Abstract
 C34H54N8O2S8Zn2, monoclinic, C2/c (no. 15), a = 20.192(7) Å, b = 16.448(5) Å, c = 14.150(5) Å, β = 102.368(8)°, V = 4590(3) Å3, Z = 4, R
 gt(F) = 0.052, wR
 ref(F
 2) = 0.123, T = 98 K.</jats:p

Arman, Hadi D.

Poplaukhin, Pavel

Tiekink, Edward R. T. *

Hadi D. Arman

Pavel Poplaukhin

Edward R.T. Tiekink

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Zeitschrift für Kristallographie - New Crystal Structures

Crystal structure of (μ
 2-N,N′-bis((pyridin-4-yl)methyl)ethanediamide-κ2
 N:N′)-tetrakis(diethylcarbamodithioato-κ2
 S,S′)dizinc(II), C34H54N8O2S8Zn2

Sunway Institutional Repository

Z. Kristallogr. NCS 2018; 233(1): 159–161Hadi D. Arman, Pavel Poplaukhin and Edward R.T. Tiekink*Crystal structure of (µ2-N,N′-bis((pyridin-4-yl)methyl)ethanediamide-κ2N:N′)-tetrakis(diethylcarbamodithioato-κ2S,S′)dizinc(II),C34H54N8O2S8Zn2https://doi.org/10.1515/ncrs-2017-0297Received October 4, 2017; accepted November 3, 2017; availableonline November 21, 2017AbstractC34H54N8O2S8Zn2, monoclinic, C2/c (no. 15), a= 20.192(7) Å,b= 16.448(5) Å, c= 14.150(5) Å, β= 102.368(8)°,V = 4590(3) Å3, Z= 4, Rgt(F)=0.052, wRref(F2)=0.123,T= 98 K.CCDC no.: 1583785The molecular structure of the title compound is shown inthe figure. Tables 1 and 2 contain details of the measurementmethod and a list of the atoms including atomic coordinatesand displacement parameters.*Corresponding author: Edward R.T. Tiekink, Research Centre forCrystalline Materials, School of Science and Technology, SunwayUniversity, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia,e-mail: edwardt@sunway.edu.myHadi D. Arman: Department of Chemistry, The University of Texas atSan Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USAPavel Poplaukhin: Chemical Abstracts Service, 2540 OlentangyRiver Rd, Columbus, Ohio, 43202, USATable 1: Data collection and handling.Crystal: Colourless prismSize: 0.30×0.17×0.08 mmWavelength: Mo Kα radiation (0.71073 Å)μ: 14.5 cm−1Diffractometer, scan mode: AFC12K/SATURN724, ω scans2θmax, completeness: 55°,>99%N(hkl)measured, N(hkl)unique, Rint: 16452, 5264, 0.062Criterion for Iobs, N(hkl)gt: Iobs > 2 σ(Iobs), 4749N(param)refined: 251Programs: Rigaku programs [1, 2],SHELX [3, 4], ORTEP [5]Table 2: Fractional atomic coordinates and isotropic or equivalentisotropic displacement parameters (Å2).Atom x y z Uiso*/UeqZn 0.21031(2) 0.20249(2) 0.73375(3) 0.01958(11)O1 0.52122(12) 0.43816(14) 0.91005(18) 0.0298(5)S1 0.28223(4) 0.08693(5) 0.73415(6) 0.02308(18)S2 0.22879(5) 0.14223(5) 0.90076(6) 0.02747(19)S3 0.09406(4) 0.24463(5) 0.70649(6) 0.02297(17)S4 0.16676(4) 0.20584(5) 0.55226(6) 0.02545(19)N1 0.30869(13) 0.01153(15) 0.90478(19) 0.0208(5)N2 0.03936(13) 0.26094(15) 0.51813(19) 0.0210(5)N3 0.27190(13) 0.30336(15) 0.75524(19) 0.0191(5)N4 0.43457(14) 0.52858(16) 0.8992(2) 0.0236(6)H4N 0.4174(18) 0.5658(17) 0.931(2) 0.028*C1 0.27747(16) 0.07369(18) 0.8533(2) 0.0215(6)C2 0.30565(17) −0.00001(19) 1.0066(2) 0.0247(7)H2A 0.3110 −0.0586 1.0227 0.030*H2B 0.2605 0.0172 1.0158 0.030*C3 0.3597(2) 0.0473(2) 1.0755(3) 0.0343(8)H3A 0.4046 0.0304 1.0670 0.051*H3B 0.3558 0.0367 1.1422 0.051*H3C 0.3536 0.1056 1.0617 0.051*C4 0.34887(17) −0.04722(19) 0.8627(3) 0.0255(7)H4A 0.3256 −0.0580 0.7949 0.031*H4B 0.3508 −0.0991 0.8988 0.031*C5 0.42110(18) −0.0190(2) 0.8643(3) 0.0327(8)H5A 0.4199 0.0350 0.8347 0.049*H5B 0.4430 −0.0576 0.8279 0.049*H5C 0.4468 −0.0163 0.9314 0.049*C6 0.09407(16) 0.23985(17) 0.5843(2) 0.0205(6)C7 −0.02380(17) 0.2883(2) 0.5439(3) 0.0273(7)H7A −0.0466 0.3284 0.4956 0.033*H7B −0.0130 0.3155 0.6078 0.033*C8 −0.0714(2) 0.2176(2) 0.5477(3) 0.0378(9)Open Access. ©2017 Hadi D. Arman et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.UnauthenticatedDownload Date | 2/8/18 10:08 AM160 | Arman et al.: C34H54N8O2S8Zn2Table 2 (continued)Atom x y z Uiso*/UeqH8A −0.0782 0.1870 0.4869 0.057*H8B −0.1151 0.2383 0.5567 0.057*H8C −0.0517 0.1818 0.6018 0.057*C9 0.03756(17) 0.2543(2) 0.4136(2) 0.0257(7)H9A −0.0096 0.2441 0.3785 0.031*H9B 0.0656 0.2075 0.4021 0.031*C10 0.0637(2) 0.3312(2) 0.3743(3) 0.0338(8)H10A 0.0366 0.3778 0.3869 0.051*H10B 0.0602 0.3255 0.3045 0.051*H10C 0.1113 0.3397 0.4064 0.051*C11 0.28589(16) 0.34213(19) 0.8404(2) 0.0225(6)H11 0.2660 0.3229 0.8913 0.027*C12 0.32830(16) 0.40935(19) 0.8573(2) 0.0220(6)H12 0.3364 0.4357 0.9184 0.026*C13 0.35884(15) 0.43817(18) 0.7848(2) 0.0203(6)C14 0.34439(17) 0.39753(19) 0.6969(2) 0.0233(6)H14 0.3640 0.4153 0.6451 0.028*C15 0.30149(17) 0.3313(2) 0.6848(2) 0.0244(7)H15 0.2924 0.3041 0.6241 0.029*C16 0.40502(17) 0.51158(18) 0.7985(2) 0.0238(6)H16A 0.4419 0.5025 0.7635 0.029*H16B 0.3789 0.5596 0.7694 0.029*C17 0.48952(16) 0.48855(18) 0.9465(2) 0.0221(6)Source of materialsThe compound was isolated from the 2:1 reaction ofZn(S2CNEt2)2 and (4-NC5H4)CH2N(H)C(=O)—C(=O)N(H)CH2-(C5H4N-4) following standard procedures [6, 7]. Colourlesscrystals were obtained by the diffusion of ethyl ether into adimethylformamide solution of the compound.M.p.:>553 Kbut, turns opaque at 513 K. IR (cm−1): ν(C–S) 1065 (s, sh),ν(C–N) 1484 (s).Experimental detailsThe C-bound H atoms were geometrically placed (C—H=0.95−0.99 Å) and refined as riding with U iso(H)= 1.2–1.5Ueq(C). The N-bound H-atoms were located in differenceFourier maps, and refined with a distance restraint of N—H=0.88(1) Å, and with U iso(H) set to 1.2Ueq(N). Owing topoor agreement, two low order reflections, i.e. (2 0 0) and(−1 1 1), were omitted from the final cycles of refinement. Themaximum and minimum residual electron density peaks of0.48 and 1.02 e Å−3, respectively, were located 1.37 and 0.81 Åfrom the Zn atom.CommentThe isomeric molecules of general formula (n-NC5H4)CH2N(H)C(=O)—C(=O)N(H)CH2-(C5H4N-n), for n= 2, 3 and4, abbreviated as nLH2, are bifunctional in the sense that theycontain a central di-amidemoiety aswell as pyridyl-N donors.With metals, the situation may be envisaged whereby thepyridyl-N atoms bridge metal centres and the diamide formssupramolecular tapes via amide-N—H· · · O(amide) hydrogenbonding. As a continuation of investigations coordinatingnLH2 with zinc dithiocarbamates, i.e. Zn(S2CNRR′)2 for R,R′= alkyl [6, 7], the title compound, [Zn[S2CNEt2]2}24LH2,was studied.The binuclear complex is disposed about a centreof inversion with the unlabelled atoms in the Figurerelated by the symmetry operation 1 − x, 1 − y, 2 − z.The Zn atom is coordinated by two dithiocarbamate ligandsforming Zn–S bonds that span the relatively narrow range2.3913(10) to 2.5306(12) Å, and the pyridyl-N atom. Theresulting NS4 coordination approximates a square pyramid,with the N atom in the apical position, as judged by thevalue of τ=0.20, cf. τ=0.0 for an ideal square pyramidand 1.0 for an ideal trigonal bipyramid [8]. In theserespects, the structure resembles literature precedents[6, 7]. Interestingly, the molecular packing does not featureconventional hydrogen bonding interactions. Instead, thethree-dimensional architecture features methylene-C—H· · · O(amide) and pyridyl-C–H· · · S interactions. This obser-vation contradicts binuclear {Zn[S2CN(Me)CH2CH2OH]2}23LH2[6], where supramolecular chains were formed as a result ofhydroxy-O—H· · · (hydroxy) hydrogen bonding. The diamidefuctionality come into play to connect centrosymmetricallyrelated chains into double chains via hydroxy-O—H· · · O(amide) hydrogen bonding. The situation changed somewhatwhen the dithiocarbamate ligand carry residues incapable offorming hydrogen bonding interactions. Thus, in binuclear{Zn[S2CN(n-Pr)2]2}23LH2 the diamide groups form amide-N—H· · · O(amide) hydrogen bonds to form supramoleculartapes [7].Acknowledgements: Sunway University is thanked for sup-port of biological and crystal engineering studies of metaldithiocarbamates.References1. Higashi, T.: ABSCOR. Rigaku Corporation, Tokyo, Japan (1995).2. Rigaku/MSC Inc.: CrystalClear. Rigaku Corporation, TheWoodlands, TX, USA (2005).3. Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64(2008) 112–122.4. Sheldrick, G. M.: Crystal structure refinement with SHELXL.Acta Crystallogr. C71 (2015) 3–8.5. Farrugia, L. J.: WinGX and ORTEP for Windows: an update. J. Appl.Cryst. 45 (2012) 849–854.6. Poplaukhin, P.; Tiekink, E. R. T.: Interwoven coordinationpolymers sustained by tautomeric forms of the bridging ligand.CrystEngComm 12 (2010) 1302–1306.UnauthenticatedDownload Date | 2/8/18 10:08 AMArman et al.: C34H54N8O2S8Zn2 | 1617. Arman, H. D.; Poplaukhin, P.; Tiekink, E. R. T.: Crystalstructures of (μ2-N,N′-bis((pyridin-3-yl)methyl)ethanediamide)-tetrakis(dimethylcarbamodithioato)-di-zinc(II) dimethyl-formamide disolvate and (μ2-N,N′-bis((pyridin-3-yl)methyl)ethanediamide)-tetrakis(di-n-propylcarbamodithioato)-di-zinc(II). Acta Crystallogr. C73 (2017) 1501–1507.8. Addison, A. W.; Rao, T. N.; Reedijk, J.; van Rijn, J.;Verschoor, G. C.: Synthesis, structure, and spectroscopicproperties of copper(II) compounds containing nitrogen–sulphurdonor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II)perchlorate. J. Chem. Soc. Dalton Trans. 264 (1984) 1349–1356.UnauthenticatedDownload Date | 2/8/18 10:08 AM

Crystal structure of (μ2-N,N′-bis((pyridin-4-yl)methyl)ethanediamide-κ2N:N′)-tetrakis(diethylcarbamodithioato-κ2S,S′)dizinc(II), C34H54N8O2S8Zn2

http://eprints.sunway.edu.my/756/1/Tiekink%20Crystal%20structure%20of%20%28u2-N%2C%20N%27%20%20%20%20.pdf

Crystal structure of (μ2-N,N′-bis((pyridin-4-yl)methyl)ethanediamide-κ2N:N′)-tetrakis(diethylcarbamodithioato-κ2S,S′)dizinc(II), C34H54N8O2S8Zn2

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