Home Crystal structure of catena-[(μ2-pyrazine-κ2N:N′)-bis(O,O′-di-ethyldithiophosphato-κ2S,S′)cadmium(II)], {C12H24CdN2O4P2S4}n
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Crystal structure of catena-[(μ2-pyrazine-κ2N:N′)-bis(O,O′-di-ethyldithiophosphato-κ2S,S′)cadmium(II)], {C12H24CdN2O4P2S4}n

  • Yee Seng Tan and Edward R.T. Tiekink ORCID logo EMAIL logo
Published/Copyright: November 6, 2019

Abstract

C12H24CdN2O4P2S4, monoclinic, P2/n (no. 13), a = 11.7844(2) Å, b = 7.6063(1) Å, c = 13.1965(2) Å, β = 111.594(2)°, V = 1099.86(3) Å3, Z = 2, Rgt(F) = 0.0171, wRref(F2) = 0.0467, T = 100 K.

CCDC no.: 1959640

Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Yellow prism
Size:0.21 × 0.11 × 0.08 mm
Wavelength:Cu Kα radiation (1.54184 Å)
μ:13.1 mm−1
Diffractometer, scan mode:XtaLAB Synergy, ω
θmax, completeness:67.1°, >99%
N(hkl)measured, N(hkl)unique, Rint:12357, 1960, 0.021
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 1949
N(param)refined:117
Programs:CrysAlisPRO [1], SHELX [2], [3], WinGX/ORTEP [4]
Table 2:

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

AtomxyzUiso*/Ueq
Cd0.2500000.26705(2)0.2500000.01170(7)
S10.13015(4)0.26199(5)0.03434(4)0.01404(11)
S20.43145(4)0.29672(6)0.17353(4)0.01542(11)
P10.29145(4)0.34260(6)0.03540(3)0.01227(11)
O10.29205(11)0.54937(16)0.01490(10)0.0155(3)
O20.30864(13)0.25480(16)−0.06730(12)0.0171(3)
N10.250000−0.0465(3)0.2500000.0126(4)
N20.2500000.5876(3)0.2500000.0125(4)
C10.19491(18)0.6268(3)−0.07831(16)0.0233(4)
H1A0.1167640.624213−0.0663640.028*
H1B0.1846060.559572−0.1453550.028*
C20.2302(2)0.8126(3)−0.0898(2)0.0410(6)
H2A0.1642030.870026−0.1490960.062*
H2B0.3047920.813320−0.1062680.062*
H2C0.2447620.876071−0.0215270.062*
C30.4168(2)0.3048(3)−0.09081(18)0.0272(5)
H3A0.4892420.309613−0.0222840.033*
H3B0.4046770.422576−0.1250740.033*
C40.4361(2)0.1723(3)−0.1658(2)0.0351(5)
H4A0.5080710.204600−0.1821050.053*
H4B0.3642450.168743−0.2335580.053*
H4C0.4487560.056297−0.1310730.053*
C50.15206(16)−0.1384(2)0.18873(14)0.0148(4)
H50.081034−0.0774280.1437380.018*
C60.15177(16)0.6792(2)0.18933(14)0.0150(4)
H60.0801410.6181750.1456370.018*

Source of material

The Cd[S2P(OEt)2]2 precursor was prepared in high yield from the in situ reaction of Cd(NO3)2⋅4 H2O (Acros Organics; 15.42 g, 0.05 mol), EtOH (Merck; 12.25 mL, 0.21 mol), P2S5 (Sigma-Aldrich; 11.11 g, 0.05 mol) and 50% w/w NaOH solution (Merck; 8.80 mL, 0.11 mol). The title compound was obtained by mixing a suspension of Cd[S2P(OEt)2]2 (0.50 g, 1.04 mmol), pyrazine (Merck, 0.09 g, 1.12 mmol) in dimethylformamide (Merck; 5 mL), followed by stirring for 30 min. at 373 K. The solution was filtered, the filtrate was dissolved in acetonitrile (Merck; 1 mL) and held in a sample vial. Yellow crystals formed after one day. Yield: 0.15 g, (25.6%, based on Cd[S2P(OEt)2]2). M.pt (MelTemp Melting Point Apparatus): 430.2–432.2 K. IR (Bruker Vertex 70 V equipped with Platinum ATR): 1160(w) ν(C—O); 1009(s) ν(P—O); 665(m) ν(P—S).

Experimental details

The C-bound H atoms were geometrically placed (C—H = 0.95–0.99 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C).

Comment

A recent review of the structural chemistry of the zinc-triad 1,1-dithiolates [e.g. dithiocarbamate (S2CNR2), xanthates (S2COR) and dithiophosphates (S2P(OR)2)] with bipyridyl-type ligands, revealed relatively few examples of structures featuring the simplest of all potentially bridging ligands of this class of molecule, namely pyrazine (pyr) [5]. For dithiocarbamates, two examples are known, i.e. binuclear {Zn[S2CN(CH2CH2OH)2]2}2(pyr), isolated in solvent-free form and as a dioxane solvate [6]. A sole example of a zinc(II) xanthate adduct is known, i.e. a linear coordination polymer [Zn(S2COEt)2(pyr)]n [7]. Similarly, there is only one dithiophosphate example, again with zinc(II), namely {Zn[S2P(O-iPr)2]2}2(pyr), i.e. binuclear [8]. In the absence of structural data for cadmium analogues, herein the crystal and molecular structures of {Cd[S2P(OEt)2]2(pyr)}n, (I), are described in continuation of long-held interest in this area [5], [9].

The immediate coordination geometry about the cadmium atom is illustrated in the figure (70% probability displacement ellipsoids). The cadmium(II) lies on a crystallographic 2-fold axis with the second dithiophosphate ligand related by the symmetry operation (i) 1/2 − x, y, 1/2 − z. The 2-fold axis bisects the pyrazine molecule with the N1 and N2 atoms lying on the axis (the remaining atoms for each residue shown in the figure are generated by translation, i.e. for the N1-pyrazine molecule, (ii) x, 1 + y, z and for the N2-pyrazine, (iii) x, −1 + y, z). The cadmium(II) centre is octahedrally coordinated within a trans-N2S4 donor set defined by two chelating dithiophosphate ligands and two pyrazine-nitrogen atoms. The Cd—S1 [2.6715(5) Å] and Cd—S2 [2.6889(4) Å] bond lengths differ by only 0.017 Å and this symmetric mode of coordination is reflected in the near equivalence of the P1—S1 [1.9924(6) Å] and P1—S2 [1.9881(6)] bond lengths. There are two independent Cd—N bond lengths, i.e. Cd—N1 [2.385(2) Å] and Cd—N2 [2.438(2) Å], and these are experimentally distinct. A noteworthy feature of the structure is the relative disposition of the dithiophosphate ligands. Often, these are co-planar in bipyridyl-type adducts of cadmium dithiophosphates [5]. However, in the present case, these are twisted as seen in the dihedral angle between the two CdS2 residues of 10.366(17)°.

The lower view of the figure highlights the extended one-dimensional coordination polymer which, from symmetry, is strictly linear and aligned along the b-axis direction. A linear coordination polymer was also noted in [Zn(S2COEt)2(pyr)]n [7]. The common feature of both the preceding structures is a trans-N2S4 donor set about the central metal atom. However, in an accompanying report [10], a cis-N2S4 donor set is found in the crystal of {Cd[S2P(O-iPr)2]2(pyr)}n, isolated as a di-acetonitrile solvate, with the result that the one-dimensional coordination polymer formed has a zig-zag topology [10].

In the crystal, the chains pack without directional interactions between them based on the criteria assumed in PLATON [11].

Acknowledgements

Sunway University Sdn Bhd is thanked for financial support of this work through Grant no. STR-RCTR-RCCM-001-2019.

References

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Received: 2019-09-03
Accepted: 2019-10-16
Published Online: 2019-11-06
Published in Print: 2020-02-25

©2019 Yee Seng Tan et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 Public License.

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  76. Crystal structure of 6-iodo-3-phenyl-2-propylquinazolin-4(3H)-one, C17H15IN2O
  77. Low temperature redetermination of the crystal structure of catena-poly[[tri-4-fluorobenzyltin(IV)]μ2-pyridine-4-carboxylato-κ2N:O], {C27H22F3NO2Sn}n
  78. Crystal structure of bis(2-propyl-1H-benzo[d]imidazol-3-ium) tetrachloridozincate(II), C10H13Cl4N2Zn
  79. The crystal structure of (Z)-3-hydrazono-5-nitroindolin-2-one – dimethyl sulfoxide (1/1), C8H6N4O3
  80. Crystal structure of bis-[N-(1-pyrazin-2-yl-ethylidene)-cyanoacetic acid-hydrazonato-κ3O,N,N′)]-zinc(II), C18H16N10O2Zn
  81. Crystal structure and photochromism of 1-(2,5-dimethyl-3-thienyl)-2-[2-methyl-5-(benzaldoxime)-3-thienyl] perfluorocyclopentene, C23H17F6NOS2
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