Crystal structure of a salt with a protonated sugar cation and a cobalt(II) complex anion: (GlcN–H, K)[Co(NCS)4]·2H2O

Peppel, T.; Detert, S.M.L.; Vogel, C.; Köckerling, M.

doi:10.1107/S2414314619011428

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 9| September 2019| x191142

https://doi.org/10.1107/S2414314619011428

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Crystal structure of a salt with a protonated sugar cation and a cobalt(II) complex anion: (GlcN–H, K)[Co(NCS)₄]·2H₂O

Tim Peppel,^a Sabine M. L. Detert,^b Christian Vogel ^b and Martin Köckerling ^c ^*

^aLeibniz-Institut für Katalyse e.V., Heterogene Photokatalyse, Albert-Einstein-Str. 29a, D-18059 Rostock, Germany, ^bUniversität Rostock, Institut für Chemie, Organische Chemie, Albert-Einstein-Str. 3a, D-18059 Rostock, Germany, and ^cUniversität Rostock, Institut für Chemie, Anorganische Festkörperchemie, Albert-Einstein-Str. 3a, D-18059 Rostock, Germany
^*Correspondence e-mail: Martin.Koeckerling@uni-rostock.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 2 July 2019; accepted 14 August 2019; online 6 September 2019)

The title compound, D-(+)-glucosammonium potassium tetrathiocyanatocobaltate(II) dihydrate, K(C₆H₁₄NO₅)[Co(NCS)₄]·2H₂O or (GlcNH)(K)[Co(NCS)₄]·2H₂O, has been obtained as a side product of an incomplete salt metathesis reaction of D-(+)-glucosamine hydrochloride (GlcN·HCl) and K₂[Co(NCS)₄]. The asymmetric unit contains a D-(+)-glucosammonium cation, a potassium cation, a tetraisothiocyanatocobalt(II) complex anion and two water molecules. The water molecules coordinate to the potassium cation, which is further coordinated via three short K⁺⋯SCN⁻ contacts involving three [Co(NCS)₄]²⁻ complex anions and via three O atoms of two D-(+)-glucosammonium cations, leading to an overall eightfold coordination around the potassium cation. Hydrogen-bonding interactions between the building blocks consolidate the three-dimensional arrangement.

Keywords: cobalt; glucosamine; ionic liquid; crystal structure.

CCDC reference: 1947086

Structure description

Over about the last two decades, ionic liquids containing paramagnetic complex anions (magnetic ionic liquids, MIL) have attracted great interest because of their unique properties and possible applications (Santos et al., 2014 ; Clark et al., 2016 ). During our ongoing efforts to synthesize cobalt-based ionic liquids with low melting points (Kozlova et al., 2009 ; Geppert-Rybczyńska et al., 2010 ; Peppel et al., 2010 ), the title compound was obtained as a side product in an attempted synthesis of new low-melting transition-metal systems containing protonated bio-molecules, i.e. sugar-based cations.

Fig. 1 shows the molecular structures of the three parts present in the asymmetric unit. The title compound consists of a potassium cation that is bonded in an eightfold fashion to two water molecules, three O atoms of two neighbouring D-(+)-glucosammonium cations, and to three S atoms of three [Co(NCS)₄]²⁻ complex anions (Fig. 2). All bond lengths and angles are in the expected ranges (Table 1).

Table 1
Selected bond lengths (Å)

Co1—N3	1.944 (2)	N4—C4	1.162 (3)
Co1—N4	1.958 (2)	C4—S4	1.629 (2)
Co1—N2	1.968 (2)	S1—K1ⁱ	3.3256 (7)
Co1—N1	1.970 (2)	S2—K1	3.3287 (8)
N1—C1	1.153 (3)	S4—K1ⁱⁱ	3.5399 (7)
C1—S1	1.638 (2)	K1—O6	2.765 (2)
N2—C2	1.171 (3)	K1—O1ⁱⁱⁱ	2.812 (1)
C2—S2	1.613 (2)	K1—O7	2.860 (2)
N3—C3	1.163 (3)	K1—O3^iv	2.864 (1)
C3—S3	1.630 (2)	K1—O5ⁱⁱⁱ	2.902 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+2, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 1
A view of the molecular structures of the cation–cation–anion triple present in the title compound, with atoms being presented as 50% displacement ellipsoids and with atom labelling.

Figure 2
View of the coordination environment of the potassium cation in (GlcNH)(K)[Co(NCS)₄]·2H₂O.

In the crystal structure, hydrogen bonds additionally connect all the structural units. All hydrogen atoms that are attached to the N and O atoms (except one H atom of O6 that represents a water O atom) are involved in hydrogen bonding. Table 2 lists all relevant interactions up to D⋯A distances of 3.3 Å. Fig. 3 shows a cut-out of the structure with hydrogen bonds shown as red dashed lines. The three-dimensional structure can be described as a sequence of anionic and cationic layers extending parallel to (011), stacked along [011], as shown in Fig. 4.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O7ⁱⁱⁱ	0.85 (1)	1.84 (1)	2.657 (2)	160 (3)
N5—H5C⋯O5^v	0.91	2.09	2.967 (2)	162
O6—H6C⋯O4^vi	0.85 (1)	2.20 (1)	3.010 (2)	160 (2)
O2—H2A⋯O4^vii	0.85 (1)	2.20 (1)	3.015 (2)	162 (3)
N5—H5B⋯N2^viii	0.91	2.26	3.145 (2)	166
N5—H5D⋯O6ⁱⁱⁱ	0.91	2.30	3.175 (2)	160
O5—H5A⋯S1	0.85 (1)	2.39 (1)	3.233 (2)	176 (2)
O4—H4A⋯S4ⁱⁱⁱ	0.85 (1)	2.43 (1)	3.266 (2)	170 (3)
O7—H7C⋯S1ⁱⁱⁱ	0.85 (1)	2.49 (1)	3.298 (2)	159 (2)
Symmetry codes: (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (vi) x, y, z+1; (vii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (viii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 3
Hydrogen-bonding contacts between the GlcNH⁺ cation, the (K(H₂O)₂)⁺ cation and the [Co(NCS)₄]^2– anion.

Figure 4
The packing of the ions in the crystal structure of the title compound.

Synthesis and crystallization

The title compound, (GlcNH)(K)[Co(NCS)₄]·2H₂O, was obtained as a side product in an incomplete salt metathesis reaction of 2 eq. D-(+)-glucosamine hydrochloride (GlcN·HCl) and 1 eq. K₂[Co(NCS)₄] (Peppel et al., 2010). K₂[Co(NCS)₄] was obtained by heating KSCN (15.0 g, 154.0 mmol, 4 eq.) and anhydrous CoCl₂ (5.0 g, 38.5 mmol, 1 eq.) under reflux in 250 ml acetone for 2 h. The solvent was completely removed in vacuo and the residue was thoroughly extracted with ethyl acetate until the filtrate became colourless. The solvent of the combined filtrates was removed in vacuo and the resulting deep-blue solid was dried overnight at 393 K (14.0 g, 98%). Dry K₂[Co(NCS)₄] (1.0 g, 2.7 mmol, 1 eq.) and GlcN·HCl (1.2 g, 5.4 mmol, 2 eq.) were heated under reflux in 50 ml of ethanol overnight. The hot solution was filtered and the filtrate was slowly cooled to room temperature. Deep-blue single crystals of (GlcNH)(K)[Co(NCS)₄]·2H₂O were deposited at the bottom of the flask.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. A few low-angle reflections were omitted from the refinement because their intensities were affected by the beam stop.

Table 3
Experimental details

Crystal data
Chemical formula	[KCo(C₆H₁₄NO₅)(NCS)₄(H₂O)₂]
M_r	546.56
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	9.3713 (2), 14.1059 (3), 15.7347 (4)
V (Å³)	2079.98 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.47
Crystal size (mm)	0.65 × 0.07 × 0.05

Data collection
Diffractometer	Bruker APEX-X8 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005 )
No. of measured, independent and observed [I > 2σ(I)] reflections	24428, 9699, 7503
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.834

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.058, 0.98
No. of reflections	9699
No. of parameters	285
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.68
Absolute structure	Flack x determined using 2715 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.004 (5)
Computer programs: APEX2 and SAINT (Bruker, 2005), SHELXS2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Crystal Impact, 2014 ) and ciftab2016 (Köckerling, 2016 ).

Structural data

CCDC reference: 1947086

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619011428/wm4108sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619011428/wm4108Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Crystal Impact, 2014); software used to prepare material for publication: ciftab2016 (Köckerling, 2016).

Poly[diaqua[µ-D-(+)-glucosammonium]tri-µ-thiocyanato-thiocyanatocobalt(II)potassium(I)] top

Crystal data top

[KCo(C₆H₁₄NO₅)(NCS)₄(H₂O)₂]	D_x = 1.745 Mg m⁻³
M_r = 546.56	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9954 reflections
a = 9.3713 (2) Å	θ = 2.6–36.0°
b = 14.1059 (3) Å	µ = 1.47 mm⁻¹
c = 15.7347 (4) Å	T = 173 K
V = 2079.98 (8) Å³	Block, blue
Z = 4	0.65 × 0.07 × 0.05 mm
F(000) = 1116

Data collection top

Bruker APEX-X8 CCD diffractometer	7503 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.031
φ and ω scans	θ_max = 36.4°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→15
	k = −23→13
24428 measured reflections	l = −26→16
9699 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.0187P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max = 0.001
9699 reflections	Δρ_max = 0.59 e Å⁻³
285 parameters	Δρ_min = −0.68 e Å⁻³
10 restraints	Absolute structure: Flack x determined using 2715 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.004 (5)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.62109 (3)	0.76616 (2)	0.48158 (2)	0.01938 (7)
N1	0.7606 (2)	0.8376 (1)	0.4133 (1)	0.0268 (4)
C1	0.8322 (2)	0.8742 (2)	0.3636 (1)	0.0191 (4)
S1	0.93387 (6)	0.92611 (4)	0.29276 (4)	0.0223 (1)
N2	0.5171 (2)	0.8625 (1)	0.5476 (1)	0.0232 (4)
C2	0.4283 (2)	0.8943 (2)	0.5915 (1)	0.0189 (4)
S2	0.30724 (6)	0.94110 (5)	0.65107 (4)	0.0305 (1)
N3	0.4981 (2)	0.6893 (1)	0.4099 (1)	0.0274 (4)
C3	0.4293 (2)	0.6383 (2)	0.3688 (1)	0.0200 (4)
S3	0.33187 (6)	0.56658 (4)	0.31185 (4)	0.0257 (1)
N4	0.7071 (2)	0.6805 (1)	0.5650 (1)	0.0250 (4)
C4	0.7734 (2)	0.6367 (1)	0.6135 (1)	0.0185 (4)
S4	0.86663 (6)	0.57317 (4)	0.67975 (3)	0.0233 (1)
K1	0.37801 (5)	0.88532 (3)	0.85226 (3)	0.02172 (9)
O1	0.5999 (1)	0.6576 (1)	0.09269 (9)	0.0165 (3)
O2	0.5319 (2)	0.6440 (1)	−0.05053 (9)	0.0199 (3)
H2A	0.615 (1)	0.635 (2)	−0.070 (2)	0.06 (1)*
O3	0.1598 (1)	0.6684 (1)	0.0965 (1)	0.0196 (3)
H3A	0.150 (3)	0.693 (2)	0.1456 (7)	0.049 (9)*
O4	0.3236 (2)	0.8390 (1)	0.12991 (9)	0.0170 (3)
H4A	0.324 (3)	0.865 (2)	0.1788 (7)	0.039 (8)*
O5	0.7725 (1)	0.8081 (1)	0.14516 (9)	0.0189 (3)
H5A	0.819 (2)	0.839 (2)	0.182 (1)	0.030 (7)*
N5	0.2920 (2)	0.5419 (1)	−0.0135 (1)	0.0168 (3)
H5B	0.3322	0.4843	−0.0242	0.025*
H5C	0.2942	0.5777	−0.0616	0.025*
H5D	0.1999	0.5338	0.0033	0.025*
C5	0.5299 (2)	0.6025 (2)	0.0295 (1)	0.0161 (4)
H5E	0.5759	0.5386	0.0263	0.019*
C6	0.3738 (2)	0.5909 (1)	0.0554 (1)	0.0141 (3)
H6A	0.3684	0.5524	0.1086	0.017*
C7	0.3019 (2)	0.6859 (1)	0.0699 (1)	0.0136 (4)
H7A	0.2983	0.7202	0.0144	0.016*
C8	0.3854 (2)	0.7460 (1)	0.1321 (1)	0.0126 (3)
H8A	0.3768	0.7189	0.1906	0.015*
C9	0.5425 (2)	0.7510 (1)	0.1063 (1)	0.0130 (4)
H9A	0.5522	0.7892	0.0530	0.016*
C10	0.6299 (2)	0.7957 (1)	0.1758 (1)	0.0169 (4)
H10A	0.5886	0.8577	0.1919	0.020*
H10B	0.6301	0.7543	0.2267	0.020*
O6	0.4544 (2)	0.9728 (1)	1.0028 (1)	0.0300 (4)
H6B	0.437 (3)	1.0320 (4)	1.001 (2)	0.048 (9)*
H6C	0.411 (3)	0.948 (2)	1.045 (1)	0.10 (2)*
O7	0.5753 (2)	0.7830 (1)	0.7483 (1)	0.0294 (4)
H7B	0.635 (2)	0.811 (1)	0.716 (1)	0.07 (1)*
H7C	0.559 (3)	0.7274 (8)	0.730 (2)	0.06 (1)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0206 (1)	0.0181 (1)	0.0194 (1)	−0.0007 (1)	0.0012 (1)	0.0005 (1)
N1	0.028 (1)	0.027 (1)	0.026 (1)	−0.0017 (9)	0.0034 (8)	0.0009 (9)
C1	0.0209 (9)	0.017 (1)	0.019 (1)	0.0008 (8)	−0.0048 (8)	−0.0036 (8)
S1	0.0236 (2)	0.0243 (3)	0.0191 (2)	−0.0077 (2)	−0.0008 (2)	0.0002 (2)
N2	0.0247 (9)	0.022 (1)	0.0229 (9)	0.0007 (8)	−0.0002 (8)	0.0010 (8)
C2	0.0215 (9)	0.018 (1)	0.018 (1)	−0.0027 (8)	−0.0057 (8)	0.0033 (9)
S2	0.0288 (3)	0.0370 (3)	0.0257 (3)	0.0123 (3)	0.0029 (2)	0.0007 (3)
N3	0.027 (1)	0.023 (1)	0.032 (1)	0.0023 (8)	−0.0017 (9)	−0.0026 (9)
C3	0.0221 (9)	0.018 (1)	0.020 (1)	0.0030 (8)	0.0028 (8)	0.0033 (9)
S3	0.0340 (3)	0.0222 (3)	0.0210 (3)	−0.0055 (2)	−0.0040 (2)	0.0022 (2)
N4	0.0235 (9)	0.026 (1)	0.025 (1)	0.0006 (8)	0.0017 (8)	0.0020 (8)
C4	0.0188 (9)	0.017 (1)	0.020 (1)	−0.0031 (8)	0.0052 (8)	−0.0037 (8)
S4	0.0280 (3)	0.0238 (3)	0.0180 (2)	0.0046 (2)	−0.0015 (2)	−0.0023 (2)
K1	0.0173 (2)	0.0256 (2)	0.0223 (2)	−0.0020 (2)	0.0021 (2)	−0.0012 (2)
O1	0.0141 (6)	0.0158 (7)	0.0196 (7)	0.0024 (5)	−0.0052 (5)	−0.0050 (6)
O2	0.0163 (7)	0.0268 (9)	0.0164 (7)	0.0006 (6)	0.0022 (6)	−0.0016 (6)
O3	0.0133 (6)	0.0248 (8)	0.0207 (8)	−0.0039 (6)	0.0027 (6)	−0.0065 (7)
O4	0.0200 (7)	0.0124 (7)	0.0187 (7)	0.0028 (6)	−0.0009 (6)	−0.0040 (6)
O5	0.0130 (6)	0.0270 (8)	0.0168 (7)	−0.0062 (6)	−0.0004 (6)	−0.0045 (6)
N5	0.0175 (7)	0.0137 (8)	0.0191 (8)	−0.0017 (6)	−0.0013 (7)	−0.0029 (7)
C5	0.0156 (8)	0.0164 (9)	0.016 (1)	0.0025 (7)	−0.0039 (7)	−0.0040 (8)
C6	0.0175 (8)	0.0123 (9)	0.0125 (8)	−0.0011 (8)	−0.0028 (8)	−0.0001 (7)
C7	0.0111 (8)	0.0145 (9)	0.0153 (9)	−0.0009 (7)	0.0007 (7)	−0.0011 (7)
C8	0.0138 (7)	0.0113 (9)	0.0126 (8)	0.0002 (7)	0.0008 (7)	0.0002 (6)
C9	0.0145 (8)	0.0111 (9)	0.0134 (8)	−0.0003 (7)	0.0011 (7)	−0.0012 (7)
C10	0.0137 (8)	0.022 (1)	0.0149 (9)	−0.0027 (8)	0.0001 (8)	−0.0043 (8)
O6	0.0395 (9)	0.0252 (9)	0.025 (1)	0.0058 (8)	0.0028 (8)	−0.0036 (7)
O7	0.0303 (8)	0.035 (1)	0.0233 (8)	−0.0009 (8)	−0.0002 (7)	−0.0037 (8)

Geometric parameters (Å, º) top

Co1—N3	1.944 (2)	O3—H3A	0.850 (1)
Co1—N4	1.958 (2)	O4—C8	1.434 (2)
Co1—N2	1.968 (2)	O4—H4A	0.850 (1)
Co1—N1	1.970 (2)	O5—C10	1.432 (2)
N1—C1	1.153 (3)	O5—K1^iv	2.902 (2)
C1—S1	1.638 (2)	O5—H5A	0.850 (1)
N2—C2	1.171 (3)	N5—C6	1.497 (2)
C2—S2	1.613 (2)	N5—H5B	0.9100
N3—C3	1.163 (3)	N5—H5C	0.9100
C3—S3	1.630 (2)	N5—H5D	0.9100
N4—C4	1.162 (3)	C5—C6	1.527 (3)
C4—S4	1.629 (2)	C5—H5E	1.0000
S1—K1ⁱ	3.3256 (7)	C6—C7	1.517 (3)
S2—K1	3.3287 (8)	C6—H6A	1.0000
S4—K1ⁱⁱ	3.5399 (7)	C7—C8	1.513 (2)
K1—O6	2.765 (2)	C7—H7A	1.0000
K1—O1ⁱⁱⁱ	2.812 (1)	C8—C9	1.529 (2)
K1—O7	2.860 (2)	C8—H8A	1.0000
K1—O3^iv	2.864 (1)	C9—C10	1.505 (3)
K1—O5ⁱⁱⁱ	2.902 (2)	C9—H9A	1.0000
K1—C10ⁱⁱⁱ	3.481 (2)	C10—K1^iv	3.481 (2)
O1—C5	1.422 (2)	C10—H10A	0.9900
O1—C9	1.440 (2)	C10—H10B	0.9900
O1—K1^iv	2.812 (1)	O6—H6B	0.850 (1)
O2—C5	1.389 (2)	O6—H6C	0.850 (1)
O2—H2A	0.850 (1)	O7—H7B	0.850 (1)
O3—C7	1.417 (2)	O7—H7C	0.850 (1)
O3—K1ⁱⁱⁱ	2.864 (1)

N3—Co1—N4	106.83 (9)	C7—O3—H3A	108 (2)
N3—Co1—N2	113.43 (8)	K1ⁱⁱⁱ—O3—H3A	75 (2)
N4—Co1—N2	106.02 (8)	C8—O4—H4A	111 (2)
N3—Co1—N1	111.26 (9)	C10—O5—K1^iv	101.4 (1)
N4—Co1—N1	114.08 (8)	C10—O5—H5A	108 (2)
N2—Co1—N1	105.25 (8)	K1^iv—O5—H5A	108 (2)
C1—N1—Co1	170.3 (2)	C6—N5—H5B	109.5
N1—C1—S1	179.9 (2)	C6—N5—H5C	109.5
C1—S1—K1ⁱ	118.29 (7)	H5B—N5—H5C	109.5
C2—N2—Co1	158.1 (2)	C6—N5—H5D	109.5
N2—C2—S2	178.4 (2)	H5B—N5—H5D	109.5
C2—S2—K1	108.43 (8)	H5C—N5—H5D	109.5
C3—N3—Co1	175.6 (2)	O2—C5—O1	113.4 (2)
N3—C3—S3	179.5 (2)	O2—C5—C6	107.4 (2)
C4—N4—Co1	171.4 (2)	O1—C5—C6	108.3 (2)
N4—C4—S4	178.6 (2)	O2—C5—H5E	109.2
C4—S4—K1ⁱⁱ	88.48 (7)	O1—C5—H5E	109.2
O6—K1—O1ⁱⁱⁱ	94.13 (5)	C6—C5—H5E	109.2
O6—K1—O7	123.22 (5)	N5—C6—C7	106.8 (2)
O1ⁱⁱⁱ—K1—O7	131.81 (5)	N5—C6—C5	110.3 (2)
O6—K1—O3^iv	68.80 (5)	C7—C6—C5	111.8 (2)
O1ⁱⁱⁱ—K1—O3^iv	135.31 (4)	N5—C6—H6A	109.3
O7—K1—O3^iv	55.32 (5)	C7—C6—H6A	109.3
O6—K1—O5ⁱⁱⁱ	119.72 (5)	C5—C6—H6A	109.3
O1ⁱⁱⁱ—K1—O5ⁱⁱⁱ	58.51 (4)	O3—C7—C8	113.1 (2)
O7—K1—O5ⁱⁱⁱ	75.74 (5)	O3—C7—C6	108.0 (2)
O3^iv—K1—O5ⁱⁱⁱ	93.51 (4)	C8—C7—C6	111.3 (2)
O6—K1—S1^v	75.35 (4)	O3—C7—H7A	108.1
O1ⁱⁱⁱ—K1—S1^v	138.60 (3)	C8—C7—H7A	108.1
O7—K1—S1^v	84.26 (4)	C6—C7—H7A	108.1
O3^iv—K1—S1^v	78.59 (3)	O4—C8—C7	106.8 (1)
O5ⁱⁱⁱ—K1—S1^v	159.46 (3)	O4—C8—C9	109.9 (1)
O6—K1—S2	139.53 (4)	C7—C8—C9	110.6 (1)
O1ⁱⁱⁱ—K1—S2	99.16 (3)	O4—C8—H8A	109.9
O7—K1—S2	72.81 (4)	C7—C8—H8A	109.9
O3^iv—K1—S2	120.94 (3)	C9—C8—H8A	109.9
O5ⁱⁱⁱ—K1—S2	99.65 (3)	O1—C9—C10	106.7 (2)
S1^v—K1—S2	69.44 (2)	O1—C9—C8	110.9 (2)
O6—K1—C10ⁱⁱⁱ	127.51 (5)	C10—C9—C8	110.5 (2)
O1ⁱⁱⁱ—K1—C10ⁱⁱⁱ	42.47 (4)	O1—C9—H9A	109.6
O7—K1—C10ⁱⁱⁱ	89.37 (5)	C10—C9—H9A	109.6
O3^iv—K1—C10ⁱⁱⁱ	117.23 (5)	C8—C9—H9A	109.6
O5ⁱⁱⁱ—K1—C10ⁱⁱⁱ	23.78 (4)	O5—C10—C9	108.3 (2)
S1^v—K1—C10ⁱⁱⁱ	154.80 (4)	O5—C10—K1^iv	54.79 (9)
S2—K1—C10ⁱⁱⁱ	85.38 (4)	C9—C10—K1^iv	88.0 (1)
O6—K1—S4^vi	87.44 (4)	O5—C10—H10A	110.0
O1ⁱⁱⁱ—K1—S4^vi	66.72 (3)	C9—C10—H10A	110.0
O7—K1—S4^vi	135.67 (4)	K1^iv—C10—H10A	160.4
O3^iv—K1—S4^vi	146.68 (3)	O5—C10—H10B	110.0
O5ⁱⁱⁱ—K1—S4^vi	119.02 (3)	C9—C10—H10B	110.0
S1^v—K1—S4^vi	72.82 (2)	K1^iv—C10—H10B	70.7
S2—K1—S4^vi	63.81 (2)	H10A—C10—H10B	108.4
C10ⁱⁱⁱ—K1—S4^vi	95.64 (3)	K1—O6—H6B	111 (2)
C5—O1—C9	115.6 (1)	K1—O6—H6C	111 (2)
C5—O1—K1^iv	121.7 (1)	H6B—O6—H6C	109.5 (2)
C9—O1—K1^iv	119.9 (1)	K1—O7—H7B	122 (2)
C5—O2—H2A	107 (2)	K1—O7—H7C	123 (2)
C7—O3—K1ⁱⁱⁱ	174.6 (1)	H7B—O7—H7C	109.5 (2)

C9—O1—C5—O2	59.7 (2)	C6—C7—C8—C9	50.5 (2)
K1^iv—O1—C5—O2	−101.0 (2)	C5—O1—C9—C10	179.1 (2)
C9—O1—C5—C6	−59.5 (2)	K1^iv—O1—C9—C10	−19.9 (2)
K1^iv—O1—C5—C6	139.9 (1)	C5—O1—C9—C8	58.7 (2)
O2—C5—C6—N5	51.3 (2)	K1^iv—O1—C9—C8	−140.2 (1)
O1—C5—C6—N5	174.2 (2)	O4—C8—C9—O1	−169.3 (1)
O2—C5—C6—C7	−67.4 (2)	C7—C8—C9—O1	−51.7 (2)
O1—C5—C6—C7	55.5 (2)	O4—C8—C9—C10	72.6 (2)
N5—C6—C7—O3	61.3 (2)	C7—C8—C9—C10	−169.8 (2)
C5—C6—C7—O3	−177.9 (1)	K1^iv—O5—C10—C9	−73.8 (2)
N5—C6—C7—C8	−174.0 (2)	O1—C9—C10—O5	65.5 (2)
C5—C6—C7—C8	−53.2 (2)	C8—C9—C10—O5	−173.8 (2)
O3—C7—C8—O4	−68.2 (2)	O1—C9—C10—K1^iv	13.8 (1)
C6—C7—C8—O4	170.0 (2)	C8—C9—C10—K1^iv	134.4 (1)
O3—C7—C8—C9	172.3 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O7ⁱⁱⁱ	0.85 (1)	1.84 (1)	2.657 (2)	160 (3)
N5—H5C···O5^vii	0.91	2.09	2.967 (2)	162
O6—H6C···O4^viii	0.85 (1)	2.20 (1)	3.010 (2)	160 (2)
O2—H2A···O4^ix	0.85 (1)	2.20 (1)	3.015 (2)	162 (3)
N5—H5B···N2^x	0.91	2.26	3.145 (2)	166
N5—H5D···O6ⁱⁱⁱ	0.91	2.30	3.175 (2)	160
O5—H5A···S1	0.85 (1)	2.38 (1)	3.233 (2)	176 (2)
O4—H4A···S4ⁱⁱⁱ	0.85 (1)	2.42 (1)	3.266 (2)	170 (3)
O7—H7C···S1ⁱⁱⁱ	0.85 (1)	2.49 (1)	3.298 (2)	159 (2)
O7—H7B···S3^iv	0.85 (1)	2.57 (1)	3.344 (2)	152 (2)
O6—H6B···N3^vi	0.85 (1)	2.69 (2)	3.378 (3)	139 (2)
C7—H7A···O5^vii	1.00	2.55	3.397 (2)	142
C5—H5E···S4^xi	1.00	2.93	3.560 (2)	122
C9—H9A···O3^ix	1.00	2.63	3.560 (2)	155
C8—H8A···S3	1.00	2.90	3.828 (2)	154

Symmetry codes: (iii) x−1/2, −y+3/2, −z+1; (iv) x+1/2, −y+3/2, −z+1; (vi) −x+1, y+1/2, −z+3/2; (vii) x−1/2, −y+3/2, −z; (viii) x, y, z+1; (ix) x+1/2, −y+3/2, −z; (x) −x+1, y−1/2, −z+1/2; (xi) −x+3/2, −y+1, z−1/2.

Acknowledgements

We gratefully acknowledge the maintenance of the XRD equipment through Dr A. Villinger (University of Rostock).

Funding information

Funding for this research was provided by: Deutsche Forschungsgemeinschaft, Priority Program SPP 1708 (grant Nos. KO-1616/8-1 and -2).

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