Crystal structure of

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(4-1-naphth-1-yl-2,3-diaza-1,3,5-heptatriene-1,6-diolato)copper(II). Acta. Crystallogr. C47 (1991) 714-716. 7. Affan, M. A.; Mustaffa, B.; Shamsuddin, M.; Sukeri, ...
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Z. Kristallogr. NCS 222 (2007) 251-252 / DOI 10.1524/ncrs.2007.0105

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Crystal structure of (isothiocyanato)(2-pyridinecarboxaldehydebenzoylhydrazonato)copper(I), Cu(C13H10N3O)(NCS) Chrysostomos BatistakisI, Yu GanII, Christine J. CardinII, Damianos G. PaschalidisIII and Constantinos A. Kavounis*,I I II III

Aristoteles University of Thessaloniki, School of Science, Physics Department, 54124 Thessaloniki, Greece School of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK Aristoteles University of Thessaloniki, Chemistry Department, 54124 Thessaloniki, Greece

Received March 19, 2007, accepted and available on-line September 25, 2007; CCDC no. 1267/2026

Abstract C14H10CuN4OS, monoclinic, P121/n1 (no. 14), a = 8.837(1) Å, b = 15.625(2) Å, c = 10.366(1) Å, 1 = 103.36(1)°, V = 1392.6 Å3, Z = 4, Rgt(F) = 0.029, wRref(F2) = 0.076, T = 150 K. Source of material Single crystals of copper complex were prepared by placing a 0.5 M solution of copper(I) chloride and 1 M ammonium thiocyanate in one arm of a narrow U-tube and an ethanolic 0.5 M solution of picolinaldehyde benzoylhydrazone and 0.5 M tetrabutylammonium hydroxide in the other arm. Suitable crystals with well formed faces appeared after a few days in the middle zone of one arm of the U-tube. _____________

Discussion In recent years, the research on supramolecular complexes has been rapidly expanding [1]. One aspect is their fascinating structural diversity. Another aspect is their potential application as functional materials in catalysis and magnetism. As part of our work on hydrazone complexes we report here the crystal structure of a new copper-hydrazone supramolecular derivative. The main structural feature is the presence of an NCS—Cu bridge that connects the crystallographic asymmetric unit to its adjacent forming continuous chains. This is caused by the bidentate ligand NCS which is N-bonded to the metal ion. The copper ion is fivecoordinated in a distorted tetragonal pyramidal arrangement. The Cu environment involves three nitrogen atoms and an oxygen atom at the base and a sulfur atom in apical position. Four of the atoms of the base of the pyramid namely the O, Cu, N2 and N3 form a least-squares plane from which the N4 deviates by 0.599(3) Å and the S atom is in the apex at a distance of 2.847(1) Å. If we consider the plane formed by the four atoms N2, N3, N4 and O then the Cu atom deviates from their plane by 0.2075(8) Å towards the apex. The two five-membered rings involving Cu (Cu, O, C7, N1, N2 and Cu, N3, C9, C8, N2) form a dihedral angle of 2.44° and the latter of these form a dihedral angle of 1.10° with the pyridine ring to which is attached. The sixmembered ring formed by the atoms C1, C2, C3, C4, C5 and C6 forms a dihedral angle of 3.31° with the best plane through the other three rings. The whole hydrazone molecule forms a leastsquares plane with an r.m.s. deviation of the fitted atoms of 0.0398 Å, from which the N4 atom deviates by 0.697(2) Å and the S atom is 2.800(1) Å away. All the bond lengths of the two fivemembered rings lie in the middle of the range observed in a number of pentacoordinated copper(II) complexes [2-6] while the apical distance (Cu—S) of 2.84 Å is quite longer than previous values as usually found for bonds in apical positions. The complex is in the enolic form (–C=N–N=), which is also confirmed by the bond lengths of C7—O of 1.28 Å and C7—N1 of 1.33 Å [7]. Table 1. Data collection and handling. Crystal: Wavelength: %: Diffractometer, scan mode: 2'max: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs:

* Correspondence author (e-mail: [email protected])

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black block, size 0.30 × 0.50 × 1.20 mm Mo K0 radiation (0.70930 Å) 17.21 cm−1 Oxford Diffraction Xcalibur, )/# 56.46° 8755, 3048 Iobs > 2 ((Iobs), 2392 230 SHELXS-97 [8], SHELXL-97 [9], PLATON [10]

252

Cu(C13H10N3O)(NCS)

Table 2. Atomic coordinates and displacement parameters (in Å2).

Table 2. Continued.

Atom

Site

x

H(10) H(12) H(5) H(3) H(11)

4e 4e 4e 4e 4e

0.739(2) 0.873(2) 0.045(2) 0.106(2) 0.877(3)

y 0.324(1) 0.463(1) −0.121(2) −0.150(1) 0.437(2)

z

Uiso

Atom

Site

0.273(2) 0.612(2) 0.650(2) 0.273(2) 0.396(3)

0.002(5) 0.016(6) 0.024(6) 0.010(5) 0.028(7)

H(13) H(4) H(8) H(6) H(2)

4e 4e 4e 4e 4e

x

y

0.725(2) −0.001(3) 0.563(3) 0.209(2) 0.270(2)

0.367(1) −0.186(2) 0.190(2) −0.007(1) −0.030(1)

z

Uiso

0.704(2) 0.444(3) 0.280(3) 0.674(2) 0.302(2)

0.013(6) 0.032(8) 0.021(6) 0.009(5) 0.019(6)

Table 3. Atomic coordinates and displacement parameters (in Å2). Atom

Site

x

Cu S N(1) N(2) N(3) N(4) O C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14)

4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e

0.52533(3) 0.26970(6) 0.4073(2) 0.4965(2) 0.6532(2) 0.6105(2) 0.3961(2) 0.2560(2) 0.2225(2) 0.1224(2) 0.0566(2) 0.0912(2) 0.1899(2) 0.3596(2) 0.5676(2) 0.6580(2) 0.7427(2) 0.8253(3) 0.8189(3) 0.7312(3) 0.1788(2)

y 0.20743(2) 0.32239(4) 0.0961(1) 0.1675(1) 0.2953(1) 0.2201(1) 0.10495(9) −0.0064(1) −0.0495(1) −0.1188(1) −0.1463(1) −0.1046(1) −0.0349(1) 0.0697(1) 0.2065(1) 0.2809(1) 0.3325(1) 0.4007(2) 0.4158(2) 0.3614(1) 0.2973(1)

z

U11

U22

U33

0.62485(2) 0.57258(5) 0.4095(2) 0.4455(2) 0.5560(2) 0.8140(2) 0.6307(1) 0.4960(2) 0.3747(2) 0.3553(2) 0.4580(2) 0.5785(2) 0.5982(2) 0.5160(2) 0.3680(2) 0.4272(2) 0.3618(2) 0.4301(2) 0.5605(2) 0.6195(2) 0.4205(2)

0.0186(2) 0.0192(3) 0.0148(8) 0.0138(9) 0.0155(9) 0.0199(9) 0.0185(7) 0.013(1) 0.015(1) 0.016(1) 0.014(1) 0.015(1) 0.018(1) 0.012(1) 0.016(1) 0.013(1) 0.017(1) 0.020(1) 0.023(1) 0.021(1) 0.015(1)

0.0150(2) 0.0212(3) 0.0111(8) 0.0113(8) 0.0139(8) 0.019(1) 0.0142(7) 0.012(1) 0.017(1) 0.017(1) 0.013(1) 0.019(1) 0.016(1) 0.012(1) 0.016(1) 0.015(1) 0.020(1) 0.023(1) 0.021(1) 0.021(1) 0.013(1)

0.0107(2) 0.0153(3) 0.0151(9) 0.0135(9) 0.0126(9) 0.013(1) 0.0131(7) 0.017(1) 0.018(1) 0.020(1) 0.030(1) 0.022(1) 0.015(1) 0.015(1) 0.010(1) 0.013(1) 0.013(1) 0.022(1) 0.022(1) 0.015(1) 0.018(1)

U12 −0.0039(1) 0.0002(2) −0.0027(7) 0.0010(7) −0.0004(7) −0.0032(7) −0.0029(6) 0.0021(8) 0.0020(8) 0.0003(8) −0.0034(9) 0.0001(9) 0.0033(8) 0.0039(8) 0.0036(8) 0.0027(8) 0.0004(9) −0.0045(9) −0.0081(9) −0.0039(9) 0.0027(8)

U13 0.0042(1) 0.0022(2) 0.0018(7) 0.0023(7) 0.0027(7) 0.0041(8) 0.0054(6) 0.0019(9) 0.0026(9) −0.0009(9) 0.001(1) 0.0050(9) 0.0029(9) 0.0008(9) 0.0016(8) 0.0003(8) 0.0035(9) 0.006(1) 0.002(1) 0.0043(9) 0.0073(9)

U23 −0.0016(1) −0.0036(2) −0.0013(7) 0.0001(7) −0.0006(7) −0.0009(8) −0.0017(6) 0.0035(9) 0.0025(9) −0.0031(9) 0.001(1) 0.007(1) −0.0007(9) 0.0007(9) 0.0015(9) 0.0012(8) 0.0019(9) 0.006(1) −0.003(1) −0.003(1) 0.0033(9)

References 1. Ratten, S. R.; Robson, R.: Interpenetrating Nets: Ordered, Periodic Entanglement. Angew. Chem., Int. Ed. 37 (1998) 1460. 2. Mangia, A.; Nardelli, M.; Pelizzi, C.; Pelizzi, G.: Structural researches on metal complexes of polydentate ligands containing carbonyl and -diimine moieties. I. Crystal structure of dichloro-2-(2*-pyridyl)-3-(N-2-picolylimino)-4-oxo-l,2,3,4-tetrahydroquinazolinecopper(II). Acta Crystallogr. B30 (1974) 17-22. 3. Mangia A.; Nardelli M.; Pelizzi, G.: Structural researches on metal complexes of polydentate ligands containing carbonyl and -diimine moieties. II. Crystal structure of dithiocyanato-(S,N)-diisothiocyanatobis[2-(2*pyridyl)-3-(N-2-picolylimino)-4-oxo-1,2,3,4-tetrahydroquinazoline]dicobalt(II). Acta Crystallogr. B30 (1974) 487-491. 4. Mangia A.; Pelizzi, C.; Pelizzi, G.: Structural Researches on Metal Complexes of Polydentate Ligands containing Carbonyl and 0-Diimine Moieties. III. Crystal Structure and Spectroscopic Properties Bis{dichloro[2,6-diacetylpyridine-bis(picolinoylhydrazonato)]dicopper(II)} dihydrate. Acta Crystallogr. B30 (1974) 2146-2150.

5. Lee, T.-J.; Lee, T.-Y.; Chung, C.-S.; Wang, Y.-M.: Structure of (Isothiocyanato)[3,3,9,9-tetramethyl-4,8-diazaundecane-2,10-dionedioximato(1–)]copper(II) monohydrate. Acta Crystallogr. C47 (1991) 711-714. 6. Fazilic, R.; Divjakovic, V.; Leovak, Y.; Chundak, S.: Transition-Metal Complexes with Hydrazides and Hydrazones. II. The Structure of Aqua(4-1-naphth-1-yl-2,3-diaza-1,3,5-heptatriene-1,6-diolato)copper(II). Acta Crystallogr. C47 (1991) 714-716. 7. Affan, M. A.; Mustaffa, B.; Shamsuddin, M.; Sukeri, M. Y.; Bohari, M. Y.: Dichloromethyl[1-(2-pyridyl)ethanone-benzoylhydrazonato]tin(IV). Acta Crystallogr. E60 (2004) m126-m128. 8. Sheldrick, G. M.: SHELXS-97. Program for the solution of Crystal Structures. University of Göttingen, Germany 1997. 9. Sheldrick, G. M.: SHELXL-97. Program for the Refinement of Crystal Structures. University of Göttingen, Germany 1997. 10. Spek, A. L.: PLATON. A Multipurpose Crystallographic Tool. University of Utrecht, The Netherlands 2004.

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