The title compound (NC4H8NCH3)(C 6H5)[N(C6H11)2]P=N-S 3N3 crystallizes in the triclinic crystal system with unit cell dimensions: a = 9.7572(2), b = 10.6845(1), c = 16.9381(3) Å, α = 71.75(1)°, β = 80.65(2)°, γ = 65.93(1)°, and Z = 2. The tricoordinated sulfur atom (S1) in the cyclotrithiazene deviates from the mean plane of the other five atoms by 0.716(6) Å, which is the highest among the known phosphiniminocyclotrithiazene structures. In the exocyclic P=N4-S1 moiety, the two bond distances are short: 1.585(6) and 1.527(6) Å; but the bond angle is large 135.3(4)°. The S1 displacement is highly correlated with the endocyclic angle at the nitrogen atom (diagonally opposite to S1), but the nature of correlation is bimodal (R = 1.0 + or -1.0) for the cyclic and acyclic substituents (R) in the (R)(C6H 5)[N(C6H11)2]P=N-S3N 3 series. On the other hand, the S1-N4 bond distances are negatively correlated (R = -0.94) with the P=N4-S1 bond angle in the above series. © 2005 Springer Science+Business Media, Inc.

G. Sreenivasa Murthy

Talla Venkata Rama Mohan

(N METHYLPIPERAZINO)(PHENYL)(DICYCLOHEXYLAMINO) PHOSPHINIMINOCYCLOTRITHIAZENE

functional group

nitrogen

PIPERAZINE DERIVATIVE

Sulfur

sulfur derivative

unclassified drug

article

chemical bond

correlation analysis

Crystal Structure

Crystallization

structure analysis

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IIT Madras

Journal of Chemical Crystallography

An electron rich "hybrid" asymmetric aminophosphine, (diisopropylamino)(morpholino) (phenyl)phosphine, L, was synthesized in good yield by step-wise aminolysis reactions with dichloro(phenyl)phosphine and structurally characterized. The complex, CuCl(L) was readily isolated from both 1:1 and 1:2 reactions of L with CuCl. Single crystal X-ray structures of L and two copper complexes, [CuCl(L)CH3CN]2 (1) and [CuCl(L) CH2Cl2]2 (2) have been determined. X-ray structures reveal pyramidal nature of phosphorus and near planar geometry of nitrogen of the phosphine ligand and the dimeric nature of the complexes with tricoordinate copper(I) centers. The asymmetric phosphine crystallizes in monoclinic system with space group P21/c and unit cell dimensions as a=17.219(1) , b=13.469(1) , c=7.395(5) , =90.00, =93.11(1), =90.00. Both acetonitrile (1) and dichloromethane (2) solvates crystallize in triclinic system with space group Pi. The unit cell dimensions of (1) are a=10.143(2) , b=13.681(3) , c=16.647(3) , =83.14(1), =76.91(1), =68.83(1) and that of (2) are a=8.899(1) , b=11.727(1) , c=11.784(1) . =66.73(1), =82.27(1), =84.04(1). This is the first report of copper(I) phosphine complexes in which the coordinated asymmetric phosphine carries two different amino substituents.

Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry

Synthesis and X-ray structural characterization of (diisopropylamino) (morpholino)(phenyl)phosphine and its dimeric copper(I)

The title compound (C6H12N)Ph2P=N-S 3N3·C7H8 crystallizes in the monoclinic space group P21/n with unit cell dimensions: a = 9.9200(5), b = 16.3316(11), c = 15.7009(17) Å, β= 91.99(1)°, and Z = 4. The cyclotrithiazene ring adopts a chair conformation with equal bond distances and the norbornadiene is fused in an exo, exo fashion to the heterocycle. Norbornadiene addition to the cyclotrithiazene influences the bonding pattern in the ring as well as the P-N-S moiety.

Crystal structure analysis of norbornadiene adduct of diphenyl hexamethylenimino phosphiniminocyclotrithiazene

The title compound (C6H5)(C4H8NO)[N(C6H 11)2]P=N-S3N3 crystallizes in a triclinic crystal system with unit cell parameters a = 9.8884(4) Å, b = 10.6075(1) Å, c = 14.2276(2) Å, α = 78.14(3)°, β = 79.31(1)°, γ = 65.42(2)°, V = 1319.44(6) Å3, Z = 2, and space group P1̄. The cyclotrithiazene ring adopts a "distorted chair" conformation with a deviation of 0.682(7) Å for the tricoordinated sulfur atom. Remarkably, a short exocyclic S-N bond length 1.489(4) Å along with a large P-N-S angle 136.2(3)° are observed with the iminophosphorus moiety. © 2003 MAIK "Nauka/Interperiodica".

Crystallography Reports

Crystal structure analysis of (morpholino)(phenyl)(dicyclohexylamino) phosphiniminocyclotrithiazene

The title compound (OC4H8N)3P=N-S3N3 crystallizes in a monoclinic crystal system with unit cell parameters a = 8.9996(3), b = 17.2895(7), and c = 12.3648(9) Å, β = 90.63(5)°, Z = 4, and space group P21/n. Strikingly the exocylic S1-N4 bond length is 1.545(3) Å and is accompanied by the largest angle at P-N4-S1 as 131.2(2)°. The tricoordinated sulfur atom of the cyclotrithiazene ring deviates from the mean plane of other five atoms by 0.654(1) Å.

Crystal structure of trismorpholino phosphiniminocyclotrithiazene

Room-temperature reactions of asymmetric phosphines, (Ph)(DCA)(R)P (R = Et2N-, Bu2nN-) with S4N4 in acetonitrile afforded phosphiniminocyclotrithiazenes, (Ph)(DCA)(R)P=N-S3N3 (R = Et2N-, I ; Bu2nN-, II) in modest yields (ca 50%). The heterocycles have been characterized by spectroscopic [IR, UV-vis, NMR (1H and 31P) and mass] and single crystal X-ray diffraction methods. Strikingly, the angle at P-N(4)-S(1) is 135° in I, the largest observed so far and is 119.3° in II. This is also accompanied by the shortest exocyclic S(1)-N(4) bond length of 1.537 Å observed in the case of I. In the unit cell of II, two types of molecules with slightly differing degree of deviation of the tricoordinate sulfur (0.664 and 0.673 Å from the mean plane [N(1)-S(2)-N(2)-S(3)-N(3)] are observed. Copyright © 1997 Elsevier Science Ltd.

Polyhedron

Cyclic S-N compounds and phosphorus reagents-XV [1]. Synthesis, spectral and X-ray structural characterization of (Ph)(DCA)(R)P=N-S3N3 [R=(C2H5)2N-; (n-C4H9)2N-]

The reactions of S4N4 with phosphines of the type PhPR2 (1-5) and PhR′PR [6-11 (R′ = dicyclohexylamino), R: 1,6 = pyrrolidino; 2,7 = piperidino; 3,8 = morpholino; 4,9 = N-methylpiperazino; 5,10 = hexamethylenimino; and 11 = anilino] afford the phosphiniminocyclotrithiazene derivatives, 12-22 at room temperature. Only in the case of the phosphine 10 was the disubstituted derivative 23 isolated (in 65% yield). The trithiazene derivatives of the chiral phosphines in refluxing CH3CN produce the acyclic compounds → PN-S3N, 24-27 in ca. 60% yield. Norbornadiene reacts at room temperature with the cyclotrithiazene derivatives to give the addition products 28-35. → P=N-S3N3 derivatives are found to be stable in 2M NaOH. © 1997 John Wiley &amp; Sons, Inc.

Journal	Journal of Chemical Crystallography
ISSN	10741542
Open Access	No