Cl Bond Lengths Research Articles

A triclinic polymorph of dichlorido(2-{[2-(isopropylammonio)ethyl]iminomethyl-κN}-5-methoxyphenolato-κO1)zinc

The title compound, [ZnCl2(C13H20N2O2)], was first reported in the monoclinic space group P21/n [Han et al. (2010 ▶). Acta Cryst. E66, m469]. This investigation reveals a triclinic polymorph in the space group P-1 with an asymmetric unit that contains two independent mol­ecules of the mononuclear zinc(II) complex. In each mol­ecule, the ZnII atoms are coordinated in a bidentate fashion by the phenolate O and imine N atoms of the Schiff base ligand. Two Cl− anions complete the tetra­hedral coordination in each case. The most obvious difference between the two forms is that the Zn—L (L = O, N, Cl) bond lengths in both unique mol­ecules are longer than those found in the monoclinic polymorph, or indeed in other similar complexes. In the crystal, mol­ecules are linked through N—H⋯O and N—H⋯Cl hydrogen bonds, forming chains along the b axis.

Trans-Dichloridobis[diphenyl(thiophen-2-yl)phosphane-κP]palladium(II)

The title compound, trans-[PdCl2(C16H13PS)2], forms a monomeric complex with a trans-square-planar geometry. The Pd—P bond lengths are 2.3387 (11) Å, as the Pd atom lies on an inversion point, while the Pd—Cl bond lengths are 2.2950 (12) Å.

Comparative Study of Ruthenium(II) and Ruthenium(III) Complexes with the Ligand dmbpy (dmbpy = 4, 4′‐Dimethyl‐2, 2′‐bipyridine)

AbstractThe complex cis‐[RuIII(dmbpy)2Cl2](PF6) (2) (dmbpy = 4, 4′‐dimethyl‐2, 2′‐bipyridine) was obtained from the reaction of cis‐[RuII(dmbpy)2Cl2] (1) with ammonium cerium(IV) nitrate followed by precipitation with saturated ammonium hexafluoridophosphate. The 1H NMR spectrum of the RuIII complex confirms the presence of paramagnetic metal atoms, whereas that of the RuII complex displays diamagnetism. The 31P NMR spectrum of the RuIII complex shows one signal for the phosphorus atom of the PF6– ion. The perspective view of each [RuII/III(dmbpy)2Cl2]0/+ unit manifests that the ruthenium atom is in hexacoordinate arrangement with two dmbpy ligands and two chlorido ligands in cis position. As the oxidation state of the central ruthenium metal atom becomes higher, the average Ru–Cl bond length decreases whereas the Ru–N (dmbpy) bond length increases. The cis‐positioned dichloro angle in RuIII is 1.3° wider than that in the RuII. The dihedral angles between pair of planar six‐membered pyridyl ring in the dmbpy ligand for the RuII are 4.7(5)° and 5.7(4)°. The observed inter‐planar angle between two dmbpy ligands in the RuII is 89.08(15)°, whereas the value for the RuIII is 85.46(20)°.

Trans-Dichloridobis[dicyclohexyl(phenyl)phosphane-κP]palladium(II)

The title compound, [PdCl2{P(C6H11)2(C6H5)}2], forms a monomeric complex with a trans-square-planar geometry. The Pd—P bond lengths are 2.3343 (5) Å, as the Pd atom lies on an inversion centre, while the Pd—Cl bond lengths are 2.3017 (4) Å. The observed structure was found to be closely related to [PdCl2{P(C6H11)3}2] [Grushin et al. (1994 ▶). Inorg. Chem. 33, 4804–4806], [PdBr2{P(C6H11)3}2] [Clarke et al. (2003 ▶). Dalton Trans. pp. 4393–4394] and [PdCl2P(C6H11)2(C7H7)}2] [Vuoti et al. (2008 ▶). Eur. J. Inorg. Chem. pp. 397–407] (C6H11 is cyclo­hexyl and C7H7 is o-tol­yl). One of the cyclo­hexyl rings is disordered with the phenyl ring in a 0.587 (9):413 (9) ratio. Five long-range C—H⋯Cl inter­actions were observed within the structure.

Quantification of the Trans Influence in Hypervalent Iodine Complexes

The trans influence of various X ligands in hypervalent iodine(III) complexes of the type CF(3)[I(X)Cl] has been quantified using the trans I-Cl bond length (d(X)), the electron density ρ(r) at the (3, -1) bond critical point of the trans I-Cl bond, and topological features of the molecular electrostatic potential (MESP). The MESP minimum at the Cl lone pair region (V(min)) is a sensitive measure of the trans influence. The trans influence of X ligands in hypervalent iodine(V) complexes is smaller than that in iodine(III) complexes, while the relative ordering of this influence is the same in both complexes. In CF(3)[I(X)Y] complexes, the mutual trans influence due to the trans disposition of the X and Y ligands is quantified using the energy E(XY) of the isodesmic reaction CF(3)[I(X)Cl] + CF(3)[I(Y)Cl] → CF(3)[I(Cl)Cl] + CF(3)[I(X)Y]. E(XY) is predicted with good accuracy using the trans-influence parameters of X and Y, measured in terms of d(X), ρ(r), or V(min). The bond dissociation energy (E(d)) of X or Y in CF(3)[I(X)Y] is significantly influenced by the trans influence as well as the mutual trans influence. This is confirmed by deriving an empirical equation to predict E(d) using one of the trans-influence parameters (d(X), ρ(r), or V(min)) and the mutual trans-influence parameter E(XY) for a large number of complexes. The quantified values of both the trans influence and the mutual trans-influence parameters may find use in assessing the stability of hypervalent iodine compounds as well as in the design of new stable hypervalent complexes. Knowledge about the I-X bond dissociation energies will be useful for explaining the reactivity of hypervalent iodine complexes and the mechanism of their reactions.

Cis-Dichloridobis[diphenyl(4-vinylphenyl)phosphane-κP]platinum(II)

The title compound, [PtCl2(C20H17P)2], forms a monomeric cis-square-planar geometry. The Pt—P bond lengths are 2.2489 (9) and 2.2627 (9) Å, whereas the Pt—Cl bond lengths are 2.3566 (9) and 2.3336 (9) Å.

Synthesis and molecular structure of the cobalt(ii) chloride complex with bis(α-pyridyl)-substituted bispidinoaza-14-crown-4

The reaction of cobalt(ii) chloride with bis(benzo)bispidinoaza-14-crown-4 (L) containing two α-pyridyl substituents affords complex [Co(L)(H2O)][CoCl4] (1). The structure of complex 1 was determined by X-ray diffraction analysis. In structure 1, molecule L is coordinated to the neutral Co(1) atoms as an N, N, N, N-tetradentate-chelating ligand. The tetrachlorocobaltate dianion acts as a counterion. The coordination polyhedron of the Co atom in complex 1 is an octahedron, and that of the Co(2) atom in the anion is a tetrahedron. The coordination polyhedra of the Co atoms in complex 1 are linked by the bridging chlorine atom. In the octahedron of the Co(1) atom, two five-membered and two six-membered nonplanar chelate metallocycles, which are conjugated with each other along the Co(1)-N(1) and Co(1)-N(2) bonds, undergo ring closure. All bond lengths of the Co(1) atom with the N atoms range from 2.098(4) to 2.228(5) A, and the Co(2)-Cl bond lengths change from 2.233(2) to 2.331(2) A. The longest Co(1)-Cl(4) bond (2.558(2) A) is that with the metal ion. A molecule of complex 1 is stabilized by strong intramolecular hydrogen bonds involving the crown ether fragment.

(2-Amidoethyl)trichlorotin(IV)complexes with amido ligands and chloride ion: supramolecular arrays from H-bonds involving the amido and chloride ions

AbstractComplexes, (H2NCOCH2CH2-C,O)(L)SnCl3(2:L= XCH2CH2CONH2; X = H or Cl), rather than (H2NCOCH2CH2-C,O)SnCl3, have been isolated from reaction mixtures containing hydrochloric acid, tin and acrylamide in Et2O solution. Ligand exchange reactions occur between (2: L= EtCONH2) and HCONMe2or HCONHBu. The anionic complex, [pyridinium][(H2NCOCH2CH2-C,O)SnCl4],3, was isolated from a reaction mixture composed of pyridine and2. In both complex types,2and3, tin is hexacoordinate, in which the octahedral geometries are somewhat distorted due to variations in the Sn—Cl bond lengths, exemplifying thetranseffect, and the small bite angles of the chelating (2-amidoethyl-C,O) ligand. The supramolecular structures are dominated by intermolecular hydrogen-bonds with the NH2groups as the donor species. A feature of each crystal structure is a double chain in which the NH2group of the (2-amidoethyl-C,O) ligand acts as donor for N—H···X (X = Cl or O) intermolecular hydrogen-bonds.

Two complexes isolated from solutions under solvothermal conditions: [CuCl 2(C 5H 14N 2) 2]·4 H 2O with the copper complex enwrapped in a unique self-assembled water layer of fused H 2O decamers and [Co(CO 3)(C 5H 14N 2) 2]Cl·H 2O with the cobalt complex fixed in an extended hydrogen bond network

The new coordination compounds [CuCl 2(C 5H 14N 2) 2]·4 H 2O ( 1) and [Co(CO 3)(C 5H 14N 2) 2]Cl·H 2O ( 2) (C 5H 14N 2 = 2,2-dimethylpropyldiamine) were synthesized under solvothermal conditions. Compound 1 crystallizes in the monoclinic space group P2 1/ n with a = 6.2175(4), b = 27.4152(17), c = 11.7975(8) Å, β = 97.702(8)°, V = 1992.8(2) Å 3, Z = 4 and 2 in the monoclinic space group P2 1/ c with a = 11.5913(8), b = 22.4797(12), c = 7.3655(5) Å, β = 96.760(8)°, V = 1905.9(2) Å 3, Z = 4. In 1 the Cu 2+ cation is octahedrally coordinated by two bidentate 2,2-dimethylpropyldiamine molecules in the basal plane and two Cl − anions located at the apices. The Cu–Cl bond lengths are very unsymmetrical which is caused by the significantly different hydrogen bonding interactions of the two Cl − anions. The H 2O molecules are joined by strong H⋯O interactions generating a (H 2O) 10 decamer which are fused to form a wavy water layer. The layer displays a new and hitherto never observed H 2O layer motif which may be described as L10(6). In 2 the Co 2+ cation is surrounded by two bidentate amine molecules and a bidentate CO 3 2− anion which was formed in situ by CO 2 uptake from the atmosphere. N–H, O and Cl are involved in an extended hydrogen bonding networks leading to the formation of layers which are arranged generating channels along [0 0 1] which are occupied by water molecules. Thermal investigations of both compounds exhibit complex decomposition patterns and successive emission of the constituents. The optical band gaps of 3.79 for 1 and 3.48 eV for 2 confirm that both compounds are isolators.

Cis-Dichloridobis{[4-(dimethylamino)phenyl]diphenylphosphane-κP}platinum(II) ethyl acetate monosolvate

The title compound, [PtCl2(C20H20P)2]·C4H8O2, crystallizes with the Pt atom in a distorted cis-square-planar geometry. The Pt—P bond lengths are 2.2490 (19) and 2.253 (2) Å, and the Pt—Cl bond lengths are 2.344 (2) and 2.3475 (18) Å. Some weak C—H⋯Cl and C—H⋯O inter­actions involving the solvate mol­ecule were observed.

Bond elongation in the anion radical of coordinated tetrazine ligands: A crystallographic, spectroscopic and computational study of a reduced {Re(CO)3Cl} complex

The binuclear complex [(μ-Me2BPTZ)(Re(CO)3Cl)2] (1), where Me2BPTZ=3,6-(5-methyl-pyridyl)-1,2,4,5-tetrazine, can be reduced by addition of bis(η5-pentamethylcyclopentadienyl) iron(II) (decamethylferrocene, Fc∗), to obtain a stable radical anion form 1−. A single-crystal X-ray diffraction study of the radical anion (1−)(Fc∗+) was conducted and compared with a computational model of the same compound in the neutral and reduced states. As such, this work presents the first structural analysis of a reduced diimine ligand that is coordinated to {Re(CO)3Cl} moieties. Bond-length changes within the tetrazine ring system were consistent with previously reported examples of tetrazine radicals and with calculated structures that show clear elongation of the azo-type NN bond. Consistently atomic charge calculations indicate that the extra electron in the radical anion resides largely at the tetrazine core. A negligible change in the Re–Cl bond length is observed and computed.

CuCl3(H2O)]−complexes aggregated to form hydrate columns in methyl-substituted pyridinium or piperidinium salts

1,2,3-Trimethylpyridinium aquatrichloridocuprate(II), (C(8)H(12)N)[CuCl(3)(H(2)O)], (I), 3,4-dimethylpyridinium aquatrichloridocuprate(II), (C(7)H(10)N)[CuCl(3)(H(2)O)], (II), and 2,3-dimethylpyridinium aquatrichloridocuprate(II), (C(7)H(10)N)[CuCl(3)(H(2)O)], (III), exhibit the same fundamental structure, with (I) and (II) isomorphous and with the unit-cell constants of (III) similar to the reduced unit-cell constants of (I) and (II). The distorted square-planar [CuCl(3)(H(2)O)](-) complex [mirror symmetric in (I) and (II)] forms two semicoordinate Cu···Cl bonds to a neighboring complex to produce a dimer with 2/m symmetry [only inversion symmetry in (III)]. The semicoordinate Cu...Cl bond length of the dimer shows significant elongation at 295 K compared with that at 100 K, while the coordinate Cu-Cl bond lengths are slightly contracted at 295 K compared with those at 100 K. The inorganic dimers are linked by eight hydrogen bonds to four neighboring dimers to establish a checkerboard network layer in the ab plane, with voids between the dimers that accommodate, on both sides, inversion-related organic cation pairs. The organic cations are required by mirror-plane symmetry to be disordered in (I) and (II). The organic cations and [CuCl(3)(H(2)O)](-) complexes are nearly coplanar and tilted out of the layer plane to establish a hybrid organic-inorganic layer structure parallel to (202) [(11-2) in (III)], with hydrate columns (defined by water molecules) and hydrophobic columns (defined by methyl groups) parallel to each other [and along the 2(1) axes in (I) and (II)]. In 1,1-dimethylpiperidinium aquatrichloridocuprate(II), (C(7)H(16)N)[CuCl(3)(H(2)O)], (IV), the bulkier organic cation prevents semicoordinate bonding between complexes, which are hydrogen bonded side-to-side in zigzag chains that place water molecules in columns along half of the 2(1) axes.

Poly[μ3-chlorido-μ2-chloridodichlorido(μ-dimethyl sulfoxide-κ2O:S)(dimethyl sulfoxide-κO)(μ-pyrimidine-κ2N:N′)ruthenium(III)sodium

The title complex, [NaRuCl4(C4H4N2)(C2H6OS)2]n, is the sodium salt of monoanionic octa­hedral [RuIIICl4(pyrimidine)(DMSO)]− in which the sulfur-bound dimethyl sulfoxide (DMSO) and pyrimidine ligand are oriented trans to one another on the RuIII atom. The average of the four Ru—Cl bond lengths is 2.355 (15) Å, and the Ru—S and Ru—N bond lengths are 2.2853 (3) and 2.1165 (11) Å, respectively. The complex forms a chain, with a six-coordinate sodium ion bridging the ruthenium(III) units. The sodium cation is coordinated by cis-chloride ligands on ruthenium [Na—Cl = 2.9576 (7) and 2.6988 (7) Å], chloride and DMSO ligands from the ruthenium complexes related by inversion [Na—Cl and Na—O = 2.8888 (7) and 2.2623 (12) Å, respectively], a nitro­gen ligand from the pyrimidine of the tetrachlorido­ruthenium(III) complex related by the twofold rotation axis [Na—N = 2.5224 (14) Å] and an oxygen-bound DMSO [Na—O = 2.3165 (12) Å].

Crystal Structure and Spectroscopic Properties of Bis[trans‐dichlorobis(2,2‐dimethylpropane‐1,3‐diamine)chromium(III)] Tetrachlorozincate

AbstractThe structure of trans‐[Cr(Me2tn)2Cl2]2ZnCl4 (Me2tn = 2,2‐dimethylpropane‐1,3‐diamine) was determined by a single‐crystal X‐ray diffraction study at 173 K. The analysis reveals that there are three crystallographically independent chromium(III) complex cations in the title compound. The chromium(III) atoms are coordinated by four nitrogen atoms of Me2tn and two chlorine atoms in a trans arrangement, displaying a distorted octahedral geometry. The two six‐membered chelate rings in three complex cations are oriented in an anti chair–chair conformation with respect to each other. The Cr–N and Cr–Cl bond lengths average 2.0862(2) and 2.3112(6) Å, respectively. The ZnCl42– have slightly distorted tetrahedral arrangement with Zn–Cl lengths and the Cl–Zn–Cl angles are influenced by hydrogen bonding. The resolved absorption maxima in the electronic d–d spectrum were fitted with a secular determinant for a quartet energy state of the d3 configuration in a tetragonal field. It is confirmed that the nitrogen atoms of the Me2tn ligand are strong σ donors, but the chloro ligands have weak σ‐ and π donor properties toward the chromium(III) ion.

Phase Behaviour of CoCl2-MnCl2Mixed Crystals

AbstractThermal properties of CoCl2, MnCl2and their mixed crystals are investigated by means of temperature dependent neutron powder diffraction and time-resolved small angle neutron scattering. The coefficients of thermal expansion of these crystals have been determined as a function of temperature. The temperature-induced structural variations can be explained by distortions of CoCl6/MnCl6octahedra and changes in Co/Mn–Cl bond lengths. CoCl2and MnCl2form homogeneous solid solutions in the entire temperature range between the solidus and 50 K. There is no indication of any miscibility gap as predicted from thermodynamic calculations.

First Halogen Anion-Bridged (MMX)n-Type One-Dimensional Coordination Polymer Built upon d10−d10 Dimers

The complex [Ag(2)(PhPPy(2))(2)(NCCH(3))(2)](ClO(4))(2) [PhPPy(2) = bis(2-pyridyl)phenylphosphine] reacts with NH(4)Cl to form an insoluble one-dimensional polymer of the type (MMX)(n), {[Ag(2)(PhPPy(2))(2)Cl](ClO(4))}(n). The binuclear unit, Ag(2)(PhPPy(2))(2)(2+), exhibits two PhPPy(2) tridentate ligands bridging the two Ag atoms in a head-to-tail fashion with C(2h) symmetry, and the Ag···Ag distance [3.0942(11) Å, X-ray] suggests argentophilic interactions. Each Ag center adopts a distorted trigonal-bipyramidal geometry, coordinated by one P atom and two pyridyl arms at the equatorial positions and interacting with one Cl ion and one Ag ion at the axial positions. The short Ag-Cl bond length [2.5791(7) Å] indicates the presence of some covalent character. The solid-state absorption bands spread all the way to 600 nm have been interpreted by means of density functional theory (DFT) and time-dependent DFT (B3LYP), and the lowest-energy excited states are assigned to metal/halide-to-pyridyl charge transfer, consistent with the d(10) electronic configuration of Ag. The calculated oscillator strengths are low because of the poor molecular orbital overlaps in the charge-transfer components. The novel material exhibits a luminescence band centered at about ∼520 nm.

Trans-Dichloridobis{[4-(dimethyl-amino)-phen-yl]diphenyl-phosphane}palladium(II).

The title compound, trans-[PdCl2{PPh2(4-Me2NC6H4)}2], crystallizes with the Pd atom on a center of symmetry, resulting in a distorted trans-PdCl2P2 square-planar geometry. The Pd—P and Pd—Cl bond lengths are 2.3550 (7) and 2.2906 (7) Å, respectively. Some weak inter­actions are observed between the aromatic rings of adjacent mol­ecules, with an inter­planar distance between two π-stacked rings of 3.505 (3) Å. Intra- and intermolecular C—H⋯Cl hydrogen bonds also occur.

Trans-Dichlorido-bis-[tris(4-meth-oxy-phenyl)-phosphane]palladium(II) toluene solvate.

In the title compound, trans-[PdCl2{P(4-MeOC6H4)3}2]·C7H8, the Pd(II) atom lies on a center of symmetry, resulting in a distorted trans-square planar geometry. The Pd—P and Pd—Cl bond lengths are 2.3409 (4) and 2.2981 (4) Å, respectively. An intra­molecular C—H⋯Cl hydrogen bond occurs. In the crystal, weak C—H⋯O inter­actions are observed between the aromatic rings of adjacent mol­ecules. The toluene solvate molecule is equally disordered over two sets of sites.

Room‐Temperature Synthesis of the Highly Polar Cluster Compound Sn[SnCl][W3Cl13

AbstractA new synthetic strategy is employed to synthesize a tungsten trinuclear cluster compound with an ionic liquid (IL) as the reaction medium. Dark brown block‐shaped crystals of Sn[SnCl][W3Cl13] were obtained at room temperature by reacting tin and WCl6 in Lewis acidic ionic liquid [BMIM]Cl/AlCl3 ([BMIM]+ = 1‐butyl‐3‐methylimidazolium). Compound Sn[SnCl][W3Cl13] crystallizes in the polar hexagonal space group P63 with cell parameters a = 959.8(1) and c = 1190.3(2) pm. The crystallographic point group of the [W3(μ3‐Cl)(μ‐Cl)3Cl9]3– cluster anions is C3, but C3v pseudosymmetry is observed within twice the standard deviation of the bond lengths. The W–W bond length is 272.18(6) pm. The tin(II) cations, which are in trigonal pyramidal and in distorted trigonal‐antiprismatic coordination spheres that comprise chloride ions, connect the clusters into layers that are stacked according to the 63 screw axis. One of the chloride ions is bound only to a single tin cation resulting in a [SnIICl]+ group with a Sn–Cl bond length of 236.1(5) pm. The pronounced polarity of the crystal structure means that its diffraction pattern exhibits huge deviations from Friedel's law. Most remarkable is that the intensity (Fc2) of reflection 004 is 175 % of the intensity of the 00$\bar {4}$ reflection.

Pentagon-Fused Hollow Fullerene in C78 Family Retrieved by Chlorination

C(78) is one of the most widely investigated higher fullerenes. Among its huge isomer family, only one non-IPR (IPR = isolated pentagon ring) cage, the C(2)-symmetric (#22010)C(78), was previously stabilized by endohedral derivatization. Here we report a new C(1)-symmetric non-IPR hollow isomer, (#23863)C(78), which was captured as (#23863)C(78)Cl(8) and then subjected to a regioselective substitution reaction with benzyl hydroperoxide to form (#23863)C(78)(OOCH(2)C(6)H(5))Cl(7). The structural connectivity of (#23863)C(78), which contains a pair of fused pentagons, was confirmed by single-crystal X-ray diffraction analysis of the (#23863)C(78)(OOCH(2)C(6)H(5))Cl(7) molecule, which shares the same fullerene core with (#23863)C(78)Cl(8); support for the structure is provided by comparable IR measurements and computation. Theoretical studies suggest that the differences in C-Cl bond length, intermediate stability, and steric effects of the involved molecules account for the chemical regioselectivity of the substitution reaction.