Synthesis of chloromethylphosphine oxides

Tsvetkov, E. N.; Крон, Т. Е.; Кабачник, М. И.

doi:10.1007/bf00949641

Cited by 6 publications

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confidence: 99%

The pseudosymmetric crystal structure of bis((dimethylphosphoryl)-methanaminium oxonium tribromide, C6H25Br3N2O3P2

Reiß¹

2013

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of material (Dimethylphosphoryl)methanamine (dpma) is easily available by a literature known synthesis [1,2]. In a typical reaction 0.3 g dpma was dissolved in 2 ml concentrated hydrobromic acid. Evaporation at room temperature yielded colourless crystals of (dpmaH) 2 (H 3 O)Br 3 . Experimental detailsAll hydrogen atoms were identified in difference Fourier synthesis. The methyl groups and the NH 3 groups were idealized and refined using rigid groups allowed to rotate about the P-C bond (AFIX 137 option of the SHELXL-2013 program [13]). The coordinates of the H-atoms at the oxonium ions were refined with the O-H distance restrained to 0.9 Å. The U iso values of the hydrogen atoms of methyl groups were set to 1.5U eq (C) and the U iso values of all other hydrogen atons were set to 1.2U eq (C, N). To get usable intensities for the mass of weak superstructure reflections the exposure time had to be extended, accepting the overexposure of some very strong reflections. DiscussionIt has been shown, that the dpmaH + cation is an excellent tecton for the construction of hydrogen bonded, one-dimensional structures [3][4][5][6]. Pseudosymmetry is a ubiquitous problem during the course of many crystal structure determinations [7]. A typical problem is the appearance of additional and weak superstructure reflections which necessiate a larger super lattice for a correct description of the true structure [8]. In more difficult cases the difference between the true symmetry and the pseudosymmetry is expressed by slightly modified intensities of reflections. In such cases additional methods should be applied (spectroscopy, optical methods, thermal analysis, etc.) [9]. It is obvious that some classes of compound are predestined for this effect. This contribution is part of our ongoing interest in the hydrogen bonding of phosphinic acids and its derivatives [10] and on the phenomenon of pseudosymmetry. The asymmetric unit of the title structure consists of four dpmaH + cations, two H 3 O + (oxonium) cations and six bromide anions. The pseudosymmetry in the title structure is caused by the fact that the bromide anions, the oxonium cations and the Me 2 PO-CH 2 -fragment of the dpmaH + cations alternatively can be described, using a halved unit cell (c' = 0.5c; P1). Accordingly, the average intensity of reflections with l = 2n+1 are much weaker than those with l = 2n. To analyze the differences within the roughly identical parts of the structure a comparative refinement of a structural model using the halved unit cell has been undertaken. This refinement yielded R-values similar to those of the true structure, which is not surprising, as the model refers to the stronger reflections. Extremely elongated ellipsoids of the bromide anions and the disorder of the aminium groups reflect the structural pseudosymmetry. In the true (super) structure all four crystallographic independent dpmaH + cations show individual O-P-C-N torsion angles (O1-P1-C3-N1 = -116.9(4)°; O2-P2-C6-N2 = 47.3(4)°; O3-P3-C9-N3 = -68.6(4)°; O4-P4-C12-N4 = 123....

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The pseudosymmetric crystal structure of bis((dimethylphosphoryl)-methanaminium oxonium tribromide, C6H25Br3N2O3P2

Reiß¹

2013

Zeitschrift Für Kristallographie - New Crystal Structures

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“…Neutral (dimethylphosphoryl)methanamine (dpma) has been synthesized decades ago [1,2], and its crystal structure is well-known [3]. Furthermore, it has been shown that dpma is a potent bidentate ligand stabilizing mononuclear [3][4][5] and oligonuclear [6] complexes as well as coordination polymers [7].…”

Section: Introductionmentioning

confidence: 99%

Constructor Graphs as Useful Tools for the Classification of Hydrogen Bonded Solids: The Case Study of the Cationic (Dimethylphosphoryl)methanaminium (dpmaH+) Tecton

Reiß

2015

Crystals

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Abstract:The structural chemistry of a series of dpmaH (dpmaH = (dimethylphosphoryl)methanaminium) salts has been investigated using constructor graph representations to visualize structural dependencies, covering the majority of known dpmaH salts. It is shown that the structurally related α-aminomethylphosphinic acid can be integrated in the systematology of the dpmaH salts. Those dpmaH salts with counter anions that are weak hydrogen bond acceptors (ClO 4´, SnCl 6 2´, IrCl 6 2´, I´) tend to form head-to-tail hydrogen bonded moieties purely consisting of dpmaH + cations as the primarily structural motif. In structures with weak to very weak hydrogen bonds between the dpmaH + cations and the counter anions, the anions fill the gaps in the structures. In salts with medium to strong hydrogen bond acceptor counter ions (Cl´, NO 3´, PdCl 4 2´) , the predominant structural motif is a double head-to-tail hydrogen bonded (dpmaH + ) 2 dimer. These dimeric units form further NH¨¨¨X hydrogen bonds to neighboring counter anions X, which results in one-dimensional and two-dimensional architectures.

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“…Details of crystal data and parameters for structure refinement of 1 and 2 are given in Table 1. dpmaHClO 4 (1) crystallizes in the centrosymmetric space group, C2/c, with one dpmaH cation and one perchlorate anion in the asymmetric unit. All bond lengths and angles of the dpmaH cation and the perchlorate anion are in the expected range (Tables 2 and 3).…”

Section: Structural Characterization Of (Dimethylphosphoryl)methanamimentioning

confidence: 99%

“…Selected bond angles [°] in 1. dpmaHClO 4 •dpma (2) crystallizes in the non-centrosymmetric space group, Pca2 1 . As illustrated in Figure 3, the asymmetric unit of 2 consists of one dpmaH cation, one dpma molecule and one nearly undistorted perchlorate anion.…”

Section: Structural Characterization Of (Dimethylphosphoryl)methanamimentioning

confidence: 99%

“…A simple compound (n = 1, R 1 , R 2 = H, R 3 , R 4 = CH 3 ) of this class is the (dimethylphosphoryl)methanamine (dpma). The synthesis of dpma has been reported more than twenty years ago [4,5], and also, the solid state structure of the dpma molecule has been determined [6]. There are structurally characterized examples for N-protonated salt structures (dpmaHCl [7], dpmaH[MnCl 3 (H 2 O) 2 ] [8]), N-methylated cationic species [9] and more complex compounds [10].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structure and Spectroscopy of Two Structurally Related Hydrogen Bonded Compounds in the dpma/HClO4 System; dpma (dimethylphosphoryl)methanamine

et al. 2013

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Abstract:The new phosphine oxide compound, (dimethylphosphoryl)methanaminium perchlorate, dpmaHClO 4 (1), was synthesized by the reaction of (dimethylphosphoryl) methanamine (dpma) with concentrated perchloric acid. (Dimethylphosphoryl)methanaminium perchlorate (dimethylphosphoryl)methanamine solvate, dpmaHClO 4 •dpma (2) was obtained by the slow evaporation of an equimolar methanolic solution of 1 and dpma at room temperature. For both compounds, single-crystal X-ray structures, IR and Raman spectra are reported. The assignment of the spectroscopic data were supported by quantum chemical calculations at the B3LYP/6-311G(2d,p) level of theory. In 1, the dpmaH cations form polymeric, polar double-strands along

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Synthesis of chloromethylphosphine oxides

Cited by 6 publications

References 5 publications

The pseudosymmetric crystal structure of bis((dimethylphosphoryl)-methanaminium oxonium tribromide, C6H25Br3N2O3P2

The pseudosymmetric crystal structure of bis((dimethylphosphoryl)-methanaminium oxonium tribromide, C6H25Br3N2O3P2

Constructor Graphs as Useful Tools for the Classification of Hydrogen Bonded Solids: The Case Study of the Cationic (Dimethylphosphoryl)methanaminium (dpmaH+) Tecton

Synthesis, Structure and Spectroscopy of Two Structurally Related Hydrogen Bonded Compounds in the dpma/HClO4 System; dpma (dimethylphosphoryl)methanamine

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