Hydrogen bonding in polyamino-polyalcohols: a monohydrated cocrystal of 1,3-di­amino-5-azaniumyl-1,3,5-tri­deoxy-cis-inositol iodide and 1,3,5-tri­amino-1,3,5-tri­deoxy-cis-inositol

In the title monohydrated cocrystal, namely 1,3-di­amino-5-azaniumyl-1,3,5-tri­deoxy-cis-inositol iodide–1,3,5-tri­amino-1,3,5-tri­deoxy-cis-inositol–water (1/1/1), C₆H₁₆N₃O₃⁺·I⁻·C₆H₁₅N₃O₃·H₂O, the neutral 1,3,5-tri­amino-1,3,5-tri­deoxy-cis-ino­sitol (taci) mol­ecule and the monoprotonated 1,3-di­amino-5-azaniumyl-1,3,5-tri­deoxy-cis-inositol cation (Htaci⁺) both adopt a chair conformation, with the three O atoms in axial and the three N atoms in equatorial positions. The cation, but not the neutral taci unit, exhibits intra­molecular O—H...O hydrogen bonding. The entire structure is stabilized by a complex three-dimensional network of inter­molecular hydrogen bonds. The neutral taci entities and the Htaci⁺ cations are each aligned into chains along [001]. In these chains, two O—H...N inter­actions generate a ten-membered ring as the predominant structural motif. The rings consist of vicinal 2-amino-1-hy­droxy­ethyl­ene units of neighbouring mol­ecules, which are paired via centres of inversion. The chains are inter­connected into undulating layers parallel to the ac plane, and the layers are further held together by O—H...N hydrogen bonds and additional inter­actions with the iodide counter-anions and solvent water mol­ecules.

S1. Introduction

With regard to hydrogen bonding, polyamino-polyalcohols (PAPAs) are a particularly inter­esting class of compounds. It has been pointed out by Ermer & Eling (1994) that the alcoholic hy­droxy group and the primary amino group represent complements, as the numbers of possible donating and accepting inter­actions are reverse in each case: a primary amino group may take part in one accepting and two donating inter­actions, whereas the alcoholic hy­droxy group is suited for one donating and two accepting inter­actions. As a consequence, the hydrogen-bonding scheme between primary aliphatic amines and aliphatic alcohols has been extensively studied, and discussed in terms of supra­molecular structure, molecular recognition and crystal engineering. It has indeed been shown by Mootz et al. (1989) that, in the crystal structure of 2-amino­ethanol, a three-dimensional network consisting of N—H···O and O—H···N hydrogen bonds is fully balanced, resulting in complete saturation of all potential hydrogen-bond valences. At first glance 1,3,5-tri­amino-1,3,5-tri­deoxy-cis-inositol (taci), with its equal number of hy­droxy and primary amino groups, appears to be an ideal candidate for the formation of such a fully saturated hydrogen-bonding network. Moreover, the title monohydrated cocrystal, Htaci⁺.I^-.taci.H₂O, (I), where the neutral taci molecule and monoprotonated Htaci⁺ cation are present in a 1:1 ratio, reflects a particularly inter­esting situation. A multitude of different hydrogen bonds could form. Beside the above-mentioned N—H···O and O—H···N hydrogen bonding, O—H···O contacts or inter­actions between an Htaci⁺ cation and a neutral taci unit by N(H₂)—H···O or N(H₂)—H···N hydrogen bonding must also be taken into account.

S2. Experimental

S2.1. Synthesis and crystallization

1,3,5-Tri­amino-1,3,5-tri­deoxy-cis-inositol (taci) was prepared as described previously (Hegetschweiler et al., 1990). Cocrystals of the title compound were grown at room temperature from an aqueous solution which was layered with EtOH.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms could be located in a difference Fourier synthesis. In the final refinement, a riding model was used for the C-bound H atoms, with C—H = 1.00 Å. The positional parameters of the N- and O-bound H atoms were refined with restraints of 0.88(s.u.?) or 0.84(s.u.?) Å for the N—H and O—H bond lengths, respectively. The U_iso(H) values were fixed at 1.2U_eq(C) or 1.5U_eq(N,O).

S3. Results and discussion

In the title monohydrated cocrystal, (I), the neutral taci molecule and the Htaci⁺ cation both adopt chair conformations, with axial hy­droxy groups and equatorial amino or aza­niumyl groups (Fig. 1). The puckering parameters (Cremer & Pople, 1975) for the taci molecule are Q = 0.531 (2) Å, θ = 3.2 (2)° and ϕ = 323 (4)°, and for the Htaci⁺ cation are Q = 0.562 (2) Å, θ = 173.5 (2)° and ϕ = 27 (2)°. However, the two conformations differ with regard to the orientation of the O—H bonds. In the Htaci⁺ cation, one of the hy­droxy groups donates its proton to a neighbouring hy­droxy group via intra­molecular 1,3-diaxial O—H···O hydrogen bonding, and the H atom is therefore located on the inside of the cation. In the neutral taci molecule, an external proton from an ammonium group is accepted by two of the axial O atoms (Fig. 2), and as a consequence all O—H groups are directed to the outside, undergoing inter­molecular donating inter­actions. A similar situation, where the hy­droxy groups of two taci frames undergo such differing types of hydrogen-bonding inter­actions in the same crystal structure, has been described previously for (H₃taci)₄[PtCl₆]Cl₁₀.6H₂O (Gencheva et al., 2000).

The crystal structures of the two isolated components of (I), i.e. taci and Htaci^+.I^-, have already been reported (Hegetschweiler et al., 1993; Reiss et al., 1999). The crystal structure of neutral taci exhibits zigzag chains with strong O—H···N hydrogen bonds (Fig. 3a). In terms of graph-set analysis (Bernstein et al., 1995), this pattern is represented by the descriptor C(5). The chains are inter­linked by much weaker N—H···O hydrogen bonds, and the resulting layers are held together by further hydrogen bonding to inter­calated water molecules. As a consequence, an H atom without an acceptor remains for all amino groups. In the crystal structure of Htaci^+.I^-, the cations are aligned to form a chain of double rings. Each cation is bonded to two neighbouring cations by pair-wise O—H···N hydrogen bonding between an amino group and a vicinal hy­droxy group (Fig. 3b; X = NH₃⁺). In view of graph-set considerations, we note that the two R₂²(10) rings have the same constitution but are crystallographically different. The resulting chain thus corresponds to a C₂²(12) motif.

In (I), i.e. in the monohydrated cocrystal of taci and Htaci^+.I^-, the neutral taci molecules form an analogous C₂²(12) chain of R₂²(10)R₂²(10) double rings (Fig. 3b; X = NH₂). The Htaci⁺ cations also adopt such a chain structure. However, in the latter case the two rings are of different constitutions (Fig. 3c). On one side, an amino group of a cation together with a vicinal hy­droxy group bind again with a neighbouring cation by pair-wise O—H···N inter­actions (Fig. 3c, highlighted in red). On the other side, an additional type of inter­action to a second neighbour occurs by pair-wise N—H···O hydrogen bonding between the aza­niumyl group and a vicinal hy­droxy group (Fig. 3c, highlighted in blue). Both chains are aligned along the crystallographic c axis. They are inter­linked into undulating layers by the above-mentioned N(H₂)—H···O hydrogen bonds, with an ammonium group donating an H atom to two hy­droxy groups of an adjacent taci molecule (asymmetric bifurcation). Additional inter­chain crosslinking occurs via donation of an amine H atom of a neutral taci molecule to a hy­droxy group of a Htaci⁺ cation. Finally, the layers are held together by O—H···N hydrogen bonds formed between a hy­droxy group of the neutral taci molecule and an amino group of the cation. Further inter­layer crosslinking occurs via the iodide counter-anion and the solvent water molecule (Fig. 2).

The iodide anion forms one strong O—H···I hydrogen bond with a hy­droxy group of the cation as a donor. An additional O—H···I hydrogen bond is formed by the water molecule. Several weak N—H···I and C—H···I contacts are observed with H···I separations > 2.9 Å. Inspection of the H···I distances exhibits a steady increase of values up to 3.5 Å, and it is not really clear which of them effectively correspond to directed bonds or should rather be regarded as simple van der Waals contacts.

In conclusion, previous work and the present contribution underline the importance of O—H···N hydrogen-bonding inter­actions in the crystal structure of taci and its monoprotonated form. In particular, the formation of R₂²(10) rings which originate from pairing of HO—CH₂—CH₂—NH₂ entities (Fig. 3, structure type A shown in red) appears to be a predominant type of inter­action in the crystal structures of such compounds. An additional pairing mechanism (Fig. 3, structure type B shown in blue) comprises pairing of an HO—CH₂—CH₂—NH₃⁺ entity via a centre of inversion with the hy­droxy group as acceptor. In (I), the monoprotonated cations are aligned into chains via alternate type A and type B inter­actions, whereas in the crystal structure of the simple Htaci^+.I^- ion pair, cation–cation inter­actions are constituted solely by the type A mechanism. It is noteworthy that the type A group is closely related to the 1,2-cyclo­hexanedi­amine–1,2-cyclo­hexane­diol pairing described by Hanessian et al. (1995). The reverse inter­action type, i.e. N—H···O hydrogen bonding, generally appears to be of less importance and leads (as expected) to weaker inter­actions (Table 2). Inter­estingly, O—H···O inter­actions between the hy­droxy groups of (I) are observed solely as intra­molecular contacts, and N—H···N inter­actions between an aza­niumyl group and an amino group are not observed at all.

Related literature

For related literature, see: Bernstein et al. (1995); Cremer & Pople (1975); Ermer & Eling (1994); Gencheva et al. (2000); Hanessian et al. (1995); Hegetschweiler et al. (1990, 1993); Mootz et al. (1989); Reiss et al. (1999).

Computing details

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. (a) The taci molecule of (I) and (b) the Htaci^+ cation of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates the intramolecular O···O hydrogen bond [OK?]
	Fig. 2. A view of the hydrogen-bonded three-dimensional network of (I), along [001] (with the unit cell). The carbon skeleton is represented as a stick model in black, and H (light grey), N (blue), O (red) and I (green) atoms are shown as spheres of arbitrary size. C-bound H atoms have been omitted for clarity, except for H2, H4 and H14, where some C—H···O, C—H···I^- and C—H···OH2 contacts are observed. Hydrogen bonds are represented by thin solid lines of the following colours: yellow for intramolecular O—H···O, light green for iodide binding, light blue for intra-chain interactions of R2^2(10) rings, and lilac for inter-chain and inter-layer interactions. [Some of the green ones are hollow - is this significant?]
	Fig. 3. Schematic representations of selected parts of the hydrogen-bonding network, showing (a) chain formation by single O—H···N interactions (green) observed in the crystal structure of taci (Hegetschweiler et al., 1993), (b) chain formation by the pair-wise R2^2(10) interaction of a vicinal HO—CH2—CH2—NH2 group (type A, red), as observed for the Htaci^+ cation in the crystal structure of taci.HI (X = NH3^+; Reiss et al., 1999) and for taci in the title compound (X = NH2), and (c) chain formation by alternate HO—CH2—CH2—NH2 (type A, red) and HO—CH2—CH2—NH3^+ (type B, blue) pairing observed for the Htaci^+ cation in the title monohydrated cocrystal, (I).

1,3-Diamino-5-azaniumyl-1,3,5-trideoxy-cis-inositol iodide–1,3,5-triamino-1,3,5-trideoxy-cis-inositol–water (1/1/1)

Crystal data

C6H16N3O3^+·I^−·C6H15N3O3·H2O	Z = 2
Mr = 500.34	F(000) = 512
Triclinic, P1	Dx = 1.702 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5055 (4) Å	Cell parameters from 9958 reflections
b = 9.9638 (4) Å	θ = 2.6–36.4°
c = 11.0646 (5) Å	µ = 1.69 mm^−1
α = 88.679 (2)°	T = 123 K
β = 76.223 (2)°	Plate, colourless
γ = 73.819 (2)°	0.88 × 0.32 × 0.06 mm
V = 976.42 (7) Å^3

Data collection

Bruker X8 APEX KappaCCD area-detector diffractometer	4257 independent reflections
Radiation source: fine-focus sealed tube	4077 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ω scans	θmax = 27.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −12→12
Tmin = 0.318, Tmax = 0.906	k = −12→12
21776 measured reflections	l = −14→14

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.055	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.029P)^2 + 1.2086P] where P = (Fo^2 + 2Fc^2)/3
4257 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.61 e Å^−3
21 restraints	Δρmin = −0.42 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	0.203819 (15)	0.065732 (13)	0.210625 (12)	0.01668 (5)
O1	0.64155 (14)	0.38361 (14)	0.38296 (12)	0.0079 (2)
H1O	0.646 (3)	0.390 (3)	0.4518 (17)	0.012*
C1	0.50575 (19)	0.34663 (18)	0.38581 (16)	0.0071 (3)
H1	0.4491	0.3512	0.4749	0.009*
C2	0.40395 (19)	0.44858 (18)	0.31629 (16)	0.0075 (3)
H2	0.3065	0.4235	0.3345	0.009*
N2	0.36796 (18)	0.59184 (17)	0.36834 (15)	0.0097 (3)
H2B	0.296 (2)	0.640 (2)	0.338 (2)	0.015*
H2A	0.442 (2)	0.622 (3)	0.340 (2)	0.015*
O3	0.58522 (14)	0.49621 (14)	0.13332 (12)	0.0089 (2)
H3O	0.557 (3)	0.564 (2)	0.098 (2)	0.013*
C3	0.4622 (2)	0.43701 (19)	0.17380 (16)	0.0078 (3)
H3	0.3777	0.4924	0.1381	0.009*
N4	0.5620 (2)	0.27818 (18)	−0.01117 (15)	0.0141 (3)
H4A	0.648 (2)	0.294 (3)	−0.026 (3)	0.021*
H4B	0.569 (3)	0.196 (2)	−0.036 (2)	0.021*
C4	0.5023 (2)	0.28528 (19)	0.12476 (17)	0.0096 (3)
H4	0.4050	0.2600	0.1398	0.012*
O5	0.75617 (15)	0.18813 (14)	0.15854 (13)	0.0110 (3)
H5O	0.812 (3)	0.113 (2)	0.141 (2)	0.016*
C5	0.6045 (2)	0.17862 (19)	0.19222 (17)	0.0088 (3)
H5	0.6060	0.0829	0.1656	0.011*
N6	0.6317 (2)	0.10148 (17)	0.40572 (16)	0.0125 (3)
H6B	0.636 (3)	0.020 (2)	0.386 (2)	0.019*
H6A	0.717 (2)	0.112 (3)	0.385 (2)	0.019*
C6	0.5387 (2)	0.19746 (19)	0.33406 (17)	0.0089 (3)
H6	0.4398	0.1751	0.3509	0.011*
C11	0.10032 (19)	0.43102 (18)	0.64886 (16)	0.0069 (3)
H11	0.1602	0.4757	0.5816	0.008*
O11	−0.05328 (14)	0.51209 (14)	0.67454 (12)	0.0096 (3)
H11O	−0.058 (3)	0.570 (2)	0.626 (2)	0.014*
C12	0.1187 (2)	0.28126 (19)	0.60370 (16)	0.0081 (3)
H12	0.2293	0.2359	0.5719	0.010*
N12	0.0497 (2)	0.28791 (18)	0.49770 (15)	0.0125 (3)
H12B	0.083 (3)	0.211 (2)	0.455 (2)	0.019*
H12A	−0.044 (2)	0.301 (3)	0.525 (2)	0.019*
C13	0.0594 (2)	0.19168 (19)	0.70739 (16)	0.0080 (3)
H13	0.0895	0.0927	0.6740	0.010*
O13	−0.10271 (15)	0.24039 (14)	0.74419 (13)	0.0107 (3)
H13O	−0.131 (3)	0.174 (2)	0.756 (2)	0.016*
C14	0.1274 (2)	0.19585 (18)	0.81908 (16)	0.0075 (3)
H14	0.2394	0.1597	0.7880	0.009*
N14	0.08031 (19)	0.09875 (17)	0.91106 (15)	0.0106 (3)
H14A	−0.0123 (19)	0.122 (3)	0.932 (2)	0.016*
H14B	0.109 (3)	0.099 (3)	0.9763 (19)	0.016*
C15	0.09355 (19)	0.34655 (18)	0.87005 (16)	0.0073 (3)
H15	0.1481	0.3432	0.9375	0.009*
O15	−0.06375 (15)	0.41057 (14)	0.92356 (12)	0.0095 (3)
H15O	−0.107 (3)	0.400 (3)	0.875 (2)	0.014*
C16	0.15941 (19)	0.43154 (18)	0.76631 (16)	0.0069 (3)
H16	0.2715	0.3903	0.7427	0.008*
N16	0.12659 (18)	0.57976 (16)	0.81046 (15)	0.0082 (3)
H16C	0.039 (2)	0.624 (2)	0.806 (2)	0.012*
H16B	0.187 (2)	0.618 (2)	0.765 (2)	0.012*
H16A	0.132 (3)	0.585 (3)	0.8859 (17)	0.012*
O1W	0.48946 (17)	0.14963 (16)	0.65979 (15)	0.0185 (3)
H1W	0.550 (3)	0.111 (3)	0.696 (3)	0.028*
H2W	0.535 (3)	0.132 (3)	0.5877 (18)	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.02114 (8)	0.01513 (8)	0.01748 (8)	−0.00861 (5)	−0.00751 (5)	0.00025 (5)
O1	0.0060 (6)	0.0130 (6)	0.0063 (6)	−0.0047 (5)	−0.0021 (5)	0.0010 (5)
C1	0.0053 (7)	0.0092 (8)	0.0073 (8)	−0.0032 (6)	−0.0011 (6)	0.0023 (6)
C2	0.0055 (8)	0.0084 (8)	0.0081 (8)	−0.0012 (6)	−0.0018 (6)	0.0007 (6)
N2	0.0088 (7)	0.0093 (7)	0.0096 (7)	0.0005 (6)	−0.0028 (6)	0.0002 (6)
O3	0.0086 (6)	0.0093 (6)	0.0105 (6)	−0.0044 (5)	−0.0032 (5)	0.0036 (5)
C3	0.0062 (8)	0.0092 (8)	0.0090 (8)	−0.0026 (6)	−0.0034 (6)	0.0018 (6)
N4	0.0216 (9)	0.0118 (8)	0.0088 (8)	−0.0037 (7)	−0.0049 (7)	−0.0013 (6)
C4	0.0123 (8)	0.0099 (8)	0.0085 (8)	−0.0047 (7)	−0.0042 (7)	0.0009 (6)
O5	0.0084 (6)	0.0084 (6)	0.0143 (7)	−0.0019 (5)	0.0001 (5)	−0.0003 (5)
C5	0.0102 (8)	0.0073 (8)	0.0100 (8)	−0.0042 (7)	−0.0022 (7)	0.0008 (6)
N6	0.0159 (8)	0.0076 (7)	0.0136 (8)	−0.0018 (6)	−0.0050 (6)	0.0033 (6)
C6	0.0095 (8)	0.0089 (8)	0.0091 (8)	−0.0039 (7)	−0.0025 (7)	0.0025 (6)
C11	0.0050 (8)	0.0084 (8)	0.0072 (8)	−0.0022 (6)	−0.0012 (6)	0.0022 (6)
O11	0.0063 (6)	0.0101 (6)	0.0117 (6)	−0.0011 (5)	−0.0029 (5)	0.0043 (5)
C12	0.0097 (8)	0.0088 (8)	0.0056 (8)	−0.0026 (6)	−0.0017 (6)	0.0010 (6)
N12	0.0182 (8)	0.0135 (8)	0.0075 (7)	−0.0055 (7)	−0.0049 (6)	0.0006 (6)
C13	0.0081 (8)	0.0075 (8)	0.0086 (8)	−0.0022 (6)	−0.0025 (6)	0.0010 (6)
O13	0.0078 (6)	0.0103 (6)	0.0160 (7)	−0.0048 (5)	−0.0043 (5)	0.0038 (5)
C14	0.0080 (8)	0.0073 (8)	0.0070 (8)	−0.0017 (6)	−0.0022 (6)	0.0020 (6)
N14	0.0131 (8)	0.0107 (8)	0.0097 (7)	−0.0051 (6)	−0.0042 (6)	0.0052 (6)
C15	0.0063 (8)	0.0080 (8)	0.0072 (8)	−0.0023 (6)	−0.0009 (6)	0.0011 (6)
O15	0.0074 (6)	0.0120 (6)	0.0082 (6)	−0.0026 (5)	0.0001 (5)	−0.0012 (5)
C16	0.0066 (8)	0.0069 (8)	0.0078 (8)	−0.0030 (6)	−0.0019 (6)	0.0007 (6)
N16	0.0081 (7)	0.0088 (7)	0.0087 (7)	−0.0040 (6)	−0.0019 (6)	0.0013 (6)
O1W	0.0152 (7)	0.0205 (8)	0.0180 (7)	−0.0042 (6)	−0.0019 (6)	0.0031 (6)

Geometric parameters (Å, º)

O1—C1	1.431 (2)	C11—C16	1.534 (2)
O1—H1O	0.777 (17)	C11—H11	1.0000
C1—C6	1.526 (2)	O11—H11O	0.780 (17)
C1—C2	1.527 (2)	C12—N12	1.466 (2)
C1—H1	1.0000	C12—C13	1.535 (2)
C2—N2	1.469 (2)	C12—H12	1.0000
C2—C3	1.537 (2)	N12—H12B	0.853 (17)
C2—H2	1.0000	N12—H12A	0.839 (17)
N2—H2B	0.854 (17)	C13—O13	1.438 (2)
N2—H2A	0.830 (17)	C13—C14	1.531 (2)
O3—C3	1.428 (2)	C13—H13	1.0000
O3—H3O	0.787 (17)	O13—H13O	0.782 (17)
C3—C4	1.531 (2)	C14—N14	1.467 (2)
C3—H3	1.0000	C14—C15	1.536 (2)
N4—C4	1.471 (2)	C14—H14	1.0000
N4—H4A	0.855 (17)	N14—H14A	0.821 (17)
N4—H4B	0.850 (17)	N14—H14B	0.828 (17)
C4—C5	1.538 (3)	C15—O15	1.434 (2)
C4—H4	1.0000	C15—C16	1.528 (2)
O5—C5	1.430 (2)	C15—H15	1.0000
O5—H5O	0.783 (17)	O15—H15O	0.772 (17)
C5—C6	1.539 (2)	C16—N16	1.490 (2)
C5—H5	1.0000	C16—H16	1.0000
N6—C6	1.467 (2)	N16—H16C	0.836 (17)
N6—H6B	0.831 (17)	N16—H16B	0.832 (17)
N6—H6A	0.823 (17)	N16—H16A	0.852 (17)
C6—H6	1.0000	O1W—H1W	0.785 (18)
C11—O11	1.421 (2)	O1W—H2W	0.808 (18)
C11—C12	1.534 (2)
C1—O1—H1O	106.6 (19)	C12—C11—C16	111.16 (14)
O1—C1—C6	111.76 (14)	O11—C11—H11	108.4
O1—C1—C2	112.08 (14)	C12—C11—H11	108.4
C6—C1—C2	109.96 (14)	C16—C11—H11	108.4
O1—C1—H1	107.6	C11—O11—H11O	106.1 (19)
C6—C1—H1	107.6	N12—C12—C11	108.59 (14)
C2—C1—H1	107.6	N12—C12—C13	112.96 (15)
N2—C2—C1	110.20 (14)	C11—C12—C13	113.44 (14)
N2—C2—C3	112.93 (14)	N12—C12—H12	107.2
C1—C2—C3	114.54 (14)	C11—C12—H12	107.2
N2—C2—H2	106.2	C13—C12—H12	107.2
C1—C2—H2	106.2	C12—N12—H12B	111.1 (18)
C3—C2—H2	106.2	C12—N12—H12A	108.4 (18)
C2—N2—H2B	105.6 (17)	H12B—N12—H12A	107 (3)
C2—N2—H2A	108.0 (18)	O13—C13—C14	110.72 (14)
H2B—N2—H2A	107 (2)	O13—C13—C12	109.55 (14)
C3—O3—H3O	107.9 (19)	C14—C13—C12	110.82 (14)
O3—C3—C4	111.96 (14)	O13—C13—H13	108.6
O3—C3—C2	111.97 (14)	C14—C13—H13	108.6
C4—C3—C2	110.83 (14)	C12—C13—H13	108.6
O3—C3—H3	107.3	C13—O13—H13O	106.5 (19)
C4—C3—H3	107.3	N14—C14—C13	109.44 (14)
C2—C3—H3	107.3	N14—C14—C15	114.96 (14)
C4—N4—H4A	107.8 (19)	C13—C14—C15	111.28 (14)
C4—N4—H4B	106.2 (19)	N14—C14—H14	106.9
H4A—N4—H4B	112 (3)	C13—C14—H14	106.9
N4—C4—C3	109.07 (15)	C15—C14—H14	106.9
N4—C4—C5	113.28 (15)	C14—N14—H14A	108.6 (18)
C3—C4—C5	114.57 (15)	C14—N14—H14B	114.8 (18)
N4—C4—H4	106.4	H14A—N14—H14B	105 (3)
C3—C4—H4	106.4	O15—C15—C16	112.12 (14)
C5—C4—H4	106.4	O15—C15—C14	113.33 (14)
C5—O5—H5O	110 (2)	C16—C15—C14	108.69 (14)
O5—C5—C4	111.39 (14)	O15—C15—H15	107.5
O5—C5—C6	111.69 (14)	C16—C15—H15	107.5
C4—C5—C6	110.19 (15)	C14—C15—H15	107.5
O5—C5—H5	107.8	C15—O15—H15O	106.9 (19)
C4—C5—H5	107.8	N16—C16—C15	110.76 (14)
C6—C5—H5	107.8	N16—C16—C11	108.12 (14)
C6—N6—H6B	108.0 (19)	C15—C16—C11	113.55 (14)
C6—N6—H6A	107.0 (19)	N16—C16—H16	108.1
H6B—N6—H6A	109 (3)	C15—C16—H16	108.1
N6—C6—C1	108.72 (15)	C11—C16—H16	108.1
N6—C6—C5	113.65 (15)	C16—N16—H16C	109.4 (17)
C1—C6—C5	113.90 (14)	C16—N16—H16B	110.2 (17)
N6—C6—H6	106.7	H16C—N16—H16B	108 (2)
C1—C6—H6	106.7	C16—N16—H16A	111.3 (17)
C5—C6—H6	106.7	H16C—N16—H16A	108 (2)
O11—C11—C12	111.23 (14)	H16B—N16—H16A	110 (2)
O11—C11—C16	109.05 (14)	H1W—O1W—H2W	103 (3)
O1—C1—C2—N2	−56.82 (18)	O11—C11—C12—N12	53.84 (19)
C6—C1—C2—N2	178.23 (14)	C16—C11—C12—N12	175.57 (14)
O1—C1—C2—C3	71.81 (19)	O11—C11—C12—C13	−72.63 (18)
C6—C1—C2—C3	−53.15 (19)	C16—C11—C12—C13	49.10 (19)
N2—C2—C3—O3	52.58 (19)	N12—C12—C13—O13	−53.91 (19)
C1—C2—C3—O3	−74.66 (19)	C11—C12—C13—O13	70.22 (18)
N2—C2—C3—C4	178.37 (14)	N12—C12—C13—C14	−176.37 (15)
C1—C2—C3—C4	51.1 (2)	C11—C12—C13—C14	−52.24 (19)
O3—C3—C4—N4	−52.39 (19)	O13—C13—C14—N14	63.74 (18)
C2—C3—C4—N4	−178.19 (14)	C12—C13—C14—N14	−174.48 (14)
O3—C3—C4—C5	75.77 (19)	O13—C13—C14—C15	−64.41 (18)
C2—C3—C4—C5	−50.0 (2)	C12—C13—C14—C15	57.36 (19)
N4—C4—C5—O5	52.6 (2)	N14—C14—C15—O15	−58.9 (2)
C3—C4—C5—O5	−73.39 (19)	C13—C14—C15—O15	66.27 (18)
N4—C4—C5—C6	177.15 (15)	N14—C14—C15—C16	175.78 (14)
C3—C4—C5—C6	51.1 (2)	C13—C14—C15—C16	−59.10 (18)
O1—C1—C6—N6	57.03 (18)	O15—C15—C16—N16	52.72 (19)
C2—C1—C6—N6	−177.83 (14)	C14—C15—C16—N16	178.78 (14)
O1—C1—C6—C5	−70.81 (19)	O15—C15—C16—C11	−69.16 (19)
C2—C1—C6—C5	54.33 (19)	C14—C15—C16—C11	56.91 (18)
O5—C5—C6—N6	−54.3 (2)	O11—C11—C16—N16	−52.48 (18)
C4—C5—C6—N6	−178.64 (15)	C12—C11—C16—N16	−175.47 (14)
O5—C5—C6—C1	70.97 (19)	O11—C11—C16—C15	70.85 (18)
C4—C5—C6—C1	−53.4 (2)	C12—C11—C16—C15	−52.14 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12B···I1	0.85 (2)	2.91 (2)	3.6656 (17)	148 (2)
N12—H12A···O13	0.84 (2)	2.45 (3)	2.864 (2)	111 (2)
O15—H15O···O13	0.77 (2)	2.16 (2)	2.7940 (19)	139 (2)
O15—H15O···O11	0.77 (2)	2.47 (2)	2.9021 (19)	117 (2)
N16—H16C···O11	0.84 (2)	2.32 (2)	2.748 (2)	113 (2)
O1W—H2W···N6	0.81 (2)	2.00 (2)	2.802 (2)	175 (3)
O1—H1O···N2^i	0.78 (2)	1.97 (2)	2.746 (2)	174 (3)
N2—H2B···O13^ii	0.85 (2)	2.27 (2)	3.123 (2)	178 (2)
N2—H2A···O1W^i	0.83 (2)	2.54 (2)	3.206 (2)	139 (2)
O3—H3O···N4^iii	0.79 (2)	2.03 (2)	2.801 (2)	166 (3)
N4—H4B···I1^iv	0.85 (2)	3.21 (2)	3.9147 (17)	142 (2)
O5—H5O···N14^v	0.78 (2)	2.10 (2)	2.870 (2)	167 (3)
N6—H6B···O1W^v	0.83 (2)	2.45 (2)	3.194 (2)	150 (2)
O11—H11O···N12^ii	0.78 (2)	1.95 (2)	2.727 (2)	175 (3)
O13—H13O···I1^vi	0.78 (2)	2.66 (2)	3.4368 (14)	175 (3)
N14—H14B···I1^vii	0.83 (2)	2.93 (2)	3.7498 (17)	173 (2)
N16—H16B···O1^i	0.83 (2)	2.02 (2)	2.781 (2)	152 (2)
N16—H16B···O5^i	0.83 (2)	2.37 (2)	2.892 (2)	121 (2)
N16—H16A···O15^viii	0.85 (2)	2.05 (2)	2.858 (2)	158 (2)
O1W—H1W···I1^v	0.79 (2)	2.90 (2)	3.6774 (16)	169 (3)

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