Literature DB >> 28932428

A one-dimensional coordination polymer, catena-poly[[[[N-ethyl-N-(pyridin-4-ylmeth-yl)di-thio-carbamato-κ2S,S']zinc(II)]-μ2-N-ethyl-N-(pyridin-4-ylmeth-yl)di-thio-carbamato-κ3S,S':N] 4-methyl-pyridine hemisolvate].

Pavel Poplaukhin1, Hadi D Arman2, Edward R T Tiekink3.   

Abstract

The title compound, {[Zn(C9H11N2S2)2]·0.5C6H7N} n , comprises two independent, but chemically similar, Zn[S2CN(Et)CH2py]2 residues and a 4-methyl-pyridine solvent mol-ecule in the asymmetric unit. The Zn-containing units are connected into a one-dimensional coordination polymer (zigzag topology) propagating in the [010] direction, with one di-thio-carbamate ligand bridging in a μ2-κ3 mode, employing one pyridyl N and both di-thio-carbamate S atoms, while the other is κ2-chelating. In each case, the resultant ZnNS4 coordination geometry approximates a square pyramid, with the pyridyl N atom in the apical position. In the crystal, the chains are linked into a three-dimensional architecture by methyl- and pyridyl-C-H⋯S, methyl-ene-C-H⋯N(pyrid-yl) and pyridyl-C-H⋯π(ZnS2C) inter-actions. The connection between the chain and the 4-methyl-pyridine solvent mol-ecule is of the type pyridyl-C-H⋯N(4-methyl-pyridine).

Entities:  

Keywords:  coordination polymer; crystal structure; di­thio­carbamate; methyl­pyridine; zinc

Year:  2017        PMID： 28932428      PMCID： PMC5598840          DOI： 10.1107/S2056989017010179

Source DB:  PubMed          Journal:  Acta Crystallogr E Crystallogr Commun


Chemical context

The most recent surveys of the structural chemistry of the binary zinc-triad di­thio­carbamates, i.e. mol­ecules of the general formula M(S2CNRR′)2 for M = Zn, Cd and Hg, indicated that up to that point, R and R′ were generally restricted to alkyl groups, with only rare examples of R being an aryl group (Tiekink, 2003 ▸; Hogarth, 2005 ▸). However, since around that time there has been increasing inter­est in elaborating di­thio­carbamate ligands to enhance their functionality for systematic structural studies. This enhancement can be achieved in two ways utilizing their facile procedure of synthesis, i.e. the reaction of CS2 with an amine in the presence of base. Hence, the utilization of di­amines can lead to bis­(di­thio­carbamates), e.g. −S2CN—R—CS2 −, R = alk­yl/aryl (e.g. Cookson & Beer, 2007 ▸; Knight et al., 2009 ▸; Oliver et al. 2011 ▸). Alternatively, the chosen amine can carry a functional group capable of additional coordination to a metal cation, typically a pyridyl group (e.g. Barba et al., 2012 ▸; Singh et al., 2014 ▸) or groups capable of forming hydrogen-bonding inter­actions (e.g. Benson et al., 2007 ▸; Howie et al., 2008 ▸). It is the former class of ligand with a pyridyl substituent which forms the focus of the present contribution. Previous structural studies have revealed a diversity of coordination modes in the zinc-triad elements coordinated by di­thio­carbamate ligands functionalized with pyridyl substituents. Thus, a two-dimensional architecture is found in centrosymmetric {Zn[S2CN(CH2ferrocen­yl)CH2py]2}, with both pyridyl N atoms being coordinating (Kumar et al., 2016 ▸). In the cadmium analogue, isolated as a 1,10-phenanthroline (phen) adduct, i.e. Cd[S2CN(CH2ferrocen­yl)CH2py]2(phen), no additional Cd—N(pyrid­yl) inter­actions are formed in the crystal as the cadmium cation is coordinatively saturated (Kumar et al., 2016 ▸). However, in {Cd{[S2CN(CH2Ph)CH2py]2} and related species, all potential donor atoms are coordinating, leading to a two-dimensional coordination polymer (Kumar et al., 2014 ▸). It is inter­esting to note that zero-dimensional aggregation can also occur, as in the case of {Cd[S2CN(1H-indol-3-ylmeth­yl)CH2(CH2py)]2}2, where the tridentate mode of coordination of one di­thio­carbamate is retained, but aggregation leads to a dimer only (Kumar et al., 2014 ▸). This may be a result of the now well established steric effects in 1,1-di­thiol­ate chemistry (Tiekink, 2003 ▸, 2006 ▸). Several related structures are also available for mercury. In {Hg[S2CN(CH2Py)2]2]}, with two pyridyl groups per di­thio­carbamate ligand, an unusual one-dimensional coordination polymer with a twisted topology is found in the crystal, as one pyridyl N atom is noncoordinating (Yadav et al., 2014 ▸; Jotani et al., 2016 ▸). When one CH2py group is replaced by a methyl substitutent, as in {Hg[S2CN(Me)CH2Py]2} (Singh et al., 2014 ▸), a one-dimensional coordination polymer is also found. Again, when one substituent is large, i.e. as in {Hg[S2CN{CH2(1-methyl-1H-pyrrol-2-yl)}CH2Py]2} (Yadav et al., 2014 ▸), no Hg—N(pyrid­yl) inter­actions are found. Very recently, the crystal structure of a binary compound, isolated as the 3-methyl­pyridine monosolvate, i.e. {Cd[S2CN(Et)CH2py]2·3-methyl­pyridine}, was described and found to feature two S,S′,N-tridentate di­thio­carbamate ligands, leading to a two-dimensional coordination polymer (Arman et al., 2017 ▸), as seen earlier in some of the precedents mentioned above (Kumar et al., 2014 ▸); the 3-methyl­pyridine solvent mol­ecules reside in square-shaped channels. In continuation of these structural studies, herein, the crystallographic characterization of a closely related zinc compound to the last mentioned species, namely {Zn[S2CN(Et)CH2py]2·(4-methyl­pyri­dine)0.5}, is described.

Structural commentary

The asymmetric unit of (I) comprises two independent Zn[S2CN(Et)CH2py]2 residues, shown in Fig. 1 ▸, and a 4-methyl­pyridine solvent mol­ecule. Each of the di­thio­carbamate ligands is chelating, forming approximately similar Zn—S bond lengths, see data in Table 1 ▸. For the Zn1-containing mol­ecule, the disparity in the Zn—S bond lengths, i.e. Δ(Zn—S) = [Zn—S(long) − Zn—S(short)], for the S1-di­thio­carbamate ligand of 0.32 Å is greater than the value of 0.10 Å for the S3-di­thio­carbamate ligand. For the Zn2-mol­ecule, these differences diminish to 0.23 and 0.09 Å for the S5- and S7-di­thio­carbamate ligands, respectively. The similarity of the structures is emphasized in the overlay diagram of Fig. 2 ▸, showing minor variations in the orientations of the pyridyl rings and in the relationship between the two chelate rings. In each of the Zn-containing mol­ecules, one di­thio­carbamate ligand coordinates in a μ2-κ3 mode, chelating one ZnII cation and simultaneously bridging another via the pyridyl N atom. It is noted that it is the di­thio­carbamate ligand that forms the more equivalent Zn—S bond lengths in each residue that forms the bridging inter­actions. The resultant coordination geometry for each ZnII cation is based on an NS4 donor set.
Figure 1

The mol­ecular structures of the two independent Zn[S2CN(Et)CH2py]2 fragments in the asymmetric unit of (I), showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

Table 1

Selected bond lengths (Å)

Zn1—N62.050 (3)Zn2—N2i 2.074 (3)
Zn1—S12.3510 (11)Zn2—S52.3723 (11)
Zn1—S22.6741 (11)Zn2—S62.5783 (12)
Zn1—S32.3962 (11)Zn2—S72.4036 (11)
Zn1—S42.4972 (11)Zn2—S82.4917 (12)

Symmetry code: (i) .

Figure 2

A mol­ecular overlay diagram of the two independent mol­ecules of Zn[S2CN(Et)CH2py]2. The Zn1-containing mol­ecule is shown in red and the mol­ecules have been overlapped so that the two more symmetrically chelating di­thio­carbamate ligands are coincident.

For five-coordinate species, the value computed for τ is a useful indicator of the adopted coordination geometry, with the values of τ ranging from 0 to 1 for ideal square-pyramidal and trigonal–bipyramidal geometries, respectively (Addison et al., 1984 ▸). In (I), the values of τ for Zn1 and Zn2 are 0.33 and 0.23, respectively, indicating that Zn2 is closer to a square pyramid than Zn1. In each case, the pyridyl N atom occupies the approximately apical position, as indicated by the range of N—Zn1—S angles of 97.62 (8)–111.76 (9)° and the narrower range of N—Zn2—S angles of 99.72 (9)–110.48 (9)°. In this description, the Zn1 cation lies 0.6827 (6) Å above the best plane through the four S atoms, i.e. S1–S4 (r.m.s. deviation = 0.1721 Å), in the direction of the pyridyl N6 atom. For the Zn2-mol­ecule, the deviation of the Zn2 cation from the S4 plane is 0.6018 (6) Å and the r.m.s. deviation through the S5–S8 atoms is 0.1273 Å. The result of the presence of equal numbers of chelating and bridging ligands in (I) is the formation of a supra­molecular polymer aligned along [010], as illustrated in Fig. 3 ▸. The topology of the chain is zigzag. Finally, the 4-methyl­pyridine solvent mol­ecule is non-coordinating.
Figure 3

The one-dimensional coordination polymer in (I), aligned along [010].

The most closely related structure in the literature for comparison is that of the aforementioned recently reported {Cd[S2CN(Et)CH2py]2·3-methyl­pyridine}, which was also isolated from an experiment attempting to coordinate isomeric methyl­pyridines to the heavy element (Arman et al., 2017 ▸). The crucial difference between the two structures is that in the cadmium crystal, both di­thio­carbamates adopt a μ2-κ3 coordination mode, leading to a cis-N2S4 coordination geometry and a two-dimensional framework with a flat topology. It is highly likely that the disparity in supra­molecular aggregation in the zinc and cadmium compounds arises from the greater ability of the larger Cd atom to expand its donor set.

Supra­molecular features

As mentioned above, the supra­molecular chains in the crystal of (I) are aligned along [010]. In the crystal, these chains are connected into a three-dimensional architecture by a number of weak inter­molecular inter­actions, as summarized in Table 2 ▸. There are two distinct C—H⋯S inter­actions, with the donors being methyl- and pyridyl-C—H groups, as well as a methyl­ene-C—H⋯N(pyrid­yl) inter­action. The other connection between chains is of the type pyridyl-C—H⋯π(Zn1,S3,S4,C10), an inter­action well known in metal di­thio­carbamates (Tiekink & Zukerman-Schpector, 2011 ▸) and, indeed, other metal systems (Tiekink, 2017 ▸). The main connection identified between the 4-methyl­pyridine solvent mol­ecule and the chain is of the type pyridyl-C—H⋯N(4-methyl­pyridine). An illustration of the mol­ecular packing is given in Fig. 4 ▸.
Table 2

Hydrogen-bond geometry (Å, °)

Cg1 is the ring centroid of the Zn1/S3/S4/C10 ring.

D—H⋯A D—HH⋯A D⋯A D—H⋯A
C11—H11B⋯N8ii 0.992.413.197 (5)136
C30—H30C⋯S8iii 0.982.863.433 (5)118
C36—H36⋯S5iv 0.952.873.773 (4)158
C6—H6⋯Cg1v 0.952.913.708 (4)142
C26—H26⋯N9vi 0.952.613.256 (5)126

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Figure 4

A view of the unit-cell contents in projection down the b axis. The C—H⋯S, C—H⋯N and C—H⋯π inter­actions are shown in orange, blue and purple dashed lines, respectively.

Database survey

The di­thio­carabmate anion, −[S2CN(Et)CH2py], found in (I) and in {Cd[S2CN(Et)CH2py]2·3-methyl­pyridine} (Arman et al., 2017 ▸), has been structurally characterized in its free form, i.e. as its potassium 1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane (i.e. 18-crown-6) salt (Arman et al., 2013 ▸). The pyridyl N atom is noncoordinating in this structure, the K+ ion being connected to S and O atoms only, within an O6S2 donor set. There is also a series of three diorganotin structures with this di­thio­carbamate ligand, i.e. of the general formula R 2Sn[S2CN(Et)CH2py]2, for R = Me, nBu and Ph (Barba et al., 2012 ▸). In only the R = Me compound is there a weak inter­molecular Sn⋯N(pyrid­yl) inter­action of 2.98 Å between the two mol­ecules comprising the asymmetric unit. This result is consistent with surveys of diorganotin bis­(di­thio­carbamate)s in general (Tiekink, 2008 ▸) which suggest that the Sn atom in these compounds does not usually increase its coordination number by forming secondary bonding inter­actions (Tiekink, 2017 ▸). Specifically, for di­methyl­tin compounds, R 2Sn(S2CNR′R′′)2, a recent survey indicated that secondary bonding inter­actions occur in only 10% of their crystal structures (Zaldi et al., 2017 ▸)

Synthesis and crystallization

The title compound was isolated from the recrystallization of Zn{[S2CN(Et)CH2py]2 (generated from the reaction of Zn(NO3)2·H2O and −[S2CN(Et)CH2py]) from 4-picoline. Suitable single crystals formed upon slow evaporation of the solvent (m.p. 337–339 K).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding-model approximation, with U iso(H) values set at 1.2–1.5U eq(C).
Table 3

Experimental details

Crystal data
Chemical formula[Zn(C9H11N2S2)2]·0.5C6H7N
M r 534.57
Crystal system, space groupTriclinic, P
Temperature (K)98
a, b, c (Å)9.419 (2), 15.299 (4), 17.149 (4)
α, β, γ (°)88.871 (9), 83.914 (8), 75.766 (6)
V (Å3)2381.8 (10)
Z 4
Radiation typeMo Kα
μ (mm−1)1.40
Crystal size (mm)0.30 × 0.20 × 0.08
 
Data collection
DiffractometerAFC12K/SATURN724
Absorption correctionMulti-scan (ABSCOR; Higashi, 1995 ▸)
T min, T max 0.549, 1
No. of measured, independent and observed [I > 2σ(I)] reflections13748, 9827, 8634
R int 0.037
 
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S 0.053, 0.120, 1.14
No. of reflections9827
No. of parameters555
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.55, −0.81

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ▸), SHELXS (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸), DIAMOND (Brandenburg, 2006 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017010179/hb7691sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017010179/hb7691Isup2.hkl CCDC reference: 1561011 Additional supporting information: crystallographic information; 3D view; checkCIF report
[Zn(C9H11N2S2)2]·0.5C6H7NZ = 4
Mr = 534.57F(000) = 1108
Triclinic, P1Dx = 1.491 Mg m−3
a = 9.419 (2) ÅMo Kα radiation, λ = 0.71069 Å
b = 15.299 (4) ÅCell parameters from 10781 reflections
c = 17.149 (4) Åθ = 2.2–40.7°
α = 88.871 (9)°µ = 1.40 mm−1
β = 83.914 (8)°T = 98 K
γ = 75.766 (6)°Block, colourless
V = 2381.8 (10) Å30.30 × 0.20 × 0.08 mm
AFC12K/SATURN724 diffractometer9827 independent reflections
Radiation source: fine-focus sealed tube8634 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω scansθmax = 26.5°, θmin = 2.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −11→11
Tmin = 0.549, Tmax = 1k = −19→18
13748 measured reflectionsl = −21→21
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.120w = 1/[σ2(Fo2) + (0.0424P)2 + 1.244P] where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.001
9827 reflectionsΔρmax = 0.55 e Å−3
555 parametersΔρmin = −0.81 e Å−3
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.
xyzUiso*/Ueq
Zn10.54704 (5)0.72964 (3)0.93393 (2)0.01760 (11)
Zn20.43549 (5)0.25774 (3)0.57576 (2)0.01760 (11)
S10.32468 (10)0.83898 (6)0.96346 (5)0.01963 (19)
S20.58234 (10)0.88714 (6)0.87543 (5)0.01821 (18)
S30.78618 (10)0.68982 (6)0.97969 (5)0.01919 (19)
S40.53708 (10)0.61206 (6)1.03606 (5)0.01912 (19)
S50.67047 (10)0.28992 (6)0.55549 (5)0.0212 (2)
S60.40191 (10)0.42263 (6)0.61908 (5)0.01971 (19)
S70.20336 (10)0.27671 (6)0.52307 (5)0.02089 (19)
S80.46521 (10)0.12755 (6)0.48528 (5)0.0217 (2)
N10.3378 (3)1.0087 (2)0.92953 (16)0.0176 (6)
N20.4298 (3)1.19659 (19)0.68468 (17)0.0187 (6)
N30.8009 (3)0.56341 (19)1.09051 (17)0.0173 (6)
N41.0896 (4)0.7366 (3)1.2448 (2)0.0345 (8)
N50.6620 (3)0.46253 (19)0.58467 (17)0.0178 (6)
N60.5447 (3)0.66729 (19)0.82948 (16)0.0162 (6)
N70.2023 (3)0.1338 (2)0.43693 (17)0.0198 (6)
N8−0.0182 (4)0.3770 (2)0.24530 (18)0.0260 (7)
N90.7781 (4)0.1256 (2)0.2852 (2)0.0318 (8)
C10.4081 (4)0.9211 (2)0.92226 (19)0.0175 (7)
C20.1861 (4)1.0407 (3)0.9680 (2)0.0258 (8)
H2A0.19001.06641.02000.031*
H2B0.14140.98860.97640.031*
C30.0895 (4)1.1112 (3)0.9207 (2)0.0242 (8)
H3A−0.01041.12830.94790.036*
H3B0.08621.08650.86880.036*
H3C0.12991.16440.91480.036*
C40.4188 (4)1.0786 (2)0.91370 (19)0.0186 (7)
H4A0.52251.05280.92350.022*
H4B0.37751.12820.95200.022*
C50.4183 (4)1.1186 (2)0.8325 (2)0.0183 (7)
C60.4609 (4)1.1986 (2)0.8213 (2)0.0187 (7)
H60.48551.22820.86430.022*
C70.4674 (4)1.2355 (2)0.7466 (2)0.0194 (7)
H70.49921.28970.73910.023*
C80.3872 (4)1.1200 (2)0.6959 (2)0.0192 (7)
H80.35981.09280.65250.023*
C90.3813 (4)1.0782 (2)0.76892 (19)0.0185 (7)
H90.35221.02300.77470.022*
C100.7165 (4)0.6157 (2)1.04110 (19)0.0151 (7)
C110.7438 (4)0.4998 (2)1.1437 (2)0.0212 (8)
H11A0.63780.52551.15960.025*
H11B0.79570.49221.19160.025*
C120.7640 (4)0.4080 (3)1.1055 (2)0.0248 (8)
H12A0.73340.36641.14410.037*
H12B0.86780.38431.08610.037*
H12C0.70360.41431.06150.037*
C130.9591 (4)0.5577 (2)1.0897 (2)0.0185 (7)
H13A0.99850.56881.03550.022*
H13B1.00920.49551.10360.022*
C140.9978 (4)0.6223 (2)1.1441 (2)0.0185 (7)
C151.1310 (4)0.6461 (3)1.1276 (2)0.0277 (9)
H151.19410.62381.08160.033*
C161.1711 (5)0.7026 (3)1.1786 (3)0.0359 (10)
H161.26230.71831.16580.043*
C170.9631 (5)0.7129 (3)1.2598 (2)0.0283 (9)
H170.90290.73561.30660.034*
C180.9122 (4)0.6575 (3)1.2122 (2)0.0249 (8)
H180.81970.64381.22610.030*
C190.5864 (4)0.3983 (2)0.58684 (19)0.0175 (7)
C200.8195 (4)0.4443 (3)0.5556 (2)0.0305 (9)
H20A0.82930.46850.50180.037*
H20B0.86110.37830.55260.037*
C210.9081 (4)0.4856 (3)0.6068 (2)0.0281 (9)
H21A1.01290.46600.58790.042*
H21B0.89240.46600.66110.042*
H21C0.87610.55150.60440.042*
C220.5849 (4)0.5575 (2)0.5968 (2)0.0202 (8)
H22A0.48570.56670.57890.024*
H22B0.63880.59450.56290.024*
C230.5673 (4)0.5923 (2)0.68008 (19)0.0170 (7)
C240.6113 (4)0.5384 (2)0.7445 (2)0.0181 (7)
H240.64920.47510.73810.022*
C250.5989 (4)0.5782 (2)0.8170 (2)0.0184 (7)
H250.63000.54110.86010.022*
C260.4962 (4)0.7180 (2)0.7679 (2)0.0189 (7)
H260.45330.78060.77620.023*
C270.5060 (4)0.6832 (2)0.6938 (2)0.0205 (8)
H270.47070.72150.65210.025*
C280.2825 (4)0.1734 (2)0.4770 (2)0.0182 (7)
C290.2630 (4)0.0457 (2)0.3968 (2)0.0241 (8)
H29A0.37190.03140.39300.029*
H29B0.23370.04990.34280.029*
C300.2093 (5)−0.0302 (3)0.4398 (3)0.0323 (10)
H30A0.2525−0.08720.41150.048*
H30B0.1016−0.01720.44230.048*
H30C0.2390−0.03510.49300.048*
C310.0470 (4)0.1766 (2)0.4283 (2)0.0213 (8)
H31A−0.00140.20490.47880.026*
H31B−0.00310.12960.41560.026*
C320.0291 (4)0.2475 (2)0.36478 (19)0.0167 (7)
C330.1391 (4)0.2508 (3)0.3047 (2)0.0229 (8)
H330.23290.20940.30320.027*
C340.1093 (4)0.3154 (3)0.2470 (2)0.0264 (9)
H340.18490.31590.20580.032*
C35−0.1227 (4)0.3728 (3)0.3038 (2)0.0275 (9)
H35−0.21480.41570.30420.033*
C36−0.1056 (4)0.3105 (3)0.3632 (2)0.0231 (8)
H36−0.18450.31050.40270.028*
C370.8173 (4)0.0465 (3)0.3202 (2)0.0282 (9)
H370.75250.03280.36240.034*
C380.9486 (4)−0.0178 (3)0.2986 (2)0.0288 (9)
H380.9703−0.07420.32450.035*
C391.0473 (4)0.0021 (3)0.2383 (2)0.0269 (8)
C401.0051 (5)0.0859 (3)0.2018 (2)0.0322 (9)
H401.06770.10270.16020.039*
C410.8712 (5)0.1440 (3)0.2271 (3)0.0353 (10)
H410.84440.20040.20150.042*
C421.1917 (5)−0.0633 (3)0.2133 (3)0.0387 (11)
H42A1.2049−0.11550.24820.058*
H42B1.2722−0.03370.21610.058*
H42C1.1921−0.08330.15930.058*
U11U22U33U12U13U23
Zn10.0182 (2)0.0187 (2)0.0157 (2)−0.00322 (16)−0.00350 (16)−0.00183 (16)
Zn20.0214 (2)0.0196 (2)0.0143 (2)−0.00902 (17)−0.00376 (16)0.00265 (16)
S10.0195 (5)0.0172 (4)0.0221 (5)−0.0057 (3)0.0010 (3)0.0019 (3)
S20.0184 (4)0.0189 (4)0.0176 (4)−0.0056 (3)−0.0010 (3)0.0013 (3)
S30.0194 (5)0.0199 (4)0.0201 (4)−0.0077 (4)−0.0040 (3)0.0040 (3)
S40.0170 (4)0.0214 (5)0.0211 (4)−0.0079 (3)−0.0044 (3)0.0017 (3)
S50.0227 (5)0.0166 (4)0.0240 (5)−0.0072 (4)0.0047 (4)−0.0042 (3)
S60.0192 (5)0.0188 (4)0.0213 (4)−0.0052 (3)−0.0014 (3)−0.0017 (3)
S70.0222 (5)0.0199 (4)0.0208 (5)−0.0040 (4)−0.0051 (4)−0.0024 (3)
S80.0195 (5)0.0237 (5)0.0222 (5)−0.0039 (4)−0.0059 (3)−0.0023 (4)
N10.0176 (16)0.0186 (15)0.0157 (15)−0.0037 (12)−0.0003 (11)0.0021 (12)
N20.0240 (17)0.0169 (15)0.0171 (15)−0.0075 (12)−0.0049 (12)0.0042 (12)
N30.0167 (15)0.0166 (15)0.0200 (15)−0.0055 (12)−0.0051 (12)0.0022 (12)
N40.038 (2)0.038 (2)0.032 (2)−0.0151 (17)−0.0091 (16)−0.0055 (16)
N50.0215 (16)0.0153 (15)0.0185 (15)−0.0095 (12)0.0012 (12)−0.0023 (12)
N60.0150 (15)0.0174 (15)0.0168 (15)−0.0042 (12)−0.0038 (11)−0.0019 (11)
N70.0173 (16)0.0196 (16)0.0224 (16)−0.0027 (12)−0.0062 (12)−0.0001 (12)
N80.0211 (17)0.0340 (19)0.0215 (17)−0.0042 (14)−0.0028 (13)0.0042 (14)
N90.028 (2)0.0290 (19)0.039 (2)−0.0058 (15)−0.0105 (16)−0.0053 (16)
C10.0194 (18)0.0211 (18)0.0123 (16)−0.0049 (14)−0.0026 (13)−0.0005 (13)
C20.022 (2)0.024 (2)0.028 (2)−0.0031 (16)0.0052 (16)0.0058 (16)
C30.020 (2)0.027 (2)0.026 (2)−0.0041 (15)−0.0064 (15)0.0005 (16)
C40.0234 (19)0.0183 (18)0.0155 (17)−0.0070 (14)−0.0042 (14)−0.0003 (14)
C50.0152 (18)0.0196 (18)0.0203 (18)−0.0050 (14)−0.0009 (13)0.0013 (14)
C60.0215 (19)0.0168 (17)0.0190 (18)−0.0061 (14)−0.0036 (14)−0.0003 (14)
C70.0222 (19)0.0175 (18)0.0207 (18)−0.0092 (14)−0.0030 (14)0.0022 (14)
C80.0225 (19)0.0207 (18)0.0153 (17)−0.0064 (15)−0.0033 (14)−0.0001 (14)
C90.025 (2)0.0180 (17)0.0153 (17)−0.0103 (15)−0.0035 (14)−0.0002 (14)
C100.0172 (17)0.0121 (16)0.0164 (17)−0.0040 (13)−0.0016 (13)−0.0030 (13)
C110.0202 (19)0.0246 (19)0.0213 (19)−0.0107 (15)−0.0034 (14)0.0083 (15)
C120.024 (2)0.024 (2)0.031 (2)−0.0141 (16)−0.0082 (16)0.0081 (16)
C130.0141 (17)0.0193 (18)0.0216 (18)−0.0024 (14)−0.0031 (14)−0.0004 (14)
C140.0183 (18)0.0182 (17)0.0200 (18)−0.0044 (14)−0.0076 (14)0.0041 (14)
C150.023 (2)0.030 (2)0.030 (2)−0.0088 (17)0.0029 (16)−0.0066 (17)
C160.028 (2)0.045 (3)0.041 (3)−0.020 (2)−0.0033 (19)−0.008 (2)
C170.031 (2)0.031 (2)0.023 (2)−0.0057 (17)−0.0042 (16)−0.0016 (16)
C180.023 (2)0.024 (2)0.028 (2)−0.0068 (16)−0.0029 (16)0.0010 (16)
C190.0235 (19)0.0225 (18)0.0086 (16)−0.0096 (15)−0.0014 (13)0.0000 (13)
C200.026 (2)0.034 (2)0.034 (2)−0.0154 (18)0.0086 (17)−0.0108 (18)
C210.028 (2)0.029 (2)0.030 (2)−0.0108 (17)−0.0022 (17)−0.0037 (17)
C220.032 (2)0.0171 (18)0.0138 (17)−0.0101 (15)−0.0033 (14)0.0015 (14)
C230.0177 (18)0.0224 (18)0.0141 (17)−0.0111 (14)−0.0007 (13)−0.0010 (14)
C240.0208 (19)0.0135 (17)0.0199 (18)−0.0041 (14)−0.0019 (14)0.0006 (14)
C250.0225 (19)0.0192 (18)0.0159 (17)−0.0096 (15)−0.0020 (14)0.0034 (14)
C260.0204 (19)0.0157 (17)0.0208 (18)−0.0033 (14)−0.0068 (14)0.0010 (14)
C270.0215 (19)0.0202 (18)0.0210 (18)−0.0057 (15)−0.0072 (14)0.0039 (15)
C280.0196 (18)0.0202 (18)0.0166 (17)−0.0076 (14)−0.0043 (14)0.0049 (14)
C290.025 (2)0.0213 (19)0.028 (2)−0.0065 (16)−0.0086 (16)−0.0061 (16)
C300.033 (2)0.020 (2)0.047 (3)−0.0070 (17)−0.0152 (19)0.0016 (18)
C310.0170 (18)0.0229 (19)0.0258 (19)−0.0067 (15)−0.0058 (14)0.0007 (15)
C320.0191 (18)0.0188 (17)0.0133 (16)−0.0059 (14)−0.0041 (13)−0.0020 (13)
C330.0158 (18)0.028 (2)0.026 (2)−0.0065 (15)−0.0048 (14)0.0016 (16)
C340.020 (2)0.038 (2)0.023 (2)−0.0103 (17)−0.0006 (15)0.0019 (17)
C350.023 (2)0.030 (2)0.024 (2)0.0010 (16)0.0029 (16)0.0011 (16)
C360.022 (2)0.028 (2)0.0168 (18)−0.0025 (16)−0.0002 (14)−0.0025 (15)
C370.024 (2)0.040 (2)0.025 (2)−0.0143 (18)−0.0054 (16)−0.0079 (17)
C380.025 (2)0.033 (2)0.034 (2)−0.0124 (17)−0.0104 (17)−0.0052 (18)
C390.021 (2)0.030 (2)0.033 (2)−0.0088 (16)−0.0095 (16)−0.0062 (17)
C400.033 (2)0.036 (2)0.028 (2)−0.0092 (19)−0.0010 (17)−0.0058 (18)
C410.040 (3)0.032 (2)0.036 (2)−0.009 (2)−0.014 (2)0.0038 (19)
C420.028 (2)0.034 (2)0.054 (3)−0.0081 (19)−0.001 (2)−0.013 (2)
Zn1—N62.050 (3)C12—H12A0.9800
Zn1—S12.3510 (11)C12—H12B0.9800
Zn1—S22.6741 (11)C12—H12C0.9800
Zn1—S32.3962 (11)C13—C141.505 (5)
Zn1—S42.4972 (11)C13—H13A0.9900
Zn2—N2i2.074 (3)C13—H13B0.9900
Zn2—S52.3723 (11)C14—C181.384 (5)
Zn2—S62.5783 (12)C14—C151.391 (5)
Zn2—S72.4036 (11)C15—C161.384 (6)
Zn2—S82.4917 (12)C15—H150.9500
S1—C11.740 (4)C16—H160.9500
S2—C11.710 (4)C17—C181.389 (5)
S3—C101.732 (3)C17—H170.9500
S4—C101.715 (3)C18—H180.9500
S5—C191.721 (4)C20—C211.518 (5)
S6—C191.718 (4)C20—H20A0.9900
S7—C281.738 (4)C20—H20B0.9900
S8—C281.711 (4)C21—H21A0.9800
N1—C11.342 (4)C21—H21B0.9800
N1—C41.465 (4)C21—H21C0.9800
N1—C21.478 (5)C22—C231.513 (5)
N2—C81.333 (4)C22—H22A0.9900
N2—C71.348 (5)C22—H22B0.9900
N2—Zn2ii2.074 (3)C23—C271.383 (5)
N3—C101.339 (4)C23—C241.402 (5)
N3—C131.469 (4)C24—C251.377 (5)
N3—C111.479 (4)C24—H240.9500
N4—C171.328 (5)C25—H250.9500
N4—C161.339 (6)C26—C271.372 (5)
N5—C191.345 (4)C26—H260.9500
N5—C221.463 (4)C27—H270.9500
N5—C201.475 (5)C29—C301.525 (5)
N6—C261.350 (4)C29—H29A0.9900
N6—C251.345 (4)C29—H29B0.9900
N7—C281.327 (4)C30—H30A0.9800
N7—C311.469 (4)C30—H30B0.9800
N7—C291.481 (5)C30—H30C0.9800
N8—C341.335 (5)C31—C321.515 (5)
N8—C351.341 (5)C31—H31A0.9900
N9—C371.327 (5)C31—H31B0.9900
N9—C411.329 (6)C32—C331.391 (5)
C2—C31.513 (5)C32—C361.394 (5)
C2—H2A0.9900C33—C341.384 (5)
C2—H2B0.9900C33—H330.9500
C3—H3A0.9800C34—H340.9500
C3—H3B0.9800C35—C361.376 (5)
C3—H3C0.9800C35—H350.9500
C4—C51.510 (5)C36—H360.9500
C4—H4A0.9900C37—C381.398 (6)
C4—H4B0.9900C37—H370.9500
C5—C91.381 (5)C38—C391.396 (6)
C5—C61.383 (5)C38—H380.9500
C6—C71.391 (5)C39—C401.401 (6)
C6—H60.9500C39—C421.503 (6)
C7—H70.9500C40—C411.384 (6)
C8—C91.397 (5)C40—H400.9500
C8—H80.9500C41—H410.9500
C9—H90.9500C42—H42A0.9800
C11—C121.521 (5)C42—H42B0.9800
C11—H11A0.9900C42—H42C0.9800
C11—H11B0.9900
N6—Zn1—S1109.98 (8)C18—C14—C13124.4 (3)
N6—Zn1—S3111.76 (9)C15—C14—C13118.7 (3)
S1—Zn1—S3137.18 (4)C16—C15—C14119.5 (4)
N6—Zn1—S4105.21 (8)C16—C15—H15120.2
S1—Zn1—S4103.71 (4)C14—C15—H15120.2
S3—Zn1—S474.11 (3)N4—C16—C15124.2 (4)
N6—Zn1—S297.62 (8)N4—C16—H16117.9
S1—Zn1—S271.89 (3)C15—C16—H16117.9
S3—Zn1—S293.44 (3)N4—C17—C18124.8 (4)
S4—Zn1—S2156.73 (3)N4—C17—H17117.6
N2i—Zn2—S5105.06 (9)C18—C17—H17117.6
N2i—Zn2—S7110.48 (9)C14—C18—C17119.2 (4)
S5—Zn2—S7144.31 (4)C14—C18—H18120.4
N2i—Zn2—S8101.93 (9)C17—C18—H18120.4
S5—Zn2—S8102.19 (4)N5—C19—S6120.9 (3)
S7—Zn2—S873.89 (3)N5—C19—S5121.2 (3)
N2i—Zn2—S699.72 (9)S6—C19—S5117.9 (2)
S5—Zn2—S672.94 (3)N5—C20—C21113.1 (3)
S7—Zn2—S697.50 (3)N5—C20—H20A108.9
S8—Zn2—S6158.31 (3)C21—C20—H20A108.9
C1—S1—Zn189.47 (13)N5—C20—H20B108.9
C1—S2—Zn179.95 (12)C21—C20—H20B108.9
C10—S3—Zn185.51 (12)H20A—C20—H20B107.8
C10—S4—Zn182.71 (11)C20—C21—H21A109.5
C19—S5—Zn287.66 (12)C20—C21—H21B109.5
C19—S6—Zn281.29 (12)H21A—C21—H21B109.5
C28—S7—Zn285.37 (12)C20—C21—H21C109.5
C28—S8—Zn283.19 (13)H21A—C21—H21C109.5
C1—N1—C4120.4 (3)H21B—C21—H21C109.5
C1—N1—C2123.2 (3)N5—C22—C23115.9 (3)
C4—N1—C2115.2 (3)N5—C22—H22A108.3
C8—N2—C7118.4 (3)C23—C22—H22A108.3
C8—N2—Zn2ii121.8 (2)N5—C22—H22B108.3
C7—N2—Zn2ii119.7 (2)C23—C22—H22B108.3
C10—N3—C13122.7 (3)H22A—C22—H22B107.4
C10—N3—C11121.6 (3)C27—C23—C24117.7 (3)
C13—N3—C11115.4 (3)C27—C23—C22118.3 (3)
C17—N4—C16115.5 (4)C24—C23—C22124.1 (3)
C19—N5—C22120.7 (3)C25—C24—C23119.2 (3)
C19—N5—C20122.2 (3)C25—C24—H24120.4
C22—N5—C20116.1 (3)C23—C24—H24120.4
C26—N6—C25117.4 (3)N6—C25—C24123.0 (3)
C26—N6—Zn1119.1 (2)N6—C25—H25118.5
C25—N6—Zn1123.3 (2)C24—C25—H25118.5
C28—N7—C31121.5 (3)N6—C26—C27122.9 (3)
C28—N7—C29122.7 (3)N6—C26—H26118.5
C31—N7—C29115.8 (3)C27—C26—H26118.5
C34—N8—C35115.7 (3)C26—C27—C23119.8 (3)
C37—N9—C41117.2 (4)C26—C27—H27120.1
N1—C1—S2121.6 (3)C23—C27—H27120.1
N1—C1—S1120.2 (3)N7—C28—S8122.7 (3)
S2—C1—S1118.2 (2)N7—C28—S7120.1 (3)
N1—C2—C3112.9 (3)S8—C28—S7117.1 (2)
N1—C2—H2A109.0N7—C29—C30112.2 (3)
C3—C2—H2A109.0N7—C29—H29A109.2
N1—C2—H2B109.0C30—C29—H29A109.2
C3—C2—H2B109.0N7—C29—H29B109.2
H2A—C2—H2B107.8C30—C29—H29B109.2
C2—C3—H3A109.5H29A—C29—H29B107.9
C2—C3—H3B109.5C29—C30—H30A109.5
H3A—C3—H3B109.5C29—C30—H30B109.5
C2—C3—H3C109.5H30A—C30—H30B109.5
H3A—C3—H3C109.5C29—C30—H30C109.5
H3B—C3—H3C109.5H30A—C30—H30C109.5
N1—C4—C5116.8 (3)H30B—C30—H30C109.5
N1—C4—H4A108.1N7—C31—C32112.6 (3)
C5—C4—H4A108.1N7—C31—H31A109.1
N1—C4—H4B108.1C32—C31—H31A109.1
C5—C4—H4B108.1N7—C31—H31B109.1
H4A—C4—H4B107.3C32—C31—H31B109.1
C9—C5—C6118.7 (3)H31A—C31—H31B107.8
C9—C5—C4123.3 (3)C33—C32—C36117.4 (3)
C6—C5—C4117.9 (3)C33—C32—C31123.1 (3)
C5—C6—C7119.4 (3)C36—C32—C31119.4 (3)
C5—C6—H6120.3C34—C33—C32118.8 (4)
C7—C6—H6120.3C34—C33—H33120.6
N2—C7—C6121.9 (3)C32—C33—H33120.6
N2—C7—H7119.1N8—C34—C33124.6 (4)
C6—C7—H7119.1N8—C34—H34117.7
N2—C8—C9122.8 (3)C33—C34—H34117.7
N2—C8—H8118.6N8—C35—C36124.5 (4)
C9—C8—H8118.6N8—C35—H35117.8
C5—C9—C8118.7 (3)C36—C35—H35117.8
C5—C9—H9120.6C35—C36—C32119.0 (3)
C8—C9—H9120.6C35—C36—H36120.5
N3—C10—S4121.8 (2)C32—C36—H36120.5
N3—C10—S3120.5 (3)N9—C37—C38123.7 (4)
S4—C10—S3117.67 (19)N9—C37—H37118.1
N3—C11—C12112.2 (3)C38—C37—H37118.1
N3—C11—H11A109.2C39—C38—C37119.0 (4)
C12—C11—H11A109.2C39—C38—H38120.5
N3—C11—H11B109.2C37—C38—H38120.5
C12—C11—H11B109.2C38—C39—C40116.8 (4)
H11A—C11—H11B107.9C38—C39—C42121.7 (4)
C11—C12—H12A109.5C40—C39—C42121.5 (4)
C11—C12—H12B109.5C41—C40—C39119.4 (4)
H12A—C12—H12B109.5C41—C40—H40120.3
C11—C12—H12C109.5C39—C40—H40120.3
H12A—C12—H12C109.5N9—C41—C40123.9 (4)
H12B—C12—H12C109.5N9—C41—H41118.1
N3—C13—C14115.2 (3)C40—C41—H41118.1
N3—C13—H13A108.5C39—C42—H42A109.5
C14—C13—H13A108.5C39—C42—H42B109.5
N3—C13—H13B108.5H42A—C42—H42B109.5
C14—C13—H13B108.5C39—C42—H42C109.5
H13A—C13—H13B107.5H42A—C42—H42C109.5
C18—C14—C15116.8 (4)H42B—C42—H42C109.5
C4—N1—C1—S2−14.0 (4)Zn2—S6—C19—N5175.0 (3)
C2—N1—C1—S2178.6 (3)Zn2—S6—C19—S5−3.67 (17)
C4—N1—C1—S1164.1 (2)Zn2—S5—C19—N5−174.7 (3)
C2—N1—C1—S1−3.4 (5)Zn2—S5—C19—S63.94 (18)
Zn1—S2—C1—N1172.1 (3)C19—N5—C20—C21−136.1 (4)
Zn1—S2—C1—S1−5.99 (17)C22—N5—C20—C2155.4 (4)
Zn1—S1—C1—N1−171.4 (3)C19—N5—C22—C2393.2 (4)
Zn1—S1—C1—S26.71 (19)C20—N5—C22—C23−98.1 (4)
C1—N1—C2—C3−132.8 (4)N5—C22—C23—C27174.9 (3)
C4—N1—C2—C359.1 (4)N5—C22—C23—C24−4.2 (5)
C1—N1—C4—C595.4 (4)C27—C23—C24—C25−3.3 (5)
C2—N1—C4—C5−96.2 (4)C22—C23—C24—C25175.8 (3)
N1—C4—C5—C9−17.5 (5)C26—N6—C25—C242.4 (5)
N1—C4—C5—C6164.2 (3)Zn1—N6—C25—C24−172.9 (3)
C9—C5—C6—C7−1.0 (5)C23—C24—C25—N60.7 (5)
C4—C5—C6—C7177.4 (3)C25—N6—C26—C27−2.9 (5)
C8—N2—C7—C6−0.9 (5)Zn1—N6—C26—C27172.6 (3)
Zn2ii—N2—C7—C6177.9 (3)N6—C26—C27—C230.3 (5)
C5—C6—C7—N21.7 (6)C24—C23—C27—C262.8 (5)
C7—N2—C8—C9−0.6 (5)C22—C23—C27—C26−176.3 (3)
Zn2ii—N2—C8—C9−179.4 (3)C31—N7—C28—S8−177.6 (2)
C6—C5—C9—C8−0.4 (5)C29—N7—C28—S81.0 (5)
C4—C5—C9—C8−178.7 (3)C31—N7—C28—S71.8 (4)
N2—C8—C9—C51.3 (6)C29—N7—C28—S7−179.7 (3)
C13—N3—C10—S4172.8 (3)Zn2—S8—C28—N7−174.7 (3)
C11—N3—C10—S4−0.2 (5)Zn2—S8—C28—S75.98 (17)
C13—N3—C10—S3−7.2 (5)Zn2—S7—C28—N7174.5 (3)
C11—N3—C10—S3179.8 (3)Zn2—S7—C28—S8−6.17 (18)
Zn1—S4—C10—N3−180.0 (3)C28—N7—C29—C30106.3 (4)
Zn1—S4—C10—S30.04 (18)C31—N7—C29—C30−75.1 (4)
Zn1—S3—C10—N3180.0 (3)C28—N7—C31—C3280.4 (4)
Zn1—S3—C10—S4−0.04 (18)C29—N7—C31—C32−98.2 (4)
C10—N3—C11—C1288.3 (4)N7—C31—C32—C3320.6 (5)
C13—N3—C11—C12−85.2 (4)N7—C31—C32—C36−162.7 (3)
C10—N3—C13—C1492.3 (4)C36—C32—C33—C34−0.2 (5)
C11—N3—C13—C14−94.3 (4)C31—C32—C33—C34176.6 (4)
N3—C13—C14—C1826.5 (5)C35—N8—C34—C33−1.2 (6)
N3—C13—C14—C15−156.3 (3)C32—C33—C34—N81.3 (6)
C18—C14—C15—C16−0.1 (6)C34—N8—C35—C360.0 (6)
C13—C14—C15—C16−177.5 (4)N8—C35—C36—C320.9 (6)
C17—N4—C16—C15−0.2 (7)C33—C32—C36—C35−0.8 (5)
C14—C15—C16—N40.5 (7)C31—C32—C36—C35−177.8 (4)
C16—N4—C17—C18−0.5 (6)C41—N9—C37—C38−1.0 (6)
C15—C14—C18—C17−0.5 (5)N9—C37—C38—C391.9 (6)
C13—C14—C18—C17176.7 (3)C37—C38—C39—C40−1.5 (5)
N4—C17—C18—C140.8 (6)C37—C38—C39—C42178.7 (4)
C22—N5—C19—S6−10.5 (4)C38—C39—C40—C410.5 (6)
C20—N5—C19—S6−178.5 (3)C42—C39—C40—C41−179.7 (4)
C22—N5—C19—S5168.1 (2)C37—N9—C41—C40−0.1 (6)
C20—N5—C19—S50.1 (5)C39—C40—C41—N90.3 (7)
D—H···AD—HH···AD···AD—H···A
C11—H11B···N8iii0.992.413.197 (5)136
C30—H30C···S8iv0.982.863.433 (5)118
C36—H36···S5v0.952.873.773 (4)158
C6—H6···Cg1vi0.952.913.708 (4)142
C26—H26···N9vii0.952.613.256 (5)126
  6 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  Exploiting the dithiocarbamate ligand in metal-directed self-assembly.

Authors:  James Cookson; Paul D Beer
Journal:  Dalton Trans       Date:  2007-03-20       Impact factor: 4.390

3.  Emerging supramolecular synthons: C-H···π(chelate) interactions in metal bis(1,1-dithiolates).

Authors:  Edward R T Tiekink; Julio Zukerman-Schpector
Journal:  Chem Commun (Camb)       Date:  2011-04-01       Impact factor: 6.222

4.  Multimetallic complexes of group 10 and 11 metals based on polydentate dithiocarbamate ligands.

Authors:  Katie Oliver; Andrew J P White; Graeme Hogarth; James D E T Wilton-Ely
Journal:  Dalton Trans       Date:  2011-03-09       Impact factor: 4.390

5.  Crystal structure refinement with SHELXL.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr C Struct Chem       Date:  2015-01-01       Impact factor: 1.172

6.  {[Eth-yl(pyridin-4-ylmeth-yl)carbamo-thio-yl]sulfanido-κ(2) S,S'}(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ(6) O)potassium.

Authors:  Hadi D Arman; Pavel Poplaukhin; Edward R T Tiekink
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2013-08-07
  6 in total

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