The reaction between two equivalents of dimethyl
N
-cyanodithioiminocarbonate, (MeS)
2
C=N–C≡N (
1
), one equivalent of
n
-butyltin trichloride, Sn(
n
-Bu)Cl
3
and one equivalent of sodium hydroxide, ...NaOH led to isolation of a dinuclear complex {Sn(
n
-Bu)Cl
2
(OH)(H
2
O)
2
} (
2
) which co-crystallized with four (MeS)
2
C=N–C≡N molecules, {Sn(
n
-Bu)Cl
2
(OH)(H
2
O)
2
(CH
3
S)
2
C=N–C≡N
4
} (
3
). The compound was investigated by single-crystal X-ray diffraction analysis and infrared spectroscopy. Compound
3
crystallizes in the triclinic space group
P
1
¯
with
a
= 9.8208(15),
b
= 11.2664(17),
c
= 12.0446(18) Å,
α
= 106.236(5),
β
= 111.510(5),
γ
= 97.710(6)°,
V
= 1147.9(3) Å
3
,
Z
= 1 and Z′ = 0.5. In the complex, two aqua-
n
-butyltinhydroxide dichloride moieties, Sn(
n
-Bu)Cl
2
(OH)(H
2
O), are bridged by the hydroxides. The hydroxide bridges bond lengths describe a static
trans
effect yielding a dissymmetry in Sn–O bonding. Two inner O2–H2D⋯Cl1 hydrogen bonds strengthen the dinuclear component. The dimethyl
N
-cyanodithioiminocarbonate molecules are linked to the dinuclear component through the hydroxide bridges and the water molecules by O1–H1⋯N2A and O2–H2C⋯N2B hydrogen bonding patterns of D type, respectively. The (MeS)
2
C=N–C≡N molecules exhibit a positional disorder. These hydrogen bonding interactions lead to cyclic patterns generating
R
1
1
(6) and
R
2
2
(8) rings. Additional C–H⋯Cl and C–H⋯N hydrogen bond patterns also contribute to the crystal structure framework: they give rise to a 3D structure.
Graphical Abstract
Reacting with
n
-BuSnCl
3
and NaOH in an aqueous mixed solvent, dimethyl
N
-cyanodithioiminocarbonate, (MeS)
2
C=N–C≡N forms a co-crystalline 4:1 assembly with the bimetallic organotin(IV) complex, Sn(
n
-Bu)Cl
2
(OH)(H
2
O)
2
, whose single crystal XRD analysis exhibits a 3D hydrogen bonded structure.
Four new adducts catena-O,O′-glutaratotriphenylstannate, (Me4N)2O2C(CH2)3CO2×4SnPh3Cl (1), (Me4N)2O2C(CH2)3CO2×3SnPh3Cl (2), (SnPh3)2O2C(CH2)3CO2×SnPh3Cl (2′) and (Cy2NH2)2O2C(CH2)3CO2×SnPh3Cl (3), ...have been isolated from the reactions carried out in solution. The compounds have been characterized by FT-IR and Mössbauer spectroscopies except for 2’ whose structure is proposed on the basis of FT-IR data. Overall, the spectra studies sheew existence of several caracteristic bands such as υ (C=O), υ (CO2–), υ (Sn–O), υ (Sn–Cl), vibrations of glutarate ions, and the intense doublet showing the presence of phenyl groups. In the solid state, the suggested structures are discrete or of infinite chain. In this work, the geometry at Sn centers, trigonal bipyramidal or tetrahedral, is ascertained by the Mössbauer parameters. The glutarate ions exhibit a monodentate, tridentate or tetradentate coordination behavior towards the Sn atoms.
The title salt, C
14
H
16
N
+
·C
6
H
7
AsNO
3
−
·H
2
O or (C
6
H
5
CH
2
)
2
NH
2
H
2
NC
6
H
4
As(OH)O
2
·H
2
O, (
I
), was synthesized by mixing an aqueous solution of (4-aminophenyl)arsonic acid ...with an ethanolic solution of dibenzylamine at room temperature. Compound
I
crystallizes in the monoclinic
P
2
1
/c space group. The three components forming
I
are linked
via
N—H...O and O—H...O intermolecular hydrogen bonds, resulting in the propagation of an infinite zigzag chain. Additional weak interactions between neighbouring chains, such as π–π and N—H...O contacts, involving phenyl rings, –NH
2
and –As(OH)O
3
functions, and H
2
O, respectively, lead to a three-dimensional network.
Four new carboxyalkylphosphonate SnR2 residue (R = Me, Ph, Bu) containing adducts and derivatives i.e. {(Cy2NH2)3(O2CCH2PO3)(SnBu2Cl2)} (1), {(SnMe2Cl)(O2CCH2PO3H2)4Cy2NH2Cl} (2), ...{(Me4N)(SnPh2Cl)O2C(CH2)2 PO3H(SnPh2)O2C(CH2)2PO3H} (3) and {(Cy2NH2)2(O2CCH2PO3H)(SnPh2Cl2)2} (4), have been synthesized from one-pot reactions carried out in solution. All compounds have been investigated by spectral techniques (infrared and Mossbauer). The spectral studies have evidenced presence of several characteristic bands, especially υ (C=O), υ (OH), υ (CO2- ), υ (PO32- ) vibrations coming from carboxyalkylphosphonate ions, with wide absorption due to the NH2 groups coming from the dicyclohexylammonium counter ion (for 1, 2 and 4) and the intense doublet which show the presence of phenyl groups (for 3 and 4). In the solid state, the proposed structures are discrete or of infinite chain however hydrogen bonding patterns may occur. Event in this investigation is the presence, for compound 3, of two types of arrangement at Sn centers viz. an octahedron and a trigonal bipyramidal whose presence are ascertained by the Mossbauer parameters. The neutral or acidic carboxyalkylphosphonate ions exhibit a diversity of coordination behavior towards the Sn atoms: monochelating (carboxylate and phosphonate O-donor), monochelating through the carboxylate and unidentate coordinating O-donor through the phosphonic acid or acidic phosphonate, bichelating with chelations from carboxylate and acidic phosphonate, and unidentate from both the carboxylate and phosphonic acid.
Five new phosphinato derivatives, adducts and complexes have been synthesized and characterized by infrared and Mössbauer spectroscopies. Based on their spectroscopic data discrete or infinite chain ...structures are proposed, the phosphinate ion behaving as a bicoordinating bridging or a monocoordinating ligand, the environments around the tin (IV) centers being octahedral or trigonal bipyramidal. In Me4N(SnPh2)2(H2PO2)2Cl3 and Cl2Sn(H2PO2)2NMe4H2PO2, the cation is involved in electrostatic interactions with the anions.
Two MX2 (M = Ni, Zn; X = Cl, Br) dimethyl N-cyanodithioiminocarbonate compounds and one CrCl2 triphenylphosphine oxide complex were isolated and elucidated by single crystal X-ray crystallography. ...NiCl2(CH3S)2C═NC≡N2 (1) features inversion-related hydrogen bonded dimers linked into chains interacting through C-H···Cl growing layers along 110 whose junction into a 3D structure is enabled by H-bonds. ZnBr2(CH3S)2C═NC≡N2 (2) also exhibits inversion-related H-bonded dimers. In contrast with 1, the structure of 2 comprises chains along 110, connected via C-H···Br and C-H···S into a 2D layer along -110. CrCl2(OPPh3)2 (3) obtaining undergone redox processes, oxidizing CH3C(O)CH2PPh3+ to form PPh3PO, and reducing Cr from CrVI to CrII. In the structure, each molecule is linked to height neighbors through H-bonds affording a 3D network.
Three organotin (IV) derivatives PhPO3HSnBu2Cl, SnBu2Ph2PO2Cl×3/2H2O, Sn(PhPO3)Cl2×2H2O obtained on allowing PhPO3H2 or propylammonium PhPO3H to react with SnBu2Cl2, SnCl2×2H2O and two adducts ...(C6H5CH2)2NH23O2C(CH2)2PO3×3SnPh3Cl, CyNH3(HO2POCH2-N(CH2CO2H)22×3SnCl4.2H2O×NH4Cl obtained on allowing (C6H5CH2)NH2)3O2C(CH2)2PO3 or CyNH3(HO2POCH2-N(CH2 CO2H)22 and SnPh3Cl or SnCl2×2H2O to react in ethanolic media have been characterized by elemental analyses, infrared and Mossbauer techniques. The suggested structures, while considering the anionic counterpart, are discrete, dimeric, double and triple metallic components or of infinite chain types, the anion behaving as a monochelating, a bichelating or a bidentate ligand. In OH containing structures, when extra hydrogen bonds are considered, supramolecular architectures may be obtained.
The synthesis and spectroscopic studies (infrared and Mössbauer) of new hydrogenoxalato derivatives and adducts containing SnRn (R=Me, Ph; n=2, 3) residues are reported. Based on their spectroscopic ...data dimeric and polymeric structures containing hexacoordinated or pentacoordinated Sn are suggested, the hydrogenoxolate anion behaving as a monocoordinating or a monochelating ligand. In two studied adducts, supramolecular architectures may be obtained when extra hydrogen bonds involving the free NH groups are considered.
On allowing cetyltrimethyl ammonium bromide (C19H42NBr) and HgCl2, CuCl2.2H2O, CoCl2.6H2O, ZnCl2, NiCl2.6H2O or NbCl5 in specific ratio in methanol, new mononuclear have been obtained and studied by ...infrared. The suggested structures are discrete, of infinite chain with octahedral or tetrahedral environments around the metallic centres. The MX2 behaves as discrete chains. For most of the structures, when intermolecular hydrogen bonds are considered, supramolecular architectures may be obtained.
Six new tin (IV), antimony (III) and antimony (V) adducts and complexes have been synthesized. Discrete structures were suggested on the basis of infrared data. Within the structures, the anion ...behaves as a bidentate, monochelating and monodentate, monodentate and tri O-chelating ligand. The environments around metallic centres are octahedral. Considering preamble of extra hydrogen bonds in compounds containing water molecules and/or OH groups, supramolecular architectures may be given rise.
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