Formation of lithium, sodium and potassium complexes with 1,3,5-tri­amino-1,3,5-tri­deoxy-cis-inositol (taci)

Single crystals of (1,3-di­amino-5-aza­niumyl-1,3,5-tri­deoxy-cis-inositol-κ³O²,O⁴,O⁶)(1,3,5-tri­amino-1,3,5-tri­deoxy-cis-inositol-κ³O²,O⁴,O⁶)lithium(I) diiodide dihydrate, [Li(C₆H₁₆N₃O₃)(C₆H₁₅N₃O₃)]I₂·2H₂O or [Li(Htaci)(taci)]I₂·2H₂O (taci is 1,3,5-tri­amino-1,3,5-tri­deoxy-cis-inositol), (I), bis­(1,3,5-tri­amino-1,3,5-tri­deoxy-cis-inositol-κ³O²,O⁴,O⁶)sodium(I) iodide, [Na(C₆H₁₅N₃O₃)₂]I or [Na(taci)₂]I, (II), and bis­(1,3,5-tri­am­ino-1,3,5-tri­deoxy-cis-inositol-κ³O²,O⁴,O⁶)potassium(I) iodide, [K(C₆H₁₅N₃O₃)₂]I or [K(taci)₂]I, (III), were grown by diffusion of MeOH into aqueous solutions of the complexes. The structures of the Na and K complexes are isotypic. In all three complexes, the taci ligands adopt a chair conformation with axial hy­droxy groups, and the metal cations exhibit exclusive O-atom coordination. The six O atoms of the resulting MO₆ unit define a centrosymmetric trigonal anti­prism with approximate D_3d symmetry. The inter­ligand O...O distances increase significantly in the order Li < Na < K. The structure of (I) exhibits a complex three-dimensional network of R—NH₂—H...NH₂—R, R—O—H...NH₂—R and R—O—H...O(H)—H...NH₂—R hydrogen bonds. The structures of the Na and K complexes consist of a stack of layers, in which each taci ligand is bonded to three neighbours via pairwise O—H...NH₂ inter­actions between vicinal HO—CH—CH—NH₂ groups.

S1. Introduction

Metal binding of 1,3,5-tri­amino-1,3,5-tri­deoxy-cis-inositol (taci) has been investigated extensively (Hegetschweiler, 1999). As a chelating agent, taci fascinates by its exceptional versatility. This versatility is based on two distinct chair conformations, providing (i) N,N,N-, (ii) N,N,O-, (iii) O,O,N- or (iv) O,O,O-binding. These four binding modes, (i)–(iv), are all restricted to facial coordination. Metal binding to three axial donor groups, as observed in modes (i) or (iv), results in an adamantane-type geometry with low strain for small metal cations (Hancock & Hegetschweiler, 1993; Hegetschweiler et al., 1996). Large metal cations preferentially undergo a `side-on' coordination to the axial–equatorial–axial site of mode (ii) or mode (iii). In continuation of this work, we present here the crystal structures of three complexes with taci, (I) (with Li⁺), (II) (with Na⁺) and (III) (with K⁺).

S2. Experimental

S2.1. Synthesis and crystallization

1,3,5-Tri­amino-1,3,5-tri­deoxy-cis-inositol (taci) was prepared as described by Hegetschweiler et al. (1990), and the metal complexes were obtained following a protocol given by Kradolfer (1995). Colourless single crystals of (I)–(III) suitable for X-ray analysis were grown by slow diffusion of MeOH into the aqueous complex solutions. Elemental analysis, calculated for C₁₂H₃₅I₂LiN₆O₈ (%): C 22.10, H 5.41, N 12.89, I 38.92; found (%): C 22.58, H 5.36, N 12.87, I 39.00; calculated for C₁₂H₃₀IN₆NaO₆ (%): C 28.58, H 6.00, N 16.66, I 25.16; found (%): C 28.81, H 5.91, N 16.40, I 25.00; calculated for C₁₂H₃₀IKN₆O₆ (%): C 27.70, H 5.81, N 16.15, I 24.39; found (%): C 27.79, H 5.70, N 15.85, I 24.50.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. A preliminary X-ray diffraction study of the Li and Na complexes was reported by Kradolfer (1995). It was realised that the Na complex crystallizes in a trigonal lattice, and in the 1995 study the structure was solved and refined in the space group R3. However, inspection of our data revealed the presence of a centre of inversion and we therefore refined the structure in the space group R3. All H atoms could be located in a difference Fourier map. They were treated as recommended by Müller et al. (2006). A riding model was used for the C-bound H atoms. The positional parameters of the O- and N-bound H atoms were refined with restraints of O—H = 0.84 (s.u.?) Å and 0.88 (s.u.?) Å, and with U_iso(H) = 1.5U_eq(parent). The H4B position of the Li complex was refined with an occupancy of 0.50 (see Discussion).

S3. Results and discussion

Li⁺, Na⁺ and K⁺ are all considered as very hard cations and highly oxophilic Lewis acids, and it is not surprising that, in complex with taci, the small Li⁺ cation does indeed undergo a type (iv) coordination [(I)]. For Na⁺ [(II)] and K⁺ [(II)], their low affinity for N-donors conflicts with the more favourable steric prerequisites of a type (iii) binding. However, the high oxophilicity of these cations obviously overrides these steric demands, and in fact all three cations form bis-complexes with a type (iv) structure (Fig. 1).

Similarly, a type (iv) coordination has been observed for the alkaline earth metal cations Mg²⁺, Ca²⁺ and Ba²⁺ (Hegetschweiler et al., 1993). The structure of these alkaline earth metal complexes differs though, as additional water molecules are bonded to the heavier congeners, forming [Ca(taci)₂(H₂O)₂]²⁺, [Sr(taci)₂(H₂O)₃]²⁺ and [Ba(taci)₂(H₂O)₃]²⁺. Such an extension of the coordination sphere was not observed for Na⁺ and K⁺, although the Na and Ca complexes, and the K and Sr complexes, exhibit similar M—O bond lengths. As a consequence, all three alkali metal cations have a coordination number of 6, with a trigonal anti­prismatic geometry. The Na and the K complexes are isotypic. Crystal structure reports of a mononuclear alkali metal cation which is exclusively coordinated to six aliphatic hy­droxy groups are still scarce (Cotton et al., 1988). The crystal structure of an Na–taci 1:1 complex has recently been described (Reiss & Hegetschweiler, 2013). Its structure exhibited a three-dimensional coordination polymer, with the Na⁺ cation again bonded to the three axial O-donors of a taci ligand and, additionally, to an equatorial N-donor of three further taci molecules. The Na centre thus has a mixed NaO₃N₃ coordination and the coordination number is also 6.

The increasing ionic radius in the order Li⁺ < Na⁺ < K⁺ is well reflected in the structures of the three title compounds (Tables 2, 4 and 6). Besides the expected increase in the M—O bond lengths, a slight increase in intra­ligand O···O distances (Li 2.791–2.803 Å; Na 2.993 Å; K 3.026 Å) and a much more pronounced increase in the inter­ligand O···O distances (Li 2.987–3.009 Å; Na 3.704 Å; K 4.345 Å) are observed. Along with these trends, a slight flattening of the cyclo­hexane chair is noted. Puckering parameters (Cremer & Pople, 1975) for the cyclo­hexane chair of (I) are Q = 0.562 (2) Å, θ = 0.0 (2)° and ϕ = 300 (13)°; for (II), Q = 0.534 (2) Å, θ = 0.75 (1)° and ϕ = 0.00°; and for (III), Q = 0.520 (2) Å, θ = 0.00 (1)° and ϕ = 0.00°. Similarly, the increasing ionic radius results in a widening of the C—O—M and inter­ligand O—M—O angles. The intra­ligand O—M—O angles, on the other hand, decrease significantly with increasing ionic radius (Tables 2, 4 and 6). These changes are well in line with the proposed increase in steric strain with increasing ionic size.

All three metal cations are located on a centre of inversion. In addition, the Na⁺ and K⁺ cations lie on a threefold rotation axis. The crystallographically imposed molecular symmetry of the entire [Na(taci)₂]⁺ and [K(taci)₂]⁺ complexes is S₆, although their MO₆ polyhedra adopt D_3d symmetry. Over the entire molecular structures of (II) and (III), the local dihedral mirror planes of the coordination polyhedra are destroyed by a characteristic alignment of the equatorial N—H bond (the axial N—H bond is oriented approximately parallel to the threefold molecular axis). As a consequence, each single taci unit is chiral (C₃ symmetry) and the metal centre (Na, K) is coordinated to an image and mirror image of this particular conformation.

Each taci unit of (II) and (III) is hydrogen-bonded to three neighbouring mirror images by pairwise O—H···N inter­actions of vicinal O—CH₂—CH₂—NH₃ groupings via a centre of inversion (Tables 5 and 7). In terms of graph-set analysis (Bernstein et al., 1995), the resulting ten-membered ring-pattern is represented by R²₂(10). It has recently been shown that the cyclic R²₂(10) motif is a predominant inter­action type for taci molecules in solid-state structures (Neis & Hegetschweiler, 2014). However, in the previous investigations, the taci molecules or Htaci⁺ cations were arranged in indefinite C²₂(12) chains, whereas in the Na and K complexes reported here, the basic R²₂(10) pattern is aligned as complex R⁶₆(30) and R⁶₆(42) rings (Fig. 2a). The honeycomb-type linking generates layers parallel to the ab plane containing large voids, which are occupied by the I^- counterions. The layers are stacked along c in a staggered arrangement, with the centre of the cavity being placed above a metal centre of a neighbouring layer, and consequently the I^- anion exhibits six contacts to the N-bound H atoms of the R⁶₆(30) ring within the same layer and to the axial H atoms of two complex molecules in neighbouring layers. Altogether, the I^- anion is surrounded by six N-bound and six C-bound H atoms, which define a distorted D_3d symmetric icosahedron (Fig. 2b). It is noteworthy that, in the K complex, (III), the N—H···I and C—H···I distances of 3.253 and 3.268 Å, respectively, are of similar size, whereas in the Na complex, (II), with corresponding values of 3.212 and 3.074 Å, the C—H···I distances are significantly shorter.

In contrast with the Na and K complexes, the Li complex, (I), crystallizes as a protonated dication, [Li(taci)(Htaci)]²⁺. Coordination of an alkali metal cation to a protonated taci frame has been observed previously by Bartholomä et al. (2010). Along all three directions (i.e. along the crystallographic a, b and c axes), the dications are arranged in chains by hydrogen bonding, and these are related via a centre of inversion (Table 3). Along [001], the dications form R—NH₂—H···NH₂—R inter­actions (Fig. 3a). This motif is represented by the basic graph set C(10). Analysis of the electron density indicates formation of an asymmetric (N—H···N) hydrogen bond, but it is clear that, in the presence of an I^- counterion, discussion of an H-atom position may be questionable. However, the presence of an asymmetric hydrogen bond is supported by the N···N separation of 2.719 (3) Å. For a symmetric N—H—N bond, with atom H4B located directly on the centre of inversion, a significantly shorter N···N distance would have been expected (Bock et al., 1997; Steiner, 1995; Knop et al., 2001; Majerz & Olovsson, 2010). We therefore inter­preted the structure in terms of a disorder based on a double minimum potential, and the H4B position was refined with an occupancy of 0.50. Based on the C_i symmetry of the complex cation of (I), both ligand entities are half protonated and the complex may be formulated as [Li(H_0.5taci)₂]²⁺.

Along [100] (Fig. 3b), the dications of (I) are connected by R—O—H···NH₂—R hydrogen bonds. Two symmetry-related bonds are formed between two neighbouring cations and the resulting pattern corresponds to a R²₂(14) motif. A similar situation is observed along [010], but an additional water molecule is inserted in the hydrogen bond to form an R—O—H···O(H)—H···NH₂—R structure (Fig. 3c), and the corresponding graph set is R⁴₄(18). The combination of such chain motifs generates a series of large `super-rings'. As an example, the R⁴₄(22) ring shown in Fig. 3(d) follows from a combination of the chain patterns along [001] and [100]. The corresponding voids accommodate the I^- counterions. These I^- anions, which are placed on general positions, form two relatively short contacts to a water molecule and an alcohol OH group, with I···H—O separations of 2.647 and 2.705 Å, respectively. Additional contacts to three amino groups, with I···H separations in the range 2.949–3.119 Å, and to four H—C groups, with I···H separations in the range 3.156–3.313 Å, sum up to a coordination number of 9, with an irregular geometry of the corresponding polyhedron.

It is noteworthy that the calculated densities of the three compounds reported here [(I) 1.943 Mg m^-1, (II) 1.680 Mg m^-1 and (III) 1.629 Mg m^-1) do not coincide with the atomic masses of the corresponding metal centres. The rather high density of the Li complex, (I), is remarkable. A search of the Cambridge Structural Database (CSD, Version?; Allen, 2002) revealed a total of 21 structures containing the elements C, H, N, O, Li and I, with densities ranging from 1.12 to 2.01 Mg m^-1 (average 1.50 Mg m^-1). The high density of our Li complex, (I), is clearly due to the presence of the two I^- counterions per Li⁺ cation, which are required to balance the additional positive charge of the protonated ligand entity. The slightly higher density of the Na complex, (II), compared with the K complex, (III), is less obvious. However, inspection of the unit-cell dimensions for these two isotypic compounds indicates that the larger volume for the K complex is based solely on a lengthening of the unit cell along c. As explained above, this lengthening is a consequence of the larger ionic radius of K⁺, which causes a significant stretching of the trigonal anti­prismatic KO₆ polyhedron along the threefold rotation axis.

In conclusion, the present investigation demonstrates again the high diversity of possible hydrogen-bonding inter­actions for polyamino-polyalcohols (PAPAs). Similar to our previous investigations into hydrogen bonding in the solid-state structures of free taci, taci.HI and a co-crystal of these two components (Hegetschweiler et al., 1993; Reiss et al., 1999; Neis & Hegetschweiler, 2014), amine–alcohol inter­actions of the type R—O—H···N(H₂)—R constitute a predominant structural motif. The pairing mechanism of the vicinal amino­ethanol substructure may result in R²₂(10) ring formation, not only for the free ligand or its protonation products but also in the corresponding metal complexes.

Related literature

For related literature, see: Allen (2002); Bartholomä et al. (2010); Bernstein et al. (1995); Bock et al. (1997); Cotton et al. (1988); Cremer & Pople (1975); Hancock & Hegetschweiler (1993); Hegetschweiler (1999); Hegetschweiler et al. (1990, 1993, 1996); Knop et al. (2001); Kradolfer (1995); Müller et al. (2006); Majerz & Olovsson (2010); Neis & Hegetschweiler (2014); Reiss & Hegetschweiler (2013); Reiss et al. (1999); Steiner (1995).

Computing details

For all compounds, 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, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

Fig. 1. The molecular structures of (a) the [Li(Htaci)(taci)]²⁺ dication of (I) (the protonation at the two symmetry-related ammonium groups (N4) is only 50%, see text), (b) the [Na(taci)₂]⁺ cation of (II), and (c) the [K(taci)₂]⁺ cation of (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2. (a) The cyclic (taci)₆ motif of the Na and K complexes, (II) and (III), generated by R²₂(10) pairing of 12 1-hydroxy-2-amino-ethylene groups, together with the encapsulated I^- counterion. The cyclohexane frame is shown as a stick model, and N (blue), O (red) and I (green) atoms are shown as displacement ellipsoids at the 50% probability level. N-bound and O-bound H atoms are shown as spheres of arbitrary size; C-bound H atoms have been omitted for clarity. (b) The D_3d icosahedron formed by the 12 H atoms which surround the I^- counterion.

Fig. 3. Hydrogen bonding in the Li complex, (I). (a) R—NH₂—H···NH₂—R interactions along [001]. Both positions of the double minimum potential of atom H4B are shown (see text). (b) The symmetry-related R—O—H···NH₂—R interactions along [100], generating an R²₂(14) motif. (c) The R⁴₄(18) motif, forming chains along [010]. (d) The R⁴₄(22) `super-ring', oriented parallel to the ac plane, obtained from a combination of the chain motifs along [100] and [001] shown in (a) and (b). Dashed lines indicate hydrogen bonds. Atoms are represented as in Fig. 2(a).

(I) (1,3-Diamino-5-azaniumyl-1,3,5-trideoxy-cis-inositol-κ³O²,O⁴,O⁶)(1,3,5-triamino-1,3,5-trideoxy-cis-inositol-κ³O²,O⁴,O⁶)lithium(I) diiodide dihydrate

Crystal data

[Li(C6H16N3O3)(C6H15N3O3)]I2·2H2O	Z = 1
Mr = 652.20	F(000) = 322
Triclinic, P1	Dx = 1.943 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1327 (18) Å	Cell parameters from 9029 reflections
b = 9.309 (2) Å	θ = 2.4–36.7°
c = 9.378 (2) Å	µ = 2.87 mm^−1
α = 68.739 (8)°	T = 123 K
β = 76.082 (10)°	Cuboid, colourless
γ = 77.494 (8)°	0.54 × 0.34 × 0.27 mm
V = 557.5 (2) Å^3

Data collection

Bruker Nonius X8 APEX diffractometer with KappaCCD area detector	2430 independent reflections
Radiation source: fine-focus sealed tube	2424 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ and ω scans	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −9→9
Tmin = 0.306, Tmax = 0.511	k = −11→11
12643 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.042	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ^2(Fo^2) + (0.0124P)^2 + 0.5599P] where P = (Fo^2 + 2Fc^2)/3
2430 reflections	(Δ/σ)max = 0.002
169 parameters	Δρmax = 0.47 e Å^−3
12 restraints	Δρmin = −0.87 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)
I1	0.559573 (16)	0.288541 (14)	0.335254 (13)	0.01281 (5)
Li1	0.0000	0.0000	0.0000	0.0098 (8)
O1	0.16742 (19)	−0.21254 (15)	0.00196 (15)	0.0087 (2)
H1O	0.240 (3)	−0.235 (3)	−0.071 (2)	0.013*
C1	0.2230 (3)	−0.3262 (2)	0.1426 (2)	0.0073 (3)
H1	0.3103	−0.4159	0.1157	0.009*
C2	0.3338 (2)	−0.2591 (2)	0.2188 (2)	0.0075 (3)
H2	0.3779	−0.3458	0.3099	0.009*
N2	0.5081 (2)	−0.1983 (2)	0.1138 (2)	0.0115 (3)
H2A	0.470 (4)	−0.119 (2)	0.038 (3)	0.017*
H2B	0.580 (3)	−0.265 (3)	0.071 (3)	0.017*
O3	0.15923 (19)	0.00070 (15)	0.15024 (15)	0.0093 (2)
H3O	0.158 (4)	0.080 (2)	0.168 (3)	0.014*
C3	0.2077 (3)	−0.1328 (2)	0.2791 (2)	0.0074 (3)
H3	0.2833	−0.1028	0.3383	0.009*
N4	−0.0993 (2)	−0.0690 (2)	0.4419 (2)	0.0125 (3)
H4C	−0.205 (3)	−0.105 (3)	0.510 (3)	0.019*
H4B	−0.045 (7)	−0.020 (6)	0.483 (6)	0.019*	0.50
H4A	−0.154 (4)	0.003 (3)	0.366 (3)	0.019*
C4	0.0242 (3)	−0.1939 (2)	0.3885 (2)	0.0079 (3)
H4	0.0658	−0.2794	0.4814	0.009*
C6	0.0417 (3)	−0.3856 (2)	0.2549 (2)	0.0075 (3)
H6	0.0870	−0.4704	0.3468	0.009*
N6	−0.0547 (2)	−0.45631 (19)	0.1815 (2)	0.0112 (3)
H6B	−0.078 (4)	−0.388 (3)	0.089 (2)	0.017*
H6A	−0.165 (3)	−0.484 (3)	0.241 (3)	0.017*
C5	−0.0918 (3)	−0.2602 (2)	0.3151 (2)	0.0076 (3)
H5	−0.2000	−0.3086	0.3967	0.009*
O5	−0.17461 (18)	−0.13452 (15)	0.19580 (15)	0.0085 (2)
H5O	−0.274 (3)	−0.154 (3)	0.183 (3)	0.013*
O1W	0.1834 (2)	0.27443 (18)	0.1671 (2)	0.0203 (3)
H1W	0.283 (3)	0.279 (4)	0.196 (3)	0.030*
H2W	0.106 (4)	0.355 (3)	0.166 (4)	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01009 (7)	0.01493 (8)	0.01306 (8)	0.00060 (5)	−0.00234 (5)	−0.00537 (5)
Li1	0.011 (2)	0.010 (2)	0.010 (2)	−0.0027 (16)	−0.0034 (16)	−0.0034 (17)
O1	0.0098 (6)	0.0101 (6)	0.0059 (6)	0.0003 (5)	−0.0010 (5)	−0.0034 (5)
C1	0.0074 (8)	0.0071 (8)	0.0077 (8)	−0.0005 (6)	−0.0018 (6)	−0.0029 (6)
C2	0.0058 (7)	0.0080 (8)	0.0094 (8)	−0.0004 (6)	−0.0024 (6)	−0.0033 (7)
N2	0.0062 (7)	0.0151 (8)	0.0140 (8)	−0.0023 (6)	−0.0010 (6)	−0.0058 (6)
O3	0.0150 (6)	0.0048 (6)	0.0100 (6)	−0.0020 (5)	−0.0067 (5)	−0.0016 (5)
C3	0.0085 (8)	0.0076 (8)	0.0076 (8)	−0.0011 (6)	−0.0038 (6)	−0.0027 (6)
N4	0.0146 (8)	0.0127 (8)	0.0103 (8)	0.0015 (6)	−0.0003 (6)	−0.0069 (6)
C4	0.0086 (8)	0.0079 (8)	0.0077 (8)	0.0007 (6)	−0.0013 (6)	−0.0043 (7)
C6	0.0081 (8)	0.0059 (8)	0.0093 (8)	−0.0019 (6)	−0.0018 (6)	−0.0027 (6)
N6	0.0102 (7)	0.0105 (8)	0.0159 (8)	−0.0039 (6)	−0.0022 (6)	−0.0066 (6)
C5	0.0079 (8)	0.0071 (8)	0.0074 (8)	−0.0019 (6)	−0.0005 (6)	−0.0019 (7)
O5	0.0062 (6)	0.0093 (6)	0.0114 (6)	−0.0012 (5)	−0.0038 (5)	−0.0033 (5)
O1W	0.0203 (8)	0.0118 (7)	0.0374 (9)	0.0035 (6)	−0.0141 (7)	−0.0157 (7)

Geometric parameters (Å, º)

Li1—O1	2.0741 (14)	N4—C4	1.464 (2)
Li1—O3	2.0137 (13)	N4—H4C	0.901 (17)
Li1—O5	2.0973 (14)	N4—H4B	0.882 (19)
O1—C1	1.440 (2)	N4—H4A	0.884 (17)
O1—H1O	0.816 (17)	C4—C5	1.531 (2)
C1—C6	1.523 (2)	C4—H4	1.0000
C1—C2	1.529 (2)	C6—N6	1.461 (2)
C1—H1	1.0000	C6—C5	1.525 (2)
C2—N2	1.465 (2)	C6—H6	1.0000
C2—C3	1.513 (2)	N6—H6B	0.895 (17)
C2—H2	1.0000	N6—H6A	0.880 (17)
N2—H2A	0.865 (17)	C5—O5	1.428 (2)
N2—H2B	0.868 (17)	C5—H5	1.0000
O3—C3	1.432 (2)	O5—H5O	0.815 (16)
O3—H3O	0.813 (17)	O1W—H1W	0.836 (18)
C3—C4	1.530 (2)	O1W—H2W	0.825 (18)
C3—H3	1.0000
O3—Li1—O3^i	180.0	C2—C3—H3	108.8
O3—Li1—O1	86.11 (5)	C4—C3—H3	108.8
O3—Li1—O1^i	93.89 (5)	C4—N4—H4C	110.1 (18)
O1—Li1—O1^i	180.0	C4—N4—H4B	118 (4)
O3—Li1—O5	85.94 (5)	H4C—N4—H4B	108 (4)
O1—Li1—O5	84.33 (5)	C4—N4—H4A	111.3 (18)
O1—Li1—O5^i	95.67 (5)	H4C—N4—H4A	101 (2)
O3—Li1—O5^i	94.06 (5)	H4B—N4—H4A	107 (4)
O5—Li1—O5^i	180.0	N4—C4—C3	109.26 (15)
C1—O1—Li1	121.84 (11)	N4—C4—C5	110.36 (15)
C1—O1—H1O	107.4 (18)	C3—C4—C5	113.36 (14)
Li1—O1—H1O	127.7 (18)	N4—C4—H4	107.9
O1—C1—C6	109.50 (14)	C3—C4—H4	107.9
O1—C1—C2	111.60 (14)	C5—C4—H4	107.9
C6—C1—C2	110.36 (14)	N6—C6—C1	108.89 (15)
O1—C1—H1	108.4	N6—C6—C5	113.91 (15)
C6—C1—H1	108.4	C1—C6—C5	112.37 (14)
C2—C1—H1	108.4	N6—C6—H6	107.1
N2—C2—C3	109.12 (15)	C1—C6—H6	107.1
N2—C2—C1	112.21 (15)	C5—C6—H6	107.1
C3—C2—C1	112.72 (14)	C6—N6—H6B	109.7 (17)
N2—C2—H2	107.5	C6—N6—H6A	110.7 (17)
C3—C2—H2	107.5	H6B—N6—H6A	109 (2)
C1—C2—H2	107.5	O5—C5—C6	112.91 (14)
C2—N2—H2A	107.6 (17)	O5—C5—C4	108.26 (14)
C2—N2—H2B	112.0 (18)	C6—C5—C4	109.41 (14)
H2A—N2—H2B	106 (2)	O5—C5—H5	108.7
C3—O3—Li1	123.63 (10)	C6—C5—H5	108.7
C3—O3—H3O	110.3 (19)	C4—C5—H5	108.7
Li1—O3—H3O	120.5 (19)	C5—O5—Li1	121.79 (10)
O3—C3—C2	109.21 (14)	C5—O5—H5O	110.7 (18)
O3—C3—C4	111.34 (14)	Li1—O5—H5O	117.7 (18)
C2—C3—C4	109.89 (14)	H1W—O1W—H2W	108 (3)
O3—C3—H3	108.8
O3^i—Li1—O1—C1	−140.44 (12)	C2—C3—C4—N4	−178.18 (14)
O3—Li1—O1—C1	39.56 (12)	O3—C3—C4—C5	66.48 (19)
O1^i—Li1—O1—C1	78 (10)	C2—C3—C4—C5	−54.65 (19)
O5—Li1—O1—C1	−46.74 (12)	O1—C1—C6—N6	59.75 (18)
O5^i—Li1—O1—C1	133.26 (12)	C2—C1—C6—N6	−177.01 (14)
Li1—O1—C1—C6	65.75 (16)	O1—C1—C6—C5	−67.40 (18)
Li1—O1—C1—C2	−56.75 (17)	C2—C1—C6—C5	55.83 (19)
O1—C1—C2—N2	−57.14 (19)	N6—C6—C5—O5	−59.0 (2)
C6—C1—C2—N2	−179.14 (15)	C1—C6—C5—O5	65.40 (19)
O1—C1—C2—C3	66.53 (19)	N6—C6—C5—C4	−179.67 (15)
C6—C1—C2—C3	−55.47 (19)	C1—C6—C5—C4	−55.24 (19)
O3^i—Li1—O3—C3	150 (100)	N4—C4—C5—O5	54.42 (18)
O1—Li1—O3—C3	−43.60 (13)	C3—C4—C5—O5	−68.50 (18)
O1^i—Li1—O3—C3	136.40 (13)	N4—C4—C5—C6	177.85 (14)
O5—Li1—O3—C3	40.98 (13)	C3—C4—C5—C6	54.93 (19)
O5^i—Li1—O3—C3	−139.02 (13)	C6—C5—O5—Li1	−58.95 (17)
Li1—O3—C3—C2	63.29 (17)	C4—C5—O5—Li1	62.34 (16)
Li1—O3—C3—C4	−58.24 (18)	O3^i—Li1—O5—C5	136.09 (12)
N2—C2—C3—O3	57.33 (18)	O3—Li1—O5—C5	−43.91 (12)
C1—C2—C3—O3	−68.04 (18)	O1—Li1—O5—C5	42.58 (12)
N2—C2—C3—C4	179.73 (14)	O1^i—Li1—O5—C5	−137.42 (12)
C1—C2—C3—C4	54.36 (19)	O5^i—Li1—O5—C5	−130 (100)
O3—C3—C4—N4	−57.04 (19)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···I1^ii	0.82 (2)	2.71 (2)	3.5152 (15)	172 (2)
N2—H2B···O1W^ii	0.87 (2)	2.47 (2)	3.189 (2)	141 (2)
O3—H3O···O1W	0.81 (2)	1.85 (2)	2.654 (2)	168 (3)
N4—H4C···I1^iii	0.90 (2)	3.12 (2)	3.9786 (19)	160 (2)
N4—H4B···N4^iii	0.88 (2)	1.84 (2)	2.719 (3)	173 (5)
N4—H4A···I1^iv	0.88 (2)	2.95 (2)	3.6398 (19)	137 (2)
N6—H6B···O1W^i	0.90 (2)	2.48 (2)	3.339 (3)	161 (2)
N6—H6A···I1^v	0.88 (2)	2.95 (2)	3.7051 (18)	145 (2)
O5—H5O···N2^iv	0.82 (2)	1.99 (2)	2.796 (2)	170 (2)
O1W—H1W···I1	0.84 (2)	2.64 (2)	3.4707 (16)	170 (3)
O1W—H2W···N6^vi	0.83 (2)	1.91 (2)	2.734 (2)	173 (3)

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

(II) Bis(1,3,5-triamino-1,3,5-trideoxy-cis-inositol-κ³O²,O⁴,O⁶)sodium(I) iodide

Crystal data

[Na(C6H15N3O3)2]I	Dx = 1.680 Mg m^−3
Mr = 504.31	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 4773 reflections
Hall symbol: -R 3	θ = 2.6–33.2°
a = 10.9637 (6) Å	µ = 1.67 mm^−1
c = 14.3641 (8) Å	T = 123 K
V = 1495.28 (14) Å^3	Plate, colourless
Z = 3	0.76 × 0.60 × 0.30 mm
F(000) = 768

Data collection

Bruker Nonius X8 APEX diffractometer with Kappa CCD area detector	733 independent reflections
Radiation source: fine-focus sealed tube	733 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
ϕ and ω scans	θmax = 27.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −13→14
Tmin = 0.364, Tmax = 0.635	k = −12→9
3194 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.012	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.034	H atoms treated by a mixture of independent and constrained refinement
S = 1.22	w = 1/[σ^2(Fo^2) + (0.0179P)^2 + 1.634P] where P = (Fo^2 + 2Fc^2)/3
733 reflections	(Δ/σ)max < 0.001
50 parameters	Δρmax = 0.42 e Å^−3
3 restraints	Δρmin = −0.30 e Å^−3

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
I1	0.0000	0.0000	0.5000	0.01250 (8)
O1	0.36478 (9)	0.52714 (9)	0.55261 (6)	0.01095 (17)
H1O	0.3686 (18)	0.4532 (16)	0.5593 (11)	0.016*
C1	0.21533 (12)	0.52260 (12)	0.42414 (8)	0.0095 (2)
H1	0.2140	0.5211	0.3545	0.011*
Na1	0.3333	0.6667	0.6667	0.0112 (2)
N2	0.09847 (11)	0.38616 (11)	0.45561 (8)	0.0129 (2)
H2B	0.109 (2)	0.381 (2)	0.5164 (9)	0.019*
H2A	0.1036 (19)	0.3156 (16)	0.4309 (12)	0.019*
C2	0.36015 (12)	0.54690 (12)	0.45451 (8)	0.0094 (2)
H2	0.3761	0.4752	0.4223	0.011*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01396 (9)	0.01396 (9)	0.00959 (10)	0.00698 (4)	0.000	0.000
O1	0.0143 (4)	0.0109 (4)	0.0100 (4)	0.0081 (3)	0.0001 (3)	0.0013 (3)
C1	0.0085 (5)	0.0081 (5)	0.0112 (5)	0.0035 (4)	−0.0004 (4)	−0.0008 (4)
Na1	0.0120 (3)	0.0120 (3)	0.0097 (5)	0.00600 (16)	0.000	0.000
N2	0.0101 (5)	0.0077 (4)	0.0194 (5)	0.0033 (4)	0.0004 (4)	−0.0002 (4)
C2	0.0094 (5)	0.0091 (5)	0.0101 (5)	0.0050 (4)	0.0004 (4)	−0.0005 (4)

Geometric parameters (Å, º)

O1—C2	1.4303 (13)	Na1—O1^i	2.3813 (8)
O1—Na1	2.3813 (8)	Na1—O1^iii	2.3813 (9)
O1—H1O	0.838 (14)	Na1—O1^iv	2.3813 (9)
C1—N2	1.4721 (15)	Na1—O1^v	2.3814 (8)
C1—C2^i	1.5309 (15)	N2—H2B	0.885 (13)
C1—C2	1.5359 (15)	N2—H2A	0.879 (14)
C1—H1	1.0000	C2—C1^iii	1.5309 (15)
Na1—O1^ii	2.3813 (9)	C2—H2	1.0000
C2—O1—Na1	123.57 (7)	O1^iii—Na1—O1^iv	180.0
C2—O1—H1O	106.4 (11)	O1—Na1—O1^iv	102.13 (3)
Na1—O1—H1O	129.4 (11)	O1^ii—Na1—O1^v	77.87 (3)
N2—C1—C2^i	109.04 (9)	O1^i—Na1—O1^v	102.12 (3)
N2—C1—C2	112.83 (9)	O1^iii—Na1—O1^v	102.12 (3)
C2^i—C1—C2	113.65 (11)	O1—Na1—O1^v	180.00 (4)
N2—C1—H1	107.0	O1^iv—Na1—O1^v	77.87 (3)
C2^i—C1—H1	107.0	C1—N2—H2B	106.9 (13)
C2—C1—H1	107.0	C1—N2—H2A	111.4 (12)
O1^ii—Na1—O1^i	180.0	H2B—N2—H2A	106.0 (17)
O1^ii—Na1—O1^iii	102.13 (3)	O1—C2—C1^iii	111.35 (9)
O1^i—Na1—O1^iii	77.88 (3)	O1—C2—C1	111.44 (9)
O1^ii—Na1—O1	102.13 (3)	C1^iii—C2—C1	110.83 (11)
O1^i—Na1—O1	77.88 (3)	O1—C2—H2	107.7
O1^iii—Na1—O1	77.88 (3)	C1^iii—C2—H2	107.7
O1^ii—Na1—O1^iv	77.88 (3)	C1—C2—H2	107.7
O1^i—Na1—O1^iv	102.12 (3)
C2—O1—Na1—O1^ii	−140.07 (6)	Na1—O1—C2—C1	−61.98 (11)
C2—O1—Na1—O1^i	39.93 (7)	N2—C1—C2—O1	−52.73 (13)
C2—O1—Na1—O1^iii	−40.07 (7)	C2^i—C1—C2—O1	72.07 (12)
C2—O1—Na1—O1^iv	139.93 (7)	N2—C1—C2—C1^iii	−177.34 (8)
Na1—O1—C2—C1^iii	62.32 (11)	C2^i—C1—C2—C1^iii	−52.53 (15)

Symmetry codes: (i) −x+y, −x+1, z; (ii) x−y+2/3, x+1/3, −z+4/3; (iii) −y+1, x−y+1, z; (iv) y−1/3, −x+y+1/3, −z+4/3; (v) −x+2/3, −y+4/3, −z+4/3.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2^vi	0.84 (1)	1.93 (1)	2.7525 (14)	167 (2)

Symmetry code: (vi) y, −x+y, −z+1.

(III) Bis(1,3,5-triamino-1,3,5-trideoxy-cis-inositol-κ³O²,O⁴,O⁶)potassium(I) iodide

Crystal data

[K(C6H15N3O3)2]I	Dx = 1.629 Mg m^−3
Mr = 520.42	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 8928 reflections
Hall symbol: -R 3	θ = 2.5–35.3°
a = 10.9149 (4) Å	µ = 1.74 mm^−1
c = 15.4297 (6) Å	T = 123 K
V = 1591.94 (10) Å^3	Cuboid, colourless
Z = 3	0.48 × 0.38 × 0.25 mm
F(000) = 792

Data collection

Bruker Nonius X8 APEX diffractometer with Kappa CCD area detector	775 independent reflections
Radiation source: fine-focus sealed tube	775 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ϕ and ω scans	θmax = 27.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −13→13
Tmin = 0.488, Tmax = 0.670	k = −13→13
6449 measured reflections	l = −17→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.011	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.030	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0149P)^2 + 2.2628P] where P = (Fo^2 + 2Fc^2)/3
775 reflections	(Δ/σ)max = 0.001
50 parameters	Δρmax = 0.43 e Å^−3
3 restraints	Δρmin = −0.18 e Å^−3

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
I1	0.0000	0.0000	0.5000	0.01441 (7)
K1	0.3333	0.6667	0.6667	0.01379 (12)
O1	0.47463 (8)	0.63415 (8)	0.53775 (5)	0.01232 (16)
H1O	0.5465 (15)	0.6301 (16)	0.5460 (10)	0.018*
C1	0.45382 (11)	0.63917 (11)	0.44695 (7)	0.0105 (2)
H1	0.5253	0.6230	0.4164	0.013*
N2	0.28609 (10)	0.38512 (10)	0.45122 (7)	0.01469 (19)
H2B	0.2149 (15)	0.3160 (15)	0.4268 (10)	0.022*
H2A	0.2664 (17)	0.3806 (18)	0.5052 (9)	0.022*
C2	0.30654 (11)	0.52122 (11)	0.41942 (7)	0.0110 (2)
H2	0.3058	0.5172	0.3547	0.013*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01480 (8)	0.01480 (8)	0.01365 (10)	0.00740 (4)	0.000	0.000
K1	0.01596 (17)	0.01596 (17)	0.0095 (2)	0.00798 (8)	0.000	0.000
O1	0.0115 (4)	0.0155 (4)	0.0127 (4)	0.0088 (3)	−0.0012 (3)	0.0000 (3)
C1	0.0098 (5)	0.0105 (5)	0.0117 (5)	0.0054 (4)	0.0005 (4)	−0.0008 (4)
N2	0.0123 (4)	0.0086 (4)	0.0226 (5)	0.0049 (4)	−0.0012 (4)	−0.0011 (4)
C2	0.0110 (5)	0.0092 (5)	0.0133 (5)	0.0054 (4)	−0.0006 (4)	−0.0012 (4)

Geometric parameters (Å, º)

K1—O1^i	2.6474 (8)	C1—C2	1.5338 (14)
K1—O1^ii	2.6474 (8)	C1—C2^ii	1.5378 (14)
K1—O1^iii	2.6474 (8)	C1—H1	1.0000
K1—O1	2.6474 (8)	N2—C2	1.4716 (14)
K1—O1^iv	2.6474 (8)	N2—H2B	0.854 (13)
K1—O1^v	2.6474 (8)	N2—H2A	0.855 (13)
O1—C1	1.4247 (13)	C2—C1^i	1.5378 (14)
O1—H1O	0.817 (13)	C2—H2	1.0000
O1^i—K1—O1^ii	69.71 (3)	K1—O1—H1O	122.0 (10)
O1^i—K1—O1^iii	110.29 (3)	O1—C1—C2	111.12 (8)
O1^ii—K1—O1^iii	180.0	O1—C1—C2^ii	111.26 (8)
O1^i—K1—O1	69.71 (3)	C2—C1—C2^ii	111.22 (10)
O1^ii—K1—O1	69.71 (3)	O1—C1—H1	107.7
O1^iii—K1—O1	110.29 (3)	C2—C1—H1	107.7
O1^i—K1—O1^iv	180.00 (2)	C2^ii—C1—H1	107.7
O1^ii—K1—O1^iv	110.29 (3)	C2—N2—H2B	110.9 (11)
O1^iii—K1—O1^iv	69.71 (3)	C2—N2—H2A	106.8 (11)
O1—K1—O1^iv	110.29 (3)	H2B—N2—H2A	106.7 (15)
O1^i—K1—O1^v	110.29 (3)	N2—C2—C1	108.74 (9)
O1^ii—K1—O1^v	110.29 (3)	N2—C2—C1^i	112.15 (9)
O1^iii—K1—O1^v	69.71 (3)	C1—C2—C1^i	114.09 (10)
O1—K1—O1^v	180.0	N2—C2—H2	107.2
O1^iv—K1—O1^v	69.71 (3)	C1—C2—H2	107.2
C1—O1—K1	128.24 (6)	C1^i—C2—H2	107.2
C1—O1—H1O	109.3 (11)
O1^i—K1—O1—C1	37.64 (6)	K1—O1—C1—C2^ii	62.06 (10)
O1^ii—K1—O1—C1	−37.44 (6)	O1—C1—C2—N2	−52.65 (11)
O1^iii—K1—O1—C1	142.56 (6)	C2^ii—C1—C2—N2	−177.19 (7)
O1^iv—K1—O1—C1	−142.36 (6)	O1—C1—C2—C1^i	73.35 (11)
O1^v—K1—O1—C1	−63 (8)	C2^ii—C1—C2—C1^i	−51.19 (15)
K1—O1—C1—C2	−62.46 (10)

Symmetry codes: (i) −x+y, −x+1, z; (ii) −y+1, x−y+1, z; (iii) y−1/3, −x+y+1/3, −z+4/3; (iv) x−y+2/3, x+1/3, −z+4/3; (v) −x+2/3, −y+4/3, −z+4/3.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2^vi	0.82 (1)	1.92 (1)	2.7283 (13)	172 (2)
N2—H2B···I1	0.85 (1)	3.25 (2)	3.8550 (10)	130 (1)

Symmetry code: (vi) −x+1, −y+1, −z+1.