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

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). 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_r = 861.40

• Trigonal, R 3c

• a = 12.6549 (18) Å

• c = 43.616 (9) Å

• V = 6049.2 (17) ų

• 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[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

• Δρ_max = 0.75 e Å⁻³

• Δρ_min = −0.32 e Å⁻³

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

• Flack parameter: 0.41 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯Cl4^i	0.90 (2)	2.38 (2)	3.218 (3)	155 (4)
N1—H12N⋯Cl2^ii	0.90 (2)	2.36 (2)	3.241 (3)	166 (4)
N1—H13N⋯Cl1^iii	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⋯Cl2^iv	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⋯Cl1^v	0.89 (2)	2.39 (3)	3.184 (3)	148 (4)
N5—H52N⋯Cl2^iii	0.91 (2)	2.26 (2)	3.171 (3)	172 (4)
N5—H53N⋯Cl1^i	0.88 (2)	2.32 (2)	3.194 (3)	171 (4)
Symmetry codes: (i) ; (ii) -x+y, -x+1, z; (iii) ; (iv) -y+1, x-y, z; (v) .

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).

Supporting information

S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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×U_eq 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

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

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.

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 H3L^3+ cations together with the disordered moieties which are found within this void, (3) the [(HSO4)(H3L)3Cl3]^5+ cage. All substituents of the H3L^3+ 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

Crystal data

3C6H18N3O^3+·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) Å^3	T = 200 K
Z = 6	Prism, colourless
F(000) = 2724	0.48 × 0.40 × 0.32 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0782P)^2 + 1.7412P] where P = (Fo^2 + 2Fc^2)/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	Absolute structure parameter: 0.41 (7)

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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

Geometric parameters (Å, º)

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—O12^i	1.493 (3)
N3—H31N	0.876 (19)	S1—O12^ii	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—O12^i	109.24 (18)
C3—N3—H31N	105 (3)	O11—S1—O12^ii	109.24 (19)
C3—N3—H32N	111 (3)	O12^i—S1—O12^ii	109.70 (18)
H31N—N3—H32N	110 (4)	O11—S1—O12	109.24 (18)
C3—N3—H33N	110 (3)	O12^i—S1—O12	109.70 (18)
H31N—N3—H33N	122 (4)	O12^ii—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)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···Cl4^iii	0.90 (2)	2.38 (2)	3.218 (3)	155 (4)
N1—H12N···Cl2^iv	0.90 (2)	2.36 (2)	3.241 (3)	166 (4)
N1—H13N···Cl1^v	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···Cl2^i	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···Cl1^vi	0.89 (2)	2.39 (3)	3.184 (3)	148 (4)
N5—H52N···Cl2^v	0.91 (2)	2.26 (2)	3.171 (3)	172 (4)
N5—H53N···Cl1^iii	0.88 (2)	2.32 (2)	3.194 (3)	171 (4)

Symmetry codes: (i) −y+1, x−y, z; (iii) −y+2/3, −x+1/3, z−1/6; (iv) −x+y, −x+1, z; (v) x−1/3, x−y+1/3, z−1/6; (vi) −x+y+2/3, y+1/3, z−1/6.