The hydrogen-bonded dimers ofN,N′,N′′-tricyclohexylphosphoric triamide in new tin(IV) and copper(II) complexes

Abstract

In the new tin(IV) and copper(II) complexes, cis-dichlorido-trans-dimethyl-cis-bis(N,N',N''-tricyclohexylphosphoric triamide-κO)tin(IV), [Sn(CH(3))(2)Cl(2)(C(18)H(36)N(3)OP)(2)], (I), and trans-diaquabis(N,N',N''-tricyclohexylphosphoric triamide-κO)copper(II) dinitrate-N,N',N''-tricyclohexylphosphoric triamide (1/2), [Cu(C(18)H(36)N(3)OP)(2)(H(2)O)(2)](NO(3))(2)·2C(18)H(36)N(3)OP, (II), the N,N',N''-tricyclohexylphosphoric triamide (PTA) ligands exist as hydrogen-bonded dimers via P=O···H-N interactions around the metal center. The asymmetric unit in (I) consists of one complete complex molecule located on a general position. The Sn(IV) coordination geometry is octahedral with two cis hydrogen-bonded PTA ligands, two cis chloride ligands and two trans methyl groups. The asymmetric unit in (II) contains one half of a [Cu(PTA)(2)(H(2)O)(2)](2+) dication on a special position (site symmetry ̅1 for the Cu atom), one nitrate anion and one free PTA molecule, both on general positions. The complex adopts a square-planar trans-[CuO(2)O(2)] coordination geometry, with the Cu(II) ion coordinated by two PTA ligands and two water molecules. Each of the noncoordinated PTA molecules is hydrogen bonded to a neighboring coordinated PTA molecule and an adjacent water molecule; the phosphoryl O atom acts as a double-H-atom acceptor. The P atoms in the PTA ligands of both complexes and in the noncoordinated hydrogen-bonded molecules in (II) adopt a slightly distorted tetrahedral environment.

Steric Effects on Uranyl Complexation: Synthetic, Structural, and Theoretical Studies of Carbamoyl Pyrazole Compounds of the Uranyl(VI) Ion

“…Such types of second sphere compounds with uranyl nitrate are known previously for the weak donor ligands, such as crown ethers or alcohols but not with a strong donor ligand amide. However, some compounds of phosphine oxide with the transition metal ions show second sphere coordination. , The average distances for U–O uranyl (1.711(7) Å), − U–O H2O (2.434(7)­Å), , and U–O NO3 (2.488(7)­Å) − agree well with the values reported earlier. The hydrogen bonding O water ···O carbonyl and O water ···N distances and angles are within the accepted values.…”

Two new organotin(IV)-phosphoryl complexes: crystal structure and Hirshfeld surface analysis

“…Hirshfeld surface analysis on the asymmetric unit of (I) shows a contribution of 5.9 % of total interactions in crystal for Sn…O contacts related to involving of four-coordinated Sn site of asymmetric unit with two oxygen atoms of two neighbouring phosphates in the coordination polymer. The Sn centre have been used in preparation of tin complexes, for example compounds with [N] 3 P(O) [11][12][13] [20,21] segments. Moreover, different coordination environments [22,23] and coordination numbers [24,25] at the Sn atom and also coordination modes (monomer [20], dimer [18,26], polymer [27][28][29] and so on [30,31]) and crystal packing diagrams have been found among through the tin-phosphoryl complexes structures deposited in the Cambridge Structural Database (CSD, version 5.35, February 2014 update) [32].…”