The crystal structure of the title compound, bis( -N,N-
dibutyldithiocarbamato- 2S:S0)bis[(N,N-dibutyldithiocarba\-
forcelb]mato- 2S,S0)zinc(II)], [Zn2(C9H18NS2)4], has
been determined at 180 K. The structure contains two
crystallographically unique Zn2+ metal centres, showing
almost identical slightly distorted tetrahedral coordination
environments, and forming a dinuclear complex with two
skew-bridging syn-N,N-dibutyldithiocarbamate ligands. Two
other dithiocarbamate ligands are connected to the Zn2+
centres in a syn,syn-chelate coordination mode

Klinowski, J

Neves, MC

Paz, FAA

Trindade, T

Acta Crystallographica Section E Structure Reports Online

English

Repositório Institucional da Universidade de Aveiro

Acta Cryst. (2003). E59, m1067±m1069 DOI: 10.1107/S160053680302419X Filipe A. Almeida Paz et al.  [Zn2(C9H18NS2)4] m1067metal-organic papersActa Crystallographica Section EStructure ReportsOnlineISSN 1600-5368The first dinuclear zinc(II) dithiocarbamatecomplex with butyl substituent groupsFilipe A. Almeida Paz,a Marcia C.Neves,b Tito Trindadeb and JacekKlinowskia*aDepartment of Chemistry, University ofCambridge, Lensfield Road, CambridgeCB2 1EW, England, and bDepartment ofChemistry, University of Aveiro, CICECO,3810-193 Aveiro, PortugalCorrespondence e-mail: jk18@cam.ac.ukKey indicatorsSingle-crystal X-ray studyT = 180 KMean (C±C) = 0.009 AÊDisorder in main residueR factor = 0.066wR factor = 0.196Data-to-parameter ratio = 27.2For details of how these key indicators wereautomatically derived from the article, seehttp://journals.iucr.org/e.# 2003 International Union of CrystallographyPrinted in Great Britain ± all rights reservedThe crystal structure of the title compound, bis(-N,N-dibutyldithiocarbamato-2S:S0)bis[(N,N-dibutyldithio-carba\-forcelb]mato-2S,S0)zinc(II)], [Zn2(C9H18NS2)4], hasbeen determined at 180 K. The structure contains twocrystallographically unique Zn2+ metal centres, showingalmost identical slightly distorted tetrahedral coordinationenvironments, and forming a dinuclear complex with twoskew-bridging syn-N,N-dibutyldithiocarbamate ligands. Twoother dithiocarbamate ligands are connected to the Zn2+centres in a syn,syn-chelate coordination mode.CommentMetal dithiocarbamate complexes have been known for a longtime, with the ®rst crystallographic result dating back 50 years,when Simonsen & Ho (1953) reported the space group andunit-cell parameters for the structure of the ethyl analogue ofthe title compound. There has been a recent renewal ofinterest in this type of compound, which can act as a molecularprecursor in the synthesis of novel metal sul®de nanomaterials(Trindade et al., 2001). Such compounds have been success-fully used as single-molecule precursors to prepare a widerange of nanocrystalline semiconductors, such as ZnS (Maliket al., 2001), CdS (Monteiro et al., 2002; Lazzel & O'Brien,1999; Trindade, O'Brien & Zhang, 1997), PbS (Trindade,O'Brien, Zhang & Motevalli, 1997) and Bi2S3 (Monteiro et al.,2001). ZnS, a technologically important material as a phosphorand as a white pigment, can be prepared from a well knownzinc(II) diethyldithiocarbamate complex [Zn2(C5H10NS2)4],the crystal structure of which has been extensively studied(Simonsen & Ho, 1953; Bonamico et al., 1965; Zvonkova et al.,1967; Tiekink, 2000). A search in the Cambridge StructuralDatabase (Allen, 2002) reveals that an analogous compoundcontaining methyl substituents, viz. [Zn2(C3H6NS2)4], hasReceived 20 October 2003Accepted 21 October 2003Online 31 October 2003metal-organic papersm1068 Filipe A. Almeida Paz et al.  [Zn2(C9H18NS2)4] Acta Cryst. (2003). E59, m1067±m1069been described (Klug, 1966; Ramalingam et al., 1998). Wereport here the ®rst crystal structure of a dinuclear zinc(II)dithiocarbamate complex with butyl substituent groups,[Zn2(C9H18NS2)4], (I).Compound (I) crystallizes in the monoclinic space groupP21/c, with one complete dinuclear [Zn2(C9H18NS2)4] complexmolecule in the asymmetric unit (Fig. 1). The crystal-lographically unique Zn2+ metal centres have approximatelyidentical distorted tetrahedral coordination environments(Table 1), and are bridged by two N,N-dibutyldithiocarbamateligands in a skew syn coordination fashion, imposing aZn1  Zn2 separation of 3.7141 (12) AÊ (Fig. 1). Each metalcentre is further connected to another organic ligand in asyn,syn-chelating coordination fashion. Molecules related bythe 21 screw axis close-pack in the bc plane to form layers(Fig. 2), which alternate in an ABAB . . . fashion along thea-axis direction (Fig. 3), leading to the complete crystalstructure of (I) (Fig. 4).ExperimentalAll chemicals were purchased from Aldrich and used without furtherpuri®cation. CS2 (4.13 mmol) was added to an ethanol suspension (ca50 ml) containing dibutylamine (C8H19N, 4.13 mmol) and freshlyprepared zinc(II) hydroxide [Zn(OH)2, 2.07 mmol], and the resultingmixture was stirred overnight at ambient temperature. A whiteprecipitate was isolated by vacuum ®ltration and was air-dried at333 K. Moderate-quality colourless crystals of the title compoundsuitable for X-ray diffraction were obtained by recrystallization fromCH2Cl2 over a period of 2 d.Figure 1The molecular structure of (I), with displacement ellipsoids drawn at the30% probability level, H atoms as small spheres, and the labelling schemefor all non-H atoms. Disordered H atoms on C17 have been omitted forclarity; atom C18 is disordered over two different positions.Figure 3Schematic representation of the alternation in an ABAB . . . fashionalong the a axis (due to the c-glide plane), of layers (in blue and orange)of [Zn2(C9H18NS2)4] molecules. H atoms have been omitted for clarity.Figure 4Perspective view of (I) along the a axis. H atoms have been omitted forclarity.Figure 2Perspective views, along the a (top) and b (bottom) axes, of the layers inthe bc plane, formed by the parallel stacking of [Zn2(C9H18NS2)4]molecules related by the 21 screw axis.Crystal data[Zn2(C9H18NS2)4]Mr = 948.20Monoclinic, P21=ca = 16.036 (3) AÊb = 16.604 (3) AÊc = 18.487 (4) AÊ = 95.10 (3)V = 4902.7 (17) AÊ 3Z = 4Dx = 1.285 Mg mÿ3Mo K radiationCell parameters from 22557re¯ections = 1.0±27.5 = 1.35 mmÿ1T = 180 (2) KBlock, colourless0.14  0.12  0.10 mmData collectionNonius KappaCCD diffractometerThin-slice ! and ’ scansAbsorption correction: multi-scan(SORTAV; Blessing, 1995)Tmin = 0.748, Tmax = 0.87730156 measured re¯ections11123 independent re¯ections7744 re¯ections with I > 2(I)Rint = 0.037max = 27.5h = ÿ20! 20k = ÿ20! 21l = ÿ18! 23Re®nementRe®nement on F 2R[F 2 > 2(F 2)] = 0.066wR(F 2) = 0.196S = 1.0411123 re¯ections409 parametersH-atom parameters constrainedw = 1/[2(Fo2) + (0.0737P)2+ 11.7125P]where P = (Fo2 + 2Fc2)/3(/)max < 0.001max = 1.64 e AÊÿ3min = ÿ0.86 e AÊ ÿ3Table 1Selected geometric parameters (AÊ , ).Zn1ÐS8 2.3164 (14)Zn1ÐS1 2.3468 (13)Zn1ÐS3 2.3659 (13)Zn1ÐS2 2.4365 (14)Zn2ÐS4 2.3118 (14)Zn2ÐS5 2.3406 (13)Zn2ÐS7 2.3660 (13)Zn2ÐS6 2.4390 (16)S1ÐC1 1.734 (5)S2ÐC1 1.719 (5)N1ÐC1 1.329 (5)S3ÐC10 1.755 (5)S4ÐC10 1.722 (5)N2ÐC10 1.316 (6)S5ÐC19 1.723 (5)S6ÐC19 1.723 (5)N3ÐC19 1.332 (6)S7ÐC28 1.747 (5)S8ÐC28 1.722 (4)N4ÐC28 1.320 (5)S8ÐZn1ÐS1 125.51 (5)S8ÐZn1ÐS3 112.59 (5)S1ÐZn1ÐS3 116.50 (5)S8ÐZn1ÐS2 110.67 (5)S1ÐZn1ÐS2 76.05 (5)S3ÐZn1ÐS2 107.05 (5)S4ÐZn2ÐS5 123.14 (5)S4ÐZn2ÐS7 112.71 (5)S5ÐZn2ÐS7 119.42 (5)S4ÐZn2ÐS6 109.85 (6)S5ÐZn2ÐS6 75.99 (5)S7ÐZn2ÐS6 106.59 (6)S2ÐC1ÐS1 117.2 (3)S4ÐC10ÐS3 118.4 (3)S6ÐC19ÐS5 117.3 (3)S8ÐC28ÐS7 118.6 (3)All H atoms were positioned geometrically and re®ned in theriding-model approximation, with Uiso(H) values ®xed at 1.2(methylene H atoms) or 1.5 (methyl H atoms) times Ueq of the parentatom. The alkyl chains were found to be severely affected bydisorder, with some C atoms showing extended ellipsoids whentreated with anisotropic displacement parameters. Attempts to modeldisorder for these alkyl chains resulted in a negligible improvement;the crystal used for data collection, the best from several batches, wasa very small block of only moderate quality. However, re®nement ofthe crystal structure with strong geometrical restraints for the alkylchains (approximately equal CÐC bond lengths and CÐCÐCangles), and common isotropic displacement parameters for some Catoms, resulted in a satisfactory solution. Disorder for atom C18 wassuccessfully modelled over two different positions (C18 and C180)with occupancy factors of 0.600 (13) and 0.400 (13), respectively. Thehighest peak in the ®nal difference map is located 0.09 AÊ from C36,and the deepest hole is 0.75 AÊ from S6.Data collection: COLLECT (Nonius, 1998); cell re®nement: HKLSCALEPACK (Otwinowski & Minor, 1997); data reduction: HKLDENZO (Otwinowski & Minor, 1997) and SCALEPACK;program(s) used to solve structure: SIR92 (Altomare et al., 1994);program(s) used to re®ne structure: SHELXTL (Bruker, 2001);molecular graphics: SHELXTL; software used to prepare materialfor publication: SHELXTL.We are grateful to the University of Aveiro (project No.3.64.33.7/NANOENG/CTS15) and the Portuguese Foundationfor Science and Technology (FCT) for ®nancial supportthrough PhD scholarship No. SFRH/BD/3024/2000 to FAAP.ReferencesAllen, F. H. (2002). Acta Cryst. B58, 380±388.Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C.,Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.Blessing, R. H. (1995). Acta Cryst. A51, 33±58.Bonamico, M., Mazzone, G., Vaciago, A. & Zambonelli, L. (1965). Acta Cryst.19, 898±909.Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison,Wisconsin, USA.Klug, H. P. (1966). Acta Cryst. 21, 536±546.Lazzel, M. & O'Brien, P. (1999). Chem. Commun. pp. 2041±2042.Malik, M. A., O'Brien, P. & Revaprasadu, N. (2001). J. Mater. Chem. 11, 2382±2386.Monteiro, O. C., Esteves, A. C. C. & Trindade, T. (2002). Chem. Mater. 14,2900±2904.Monteiro, O. C., Nogueira, H. I. S., Trindade, T. & Motevalli, M. (2001). Chem.Mater. 13, 2103±2111.Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,Macromolecular Crystallography, Part A, edited by C. W. Carter Jr andR. M. Sweet, pp. 307±326. New York: Academic Press.Ramalingam, K., bin Shawkataly, O., Fun, H.-K. & Razak, I. A. (1998). Z.Kristallogr. New Cryst. Struct. 213, 371±372.Simonsen, S. H. & Ho, J. W. (1953). Acta Cryst. 6, 430.Tiekink, E. R. T. (2000). Z. Kristallogr. New Cryst. Struct. 215, 445±446.Trindade, T., O'Brien, P. & Pickett, N. (2001). Chem. Mater. 13, 3843±3858.Trindade, T., O'Brien, P. & Zhang, X. (1997). Chem. Mater. 9, 523±530.Trindade, T., O'Brien, P., Zhang, X. & Motevalli, M. (1997). J. Mater. Chem. 7,1011±1016.Zvonkova, Z. V., Khvatkina, A. N. & Isanova, N. S. (1967). Kristallogra®ya(Russ.) (Crystallogr. Rep.), 12, 1065.Acta Cryst. (2003). E59, m1067±m1069 Filipe A. Almeida Paz et al.  [Zn2(C9H18NS2)4] m1069metal-organic papers

COLLECT. Nonius BV,

E59, m1067±m1069 Filipe A. Almeida Paz et al.

Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by

The first dinuclear zinc(II) dithiocarbarnate complex with butyl substituent groups

The first dinuclear zinc(II) dithiocarbarnate complex with butyl substituent groups

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