Redetermination of 1,3-diammonio-1,2,3-tride­oxy-cis-inositol dichloride

Neis, C.; Merten, G.J.; Altenhofer, P.; Hegetschweiler, K.

doi:10.1107/S1600536812012366

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1411-o1412

doi:10.1107/S1600536812012366

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Redetermination of 1,3-diammonio-1,2,3-trideoxy-cis-inositol dichloride

Christian Neis,^a Günter J. Merten,^a Philipp Altenhofer ^a and Kaspar Hegetschweiler ^a ^*

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

(Received 13 March 2012; accepted 21 March 2012; online 18 April 2012)

The crystal structure of the title compound, C₆H₁₆N₂O₃²⁺·2Cl⁻, has been reported previously by Palm [Acta Cryst. (1967 ), 22, 209–216] from Weisenberg camera data, with R1 = 10.5%, isotropic refinement of non-H atoms and H atoms not located. We remeasured a data set of the title compound and present a more precise structure determination. The asymmetric unit contains two unique 1,3-diammonio-1,2,3-trideoxy-cis-inositol cations and four Cl⁻ counter-ions. The cyclohexane rings of both inositol cations adopt chair conformations with two axial hydroxy groups. An extended network of hydrogen bonds is formed. The four chloride counter ions are hydrogen bonded to the hydroxy and ammonium groups of the cations by N—H⋯Cl and O—H⋯Cl interactions. The cations are aligned into wavy layers by cation⋯cation interactions of the form N—H⋯O(ax), N—H⋯O(eq) and O(ax)—H⋯O(eq). Intramolecular hydrogen bonding between the axial hydroxy groups is, however, not observed.

Related literature

An earlier, less accurate structure determination of the title compound was performed by Palm (1967). The crystal structure of 1,3-diammonio-1,2,3-trideoxy-cis-inositol sulfate has been reported by Neis et al. (2012 ). The importance of intramolecular hydrogen bonding in 1,3,5-trisubstituted cyclohexane derivatives has been described by Gencheva et al. (2000 ), Saaidi et al. (2008 ) and Neis et al. (2010 ), and the implication of increased 1,3-diaxial repulsion on the conformation of a cyclohexane ring has been discussed by Fritsche-Lang et al. (1985 ), Kramer et al. (1998 ) and Kuppert et al. (2006 ). For the synthesis, see: Merten et al. (2012 ). For the treatment of hydrogen atoms in SHELXL, see: Müller et al. (2006 ).

Experimental

Crystal data

C₆H₁₆N₂O₃²⁺·2Cl⁻
M_r = 235.11
Monoclinic, P 2₁
a = 7.7899 (4) Å
b = 10.1254 (5) Å
c = 13.0136 (7) Å
β = 91.156 (2)°
V = 1026.25 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 130 K
0.30 × 0.22 × 0.15 mm

Data collection

Bruker–Nonius X8 APEX KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ) T_min = 0.838, T_max = 0.914
16242 measured reflections
4459 independent reflections
4429 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.047
S = 1.06
4459 reflections
289 parameters
19 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983 ), 2093 Friedel pairs
Flack parameter: 0.01 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N18—H18A⋯Cl4	0.89 (1)	2.28 (1)	3.1411 (11)	163 (2)
N18—H18B⋯Cl1ⁱ	0.90 (1)	2.37 (2)	3.2646 (12)	177 (2)
N18—H18C⋯Cl3ⁱⁱ	0.91 (1)	2.26 (1)	3.1634 (11)	175 (2)
N22—H22C⋯Cl4ⁱⁱⁱ	0.87 (1)	2.21 (1)	3.0761 (11)	172 (2)
N22—H22A⋯Cl1	0.88 (2)	2.28 (2)	3.1466 (12)	168 (2)
N22—H22B⋯Cl3	0.87 (1)	2.32 (2)	3.1518 (12)	162 (2)
O19—H19⋯O9^iv	0.81 (2)	1.91 (2)	2.7168 (13)	172 (2)
O20—H20⋯Cl2^v	0.88 (2)	2.48 (2)	3.2220 (10)	143 (2)
O21—H21⋯Cl2	0.83 (1)	2.39 (2)	3.2096 (10)	174 (2)
N7—H7C⋯O20^vi	0.89 (1)	2.05 (2)	2.8560 (15)	151 (2)
N7—H7B⋯O19	0.85 (1)	2.11 (2)	2.9404 (14)	164 (2)
N7—H7A⋯Cl3	0.89 (1)	2.70 (2)	3.4038 (11)	138 (1)
O8—H8⋯Cl2^vi	0.84 (1)	2.29 (2)	3.1256 (10)	175 (2)
O9—H9⋯Cl1^iv	0.80 (2)	2.27 (2)	3.0144 (10)	156 (2)
O10—H10⋯Cl4^vii	0.85 (2)	2.14 (2)	2.9889 (10)	177 (2)
N11—H11C⋯Cl2^v	0.89 (2)	2.37 (2)	3.2132 (12)	159 (2)
N11—H11B⋯Cl1^v	0.86 (1)	2.51 (2)	3.3007 (11)	154 (2)
N11—H11A⋯Cl2	0.90 (2)	2.61 (2)	3.4618 (13)	158 (2)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (v) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (vi) x-1, y, z; (vii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812012366/sj5213sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012366/sj5213Isup2.hkl

checkCIF report

Comment top

The title compound contains two independent 1,3-diammonio-1,2,3-trideoxy-cis-inositol dications (denoted as cation 1 and cation 2). As already noted by Palm (1967), the cyclohexane rings of both cations adopt a chair conformation, having one hydroxy and two ammonium groups in equatorial and two hydroxy groups in axial position. The puckering parameters of the two cyclohexane rings are: Q = 0.59 Å, θ = 4.3 °, ϕ = 337.8 ° (cation 1); Q = 0.58 Å, θ = 5.0 °, ϕ = 87.0 ° (cation 2). The cations are aligned to wavy layers, oriented parallel to the ab plane, by direct cation 1···cation 2 interactions of the form N—H···O(ax), N—H···O(eq) and O(ax)—H···O(eq). In these layers, each cation of one type is interlinked with three cations of the other. In addition, cation 1···cation 1 interactions are formed by weak C—H···O hydrogen bonds between the axial oxygen atoms and two axial C—H hydrogen atoms of a neighbour (O···C distances: 3.277 and 3.215 Å, O···H distances: 2.470 and 2.485 Å, O···H—C angles 137 and 129 °). Cation 2···cation 2 hydrogen bonding is not observed. The four chloride counter ions are also involved in the extended hydrogen bonding network. Considering Cl···H distances up to 2.7 Å, Cl1 has a coordination number of four (irregular geometry). The coordination number of Cl2 is 5 and its geometry lies closer to a tetragonal pyramid than to a trigonal bipyramid (τ = 1/4). Cl3 and Cl4 have coordination numbers of three. The geometry is again irregular. All O—H and N—H groups in the two cations act as hydrogen donors, however, not all of the axial hydroxy groups act as hydrogen acceptors (if the abovementioned, weak C—H···O contacts are disregarded). This observation is in agreement with the well established concept that axial substituents are sterically more encumbered. In particular, it is of interest that no intramolecular O—H···O hydrogen bonding has been found for the axial hydroxy groups, although the corresponding O···O separations fall in the almost ideal range of 2.893 - 2.906 Å. For corresponding structures with three axial hydroxy or amino groups in a syn-1,3,5-triaxial arrangement, a different behaviour has frequently been noted (Gencheva et al., 2000; Saaidi et al., 2008; Neis et al., 2010). If a third syn-axial substituent is present, it appears that formation of such intramolecular hydrogen bonds is sometimes even a prerequisite for the adoption of a stable cyclohexane chair. Disabling of hydrogen bonding (for instance by protonation of an amino group or by converting it into an amide) enforces the structure to escape the increasing repulsion by switching to a twisted boat conformation (Fritsche-Lang et al., 1985; Kramer et al., 1998; Kuppert et al., 2006). It is thus noteworthy that in both cations of the title compound, such intramolecular O—H···O stabilisation is not required. Also in a corresponding sulphate salt (Neis et al., 2012) no intramolecular hydrogen bonding between the two axial hydroxy groups has been found.

Related literature top

An early, less accurate structure determination of the title compound has been performed by Palm (1967). The crystal structure of 1,3-diammonio-1,2,3-trideoxy-cis-inositol sulfate has been reported by Neis et al. (2012). The importance of intramolecular hydrogen bonding in 1,3,5-trisubstituted cyclohexane derivatives has been described by Gencheva et al. (2000), Saaidi et al. (2008) and Neis et al. (2010), and the implication of increased 1,3-diaxial repulsion on the conformation of a cyclohexane ring has been discussed by Fritsche-Lang et al. (1985), Kramer et al. (1998) and Kuppert et al. (2006). For the synthesis, see: Merten et al. (2012). For the treatment of hydrogen atoms in SHELXL, see: Müller et al. (2006).

Experimental top

The title compound was prepared following the protocol given by Merten et al. (2012). ¹H-NMR (D₂O, pH 1.0): δ (p.p.m.) = 4.17 (2H), 3.74 (1H), 3.56 (2H), 2.12 (2H). ¹³C-NMR (D₂O, pH 1.0): δ (p.p.m.) = 25.2, 43.0, 63.7, 68.2. Single crystals were grown from an aqueous solution by slow evaporation at 298 K.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the title compound. The asymmetric unit comprising two crystallographically independent cations and four crystallographically independent chloride counter ions is shown. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Section of the puckered layer, which is formed by hydrogen bonding between cation 1 and cation 2 entities (ball and stick model).

1,3-diammonio-1,2,3-trideoxy-cis-inositol dichloride top

Crystal data top

C₆H₁₆N₂O₃²⁺·2Cl⁻	F(000) = 496
M_r = 235.11	D_x = 1.522 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 9336 reflections
a = 7.7899 (4) Å	θ = 2.6–40.5°
b = 10.1254 (5) Å	µ = 0.61 mm⁻¹
c = 13.0136 (7) Å	T = 130 K
β = 91.156 (2)°	Prism, colorless
V = 1026.25 (9) Å³	0.30 × 0.22 × 0.15 mm
Z = 4

Data collection top

Bruker–Nonius X8 APEX KappaCCD diffractometer	4459 independent reflections
Radiation source: fine-focus sealed tube	4429 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 27.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −9→9
T_min = 0.838, T_max = 0.914	k = −12→12
16242 measured reflections	l = −16→16

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)] = 0.017	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.047	w = 1/[σ²(F_o²) + (0.0292P)² + 0.1788P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4459 reflections	Δρ_max = 0.27 e Å⁻³
289 parameters	Δρ_min = −0.15 e Å⁻³
19 restraints	Absolute structure: Flack (1983), 2093 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (3)

Crystal data top

C₆H₁₆N₂O₃²⁺·2Cl⁻	V = 1026.25 (9) Å³
M_r = 235.11	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 7.7899 (4) Å	µ = 0.61 mm⁻¹
b = 10.1254 (5) Å	T = 130 K
c = 13.0136 (7) Å	0.30 × 0.22 × 0.15 mm
β = 91.156 (2)°

Data collection top

Bruker–Nonius X8 APEX KappaCCD diffractometer	4459 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	4429 reflections with I > 2σ(I)
T_min = 0.838, T_max = 0.914	R_int = 0.017
16242 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.047	Δρ_max = 0.27 e Å⁻³
S = 1.06	Δρ_min = −0.15 e Å⁻³
4459 reflections	Absolute structure: Flack (1983), 2093 Friedel pairs
289 parameters	Absolute structure parameter: 0.01 (3)
19 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

	x	y	z	U_iso*/U_eq
C1	0.65695 (15)	0.78053 (13)	0.49259 (9)	0.0116 (2)
H1A	0.7440	0.8297	0.4535	0.014*
H1B	0.6742	0.6850	0.4805	0.014*
C2	0.47789 (15)	0.82069 (11)	0.45618 (9)	0.0109 (2)
H2	0.4629	0.9177	0.4672	0.013*
C3	0.33980 (16)	0.74645 (11)	0.51435 (9)	0.0117 (2)
H3	0.2245	0.7822	0.4936	0.014*
C4	0.36884 (16)	0.76840 (13)	0.63009 (9)	0.0135 (2)
H4	0.3478	0.8638	0.6453	0.016*
C5	0.54882 (17)	0.73308 (12)	0.66995 (9)	0.0141 (2)
H5	0.5605	0.7597	0.7438	0.017*
C6	0.67808 (15)	0.81082 (12)	0.60699 (9)	0.0129 (2)
H6	0.6605	0.9075	0.6185	0.015*
N18	0.72743 (14)	1.01783 (11)	0.05624 (8)	0.0149 (2)
H18A	0.6277 (19)	1.0191 (18)	0.0889 (12)	0.022*
H18B	0.789 (2)	1.0895 (16)	0.0746 (14)	0.022*
H18C	0.706 (2)	1.0188 (19)	−0.0129 (10)	0.022*
N22	0.73895 (14)	0.53468 (11)	0.10007 (8)	0.0154 (2)
H22C	0.706 (2)	0.5268 (19)	0.0357 (11)	0.023*
H22A	0.801 (2)	0.4651 (17)	0.1183 (13)	0.023*
H22B	0.646 (2)	0.5385 (19)	0.1356 (13)	0.023*
O19	0.75839 (12)	0.93190 (9)	0.26803 (7)	0.01429 (18)
H19	0.751 (2)	1.0080 (15)	0.2863 (13)	0.021*
O20	1.09187 (12)	0.81557 (10)	0.32436 (7)	0.0206 (2)
H20	1.028 (2)	0.8689 (19)	0.3606 (14)	0.031*
O21	0.78841 (12)	0.64823 (10)	0.28780 (7)	0.01674 (19)
H21	0.837 (2)	0.6185 (18)	0.3397 (12)	0.025*
N7	0.45629 (14)	0.79085 (11)	0.34387 (8)	0.0132 (2)
H7C	0.3542 (19)	0.8197 (17)	0.3215 (13)	0.020*
H7B	0.537 (2)	0.8271 (17)	0.3103 (13)	0.020*
H7A	0.462 (2)	0.7050 (14)	0.3315 (13)	0.020*
C13	0.83453 (16)	0.90192 (12)	0.08871 (9)	0.0140 (2)
H13	0.9361	0.8970	0.0431	0.017*
O8	0.34834 (12)	0.61091 (9)	0.48626 (7)	0.01400 (17)
H8	0.2471 (19)	0.5838 (18)	0.4902 (14)	0.021*
C14	0.89926 (16)	0.92022 (12)	0.19938 (9)	0.0131 (2)
H14	0.9704	1.0023	0.2037	0.016*
O9	0.24058 (12)	0.69200 (10)	0.68068 (7)	0.01881 (19)
H9	0.213 (2)	0.7301 (18)	0.7312 (13)	0.028*
C15	1.01194 (16)	0.80171 (13)	0.22624 (9)	0.0152 (2)
H15	1.1064	0.8011	0.1754	0.018*
O10	0.58596 (14)	0.59647 (10)	0.66089 (7)	0.0204 (2)
H10	0.601 (2)	0.5671 (19)	0.7219 (12)	0.031*
C16	0.92115 (16)	0.66793 (12)	0.21605 (9)	0.0134 (2)
H16	1.0084	0.5963	0.2255	0.016*
N11	0.85723 (14)	0.77409 (13)	0.63986 (8)	0.0182 (2)
H11C	0.931 (2)	0.8269 (18)	0.6089 (14)	0.027*
H11B	0.872 (2)	0.780 (2)	0.7055 (11)	0.027*
H11A	0.883 (2)	0.6931 (16)	0.6164 (14)	0.027*
C17	0.84314 (16)	0.65722 (12)	0.10753 (9)	0.0132 (2)
H17	0.9392	0.6500	0.0580	0.016*
C12	0.73148 (16)	0.77507 (13)	0.07590 (9)	0.0137 (2)
H12A	0.6929	0.7652	0.0033	0.016*
H12B	0.6285	0.7786	0.1192	0.016*
Cl1	0.95255 (4)	0.27346 (3)	0.13119 (2)	0.01574 (7)
Cl2	0.96850 (3)	0.51134 (3)	0.48456 (2)	0.01623 (6)
Cl3	0.36075 (4)	0.53635 (3)	0.18167 (2)	0.02006 (7)
Cl4	0.34728 (4)	0.98731 (3)	0.12868 (2)	0.02147 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0106 (5)	0.0148 (6)	0.0092 (5)	−0.0009 (4)	−0.0005 (4)	0.0008 (4)
C2	0.0121 (5)	0.0109 (5)	0.0096 (5)	−0.0002 (4)	−0.0004 (4)	−0.0002 (4)
C3	0.0111 (5)	0.0103 (5)	0.0138 (5)	0.0004 (4)	0.0021 (4)	−0.0004 (4)
C4	0.0166 (6)	0.0108 (5)	0.0134 (5)	−0.0016 (4)	0.0059 (4)	−0.0001 (4)
C5	0.0203 (6)	0.0122 (5)	0.0097 (5)	−0.0014 (5)	0.0021 (4)	0.0003 (4)
C6	0.0138 (6)	0.0140 (6)	0.0107 (5)	−0.0020 (4)	−0.0015 (4)	0.0004 (4)
N18	0.0175 (5)	0.0141 (5)	0.0131 (4)	−0.0007 (4)	−0.0003 (4)	0.0020 (4)
N22	0.0177 (5)	0.0142 (5)	0.0140 (5)	0.0010 (4)	−0.0013 (4)	−0.0019 (4)
O19	0.0168 (4)	0.0137 (4)	0.0125 (4)	0.0013 (3)	0.0033 (3)	−0.0020 (3)
O20	0.0189 (5)	0.0250 (5)	0.0176 (4)	0.0031 (4)	−0.0048 (4)	−0.0033 (4)
O21	0.0170 (5)	0.0219 (5)	0.0114 (4)	0.0020 (4)	0.0003 (3)	0.0017 (3)
N7	0.0133 (5)	0.0159 (5)	0.0104 (5)	−0.0016 (4)	−0.0012 (4)	0.0010 (4)
C13	0.0158 (6)	0.0136 (6)	0.0125 (5)	0.0003 (4)	0.0017 (4)	0.0005 (4)
O8	0.0129 (4)	0.0115 (4)	0.0177 (4)	−0.0025 (3)	0.0029 (3)	−0.0030 (3)
C14	0.0113 (5)	0.0139 (6)	0.0140 (6)	−0.0012 (4)	0.0011 (4)	−0.0014 (4)
O9	0.0214 (5)	0.0175 (5)	0.0180 (4)	−0.0036 (4)	0.0115 (4)	−0.0020 (4)
C15	0.0115 (5)	0.0173 (6)	0.0167 (6)	0.0015 (4)	−0.0028 (4)	−0.0033 (5)
O10	0.0302 (5)	0.0148 (4)	0.0162 (4)	0.0005 (4)	−0.0002 (4)	0.0018 (4)
C16	0.0128 (6)	0.0142 (6)	0.0133 (5)	0.0022 (4)	−0.0005 (4)	−0.0003 (4)
N11	0.0171 (5)	0.0222 (6)	0.0151 (5)	−0.0032 (5)	−0.0055 (4)	0.0027 (5)
C17	0.0135 (6)	0.0133 (6)	0.0127 (5)	0.0000 (4)	0.0021 (4)	−0.0020 (4)
C12	0.0166 (5)	0.0144 (6)	0.0101 (5)	0.0001 (5)	−0.0015 (4)	−0.0010 (4)
Cl1	0.01912 (14)	0.01465 (13)	0.01360 (12)	−0.00009 (11)	0.00369 (10)	0.00124 (10)
Cl2	0.01362 (13)	0.01454 (13)	0.02052 (14)	−0.00019 (10)	0.00009 (10)	0.00263 (11)
Cl3	0.01973 (14)	0.02535 (17)	0.01513 (13)	−0.00115 (12)	0.00145 (10)	−0.00093 (12)
Cl4	0.01848 (14)	0.03068 (18)	0.01520 (13)	−0.00287 (12)	−0.00074 (10)	0.00097 (12)

Geometric parameters (Å, º) top

C1—C2	1.5195 (16)	O19—H19	0.809 (15)
C1—C6	1.5257 (15)	O20—C15	1.4163 (15)
C1—H1A	0.9900	O20—H20	0.878 (15)
C1—H1B	0.9900	O21—C16	1.4212 (15)
C2—N7	1.4987 (14)	O21—H21	0.825 (14)
C2—C3	1.5258 (16)	N7—H7C	0.890 (14)
C2—H2	1.0000	N7—H7B	0.852 (14)
C3—O8	1.4222 (14)	N7—H7A	0.885 (14)
C3—C4	1.5347 (16)	C13—C12	1.5221 (18)
C3—H3	1.0000	C13—C14	1.5275 (16)
C4—O9	1.4341 (14)	C13—H13	1.0000
C4—C5	1.5275 (18)	O8—H8	0.838 (14)
C4—H4	1.0000	C14—C15	1.5232 (17)
C5—O10	1.4186 (15)	C14—H14	1.0000
C5—C6	1.5291 (16)	O9—H9	0.796 (15)
C5—H5	1.0000	C15—C16	1.5326 (17)
C6—N11	1.4983 (16)	C15—H15	1.0000
C6—H6	1.0000	O10—H10	0.854 (15)
N18—C13	1.4959 (16)	C16—C17	1.5299 (16)
N18—H18A	0.893 (14)	C16—H16	1.0000
N18—H18B	0.900 (14)	N11—H11C	0.885 (15)
N18—H18C	0.911 (13)	N11—H11B	0.862 (14)
N22—C17	1.4848 (16)	N11—H11A	0.898 (15)
N22—H22C	0.874 (14)	C17—C12	1.5283 (17)
N22—H22A	0.883 (15)	C17—H17	1.0000
N22—H22B	0.865 (14)	C12—H12A	0.9900
O19—C14	1.4339 (15)	C12—H12B	0.9900

C2—C1—C6	109.31 (10)	C2—N7—H7C	109.6 (11)
C2—C1—H1A	109.8	C2—N7—H7B	110.1 (12)
C6—C1—H1A	109.8	H7C—N7—H7B	110.5 (16)
C2—C1—H1B	109.8	C2—N7—H7A	111.7 (12)
C6—C1—H1B	109.8	H7C—N7—H7A	107.9 (17)
H1A—C1—H1B	108.3	H7B—N7—H7A	106.9 (17)
N7—C2—C1	109.54 (9)	N18—C13—C12	109.95 (10)
N7—C2—C3	108.55 (9)	N18—C13—C14	110.05 (10)
C1—C2—C3	111.43 (9)	C12—C13—C14	111.65 (10)
N7—C2—H2	109.1	N18—C13—H13	108.4
C1—C2—H2	109.1	C12—C13—H13	108.4
C3—C2—H2	109.1	C14—C13—H13	108.4
O8—C3—C2	108.11 (9)	C3—O8—H8	104.6 (12)
O8—C3—C4	112.66 (10)	O19—C14—C15	111.51 (10)
C2—C3—C4	108.91 (10)	O19—C14—C13	110.81 (10)
O8—C3—H3	109.0	C15—C14—C13	107.37 (10)
C2—C3—H3	109.0	O19—C14—H14	109.0
C4—C3—H3	109.0	C15—C14—H14	109.0
O9—C4—C5	111.16 (10)	C13—C14—H14	109.0
O9—C4—C3	106.39 (10)	C4—O9—H9	108.6 (14)
C5—C4—C3	114.55 (10)	O20—C15—C14	111.69 (10)
O9—C4—H4	108.2	O20—C15—C16	111.06 (10)
C5—C4—H4	108.2	C14—C15—C16	114.43 (10)
C3—C4—H4	108.2	O20—C15—H15	106.4
O10—C5—C4	112.79 (10)	C14—C15—H15	106.4
O10—C5—C6	108.65 (10)	C16—C15—H15	106.4
C4—C5—C6	107.90 (10)	C5—O10—H10	106.7 (13)
O10—C5—H5	109.1	O21—C16—C17	108.41 (10)
C4—C5—H5	109.1	O21—C16—C15	114.07 (10)
C6—C5—H5	109.1	C17—C16—C15	108.45 (10)
N11—C6—C1	108.07 (10)	O21—C16—H16	108.6
N11—C6—C5	109.81 (10)	C17—C16—H16	108.6
C1—C6—C5	111.11 (10)	C15—C16—H16	108.6
N11—C6—H6	109.3	C6—N11—H11C	109.0 (12)
C1—C6—H6	109.3	C6—N11—H11B	111.6 (13)
C5—C6—H6	109.3	H11C—N11—H11B	109.4 (18)
C13—N18—H18A	111.2 (12)	C6—N11—H11A	109.9 (12)
C13—N18—H18B	105.4 (12)	H11C—N11—H11A	104.3 (17)
H18A—N18—H18B	109.1 (17)	H11B—N11—H11A	112.3 (18)
C13—N18—H18C	112.1 (11)	N22—C17—C12	109.12 (10)
H18A—N18—H18C	109.2 (15)	N22—C17—C16	109.03 (10)
H18B—N18—H18C	109.8 (17)	C12—C17—C16	113.99 (10)
C17—N22—H22C	106.7 (12)	N22—C17—H17	108.2
C17—N22—H22A	110.8 (12)	C12—C17—H17	108.2
H22C—N22—H22A	109.4 (17)	C16—C17—H17	108.2
C17—N22—H22B	112.8 (13)	C13—C12—C17	109.47 (10)
H22C—N22—H22B	106.6 (16)	C13—C12—H12A	109.8
H22A—N22—H22B	110.3 (17)	C17—C12—H12A	109.8
C14—O19—H19	108.9 (13)	C13—C12—H12B	109.8
C15—O20—H20	107.5 (13)	C17—C12—H12B	109.8
C16—O21—H21	105.0 (13)	H12A—C12—H12B	108.2

C6—C1—C2—N7	−179.87 (10)	N18—C13—C14—O19	59.93 (13)
C6—C1—C2—C3	−59.74 (13)	C12—C13—C14—O19	−62.45 (13)
N7—C2—C3—O8	53.24 (12)	N18—C13—C14—C15	−178.07 (10)
C1—C2—C3—O8	−67.46 (12)	C12—C13—C14—C15	59.55 (13)
N7—C2—C3—C4	175.96 (9)	O19—C14—C15—O20	−64.11 (13)
C1—C2—C3—C4	55.26 (12)	C13—C14—C15—O20	174.33 (10)
O8—C3—C4—O9	−57.58 (13)	O19—C14—C15—C16	63.16 (13)
C2—C3—C4—O9	−177.52 (9)	C13—C14—C15—C16	−58.41 (13)
O8—C3—C4—C5	65.65 (14)	O20—C15—C16—O21	61.04 (13)
C2—C3—C4—C5	−54.29 (13)	C14—C15—C16—O21	−66.54 (13)
O9—C4—C5—O10	55.85 (13)	O20—C15—C16—C17	−178.05 (10)
C3—C4—C5—O10	−64.77 (13)	C14—C15—C16—C17	54.36 (13)
O9—C4—C5—C6	175.88 (9)	O21—C16—C17—N22	−49.61 (13)
C3—C4—C5—C6	55.25 (13)	C15—C16—C17—N22	−173.95 (10)
C2—C1—C6—N11	−178.30 (10)	O21—C16—C17—C12	72.58 (13)
C2—C1—C6—C5	61.17 (13)	C15—C16—C17—C12	−51.77 (13)
O10—C5—C6—N11	−54.54 (13)	N18—C13—C12—C17	179.03 (10)
C4—C5—C6—N11	−177.14 (10)	C14—C13—C12—C17	−58.53 (13)
O10—C5—C6—C1	64.96 (13)	N22—C17—C12—C13	177.03 (10)
C4—C5—C6—C1	−57.64 (13)	C16—C17—C12—C13	54.90 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N18—H18A···Cl4	0.89 (1)	2.28 (1)	3.1411 (11)	163 (2)
N18—H18B···Cl1ⁱ	0.90 (1)	2.37 (2)	3.2646 (12)	177 (2)
N18—H18C···Cl3ⁱⁱ	0.91 (1)	2.26 (1)	3.1634 (11)	175 (2)
N22—H22C···Cl4ⁱⁱⁱ	0.87 (1)	2.21 (1)	3.0761 (11)	172 (2)
N22—H22A···Cl1	0.88 (2)	2.28 (2)	3.1466 (12)	168 (2)
N22—H22B···Cl3	0.87 (1)	2.32 (2)	3.1518 (12)	162 (2)
O19—H19···O9^iv	0.81 (2)	1.91 (2)	2.7168 (13)	172 (2)
O20—H20···Cl2^v	0.88 (2)	2.48 (2)	3.2220 (10)	143 (2)
O21—H21···Cl2	0.83 (1)	2.39 (2)	3.2096 (10)	174 (2)
N7—H7C···O20^vi	0.89 (1)	2.05 (2)	2.8560 (15)	151 (2)
N7—H7B···O19	0.85 (1)	2.11 (2)	2.9404 (14)	164 (2)
N7—H7A···Cl3	0.89 (1)	2.70 (2)	3.4038 (11)	138 (1)
O8—H8···Cl2^vi	0.84 (1)	2.29 (2)	3.1256 (10)	175 (2)
O9—H9···Cl1^iv	0.80 (2)	2.27 (2)	3.0144 (10)	156 (2)
O10—H10···Cl4^vii	0.85 (2)	2.14 (2)	2.9889 (10)	177 (2)
N11—H11C···Cl2^v	0.89 (2)	2.37 (2)	3.2132 (12)	159 (2)
N11—H11B···Cl1^v	0.86 (1)	2.51 (2)	3.3007 (11)	154 (2)
N11—H11A···Cl2	0.90 (2)	2.61 (2)	3.4618 (13)	158 (2)

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

Experimental details

Crystal data
Chemical formula	C₆H₁₆N₂O₃²⁺·2Cl⁻
M_r	235.11
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	130
a, b, c (Å)	7.7899 (4), 10.1254 (5), 13.0136 (7)
β (°)	91.156 (2)
V (Å³)	1026.25 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.30 × 0.22 × 0.15

Data collection
Diffractometer	Bruker–Nonius X8 APEX KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2010)
T_min, T_max	0.838, 0.914
No. of measured, independent and observed [I > 2σ(I)] reflections	16242, 4459, 4429
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.047, 1.06
No. of reflections	4459
No. of parameters	289
No. of restraints	19
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.15
Absolute structure	Flack (1983), 2093 Friedel pairs
Absolute structure parameter	0.01 (3)

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2011), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N18—H18A···Cl4	0.893 (14)	2.278 (14)	3.1411 (11)	162.5 (15)
N18—H18B···Cl1ⁱ	0.900 (14)	2.365 (15)	3.2646 (12)	177.2 (16)
N18—H18C···Cl3ⁱⁱ	0.911 (13)	2.255 (14)	3.1634 (11)	175.0 (16)
N22—H22C···Cl4ⁱⁱⁱ	0.874 (14)	2.208 (14)	3.0761 (11)	172.1 (17)
N22—H22A···Cl1	0.883 (15)	2.277 (15)	3.1466 (12)	168.3 (16)
N22—H22B···Cl3	0.865 (14)	2.317 (15)	3.1518 (12)	162.3 (16)
O19—H19···O9^iv	0.809 (15)	1.913 (15)	2.7168 (13)	172.4 (18)
O20—H20···Cl2^v	0.878 (15)	2.478 (17)	3.2220 (10)	142.9 (17)
O21—H21···Cl2	0.825 (14)	2.388 (15)	3.2096 (10)	174.3 (18)
N7—H7C···O20^vi	0.890 (14)	2.045 (15)	2.8560 (15)	150.8 (16)
N7—H7B···O19	0.852 (14)	2.111 (15)	2.9404 (14)	164.3 (16)
N7—H7A···Cl3	0.885 (14)	2.697 (16)	3.4038 (11)	137.6 (14)
O8—H8···Cl2^vi	0.838 (14)	2.290 (15)	3.1256 (10)	174.7 (17)
O9—H9···Cl1^iv	0.796 (15)	2.271 (16)	3.0144 (10)	155.8 (18)
O10—H10···Cl4^vii	0.854 (15)	2.136 (15)	2.9889 (10)	176.6 (19)
N11—H11C···Cl2^v	0.885 (15)	2.372 (16)	3.2132 (12)	158.8 (16)
N11—H11B···Cl1^v	0.862 (14)	2.505 (16)	3.3007 (11)	153.8 (16)
N11—H11A···Cl2	0.898 (15)	2.612 (16)	3.4618 (13)	158.1 (16)

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

Acknowledgements

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

References

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2010). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fritsche-Lang, W., Wilharm, P., Hädicke, E., Fritz, H. & Prinzbach, H. (1985). Chem. Ber. 118, 2044–2078. CAS Google Scholar
Gencheva, G., Bontchev, P. R., Sander, J. & Hegetschweiler, K. (2000). Z. Kristallogr. New Cryst. Struct. 215, 183–185. CAS Google Scholar
Kramer, A., Alberto, R., Egli, A., Novak-Hofer, I., Hegetschweiler, K., Abram, U., Bernhardt, P. V. & Schubiger, P. A. (1998). Bioconjugate Chem. 9, 691–702. Web of Science CSD CrossRef CAS Google Scholar
Kuppert, D., Comba, P. & Hegetschweiler, K. (2006). Eur. J. Inorg. Chem. pp. 2792–2807. Web of Science CSD CrossRef Google Scholar
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. Web of Science CSD CrossRef Google Scholar
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. Google Scholar
Neis, C., Merten, G. J. & Hegetschweiler, K. (2012). Acta Cryst. E68, o1425–o1426. CSD CrossRef IUCr Journals Google Scholar
Neis, C., Petry, D., Demangeon, A., Morgenstern, B., Kuppert, D., Huppert, J., Stucky, S. & Hegetschweiler, K. (2010). Inorg. Chem. 49, 10092–10107. Web of Science CSD CrossRef CAS PubMed Google Scholar
Palm, J. H. (1967). Acta Cryst. 22, 209–216. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Saaidi, P.-L., Chazal, P.-E., Maurin, P., Jeanneau, E. & Hasserodt, J. (2008). Acta Cryst. E64, o803–o804. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar