Crystal structure of dipotassium N-carbodi­thio­ato-l-prolinate trihydrate

Liebing, P.

doi:10.1107/S2056989017011999

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Volume 73| Part 9| September 2017| Pages 1375-1378

https://doi.org/10.1107/S2056989017011999

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Crystal structure of dipotassium N-carbodithioato-L-prolinate trihydrate

Phil Liebing ^a ^*

^aETH Zurich, Laboratory for Inorganic Chemistry, Vladimir-Prelog-Weg 1-5, 10, 8093 Zurich, Switzerland
^*Correspondence e-mail: liebing@inorg.chem.ethz.ch

Edited by M. Zeller, Purdue University, USA (Received 17 August 2017; accepted 18 August 2017; online 25 August 2017)

The molecular and crystal structure of the L-proline-derived dithiocarbamate–carboxylate compound poly[tri-μ-aqua-(μ-2-carboxylatopyrrolidine-1-carbodithioato)dipotassium], [K₂(C₆H₇NO₂S₂)(H₂O)₃]_n or K₂(SSC–NC₄H₇–COO)·3H₂O, has been determined. The dithiocarbamate moiety displays a unique coordination mode, comprising a `side-on' π-coordinated K⁺ cation besides a commonly σ-chelated K⁺ cation. By bridging coordination of the CSS group, COO group and water molecules, the K⁺ cations are linked into a two-dimensional coordination polymer extending parallel to the ab plane. These layers are again interconnected by O—H⋯S hydrogen bonds.

Keywords: crystal structure; proline; amino acid; dithiocarbamate; π-coordination; coordination polymer; hydrogen bond.

CCDC reference: 1569563

1. Chemical context

Natural amino acids react readily with carbon disulfide in an alkaline environment to give dithiocarbamate-functionalized carboxylates. Since the first report on a series of barium salts in the 1950s (Zahradnik, 1956 ), numerous transition metal complexes have been explored. More recently, various late transition metal complexes of this family have been investigated due to their biological activity (e.g. Giovagnini et al., 2005 ; Cachapa et al., 2006 ; Nagy et al., 2012 ). In most cases, the dithiocarbamate moiety acts as a classical small-bite chelate ligand, while the carboxylate group (often esterified) does not contribute to metal coordination. The structural chemistry of main group derivatives of dithiocarbamate-derived amino acids is much less explored, even though alkali metal and alkaline earth metal salts are frequently used as precursors for other metal complexes. A key intermediate in our ongoing reasearch on coordination polymers with dithiocarbamate–carboxylates is the L-proline-derived potassium salt K₂(SSC–NC₄H₇–COO). This compound crystallizes from aqueous solution as a trihydrate, which has been structurally characterized in the course of this work.

2. Structural commentary

The title compound, K₂(SSC–NC₄H₇–COO)·3H₂O, crystallized as colourless plates in the orthorhombic space group P2₁2₁2₁, with one formula moiety in the asymmetric unit (Fig. 1). One K atom (K2) is bonded in a typical chelating fashion by the CSS group, while K1 is coordinated `side-on' to the CSS group, certainly under participation of the delocalized π electrons. This rather uncommon coordination mode might be supported by additional coordination of a carboxylate O atom (O1) to K1. K1 adopts a low-symmetric seven-coordination by four carboxylate O atoms, two H₂O molecules and the π-coordinating CSS group. K2 is eight-coordinated by three S atoms and five H₂O molecules (Fig. 2). Consequently, the full coordination mode of the carboxylate group is μ₃-κ⁴O,O′:O:O′, and the dithiocarbamate group adopts a μ₃-κ⁶S,S′,C:S,S′:S coordination. One H₂O molecule displays a μ₃-coordination (O3) and the remaining two H₂O molecules are coordinating in a μ-bridging mode (O4 and O5). The K—S distances at the σ-chelated K⁺ cation (K2) are 3.2176 (8) and 3.2650 (9) Å, while the K—S separations at the π-coordinated K⁺ cation (K1) are significantly longer at 3.2956 (9) and 3.4463 (8) Å. The coordination mode of the dithiocarbamate group in the title compound [see (C) in Fig. 3] is unique, to our knowledge. The most frequently observed coordination pattern in dithiocarbamates of the heavier alkali metals (K, Rb and Cs) is a symmetric double-chelating mode, leading to a puckered S₂M₂ ring (e.g. Howie et al., 2008 ; Reyes-Martínez et al., 2009 ; Mafud, 2012 ; see (B) in Fig. 3]. Nonetheless, the values of the K—S separations in the title compound cover the same range as observed in the reference compounds. A simple chelating coordination with significantly shorter K—S contacts is realized when the K⁺ cation is coordinatively highly saturated, as has been observed in a crown ether complex [Arman et al., 2013 ; see (A) in Fig. 3]. In the title compound, three of the four K—O(carboxylate) contacts are in a range 2.676 (2)–2.802 (2) Å, which is consistent with the values observed in other potassium carboxylates (e.g. Ilczyszyn et al., 2009 ; Liebing et al., 2016 ). However, one contact (K1′—O1) is strongly elongated to 3.358 (2) Å. The K—O(H₂O) bond lengths cover a range of 2.723 (2)–3.065 (3) Å.

Figure 1
The asymmetric unit of the title compound. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level and H atoms attached to C atoms have been omitted for clarity. Adjacent symmetry-related K⁺ cations are illustrated as semi-transparent spheres.

Figure 2
Illustration of the coordination environment of the two K⁺ cations.

Figure 3
The different coordination modes of the dithiocarbamate group in potassium complexes: single-chelating (A), symmetric double-chelating (B) and single-chelating combined with π-coordination (this work; C).

3. Supramolecular features

As a result of the bridging coordination of the carboxylate group, the dithiocarbamate group and the water molecules, a two-dimensional polymeric structure parallel to the ab plane is built (Figs. 4 and 5). This arrangement is likely supported by O3—H⋯O1ⁱ, O3—H⋯S2ⁱⁱ, O4—H⋯O2ⁱⁱⁱ and O5—H⋯O1 hydrogen bonds within the layer (Table 1). The layer surfaces are defined by the hydrophobic hydrocarbon backbones, but additionally the two-dimensional arrays are apparently interconnected by O5—H⋯S1^iv hydrogen bonds.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H9⋯O1ⁱ	0.83 (2)	1.93 (2)	2.752 (3)	170 (4)
O3—H8⋯S2ⁱⁱ	0.81 (2)	2.57 (2)	3.3123 (19)	153 (3)
O4—H11⋯O2ⁱⁱⁱ	0.80 (2)	2.22 (2)	3.000 (3)	166 (4)
O5—H13⋯O1	0.81 (2)	1.99 (3)	2.724 (3)	150 (3)
O5—H12⋯S1^iv	0.81 (2)	2.55 (2)	3.341 (2)	163 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (ii) x+1, y, z; (iii) x+1, y+1, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 4
Supramolecular crystal structure comprising polymeric layers extending parallel to (001), viewed in a projection on (100). The bold black lines mark the unit-cell dimensions.

Figure 5
The supramolecular layer illustrated in Fig. 4

, viewed in a projection on (010).

4. Database survey

For other potassium dithiocarbamates, see e.g. Cambridge Structural Database (CSD; Groom et al., 2016 ) refcode AGEHIF (Arman et al., 2013), KOLLIH (Howie et al., 2008), LEHRUN (Mafud, 2012).

For other potassium carboxylates, see e.g. CONWOS (Ilczyszyn et al., 2009), and BIFMIN01 and BIFMUZ01 (Liebing et al., 2016).

5. Synthesis and crystallization

A slight excess of carbon disulfide (approximately 4 ml, 0.06 mol) was added to a solution of L-proline (5.76 g, 0.05 mol) and potassium hydroxide (5.61 g, 0.10 mol) in 30 ml water and the resulting solution was stirred vigorously overnight. The yellow solution obtained was filtered and reduced to dryness in vacuo. The crystalline residue was washed with several portions of tetrahydrofuran and diethyl ether, and dried in vacuo, providing analytically pure K₂(SSC–NC₄H₇–COO)·3H₂O in almost quantitative (>95%) yield as colourless to light-brown low-melting plates, which are very soluble in water. Single crystals suitable for X-ray structure analysis were obtained by slow evaporation of a concentrated aqueous solution at room temperature. IR: 3372 (s br), 3226 (sh br), 2985 (m), 2949 (m), 2875 (w), 1641 (sh), 1603 (sh), 1587 (s), 1497 (s), 1443 (s), 1374 (s), 1338 (m), 1316 (w), 1290 (s), 1257 (m), 1230 (w), 1176 (m), 1155 (s), 1083 (w), 1050 (w), 1003 (m), 948 (m), 918 (m), 899 (w), 846 (m), 794 (m), 666 (s br), 562 (s), 479 (s), 446 (m) cm^{−1. 1}H NMR [400 MHz, D₂O, 298 (2) K]: δ 1.89–1.98 (3 × m, 3H; 3-CH₂ + 4-CH₂), 2.24 (m, 1H; 3-CH₂), 3.75 (m, 1H; 5-CH₂), 3.83 (m, 1H; 5-CH₂), 4.72 (dd, J₁ = 8.7, J₂ = 3.2 Hz, 1H; 2-CH). ¹³C NMR [100 MHz, D₂O, 298 (2) K]: δ 24.6 (4-CH₂), 31.5 (3-CH₂), 55.7 (5-CH₂), 69.5 (2-CH), 179.9 (COO), 205.8 (CSS).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms on C atoms were fixed geometrically and refined using a riding model, with U_iso(H) = 1.2U_eq(C). C—H distances within the CH₂ groups were constrained to 0.99 Å and that within the CH group to 1.00 Å. The water H-atom sites were located in difference Fourier maps and refined using restraints on the O—H distance [target value = 0.84 (2) Å]. The corresponding U_iso(H) values were set at 1.5U_eq(O). The reflection (002) disagreed strongly with the structural model and was therefore omitted from the refinement.

Table 2
Experimental details

Crystal data
Chemical formula	[K₂(C₆H₇NO₂S₂)(H₂O)₃]
M_r	321.49
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	153
a, b, c (Å)	7.1700 (3), 8.9723 (4), 19.8379 (7)
V (Å³)	1276.20 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.07
Crystal size (mm)	0.44 × 0.10 × 0.07

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Numerical (X-AREA and X-RED; Stoe & Cie, 2002 )
T_min, T_max	0.741, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	8831, 2794, 2511
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.042, 0.97
No. of reflections	2794
No. of parameters	164
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22
Absolute structure	Flack x determined using 979 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.00 (4)
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SIR97 (Altomare et al., 1999 ), SHELXL2016 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1569563

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017011999/zl2712sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017011999/zl2712Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA and X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[tri-µ-aqua-(µ-2-carboxylatopyrrolidine-1-carbodithioato)dipotassium] top

Crystal data top

[K₂(C₆H₇NO₂S₂)(H₂O)₃]	D_x = 1.673 Mg m⁻³
M_r = 321.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 10736 reflections
a = 7.1700 (3) Å	θ = 2.5–29.2°
b = 8.9723 (4) Å	µ = 1.07 mm⁻¹
c = 19.8379 (7) Å	T = 153 K
V = 1276.20 (9) Å³	Plate, colorless
Z = 4	0.44 × 0.10 × 0.07 mm
F(000) = 664

Data collection top

Stoe IPDS 2T diffractometer	2794 independent reflections
Radiation source: fine-focus sealed tube	2511 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.038
ω scan	θ_max = 27.0°, θ_min = 2.5°
Absorption correction: numerical (X-AREA and X-RED; Stoe & Cie, 2002)	h = −9→9
T_min = 0.741, T_max = 0.935	k = −11→11
8831 measured reflections	l = −22→25

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²) + (0.0175P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.042	(Δ/σ)_max = 0.001
S = 0.97	Δρ_max = 0.25 e Å⁻³
2794 reflections	Δρ_min = −0.22 e Å⁻³
164 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.0051 (7)
Primary atom site location: heavy-atom method	Absolute structure: Flack x determined using 979 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (4)

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
C1	0.0231 (3)	0.2133 (3)	0.89993 (13)	0.0120 (5)
C2	−0.0116 (3)	0.3153 (3)	0.83918 (13)	0.0103 (5)
H1	−0.098814	0.397715	0.851816	0.012*
C3	0.2180 (4)	0.3035 (3)	0.74906 (14)	0.0140 (6)
H3	0.348536	0.268134	0.751636	0.017*
H2	0.205712	0.372618	0.710395	0.017*
C4	0.0837 (4)	0.1734 (3)	0.74238 (15)	0.0157 (6)
H5	0.135307	0.082539	0.763649	0.019*
H4	0.056006	0.152175	0.694439	0.019*
C5	−0.0907 (4)	0.2267 (3)	0.77943 (14)	0.0156 (6)
H6	−0.166526	0.141324	0.795180	0.019*
H7	−0.168314	0.290872	0.750111	0.019*
C6	0.2657 (3)	0.4759 (3)	0.84517 (12)	0.0098 (5)
N	0.1619 (3)	0.3766 (2)	0.81226 (11)	0.0092 (4)
O1	0.1821 (2)	0.1556 (2)	0.90730 (10)	0.0157 (4)
O2	−0.1122 (2)	0.1894 (2)	0.93751 (12)	0.0207 (4)
O3	0.7663 (3)	0.5383 (3)	0.98964 (10)	0.0217 (4)
H8	0.856 (4)	0.512 (4)	0.9680 (15)	0.033*
H9	0.747 (4)	0.471 (4)	1.0179 (15)	0.033*
O4	0.9025 (3)	0.8561 (2)	0.92654 (13)	0.0280 (5)
H10	0.999 (4)	0.821 (4)	0.912 (2)	0.042*
H11	0.914 (5)	0.943 (3)	0.934 (2)	0.042*
O5	0.4779 (3)	0.0059 (2)	0.85399 (10)	0.0240 (5)
H13	0.373 (3)	0.038 (4)	0.8575 (18)	0.036*
H12	0.505 (4)	−0.005 (4)	0.8144 (12)	0.036*
K1	0.53230 (8)	0.28003 (6)	0.93500 (3)	0.01712 (14)
K2	0.54335 (7)	0.76029 (6)	0.93744 (3)	0.01595 (13)
S1	0.47870 (8)	0.52667 (8)	0.81344 (3)	0.01487 (14)
S2	0.18705 (8)	0.54540 (7)	0.92079 (3)	0.01487 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0121 (11)	0.0107 (12)	0.0133 (13)	−0.0024 (9)	−0.0008 (10)	−0.0016 (9)
C2	0.0068 (11)	0.0108 (11)	0.0134 (13)	0.0003 (9)	−0.0006 (10)	0.0007 (9)
C3	0.0154 (14)	0.0153 (13)	0.0112 (14)	−0.0017 (10)	0.0030 (10)	−0.0030 (11)
C4	0.0192 (14)	0.0133 (13)	0.0145 (15)	−0.0047 (10)	−0.0023 (10)	−0.0031 (11)
C5	0.0151 (12)	0.0151 (14)	0.0167 (15)	−0.0028 (10)	−0.0038 (10)	−0.0007 (11)
C6	0.0097 (10)	0.0096 (11)	0.0100 (12)	0.0016 (10)	−0.0005 (8)	0.0021 (11)
N	0.0095 (9)	0.0086 (10)	0.0096 (11)	−0.0024 (8)	−0.0003 (8)	−0.0004 (8)
O1	0.0135 (8)	0.0164 (9)	0.0171 (11)	0.0057 (8)	0.0000 (8)	0.0034 (8)
O2	0.0127 (8)	0.0312 (12)	0.0183 (11)	−0.0002 (7)	0.0040 (9)	0.0082 (10)
O3	0.0206 (9)	0.0208 (10)	0.0237 (11)	0.0048 (8)	0.0084 (8)	0.0098 (10)
O4	0.0223 (10)	0.0214 (11)	0.0403 (16)	−0.0048 (8)	0.0009 (10)	−0.0010 (12)
O5	0.0233 (9)	0.0330 (13)	0.0158 (10)	0.0126 (9)	0.0033 (8)	0.0009 (9)
K1	0.0115 (2)	0.0201 (3)	0.0197 (3)	0.0003 (2)	−0.0003 (3)	0.0014 (2)
K2	0.0146 (3)	0.0140 (3)	0.0192 (3)	−0.0005 (2)	−0.0023 (3)	−0.0006 (2)
S1	0.0125 (3)	0.0187 (3)	0.0134 (3)	−0.0058 (3)	0.0023 (2)	−0.0005 (3)
S2	0.0135 (3)	0.0182 (3)	0.0129 (3)	−0.0022 (3)	0.0020 (2)	−0.0062 (3)

Geometric parameters (Å, º) top

C1—O2	1.242 (3)	O3—K1	3.060 (2)
C1—O1	1.261 (3)	O3—H8	0.81 (2)
C1—C2	1.533 (4)	O3—H9	0.83 (2)
C1—K1ⁱ	3.276 (3)	O4—K2	2.723 (2)
C2—N	1.462 (3)	O4—K2ⁱⁱⁱ	3.065 (3)
C2—C5	1.536 (4)	O4—H10	0.81 (2)
C2—H1	1.0000	O4—H11	0.80 (2)
C3—N	1.471 (3)	O5—K2^iv	2.796 (2)
C3—C4	1.519 (4)	O5—K1	2.964 (2)
C3—H3	0.9900	O5—H13	0.81 (2)
C3—H2	0.9900	O5—H12	0.81 (2)
C4—C5	1.527 (4)	K1—O2^v	2.6758 (19)
C4—H5	0.9900	K1—O2^vi	2.747 (2)
C4—H4	0.9900	K1—C1^vi	3.276 (3)
C5—H6	0.9900	K1—S1	3.2956 (9)
C5—H7	0.9900	K1—O1^vi	3.358 (2)
C6—N	1.332 (3)	K1—S2	3.4463 (8)
C6—S1	1.714 (2)	K1—H9	2.83 (4)
C6—S2	1.719 (3)	K1—H13	2.90 (4)
C6—K1	3.150 (2)	K2—O5^vii	2.796 (2)
O1—K1	2.8023 (19)	K2—O3^viii	3.050 (2)
O1—K1ⁱ	3.358 (2)	K2—O4^viii	3.065 (3)
O2—K1ⁱⁱ	2.6758 (19)	K2—S2	3.2176 (8)
O2—K1ⁱ	2.747 (2)	K2—S1	3.2650 (9)
O3—K2	2.756 (2)	K2—S2ⁱⁱⁱ	3.4656 (9)
O3—K2ⁱⁱⁱ	3.050 (2)	S2—K2^viii	3.4656 (9)

O2—C1—O1	124.5 (2)	C6—K1—K2	57.29 (5)
O2—C1—C2	116.6 (2)	C1^vi—K1—K2	88.33 (4)
O1—C1—C2	118.9 (2)	S1—K1—K2	48.625 (16)
O2—C1—K1ⁱ	54.47 (14)	O1^vi—K1—K2	79.14 (4)
O1—C1—K1ⁱ	82.72 (15)	S2—K1—K2	47.420 (14)
C2—C1—K1ⁱ	141.07 (16)	O2^v—K1—K1^vi	35.39 (5)
N—C2—C1	111.93 (19)	O2^vi—K1—K1^vi	77.43 (4)
N—C2—C5	103.1 (2)	O1—K1—K1^vi	141.94 (4)
C1—C2—C5	110.9 (2)	O5—K1—K1^vi	108.66 (4)
N—C2—H1	110.2	O3—K1—K1^vi	56.26 (4)
C1—C2—H1	110.2	C6—K1—K1^vi	152.21 (5)
C5—C2—H1	110.2	C1^vi—K1—K1^vi	55.88 (5)
N—C3—C4	104.1 (2)	S1—K1—K1^vi	126.83 (2)
N—C3—H3	110.9	O1^vi—K1—K1^vi	39.01 (3)
C4—C3—H3	110.9	S2—K1—K1^vi	135.23 (3)
N—C3—H2	110.9	K2—K1—K1^vi	95.725 (18)
C4—C3—H2	110.9	O2^v—K1—H9	69.9 (7)
H3—C3—H2	109.0	O2^vi—K1—H9	67.0 (6)
C3—C4—C5	103.7 (2)	O1—K1—H9	147.4 (6)
C3—C4—H5	111.0	O5—K1—H9	152.8 (7)
C5—C4—H5	111.0	O3—K1—H9	15.6 (5)
C3—C4—H4	111.0	C6—K1—H9	108.6 (6)
C5—C4—H4	111.0	C1^vi—K1—H9	54.5 (5)
H5—C4—H4	109.0	S1—K1—H9	94.6 (5)
C4—C5—C2	103.4 (2)	O1^vi—K1—H9	35.0 (5)
C4—C5—H6	111.1	S2—K1—H9	91.1 (6)
C2—C5—H6	111.1	K2—K1—H9	51.5 (6)
C4—C5—H7	111.1	K1^vi—K1—H9	45.5 (6)
C2—C5—H7	111.1	O2^v—K1—H13	99.1 (5)
H6—C5—H7	109.0	O2^vi—K1—H13	114.5 (7)
N—C6—S1	119.70 (18)	O1—K1—H13	40.8 (5)
N—C6—S2	119.16 (17)	O5—K1—H13	15.8 (4)
S1—C6—S2	121.09 (15)	O3—K1—H13	166.5 (6)
N—C6—K1	104.05 (16)	C6—K1—H13	83.0 (6)
S1—C6—K1	79.34 (8)	C1^vi—K1—H13	122.4 (7)
S2—C6—K1	84.71 (9)	S1—K1—H13	94.0 (7)
C6—N—C2	123.2 (2)	O1^vi—K1—H13	138.6 (7)
C6—N—C3	124.3 (2)	S2—K1—H13	101.0 (5)
C2—N—C3	112.12 (18)	K2—K1—H13	139.7 (7)
C1—O1—K1	132.01 (16)	K1^vi—K1—H13	122.3 (6)
C1—O1—K1ⁱ	75.41 (15)	H9—K1—H13	167.8 (8)
K1—O1—K1ⁱ	92.03 (5)	O4—K2—O3	73.12 (7)
C1—O2—K1ⁱⁱ	132.87 (17)	O4—K2—O5^vii	82.11 (7)
C1—O2—K1ⁱ	103.94 (16)	O3—K2—O5^vii	152.81 (6)
K1ⁱⁱ—O2—K1ⁱ	110.25 (8)	O4—K2—O3^viii	117.80 (6)
K2—O3—K2ⁱⁱⁱ	97.35 (7)	O3—K2—O3^viii	128.88 (4)
K2—O3—K1	95.52 (6)	O5^vii—K2—O3^viii	72.82 (6)
K2ⁱⁱⁱ—O3—K1	166.87 (8)	O4—K2—O4^viii	119.29 (6)
K2—O3—H8	118 (2)	O3—K2—O4^viii	67.29 (6)
K2ⁱⁱⁱ—O3—H8	85 (3)	O5^vii—K2—O4^viii	137.28 (6)
K1—O3—H8	92 (3)	O3^viii—K2—O4^viii	64.51 (6)
K2—O3—H9	133 (2)	O4—K2—S2	158.71 (6)
K2ⁱⁱⁱ—O3—H9	103 (2)	O3—K2—S2	93.79 (5)
K1—O3—H9	66 (2)	O5^vii—K2—S2	106.15 (5)
H8—O3—H9	106 (3)	O3^viii—K2—S2	83.48 (4)
K2—O4—K2ⁱⁱⁱ	97.70 (8)	O4^viii—K2—S2	67.94 (5)
K2—O4—H10	135 (3)	O4—K2—S1	106.09 (6)
K2ⁱⁱⁱ—O4—H10	84 (3)	O3—K2—S1	84.35 (5)
K2—O4—H11	113 (2)	O5^vii—K2—S1	92.06 (5)
K2ⁱⁱⁱ—O4—H11	98 (3)	O3^viii—K2—S1	130.18 (4)
H10—O4—H11	111 (4)	O4^viii—K2—S1	113.44 (5)
K2^iv—O5—K1	108.11 (6)	S2—K2—S1	54.915 (17)
K2^iv—O5—H13	113 (3)	O4—K2—S2ⁱⁱⁱ	67.95 (6)
K1—O5—H13	77 (3)	O3—K2—S2ⁱⁱⁱ	83.46 (5)
K2^iv—O5—H12	116 (3)	O5^vii—K2—S2ⁱⁱⁱ	97.70 (5)
K1—O5—H12	126 (3)	O3^viii—K2—S2ⁱⁱⁱ	60.71 (4)
H13—O5—H12	110 (3)	O4^viii—K2—S2ⁱⁱⁱ	63.57 (5)
O2^v—K1—O2^vi	111.87 (5)	S2—K2—S2ⁱⁱⁱ	128.38 (2)
O2^v—K1—O1	137.40 (6)	S1—K2—S2ⁱⁱⁱ	167.58 (2)
O2^vi—K1—O1	83.24 (6)	O4—K2—K1	109.40 (5)
O2^v—K1—O5	83.31 (6)	O3—K2—K1	44.96 (5)
O2^vi—K1—O5	122.17 (6)	O5^vii—K2—K1	141.10 (5)
O1—K1—O5	56.29 (5)	O3^viii—K2—K1	125.84 (4)
O2^v—K1—O3	72.61 (6)	O4^viii—K2—K1	70.31 (4)
O2^vi—K1—O3	78.76 (6)	S2—K2—K1	52.061 (16)
O1—K1—O3	149.61 (6)	S1—K2—K1	49.238 (17)
O5—K1—O3	153.24 (6)	S2ⁱⁱⁱ—K2—K1	121.17 (2)
O2^v—K1—C6	139.31 (7)	O4—K2—K2ⁱⁱⁱ	44.10 (5)
O2^vi—K1—C6	103.67 (6)	O3—K2—K2ⁱⁱⁱ	43.88 (5)
O1—K1—C6	64.38 (6)	O5^vii—K2—K2ⁱⁱⁱ	120.53 (5)
O5—K1—C6	94.38 (6)	O3^viii—K2—K2ⁱⁱⁱ	106.88 (4)
O3—K1—C6	96.35 (6)	O4^viii—K2—K2ⁱⁱⁱ	75.86 (5)
O2^v—K1—C1^vi	90.35 (7)	S2—K2—K2ⁱⁱⁱ	133.26 (3)
O2^vi—K1—C1^vi	21.59 (6)	S1—K2—K2ⁱⁱⁱ	121.19 (2)
O1—K1—C1^vi	100.67 (6)	S2ⁱⁱⁱ—K2—K2ⁱⁱⁱ	46.809 (17)
O5—K1—C1^vi	123.68 (6)	K1—K2—K2ⁱⁱⁱ	88.808 (18)
O3—K1—C1^vi	69.09 (6)	O4—K2—K2^viii	146.64 (6)
C6—K1—C1^vi	122.90 (6)	O3—K2—K2^viii	103.43 (5)
O2^v—K1—S1	109.19 (5)	O5^vii—K2—K2^viii	103.43 (4)
O2^vi—K1—S1	124.25 (4)	O3^viii—K2—K2^viii	38.77 (4)
O1—K1—S1	91.12 (4)	O4^viii—K2—K2^viii	38.20 (4)
O5—K1—S1	98.34 (4)	S2—K2—K2^viii	51.744 (13)
O3—K1—S1	79.31 (4)	S1—K2—K2^viii	106.540 (19)
C6—K1—S1	30.73 (4)	S2ⁱⁱⁱ—K2—K2^viii	78.70 (2)
C1^vi—K1—S1	135.80 (5)	K1—K2—K2^viii	87.075 (19)
O2^v—K1—O1^vi	74.35 (6)	K2ⁱⁱⁱ—K2—K2^viii	110.46 (3)
O2^vi—K1—O1^vi	41.03 (5)	O4—K2—K1^vii	72.51 (5)
O1—K1—O1^vi	122.54 (5)	O3—K2—K1^vii	137.42 (5)
O5—K1—O1^vi	133.64 (5)	O5^vii—K2—K1^vii	37.15 (4)
O3—K1—O1^vi	50.52 (5)	O3^viii—K2—K1^vii	53.25 (4)
C6—K1—O1^vi	128.70 (6)	O4^viii—K2—K1^vii	110.14 (5)
C1^vi—K1—O1^vi	21.87 (5)	S2—K2—K1^vii	125.77 (2)
S1—K1—O1^vi	127.12 (4)	S1—K2—K1^vii	129.17 (2)
O2^v—K1—S2	153.59 (5)	S2ⁱⁱⁱ—K2—K1^vii	60.694 (17)
O2^vi—K1—S2	74.66 (4)	K1—K2—K1^vii	177.62 (2)
O1—K1—S2	67.40 (4)	K2ⁱⁱⁱ—K2—K1^vii	93.565 (18)
O5—K1—S2	115.75 (4)	K2^viii—K2—K1^vii	91.962 (18)
O3—K1—S2	84.23 (4)	C6—S1—K2	91.16 (9)
C6—K1—S2	29.79 (5)	C6—S1—K1	69.92 (8)
C1^vi—K1—S2	93.14 (5)	K2—S1—K1	82.14 (2)
S1—K1—S2	52.585 (17)	C6—S2—K2	92.67 (8)
O1^vi—K1—S2	100.79 (4)	C6—S2—K1	65.51 (8)
O2^v—K1—K2	106.61 (4)	K2—S2—K1	80.519 (19)
O2^vi—K1—K2	84.08 (4)	C6—S2—K2^viii	171.04 (10)
O1—K1—K2	114.65 (4)	K2—S2—K2^viii	81.447 (18)
O5—K1—K2	146.95 (4)	K1—S2—K2^viii	119.65 (2)
O3—K1—K2	39.52 (4)

O2—C1—C2—N	160.5 (2)	C4—C3—N—C2	−8.5 (3)
O1—C1—C2—N	−21.9 (3)	O2—C1—O1—K1	−116.4 (2)
K1ⁱ—C1—C2—N	95.0 (3)	C2—C1—O1—K1	66.3 (3)
O2—C1—C2—C5	−84.9 (3)	K1ⁱ—C1—O1—K1	−79.32 (18)
O1—C1—C2—C5	92.6 (3)	O2—C1—O1—K1ⁱ	−37.0 (2)
K1ⁱ—C1—C2—C5	−150.4 (2)	C2—C1—O1—K1ⁱ	145.6 (2)
N—C3—C4—C5	28.1 (3)	O1—C1—O2—K1ⁱⁱ	−176.93 (17)
C3—C4—C5—C2	−37.1 (3)	C2—C1—O2—K1ⁱⁱ	0.5 (3)
N—C2—C5—C4	31.5 (3)	K1ⁱ—C1—O2—K1ⁱⁱ	135.8 (2)
C1—C2—C5—C4	−88.5 (3)	O1—C1—O2—K1ⁱ	47.3 (3)
S1—C6—N—C2	173.28 (17)	C2—C1—O2—K1ⁱ	−135.35 (18)
S2—C6—N—C2	−4.1 (3)	N—C6—S1—K2	178.61 (19)
K1—C6—N—C2	87.7 (2)	S2—C6—S1—K2	−4.09 (15)
S1—C6—N—C3	0.5 (3)	K1—C6—S1—K2	−81.19 (4)
S2—C6—N—C3	−176.82 (19)	N—C6—S1—K1	−100.2 (2)
K1—C6—N—C3	−85.1 (2)	S2—C6—S1—K1	77.11 (14)
C1—C2—N—C6	−68.8 (3)	N—C6—S2—K2	−178.53 (19)
C5—C2—N—C6	171.9 (2)	S1—C6—S2—K2	4.15 (15)
C1—C2—N—C3	104.8 (2)	K1—C6—S2—K2	78.32 (4)
C5—C2—N—C3	−14.5 (3)	N—C6—S2—K1	103.2 (2)
C4—C3—N—C6	165.0 (2)	S1—C6—S2—K1	−74.17 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H9···O1^vi	0.83 (2)	1.93 (2)	2.752 (3)	170 (4)
O3—H8···S2^v	0.81 (2)	2.57 (2)	3.3123 (19)	153 (3)
O4—H11···O2^ix	0.80 (2)	2.22 (2)	3.000 (3)	166 (4)
O5—H13···O1	0.81 (2)	1.99 (3)	2.724 (3)	150 (3)
O5—H12···S1^x	0.81 (2)	2.55 (2)	3.341 (2)	163 (3)

Symmetry codes: (v) x+1, y, z; (vi) x+1/2, −y+1/2, −z+2; (ix) x+1, y+1, z; (x) −x+1, y−1/2, −z+3/2.

Acknowledgements

General financial support of this work by the Otto-von-Guericke-Universität Magdeburg, Germany, is gratefully acknowledged.

References

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