Structure determination of nitrato‐κO‐bis[2‐(2‐pyridyl‐κN)amino‐5,6‐dihydro‐4H‐1,3‐thiazine‐κN]copper(II) nitrate via molecular modelling coupled with X‐ray powder diffractometry

The title copper(II) coordination compound, C 18 H 22 CuN 8 O 6 S 2 {[Cu(NO 3 )-(PyTz) 2 ]NO 3 }, was synthesized in the form of small crystals unsuitable for structure determination by single-crystal X-ray diffractometry. It was therefore characterized by molecular modelling coupled with X-ray powder diffractometry [monoclinic, space group P2 1 /n, a = 20.695 (7) A. b = 8.054 (2) A, c = 15.157 (4) A, β=112.09 (2) and R wp = 0.129]. The procedure used to resolve the structure followed direct space methods with a 'Monte Carlo/parallel tempering' search algorithm, where the starting configuration was obtained by means of molecular mechanics. A final refinement was performed with the Rietveld method. Bond distances, bond angles and torsion angles were compared with those of similar compounds deposited in the Cambridge Structural Database.

[1]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[2]  R. Lord,et al.  The Vibrational Spectra of Pyridine and Pyridine‐d5 , 1953 .

[3]  G. L. Cook,et al.  Correlations of the infrared spectra of some pyridines , 1957 .

[4]  A. Meyers.  An Infrared Examination of the C=N Link in Dihydro-1,3-oxazines and Dihydro-1,3-thiazines1 , 1961 .

[5]  B. S. Ramaswamy,et al.  Infrared Combination Frequencies in Coordination Complexes containing Nitrate Groups in various Coordination Environments. A Probe for the Metal–Nitrate Interaction , 1971 .

[6]  D. Cremer,et al.  General definition of ring puckering coordinates , 1975 .

[7]  Norman L. Allinger,et al.  Conformational analysis. 130. MM2. A hydrocarbon force field utilizing V1 and V2 torsional terms , 1977 .

[8]  A. Korolkovas,et al.  Compendio esencial de química farmaceútica , 1978 .

[9]  K. Nakamoto.  Infrared and Raman Spectra of Inorganic and Coordination Compounds , 1978 .

[10]  Far-infrared and raman spectral assignments for 1:1 complexes of metal dihalides with unidentate ligands. Double-strand halogen-bridged chain structures of MX2(pyridine) polymers , 1979 .

[11]  Joseph L. Walter,et al.  The Infrared Spectra of Complex Molecules , 1982 .

[12]  I. Brown,et al.  A real‐space computer‐based symmetry algebra , 1987 .

[13]  W. Pritzkow,et al.  POSIT – a method for structure determination of small partially known molecules from powder diffraction data.Structure of 6-methyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (6-methyluracil) , 1988 .

[14]  Colin Eaborn,et al.  Comprehensive Coordination Chemistry , 1988 .

[15]  J. M. Newsam,et al.  Determination of 4-connected framework crystal structures by simulated annealing , 1989, Nature.

[16]  D. A. Thornton.  Metal complexes of pyridine: infrared and raman spectra with particular reference to isotopic labelling studies , 1990 .

[17]  S. Haddad,et al.  Polymerized isomers of CuCl2(C8H12N2S2). The X-ray crystal structures of dichloro(5,5′-6,6′-tetrahydro-2,2′-bi-4H-1,3-thiazine-N3, N3′)copper(II) and di-μ-chloro-bis[chloro(5,5′-6,6′-tetrahydro-2, 2′-bi-4H-1,3-thiazine-N3,N3′)copper(II)] , 1993 .

[18]  R. Bergeron,et al.  The desferrithiocin pharmacophore. , 1994, Journal of medicinal chemistry.

[19]  Kenneth D. M. Harris,et al.  CRYSTAL STRUCTURE DETERMINATION FROM POWDER DIFFRACTION DATA BY MONTE CARLO METHODS , 1994 .

[20]  G. Chiou,et al.  Prevention and treatment of ocular inflammation with a new class of non-steroidal anti-inflammatory agents. , 1994, Journal of ocular pharmacology.

[21]  M. Nardelli,et al.  PARST95 – an update to PARST: a system of Fortran routines for calculating molecular structure parameters from the results of crystal structure analyses , 1995 .

[22]  P. Sohár,et al.  Synthesis and pharmacological study of new 3,4-dihydro-2H,6H-pyrimido-[2,1-b][1,3]thiazines , 1996 .

[23]  K. Harris,et al.  The application of a genetic algorithm for solving crystal structures from powder diffraction data , 1997 .

[24]  Roy L. Johnston,et al.  The genetic algorithm : Foundations and applications in structure solution from powder diffraction data , 1998 .

[25]  Louis J. Farrugia,et al.  WinGX suite for small-molecule single-crystal crystallography , 1999 .

[26]  D. Kyriakidis,et al.  Antiproliferative activity of mixed-ligand dien-Cu(II) complexes with thiazole, thiazoline and imidazole derivatives. , 2002, Journal of inorganic biochemistry.

[27]  E. Yeşilada,et al.  Synthesis of some 1,2,4-triazolo[3,2-b]-1,3-thiazine-7-ones with potential analgesic and antiinflammatory activities. , 2002, Farmaco.

[28]  V. Favre-Nicolin,et al.  FOX, `free objects for crystallography': a modular approach to ab initio structure determination from powder diffraction , 2002 .

[29]  W. Xu,et al.  Ab initio structure determination of rofecoxib from powder diffraction data using molecular packing analysis method and direct space method. , 2003, International journal of pharmaceutics.

[30]  Bernard Viossat,et al.  Low-temperature (180 K) crystal structure, electron paramagnetic resonance spectroscopy, and propitious anticonvulsant activities of CuII2(aspirinate)4(DMF)2 and other CuII2(aspirinate)4 chelates. , 2003, Journal of inorganic biochemistry.

[31]  R. Peschar,et al.  A Monte Carlo approach to crystal structure determination from powder diffraction data , 2003 .

[32]  C. Giacovazzo,et al.  Solution of organic crystal structures from powder diffraction by combining simulated annealing and direct methods , 2003 .

[33]  F. Sánchez-Bajo,et al.  Ab initio structural determination of 2-(2-pyridyl)imino-N-(2-thiazolin-2-yl)thiazolidine from powder diffraction data , 2004 .

[34]  A. Dzyabchenko,et al.  Ab initio structure determination of m-toluidine by powder X-ray diffraction , 2004 .

[35]  Thomas J. Meyer,et al.  Comprehensive Coordination Chemistry II , 2004 .

[36]  F. Luna-Giles,et al.  Synthesis and physic-chemical properties of a copper(II) complex with 2-(2-pyridyl)iminotetrahydro-1,3-thiazine hydrochloride-water (1/2) (PyTzHCl.2H2O). Crystal structure of PyTz and [[CuCl(PyTz)]2(mu-Cl)2]. , 2004, Journal of inorganic biochemistry.