Syntheses, spectroscopic characterization and crystal structures of some new phosphoramidates and an organotin(IV) complex of N-(4-fluorobenzoyl)-N 0 ,N 00 -bis(piperidinyl)phosphoric triamide Khodayar Gholivand * , Zahra Shariatinia, Mehrdad Pourayoubi Department of Chemistry, Tarbiat Modarres University, Gisha Bridge, P.O. Box 14115-175, Tehran, Iran Received 18 June 2005; accepted 25 July 2005 Available online 30 August 2005 Abstract Some new phosphoramidates with formula 4-F-C 6 H 4 C(O)N(H)P(O)X 2 , X = NC 4 H 8 (1), NC 5 H 10 (2), 4-CH 3 -NC 5 H 9 (3), NC 4 H 8 O(4), NC 6 H 12 (5), N(CH 2 CH 3 ) 2 (6), N(CH 2 CH 2 CH 3 ) 2 (7) were synthesized. The reaction of compound 2 with dimethyl- tin(IV) dichloride leads to an octahedral organotin(IV) complex, SnCl 2 (CH 3 ) 2 [4-F-C 6 H 4 C(O)N(H)P(O)(NC 5 H 10 ) 2 ] 2 (8) with equal ligands in trans positions. These compounds were characterized by IR, 1 H, 13 C, 31 P, 119 Sn NMR, mass spectroscopy and elemental analysis. The structures have been determined for compounds 1, 2, 4, 5 and 8. Compound 2 exists as four symmetrically independent molecules in the crystalline lattice. Compounds 1, 4 and 5 form dimmers via intermolecular –P@OH–N– hydrogen bonds that in 1 is centrosymmetric. In compound 2, two dimmers were formed; each of them was produced between two adjacent independent mol- ecules. In compounds 1, 2, 3, 4 and 8, containing five- and six-membered ring amine groups, 3 J(P,C aliphatic )> 2 J(P,C aliphatic ). Com- pound 5 with seven-membered ring amine, similar to compounds 6 and 7 with acyclic aliphatic amines, shows that 2 J(P,C aliphatic )> 3 J(P,C aliphatic ). Mass spectra of these compounds indicate the 4-F-C 6 H 4 CO + and 4-F-C 6 H 4 CN + fragments. Ó 2005 Elsevier Ltd. All rights reserved. Keywords: X-ray crystallography; NMR spectroscopy; Phosphoramidate; Organotin(IV) complex 1. Introduction The chemistry of phosphoramidates is recently devel- oped due to the biological activity [1–3] and also the coordination chemistry [4–6] of these compounds. Some of them with RCðOÞNðHÞPðOÞR 1 2 formula were used as O,O 0 -donor ligands for metal ions, particularly for rare earth metal cations [7,8]. Although the crystal structures of several phosphoramidates and their complexes are al- ready known [4–6,9–12], there are little discussions about the substituent effects on the structural and NMR parameters. Among coordination compounds, the organometallic compounds of tin(IV) are very important antitumor agents [13,14]. Organotin(IV) com- pounds have been extensively used as wood preserva- tives, agrochemical fungicides and biocides [15,16]. The coordination compounds of organotin(IV) are a matter of interest in recent researches [17–20]. In our previous studies, we obtained some structures with two conformers in the lattice [21–23]. Cain et al. reported the crystal structure of compound {(5R,4S)-N-Pr-ephed- rine}P(S)[NH(Si)(CH 3 ) 3 ] that has three independent molecules in the unit cell [24]. The first phosphoramidate with four crystallographically independent molecules in the crystalline network was C 6 H 5 C(O)N(H)P(O)- (NC 5 H 10 ) 2 [25] and in this work we report its analo- gous compound 4-F-C 6 H 4 C(O)N(H)P(O)(NC 5 H 10 ) 2 (2). There are several articles that have been discussed 0277-5387/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2005.07.035 * Corresponding author. Tel. +98 21 8011001x3443; fax: +98 21 8006544. E-mail address: gholi_kh@modares.ac.ir (K. Gholivand). www.elsevier.com/locate/poly Polyhedron 25 (2006) 711–721