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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 6| June 2012| Pages o1899-o1900

Tris(cis-2-hy­dr­oxy­cyclo­hexane-1,3,5-tri­aminium) hydrogen sulfate octa­chloride dihydrate

aFachrichtung Chemie, Universität des Saarlandes, Postfach 151150, D-66041 Saarbrücken, Germany
*Correspondence e-mail: hegetschweiler@mx.uni-saarland.de

(Received 27 April 2012; accepted 16 May 2012; online 26 May 2012)

The 2-hy­droxy­cyclo­hexane-1,3,5-triaminium (= H3L3+) cation of the title compound, 3C6H18N3O3+·8Cl·HSO4·2H2O, exhibits a cyclo­hexane chair with three equatorial ammonium groups and one axial hy­droxy group in an all-cis configuration. The hydrogen sulfate anion and two water mol­ecules 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 C3-symmetric motifs can be identified in the structure: (i) Two chloride ions (on the C3-axis) together with three H3L3+ cations constitute an [(H3L)3Cl2]7+ cage. (ii) The lipophilic C6H6-sides of three H3L3+ cations, which are oriented directly towards the C3-axis, generate a lipophilic void. The void is filled with the disordered water mol­ecules and with the disordered part of the hydrogen sulfate ion. The hydrogen atoms of these disordered moieties were not located. (iii) Three H3L3+ cations together with one HSO4 and three Cl counter-ions form an [(HSO4)(H3L)3Cl3]5+ cage. Looking along the C3-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 H3L3+ as well as metal complex formation of L has been reported by Merten et al. (2012[Merten, G. J., Neis, C., Stucky, S., Huch, V., Rentschler, E., Natter, H., Hempelmann, R., Stöwe, K. & Hegetschweiler, K. (2012). Eur. J. Inorg. Chem. pp. 31-35.]). For the synthesis of a diastereomeric form of L, see: Castellanos et al. (1980[Castellanos, L., Cleophax, J., Colas, C., Gero, S. D., Leboul, J., Mercier, D., Olesker, A., Rolland, A., Quiclet-Sire, B. & Sepulchre, A.-M. (1980). Carbohydr. Res. 82, 283-301.]). The hydrogen-bonding ability of axial versus equatorial hy­droxy groups is discussed by Bonnet et al. (2005[Bonnet, A., Chisholm, J., Motherwell, W. D. S. & Jones, W. (2005). CrystEngComm, 7, 71-75.]), and further examples in related structures are provided by Neis, Merten & Hegetschweiler (2012[Neis, C., Merten, G. J. & Hegetschweiler, K. (2012). Acta Cryst. E68, o1425-o1426.]) and Neis, Merten, Altenhofer & Hegetschweiler (2012[Neis, C., Merten, G. J., Altenhofer, P. & Hegetschweiler, K. (2012). Acta Cryst. E68, o1411-o1412.]). Puckering parameters have been calculated according to Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]). For the treatment of hydrogen atoms in SHELXL, see: Müller et al. (2006[Müller, P., Herbst-Irmer, R., Spek, A. L., Schneider, T. R. & Sawaya, M. R. (2006). Crystal Structure Refinement - A Crystallographer's Guide to SHELXL. Oxford University Press.]).

[Scheme 1]

Experimental

Crystal data
  • 3C6H18N3O3+·8Cl·HSO4·2H2O

  • Mr = 861.40

  • Trigonal, R 3c

  • 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)

  • Rint = 0.075

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 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[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 1255 Friedel pairs

  • Flack parameter: 0.41 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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) [-y+{\script{2\over 3}}, -x+{\script{1\over 3}}, z-{\script{1\over 6}}]; (ii) -x+y, -x+1, z; (iii) [x-{\script{1\over 3}}, x-y+{\script{1\over 3}}, z-{\script{1\over 6}}]; (iv) -y+1, x-y, z; (v) [-x+y+{\script{2\over 3}}, y+{\script{1\over 3}}, z-{\script{1\over 6}}].

Data collection: Stoe IPDS Software (Stoe & Cie, 1997[Stoe & Cie (1997). IPDS Software. Stoe & Cie, Darmstadt, Germany.]); cell refinement: Stoe IPDS Software; data reduction: Stoe IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2012[Brandenburg, K. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

All-cis-2-hydroxycyclohexane-1,3,5-triamine (= L) has been prepared very recently in our laboratory for the first time by hydrogenation of picric acid (Merten et al., 2012). Due to its two distinct, facially coordinating metal binding sites (N,N,N versus N,O,N), it is an interesting chelating agent. A corresponding diastereomer with the hydroxy group in trans-position has been known for many years (Castellanos et al., 1980).

In the crystal structure of the title compound, the cyclohexane ring of the H3L3+ cation exhibits a chair conformation with the hydroxy group in axial and the three ammonium groups in equatorial position. Puckering parameters of the cyclohexane ring according to Cremer and Pople (1975) are Q = 0.588 Å, θ = 179.2 °, ϕ = 182.4 °. Due to the particular all-cis-configuration, the cation has an amphiphilic shape with a lipophilic (C6H6) and a hydrophilic (OH, NH3+) side. It is noteworthy that the lipophilic side of H3L3+ is directly oriented towards the C3-axis, generating thus a lipophilic void with a trigonal geometry. This void is filled with a part of the hydrogen sulfate anion and the water of crystallization, both located either on, or close to, the threefold axis. The moieties within this void are all disordered (see the experimental refinement section). The crystal structure is basically made up by a complex net of N—H···Cl hydrogen bonds. Additionally, the oxo oxygen atom O11 of the HSO4- anion accepts three H(—N) hydrogen atoms, and the hydroxy group (O2) of the H3L3+ cation donates its proton to Cl3. O2 does, however, not act as an acceptor. A similar behaviour has recently been noted in related structures (Neis, Merten & Hegetschweiler, 2012; Neis, Merten & Altenhofer et al., 2012). It is well known that the ability of axial hydroxy groups for forming hydrogen bonds is restricted on steric grounds (Bonnet et al., 2005). Cl1 has a coordination number of four with a distorted tetrahedral geometry. Cl2 also accepts four H(—N) hydrogen atoms. However, if the Cl2···O2W distance of 3.225 Å is interpreted in terms of an O—H···Cl hydrogen bond, the coordination number is five with a geometry intermediate between a trigonal bipyramid and a square pyramid (τ = 0.43). It must, however, be emphasized that O2W is only partially occupied and the hydrogen atom in consideration could not be located (see again the experimental refinement section). Cl3 and Cl4 (lying on the C3-axis) have both a coordination number of three with a trigonal pyramidal geometry.

Viewing the structure along the threefold axis, three distinct structural motives can be recognized. (i) Cl3 and Cl4 together with three symmetry equivalent H3L3+ cations constitute a [(H3L)3Cl2]7+ cage, where Cl3 is hydrogen bonded to three hydroxy groups and Cl4 is hydrogen bonded to three ammonium groups of the three cations. (ii) The lipophilic void, formed by the C6H6-sides of three H3L3+ cations has already been mentioned. The three cations are interlinked by three Cl2 ions via N—H···Cl···H—N hydrogen bonding. The disorder that is observed for the moieties within this void, is probably caused by the absence of suitable hydrophilic hydrogen acceptors. (iii) Three H3L3+ cations together with a HSO4- and three Cl- counter ions form a [(H3L)3Cl3(HSO4)]5+ cage with the Cl- anions and three ammonium groups (N5) forming an almost planar, hydrogen bonded N3H6Cl3 ring. Looking along the C3-axis, these three motives are arranged in the order cage 1 ··· lipophilic void ··· cage 2 ···.

Related literature top

The synthesis of a sulfate salt of H3L3+ 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 top

A hydrated sulfate salt (H3L)2(SO4)3.5H2O has been prepared following the protocol given by Merten et al. (2012). 1H-NMR (D2O): δ (p.p.m.) = 1.92 (q, 2H), 2.25 (td, 2H), 3.51 (tt, 1H), 3.59 (ddd, 2H) 4.32 (t, 1H). 13C-NMR (D2O): δ (p.p.m.) = 29.7, 47.8, 52.0, 66.5. Elemental analysis calculated for C12H46N6O19S3 (%): C 21.36, H 6.87, N 12.46; found (%): C 21.47, H 6.13, N 12.07. Single crystals were obtained from an aqueous solution of the sulfate salt which has been acidified with conc. hydrochloric acid to pH < 1. The solution was allowed to evaporate slowly at ambient conditions (295 K). Single crystals appeared after a period of several days.

Refinement top

The H3L3+ cation could be refined without problems, and its hydrogen atoms could all be located. They were treated as recommended by Müller et al. (2006): A riding model was used for H(—C) atoms. The positional parameters of the O- and N-bonded H-atoms were refined using isotropic displacement parameters which were set to 1.5×Ueq of the pivot atom. In addition, restraints of 0.84 and 0.88 Å were used for the O—H and N—H distances. A total of four chloride positions were located; two of them (Cl3 and Cl4) are placed on the threefold axis, adding up altogether to a total charge of -2.667. Moreover, an SO4 moiety was located on the three fold axis. Although a hydrogen atom could not be found in proximity to any of the sulfate oxygen atoms, charge balance considerations require that this moiety must be formulated as HSO4- (this is reasonable, if the acidic medium used for crystal growth is considered). In agreement with such an interpretation, two distinctly different S—O bond lengths were observed. O11, lying again on a threefold axis, forms a short S=O bond. O12, which forms a longer S—O bond, lies, however, on a general position. It appears thus that the hydrogen atom of the HSO4- ion is distributed over three symmetry equivalent sites, and O12 is occupied in a 33%: 66% ratio by a hydroxy and an oxo group, respectively. Such a disorder is also reflected by the relatively large displacement of O12. In proximity to the disordered hydrogen sulfate anion, two additional peaks, O1W and O2W, were localized and were interpreted as disordered water molecules. O1W was again located on the threefold axis, whereas O2W lies on a general position. The short O1W···O2W interatomic distance of 2.46 Å precludes a simultaneous occupation of both positions. The occupancies of O1W and O2W were therefore constrained to add up to a value of 100%. The refinement exhibited equal distribution of 50% each, indicating that either one water molecule on O1W or three water molecules on O2W are present, resulting in a H3L3+: H2O ratio of 3:2. Due to this disorder, it was again not possible to locate any hydrogen atoms, and the relatively large displacement of O1W and O2W was refined isotropically. The Flack parameter (1255 Friedel pairs) refined to a value of 0.41 (7), indicating formation of an inversion-twin with roughly equal portions of the two domains. As a consequence, the TWIN option of SHELXL was used in the final refinement resulting in a marginal drop of wR2 from 10.3 to 10.1%. In agreement with the Flack parameter, the BASF parameter was found to be 41%.

Computing details top

Data collection: Stoe IPDS Software (Stoe & Cie, 1997); cell refinement: Stoe IPDS Software (Stoe & Cie, 1997); data reduction: Stoe IPDS Software (Stoe & Cie, 1997); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Ellipsoid plot (50% probability level) and numbering scheme of the title compound. Symmetry Codes: O12' 1 - y, x-y, z; O12" 1 - x + y, 1 - x, z.
[Figure 2] Fig. 2. The three structural motives which are arranged along the threefold axis. (1) The [(H3L)3Cl2]7+ cage, (2) the lipophilic void generated by the C6H6-sides of three H3L3+ cations together with the disordered moieties which are found within this void, (3) the [(HSO4)(H3L)3Cl3]5+ cage. All substituents of the H3L3+ cation which are not essential have been omitted for clarity. (b) shows views along the threefold axis, (a) displays views for a perpendicular orientation. In 2b) the three chloride anions which keep the three cations together are also shown. They are omitted in 2a) for clarity.
Tris(cis-2-hydroxycyclohexane-1,3,5-triaminium) hydrogen sulfate octachloride dihydrate top
Crystal data top
3C6H18N3O3+·8Cl·HSO4·2H2ODx = 1.419 Mg m3
Mr = 861.40Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3cCell parameters from 5824 reflections
a = 12.6549 (18) Åθ = 3.3–38.0°
c = 43.616 (9) ŵ = 0.66 mm1
V = 6049.2 (17) Å3T = 200 K
Z = 6Prism, colourless
F(000) = 27240.48 × 0.40 × 0.32 mm
Data collection top
Stoe IPDS image plate
diffractometer
2442 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.075
Graphite monochromatorθmax = 25.5°, θmin = 2.6°
phi scansh = 1415
14259 measured reflectionsk = 1515
2518 independent reflectionsl = 5252
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H 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 reflectionsΔρmax = 0.75 e Å3
169 parametersΔρmin = 0.32 e Å3
11 restraintsAbsolute structure: Flack (1983), 1255 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.41 (7)
Crystal data top
3C6H18N3O3+·8Cl·HSO4·2H2OZ = 6
Mr = 861.40Mo Kα radiation
Trigonal, R3cµ = 0.66 mm1
a = 12.6549 (18) ÅT = 200 K
c = 43.616 (9) Å0.48 × 0.40 × 0.32 mm
V = 6049.2 (17) Å3
Data collection top
Stoe IPDS image plate
diffractometer
2442 reflections with I > 2σ(I)
14259 measured reflectionsRint = 0.075
2518 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101Δρmax = 0.75 e Å3
S = 1.07Δρmin = 0.32 e Å3
2518 reflectionsAbsolute structure: Flack (1983), 1255 Friedel pairs
169 parametersAbsolute structure parameter: 0.41 (7)
11 restraints
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
xyzUiso*/UeqOcc. (<1)
Cl10.25081 (6)0.28514 (6)0.523148 (15)0.02924 (18)
C10.2004 (2)0.3248 (2)0.40899 (6)0.0217 (5)
H10.22320.41240.41100.026*
N10.0651 (2)0.2485 (2)0.40665 (6)0.0260 (5)
H11N0.049 (4)0.172 (2)0.4029 (10)0.039*
H12N0.033 (3)0.264 (4)0.4234 (7)0.039*
H13N0.037 (4)0.269 (4)0.3907 (7)0.039*
C20.2434 (2)0.2867 (2)0.43791 (6)0.0201 (5)
H20.20790.30270.45660.024*
O20.20562 (18)0.16022 (19)0.43620 (4)0.0257 (4)
H2O0.153 (3)0.111 (3)0.4479 (8)0.039*
C30.3833 (2)0.3621 (3)0.43928 (6)0.0221 (5)
H30.40840.45010.44180.027*
N30.4276 (2)0.3228 (3)0.46641 (5)0.0272 (5)
H31N0.382 (3)0.321 (4)0.4818 (7)0.041*
H32N0.418 (4)0.248 (2)0.4636 (9)0.041*
H33N0.5097 (18)0.365 (3)0.4673 (10)0.041*
C40.4447 (2)0.3482 (3)0.41051 (6)0.0232 (5)
H4A0.53430.40140.41210.028*
H4B0.42620.26270.40860.028*
C50.3974 (3)0.3838 (2)0.38230 (6)0.0224 (5)
H50.42310.47230.38360.027*
N50.4537 (2)0.3630 (2)0.35426 (5)0.0255 (5)
H51N0.5342 (18)0.413 (3)0.3532 (9)0.038*
H52N0.424 (4)0.373 (4)0.3361 (6)0.038*
H53N0.438 (4)0.287 (2)0.3530 (9)0.038*
C60.2583 (2)0.3090 (3)0.37982 (6)0.0214 (5)
H6A0.23230.22180.37690.026*
H6B0.23080.33650.36180.026*
S10.66670.33330.51658 (4)0.0494 (4)
O110.66670.33330.48521 (12)0.0487 (11)
O120.5574 (4)0.3375 (4)0.52786 (9)0.0796 (11)
Cl20.65819 (7)0.61189 (6)0.460229 (16)0.03246 (19)
Cl30.00000.00000.48180 (3)0.0243 (3)
Cl40.33330.66670.53799 (3)0.0309 (3)
O1W0.33330.66670.4283 (5)0.113 (6)*0.502 (13)
O2W0.2408 (13)0.5251 (14)0.4717 (3)0.127 (5)*0.498 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0288 (3)0.0305 (3)0.0258 (3)0.0128 (3)0.0011 (3)0.0080 (3)
C10.0228 (13)0.0266 (13)0.0200 (12)0.0155 (11)0.0017 (10)0.0011 (10)
N10.0236 (12)0.0382 (13)0.0228 (12)0.0205 (11)0.0001 (10)0.0006 (10)
C20.0195 (12)0.0250 (13)0.0157 (12)0.0111 (11)0.0007 (9)0.0012 (9)
O20.0232 (10)0.0249 (10)0.0256 (10)0.0094 (8)0.0020 (8)0.0070 (8)
C30.0224 (13)0.0241 (13)0.0164 (12)0.0090 (11)0.0022 (10)0.0020 (10)
N30.0227 (12)0.0378 (14)0.0165 (12)0.0117 (11)0.0040 (9)0.0008 (10)
C40.0165 (12)0.0293 (14)0.0211 (14)0.0096 (12)0.0013 (10)0.0035 (11)
C50.0253 (13)0.0216 (12)0.0184 (12)0.0103 (11)0.0051 (10)0.0041 (10)
N50.0250 (12)0.0334 (13)0.0171 (11)0.0139 (10)0.0029 (9)0.0042 (10)
C60.0213 (12)0.0262 (13)0.0167 (12)0.0119 (11)0.0011 (9)0.0039 (10)
S10.0587 (6)0.0587 (6)0.0308 (7)0.0294 (3)0.0000.000
O110.0493 (17)0.0493 (17)0.047 (3)0.0246 (8)0.0000.000
O120.073 (2)0.085 (3)0.090 (2)0.046 (2)0.041 (2)0.003 (2)
Cl20.0304 (4)0.0296 (3)0.0231 (3)0.0044 (3)0.0005 (3)0.0005 (3)
Cl30.0252 (3)0.0252 (3)0.0225 (5)0.01259 (17)0.0000.000
Cl40.0292 (4)0.0292 (4)0.0343 (6)0.01459 (19)0.0000.000
Geometric parameters (Å, º) top
C1—N11.490 (3)N3—H33N0.901 (19)
C1—C61.530 (4)C4—C51.531 (4)
C1—C21.543 (4)C4—H4A0.9900
C1—H11.0000C4—H4B0.9900
N1—H11N0.896 (19)C5—N51.504 (4)
N1—H12N0.904 (19)C5—C61.529 (4)
N1—H13N0.875 (19)C5—H51.0000
C2—O21.425 (3)N5—H51N0.893 (19)
C2—C31.536 (4)N5—H52N0.912 (19)
C2—H21.0000N5—H53N0.881 (19)
O2—H2O0.823 (19)C6—H6A0.9900
C3—N31.497 (3)C6—H6B0.9900
C3—C41.531 (4)S1—O111.368 (5)
C3—H31.0000S1—O12i1.493 (3)
N3—H31N0.876 (19)S1—O12ii1.493 (3)
N3—H32N0.901 (19)S1—O121.493 (3)
N1—C1—C6109.2 (2)C5—C4—C3109.2 (2)
N1—C1—C2108.9 (2)C5—C4—H4A109.8
C6—C1—C2111.8 (2)C3—C4—H4A109.8
N1—C1—H1108.9C5—C4—H4B109.8
C6—C1—H1108.9C3—C4—H4B109.8
C2—C1—H1108.9H4A—C4—H4B108.3
C1—N1—H11N106 (3)N5—C5—C6109.5 (2)
C1—N1—H12N108 (3)N5—C5—C4108.2 (2)
H11N—N1—H12N119 (4)C6—C5—C4111.9 (2)
C1—N1—H13N112 (3)N5—C5—H5109.1
H11N—N1—H13N105 (4)C6—C5—H5109.1
H12N—N1—H13N107 (4)C4—C5—H5109.1
O2—C2—C3109.6 (2)C5—N5—H51N113 (3)
O2—C2—C1109.6 (2)C5—N5—H52N114 (3)
C3—C2—C1108.3 (2)H51N—N5—H52N105 (4)
O2—C2—H2109.8C5—N5—H53N112 (3)
C3—C2—H2109.8H51N—N5—H53N109 (4)
C1—C2—H2109.8H52N—N5—H53N103 (4)
C2—O2—H2O121 (3)C5—C6—C1109.8 (2)
N3—C3—C4108.3 (2)C5—C6—H6A109.7
N3—C3—C2109.3 (2)C1—C6—H6A109.7
C4—C3—C2112.9 (2)C5—C6—H6B109.7
N3—C3—H3108.7C1—C6—H6B109.7
C4—C3—H3108.7H6A—C6—H6B108.2
C2—C3—H3108.7O11—S1—O12i109.24 (18)
C3—N3—H31N105 (3)O11—S1—O12ii109.24 (19)
C3—N3—H32N111 (3)O12i—S1—O12ii109.70 (18)
H31N—N3—H32N110 (4)O11—S1—O12109.24 (18)
C3—N3—H33N110 (3)O12i—S1—O12109.70 (18)
H31N—N3—H33N122 (4)O12ii—S1—O12109.70 (18)
H32N—N3—H33N98 (4)
N1—C1—C2—O258.1 (3)N3—C3—C4—C5178.1 (2)
C6—C1—C2—O262.7 (3)C2—C3—C4—C556.8 (3)
N1—C1—C2—C3177.6 (2)C3—C4—C5—N5177.0 (2)
C6—C1—C2—C356.8 (3)C3—C4—C5—C656.3 (3)
O2—C2—C3—N358.0 (3)N5—C5—C6—C1177.2 (2)
C1—C2—C3—N3177.5 (2)C4—C5—C6—C157.2 (3)
O2—C2—C3—C462.7 (3)N1—C1—C6—C5178.3 (2)
C1—C2—C3—C456.8 (3)C2—C1—C6—C557.7 (3)
Symmetry codes: (i) y+1, xy, z; (ii) x+y+1, x+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H11N···Cl4iii0.90 (2)2.38 (2)3.218 (3)155 (4)
N1—H12N···Cl2iv0.90 (2)2.36 (2)3.241 (3)166 (4)
N1—H13N···Cl1v0.88 (2)2.29 (2)3.143 (3)165 (4)
O2—H2O···Cl30.82 (2)2.28 (2)3.092 (2)170 (4)
N3—H31N···Cl10.88 (2)2.34 (2)3.208 (3)171 (4)
N3—H32N···Cl2i0.90 (2)2.39 (2)3.289 (3)176 (4)
N3—H33N···O110.90 (2)2.35 (3)3.072 (3)137 (3)
N3—H33N···Cl20.90 (2)2.74 (3)3.361 (3)127 (3)
N5—H51N···Cl1vi0.89 (2)2.39 (3)3.184 (3)148 (4)
N5—H52N···Cl2v0.91 (2)2.26 (2)3.171 (3)172 (4)
N5—H53N···Cl1iii0.88 (2)2.32 (2)3.194 (3)171 (4)
Symmetry codes: (i) y+1, xy, z; (iii) y+2/3, x+1/3, z1/6; (iv) x+y, x+1, z; (v) x1/3, xy+1/3, z1/6; (vi) x+y+2/3, y+1/3, z1/6.

Experimental details

Crystal data
Chemical formula3C6H18N3O3+·8Cl·HSO4·2H2O
Mr861.40
Crystal system, space groupTrigonal, R3c
Temperature (K)200
a, c (Å)12.6549 (18), 43.616 (9)
V3)6049.2 (17)
Z6
Radiation typeMo Kα
µ (mm1)0.66
Crystal size (mm)0.48 × 0.40 × 0.32
Data collection
DiffractometerStoe IPDS image plate
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
14259, 2518, 2442
Rint0.075
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.101, 1.07
No. of reflections2518
No. of parameters169
No. of restraints11
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.75, 0.32
Absolute structureFlack (1983), 1255 Friedel pairs
Absolute structure parameter0.41 (7)

Computer programs: Stoe IPDS Software (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H11N···Cl4i0.896 (19)2.38 (2)3.218 (3)155 (4)
N1—H12N···Cl2ii0.904 (19)2.36 (2)3.241 (3)166 (4)
N1—H13N···Cl1iii0.875 (19)2.29 (2)3.143 (3)165 (4)
O2—H2O···Cl30.823 (19)2.28 (2)3.092 (2)170 (4)
N3—H31N···Cl10.876 (19)2.34 (2)3.208 (3)171 (4)
N3—H32N···Cl2iv0.901 (19)2.39 (2)3.289 (3)176 (4)
N3—H33N···O110.901 (19)2.35 (3)3.072 (3)137 (3)
N3—H33N···Cl20.901 (19)2.74 (3)3.361 (3)127 (3)
N5—H51N···Cl1v0.893 (19)2.39 (3)3.184 (3)148 (4)
N5—H52N···Cl2iii0.912 (19)2.26 (2)3.171 (3)172 (4)
N5—H53N···Cl1i0.881 (19)2.32 (2)3.194 (3)171 (4)
Symmetry codes: (i) y+2/3, x+1/3, z1/6; (ii) x+y, x+1, z; (iii) x1/3, xy+1/3, z1/6; (iv) y+1, xy, z; (v) x+y+2/3, y+1/3, z1/6.
 

Acknowledgements

We thank Dr Volker Huch (Universität des Saarlandes) for the collection of the data set.

References

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Volume 68| Part 6| June 2012| Pages o1899-o1900
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