2.38 (2)	3.218 (3)	155 (4)
N1—H12N···Cl2iv	0.90 (2)	2.36 (2)	3.241 (3)	166 (4)
N1—H13N···Cl1v	0.88 (2)	2.29 (2)	3.143 (3)	165 (4)
O2—H2O···Cl3	0.82 (2)	2.28 (2)	3.092 (2)	170 (4)
N3—H31N···Cl1	0.88 (2)	2.34 (2)	3.208 (3)	171 (4)
N3—H32N···Cl2i	0.90 (2)	2.39 (2)	3.289 (3)	176 (4)
N3—H33N···O11	0.90 (2)	2.35 (3)	3.072 (3)	137 (3)
N3—H33N···Cl2	0.90 (2)	2.74 (3)	3.361 (3)	127 (3)
N5—H51N···Cl1vi	0.89 (2)	2.39 (3)	3.184 (3)	148 (4)
N5—H52N···Cl2v	0.91 (2)	2.26 (2)	3.171 (3)	172 (4)
N5—H53N···Cl1iii	0.88 (2)	2.32 (2)	3.194 (3)	171 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯Cl4i	0.90 (2)	2.38 (2)	3.218 (3)	155 (4)
N1—H12N⋯Cl2ii	0.90 (2)	2.36 (2)	3.241 (3)	166 (4)
N1—H13N⋯Cl1iii	0.88 (2)	2.29 (2)	3.143 (3)	165 (4)
O2—H2O⋯Cl3	0.82 (2)	2.28 (2)	3.092 (2)	170 (4)
N3—H31N⋯Cl1	0.88 (2)	2.34 (2)	3.208 (3)	171 (4)
N3—H32N⋯Cl2iv	0.90 (2)	2.39 (2)	3.289 (3)	176 (4)
N3—H33N⋯O11	0.90 (2)	2.35 (3)	3.072 (3)	137 (3)
N3—H33N⋯Cl2	0.90 (2)	2.74 (3)	3.361 (3)	127 (3)
N5—H51N⋯Cl1v	0.89 (2)	2.39 (3)	3.184 (3)	148 (4)
N5—H52N⋯Cl2iii	0.91 (2)	2.26 (2)	3.171 (3)	172 (4)
N5—H53N⋯Cl1i	0.88 (2)	2.32 (2)	3.194 (3)	171 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .