From Alkynols to Alkynol Complexes. A Molecular Assembly Study

Abstract

The solid state supramolecular assembly of prop-2-yn-1-ol and alkynediol transition metal complexes of Pt and Ni has been examined in light of the intermolecular interactions and hydrogen-bonding patterns established by alkyne monoalcohols and diols in the solid state. The analysis has been based on the crystal structure determination of the alcohols 1,1-dimethyl-3-tert-butylprop-2-yn-1-ol (1), tert-butylbis(ethyl)prop-2-yn-1-ol (2), tert-butylcyclohexylprop-2-yn-1-ol (3), and tetramethylalkynediol (4), as well as of the complexes bis(t-butylcyclohexylprop-2-yn-1-ol)M(0) (M = Pt (6a) and Ni (6b) and bis(t-butylcyclopentylprop-2-yn-1-ol)Pt(0) (7), integrated with the data available in the Cambridge Structural Database. It has been shown that the most common hydrogen-bond pattern is that based on a tetramer of −OH groups forming a square, a rhombus, or an open butterfly, irrespective of the molecular complexity. Larger ring systems or chains are established depending on the steric bulk of the substituents on the prop-2-yn-1-ol. Intermolecular and intramolecular hydrogen bond distances have been shown to depend on the type of alcohols, differences having largely a steric origin. The change in the Raman/IR stretching frequency of the C⋮C bond upon coordination of alkynediols to the metal centers has been examined for the nickel compounds and shown to provide a diagnostic tool for recognition of hydrogen-bond formation and typology.

Stereochemistry of Platinum Organometallics

“…One derivative contains three such molecules [72] and another one derivatives has four such molecules [73]. In these derivatives the platinum atoms are found in the oxidation states of zero (x5) [38][39][40][41][42], +2 (x 27) [12, 37, 43-65, 72, 73] and +4 (x 6) [66][67][68][69][70][71]. The derivatives belong to the triclinic (x 17), monoclinic (x 16) and orthorhombic (x 5) classes.…”

“…In pale yellow Pt( 2 -bchp) 2 [38] the pair of homobidentate bchp ligands (C, C´-donors) with two three -membered rings creating a distorted tetrahedral geometry about the Pt(O) atom (PtC 4 ) with differing degrees of distortion. The mean Pt -C bond distances are 1.99 Å (molecule 1) and 2.01Å (molecule 2).…”

“…There are thirty six examples (Pt(0) [38][39][40][41][42], Pt(II) [12,37,, Pt(IV) [66][67][68][69][70][71]) which contains two crystallographicaly independent molecules. One example, [Pt(II)( 4 -bdpb)Cl]Cl [72] contains three such molecules and another one [Pt(II)( 2 -dmaen)( 2 -msedpa)].ClO 4 [73] contains even four such molecules.…”

“…In this series of distortion isomers the Pt(0) atoms are tetrahedrally coordinated (PtP 3 C [7,8], PtC 4 [38], PtC 2 P 2 [39][40][41][42], PtC 2 PPt´ [84,87]). The mean Pt(0) -L bond distances elongated in the order: 1.86 Å (CO) < 2.055 Å ( -CO) The Pt(I) is tetrahedrally coordinated (PtCSPPt´) [74] with the mean Pt(1) -L bond distances elongated in the order: 1.845 Å (CO) < 2.263 Å ( -S) < 2.267 Å ( -PL) < (3) 11.991 (4) 22.602 (4) 90.50 (1) PtC2P2 C P 2.05 (2) 1.97 (2) 2.340 (4) 2.286 (4) C,C P,P C,P 84.3 (7) 100.3 (1) 87.7 (5,4.6) 171.9(4,4.7)…”

Different molecular assemblies in two new phosphoric triamides with the same C(O)NHP(O)(NH)2 skeleton: crystallographic study and Hirshfeld surface analysis

“…The engineering of molecular crystals as well as the construction of supramolecular assemblies are both concerned with intermolecular interactions and hence are conceptually connected (Braga and Grepioni 1997). There is no doubt that the intermolecular contacts, especially hydrogen bonds, play a fundamental role in crystal engineering and stabilization of crystalline solids (Prins et al 2001;Steiner 2002;Metrangolo and Resnati 2008) and thus it is crucial to distinguish different types of interactions in any design strategy (Resnati et al 2015).…”