Trimethylurea

Döring, Cindy; Taouss, Christina; Jones, Peter G.

doi:10.1107/s0108270112005495

Cited by 7 publications

(8 citation statements)

References 15 publications

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“…The N-P O group is the basic skeleton of a large family of compounds called phosphoramides. The environment of the N atom bonded to the P atom in these compounds tends toward planarity (Pourayoubi et al, 2011), similar to N atoms bonded to C atoms in organic amides (Dö ring et al, 2012), unless the N atom is in an environment with an inherent distortion (Rebrova et al, 1992).…”

Section: Commentmentioning

confidence: 99%

Three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂phosphoric triamides (X= CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]₂core

et al. 2012

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In the phosphoric triamides N,N,N',N'-tetrabenzyl-N''-(2-chloro-2,2-difluoroacetyl)phosphoric triamide, C(30)H(29)ClF(2)N(3)O(2)P, (I), N,N,N',N'-tetrabenzyl-N''-(3-fluorobenzoyl)phosphoric triamide, C(35)H(33)FN(3)O(2)P, (II), and N,N,N',N'-tetrabenzyl-N''-(3,5-difluorobenzoyl)phosphoric triamide, C(35)H(32)F(2)N(3)O(2)P, (III), the tertiary N atoms of the dibenzylamido groups have sp(2) character with minimal deviation from planarity. The sums of the three bond angles about the N atoms in (I)-(III) deviate by less than 8° from the planar value of 360°. The geometries of the tertiary N atoms in all phosphoric triamides with C(O)NHP(O)[N](2) skeletons deposited in the Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B58, 380-388] have been examined and the bond-angle sums at the two tertiary N atoms (SUM1 and SUM2) and the parameter ΔSUM (= SUM1 - SUM2) considered. It was found that in compounds with a considerable ΔSUM value, the more pyramidal N atoms are usually oriented so that the corresponding lone electron pair is anti with respect to the P=O group. In (I), (II) and (III), the phosphoryl and carbonyl groups, separated by an N atom, are anti with respect to each other. In the C(O)NHP(O) fragment of (I)-(III), the P-N bond is longer and the O-P-N angle is contracted compared with the other two P-N bonds and the O-P-N angles in the molecules. These effects are also seen in analogous compounds deposited in the CSD. Compounds with [C(O)NH]P(O)[N]X (X ≠ N), such as compounds with a [C(O)NH]P(O)[N][O] skeleton, have not been considered here. Also, compounds with a [C(O)NH](2)P(O)[N] fragment have not been reported to date. In the crystal structures of all three title compounds, adjacent molecules are linked via pairs of P=O···H-N hydrogen bonds, forming dimers with C(i) symmetry.

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Section: Commentmentioning

confidence: 99%

Three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂phosphoric triamides (X= CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]₂core

et al. 2012

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“…10 For thiourea, all ordered solvates are 3 : 1 clathrates with cyclic hydrocarbons or related materials; 11 to the best of our knowledge, no structure of a thiourea solvate involving a simple solvent has been published, 12 although the cell constants [a 9.7, b 7.2, c 14.2 Å, b 98u, space group P2/m, refcode FIBSIS] of a ''3.82 : 1 thiourea : 1,4-dioxane clathrate'' were reported in 1987. 13 We are interested in the structures and polymorphism of simple urea and thiourea derivatives; our recent publications include reports on the structures of trimethylurea 14 and tetramethylthiourea 15 and on polymorphism in 1,3-dimethylurea 16 and trimethylthiourea. 17 In all cases particular interest attached to the packing patterns, which are generally determined by classical hydrogen bonding.…”

Section: Introductionmentioning

confidence: 99%

Packing principles for urea and thiourea solvates: structures of urea : morpholine (1 : 1), urea : 1,4-dioxane (1 : 1), thiourea : morpholine (4 : 3) and thiourea : 1,4-dioxane (4 : 1)

2013

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The solvents 1,4-dioxane and morpholine have been employed to synthesize solvates of urea and thiourea.The structures confirm the tendency of urea to form more rigid systems of hydrogen bonds in the plane of the N 2 CLO moiety, thus forming layer structures with close complementarity of the donors and acceptors, whereas the more flexible sulfur acceptor of thiourea can also accept hydrogen bonds from donors that lie far from the N 2 CLS plane, forming three-dimensional packing patterns with much more variable parameters. A database investigation confirms these tendencies. The solvate urea : morpholine (1 : 1) crystallizes in Pbcm with Z = 4. The complete urea molecule lies in the mirror plane, as do the heteroatoms of the morpholine molecule. The molecular packing is a layer structure. The solvate urea : 1,4-dioxane (1 : 1) crystallizes in P2/c with Z = 2. The CLO bond of the urea molecule lies along a twofold axis, whereas the dioxane molecule lies across an inversion centre. The molecules form a layer structure analogous to that of the morpholine solvate. The thiourea solvates are more complex, and both involve a more irregular hydrogen bonding geometry at sulfur. The solvate thiourea : morpholine (4 : 3) crystallizes in P2 1 /c with Z = 2. The asymmetric unit contains two independent molecules of thiourea, one morpholine on a general position, and one morpholine disordered over an inversion centre. The thiourea molecules combine to form an open framework with a series of channels, in which the morpholine molecules are attached. The solvate thiourea : 1,4-dioxane (4 : 1) crystallizes in P2 1 /n with Z = 2. The asymmetric unit contains two independent molecules of thiourea and one molecule of dioxane across an inversion centre. One thiourea molecule and the dioxane combine to form a layer structure. The second thiourea molecule links these layers in the third dimension.

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“…Three of them have been selected as examples to illustrate the ability of this type of complexes to establish π‐hole regium bonding, which are represented in Figure 2. The refcode ZINTIB [57] corresponds to bis (4‐picoline)‐gold(I) complex where the gold atom establishes two noncovalent Au⋅⋅⋅Br contacts with the electron rich dibromidoaurate counterions (see Figure 2a). The distance (3.650 Å) is clearly too long to be considered a coordination bond.…”

Section: Resultsmentioning

confidence: 99%

Substituent Effects in π‐Hole Regium Bonding Interactions Between Au(p‐X‐Py)₂Complexes and Lewis Bases: Anab initioStudy

et al. 2022

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Long range substituent effects in regium bonding interactions involving Au(I) linear complexes are investigated for the first time. The Au(I) atom is coordinated to two para-substituted pyridine ligands. The interaction energy (RI-MP2/def2-TZVP level of theory) of the π-hole regium bonding assemblies is affected by the pyridine substitution. The Hammett's plot representations for several sets of Lewis bases have been carried out and, in all cases, good regression plots have been obtained (interaction energies vs. Hammett's σ parameter). The Bader's theory of "atoms-in-molecules" has been used to evidence that the electron density computed at the bond critical point that connects the Au-atom to the electron donor can be used as a measure of bond order in regium bonding. Several X-ray structures retrieved from the Cambridge Structural Database (CSD) provide experimental support to the existence of π-hole regium bonding in [Au(Py) 2 ] + derivatives.

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Trimethylurea

Cited by 7 publications

References 15 publications

Three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂phosphoric triamides (X= CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]₂core

Three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂phosphoric triamides (X= CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]₂core

Packing principles for urea and thiourea solvates: structures of urea : morpholine (1 : 1), urea : 1,4-dioxane (1 : 1), thiourea : morpholine (4 : 3) and thiourea : 1,4-dioxane (4 : 1)

Substituent Effects in π‐Hole Regium Bonding Interactions Between Au(p‐X‐Py)₂Complexes and Lewis Bases: Anab initioStudy

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Trimethylurea

Cited by 7 publications

References 15 publications

Three new [XC(O)NH]P(O)[N(CH2C6H5)2]2phosphoric triamides (X= CClF2, 3-F-C6H4and 3,5-F2-C6H3): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]2core

Three new [XC(O)NH]P(O)[N(CH2C6H5)2]2phosphoric triamides (X= CClF2, 3-F-C6H4and 3,5-F2-C6H3): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]2core

Packing principles for urea and thiourea solvates: structures of urea : morpholine (1 : 1), urea : 1,4-dioxane (1 : 1), thiourea : morpholine (4 : 3) and thiourea : 1,4-dioxane (4 : 1)

Substituent Effects in π‐Hole Regium Bonding Interactions Between Au(p‐X‐Py)2Complexes and Lewis Bases: Anab initioStudy

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Three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂phosphoric triamides (X= CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]₂core

Three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂phosphoric triamides (X= CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]₂core

Substituent Effects in π‐Hole Regium Bonding Interactions Between Au(p‐X‐Py)₂Complexes and Lewis Bases: Anab initioStudy