A mean-square displacement amplitude analysis of terminally bound CO groups in transition-metal clusters

Braga, Dario; Koetzle, T. F.

doi:10.1107/s0108768187011790

Cited by 20 publications

(13 citation statements)

References 12 publications

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“…The reason is obviously the nonspherical electron distribution of the triple bond, which cannot be adequately modelled with spherical scattering factors. A similar situation is well known from metal-carbonyl complexes (Braga & Koetzle, 1988). It should be noted that the absolute magnitudes for the Ám.s.d.a.…”

Section: Commentsupporting

confidence: 79%

catena-Poly[[bis(acetonitrile-κN)manganese(II)]-bis(μ-trifluoromethanesulfonato-κ²O:O′)]

et al. 2009

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The title compound, [Mn(CF 3 SO 3 ) 2 (CH 3 CN) 2 ] n , has an Mn II cation on an inversion centre in an octahedral environment. The trifluoromethanesulfonate anions act as bridging ligands and form a one-dimensional coordination polymer in the direction of the a axis. The F atoms of the trifluoromethanesulfonate anions form layers parallel to the ab plane, but despite short intermolecular distances, no stabilizing FÁ Á ÁF interactions are detected. The Mn-N and C-C bonds of the acetonitrile ligand are analyzed according to the Hirshfeld rigid-bond test. Renninger effects in the reflection data are considered, explored and discussed. CommentThe title compound, (I), was prepared as a starting material for complexation reactions with biomimetic ligands. In the literature, the stoichiometry of the compound is given as Mn(SO 3 CF 3 ) 2 ÁCH 3 CN (Bryan & Dabrowiak, 1975), but also contains indications of a variable composition. The present crystal structure determination proves the presence of two coordinated acetonitrile molecules and thus the composition [Mn(SO 3 CF 3 ) 2 Á2CH 3 CN] n , with the manganese in a 2+ oxidation state (Fig. 1).The Mn II ion in (I) is located on an inversion centre and surrounded by six donor atoms in a slightly distorted octahedral geometry. The equatorial plane is formed by four O atoms of the trifluoromethanesulfonate anions, with Mn-O distances in the expected range for Mn II . The axial positions are occupied by acetonitrile ligands, with similar Mn-N distances to those observed in the [Mn(CH 3 CN) 6 ] 2+ cation (Weller et al., 1996). Due to the inversion symmetry, the equatorial plane is exactly planar and the axial donor atoms are exactly trans. Consequently, the angular variance (Robinson et al., 1971) is very small (0.75 2 ). The slight octahedral distortion can be seen in the small difference between Mn-O and Mn-N distances.The trifluoromethanesulfonate anions, which are located on general positions, act as bridging ligands between the Mn II cations. Bridging trifluoromethanesulfonate anions occur mainly in copper and silver complexes. In fact, there is only one previously known Mn complex with a bridging trifluoromethanesulfonate anion (Berben & Peters, 2008), but there the bridging is supported by an additional bridging isopropoxide linker, resulting in a discrete binuclear complex. In (I), the Mn II cations are connected only by trifluoromethanesulfonate anions. In this way, a one-dimensional chain is formed in the direction of the crystallographic a axis. The distance between the Mn II ions in the chain therefore corresponds to the length of the a axis

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Section: Commentsupporting

confidence: 79%

catena-Poly[[bis(acetonitrile-κN)manganese(II)]-bis(μ-trifluoromethanesulfonato-κ²O:O′)]

et al. 2009

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“…27 These adamantane derivatives show a rich polymorphic behavior that has largely been studied. [28][29][30][31][32][33][34][35][36] The physical and chemical properties, even for the simple adamantane derivatives have not been studied for some of them in which the substitution concerns more than a halogen atom.…”

Section: -mentioning

confidence: 99%

Phase Transition in Hydrogen-Bonded 1-Adamantane-methanol

Hassine

Négrier

Barrio

et al. 2015

Crystal Growth & Design

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The polymorphism of 1-adamantane-methanol C 11 H 18 O has been investigated by differential thermal analysis and single-crystal and powder X-ray diffraction. Below the melting temperature (389.5 ± 0.4 K), this compound exhibits an orthorhombic phase (Phase I, Pnnm, Z=12, Z'=1.5). The melting enthalpy was determined to be 20.5 ± 0.4 kJ mol −1 , i.e.,with an entropy change of (6.34 ± 0.13)R, which is much higher than the quoted value fromTimmermans for the melting orientationally disordered phases (2.5R), thus supporting the orientationelly ordered character of phase I. This orthorhombic phase I exhibits a statistical disorder of the hydrogen atom related to the oxygen atom, due to the position of one independent molecule on the mirror. At ca. 272 K, phase I transforms continuously through an order-disorder transition to a low-temperature monoclinic phase II (P2 1 /n, Z=12, Z'=3). The monoclinic and orthorhombic phases are related by a group-subgroup relationship, which perfectly agrees with the continuous character of the II to I transition. Moreover, by a convenient choice of an order parameter related to the continuous tilt of the c-axis, the critical exponent for this transition is found to be close to the theoretical prediction of 3D-Ising model (with a critical exponent is of ca. 0.27).

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“…For related amidine complexes in which Mo(CO) 3 is coordinated in a very similar manner, see; Boeré, Klassen & Wolmershä user (1998. For thermal motion of carbonyl group oxygen atoms, see: Braga & Koetzle (1988)…”

Section: Related Literaturementioning

confidence: 99%

Tricarbonyl[N,N′,N′′-tris(2,6-diisopropylphenyl)guanidine]molybdenum(0)

Boeré

Masuda

2011

Acta Cryst E

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In the title compound, [Mo(C37H53N3)(CO)3], the Mo atom to ring-centroid distance in the η6-coordinated tricarbonylmolybdenum group is 1.958 (1) Å. The three C O groups are pseudo-octahedrally disposed with C—Mo—C angles ranging from 80.7 (1) to 87.4 (1)°. The two uncoordinated 2,6-diisopropylphenyl-substituted benzene rings form dihedral angles of 75.96 (8) and 78.01 (9)° with the mean plane of the guanidine group. The coordinated benzene ring is in a slight sofa conformation with the N-substituted C atom and the bonded N atom dispaced by 0.090 (3) and 0.458 (4) Å, respectively, from the mean plane of the remaining ring atoms. In the crystal, despite there being two N—H donor groups, no conventional hydrogen bonds are present. This may be because of the steric effects of the bulky diisopropylphenyl groups.

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A mean-square displacement amplitude analysis of terminally bound CO groups in transition-metal clusters

Cited by 20 publications

References 12 publications

catena-Poly[[bis(acetonitrile-κN)manganese(II)]-bis(μ-trifluoromethanesulfonato-κ²O:O′)]

catena-Poly[[bis(acetonitrile-κN)manganese(II)]-bis(μ-trifluoromethanesulfonato-κ²O:O′)]

Phase Transition in Hydrogen-Bonded 1-Adamantane-methanol

Tricarbonyl[N,N′,N′′-tris(2,6-diisopropylphenyl)guanidine]molybdenum(0)

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A mean-square displacement amplitude analysis of terminally bound CO groups in transition-metal clusters

Cited by 20 publications

References 12 publications

catena-Poly[[bis(acetonitrile-κN)manganese(II)]-bis(μ-trifluoromethanesulfonato-κ2O:O′)]

catena-Poly[[bis(acetonitrile-κN)manganese(II)]-bis(μ-trifluoromethanesulfonato-κ2O:O′)]

Phase Transition in Hydrogen-Bonded 1-Adamantane-methanol

Tricarbonyl[N,N′,N′′-tris(2,6-diisopropylphenyl)guanidine]molybdenum(0)

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About

catena-Poly[[bis(acetonitrile-κN)manganese(II)]-bis(μ-trifluoromethanesulfonato-κ²O:O′)]

catena-Poly[[bis(acetonitrile-κN)manganese(II)]-bis(μ-trifluoromethanesulfonato-κ²O:O′)]