The crystal structure of chromium(II) chloride

Tracy, J. W.; Gregory, N. W.; Lingafelter, E. C.; Dunitz, Jack D.; Mez, Hans‐Christian; Rundle, R. E.; Scheringer, C.; Yakel, H. L.; Wilkinson, M. K.

doi:10.1107/s0365110x61002710

Cited by 38 publications

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“…The somewhat larger value compared to the sum of effective (high-spin octahedral) ionic radii (2.61Å) [11] is due to the d 4 chromium(II) ion with a high-spin electronic configuration (t 2g ) 3 (e g ) 1 . Similar findings, e. g., Cr-Cl = 2.40Å (4×) and 2.91Å (2×), are known from CrCl 2 [12].…”

Section: Resultssupporting

confidence: 68%

Syntheses, Crystal Structures and Magnetic Properties of Cr(NCNH₂)₄Cl₂ and Mn(NCNH₂)₄Cl₂

Tang

Speldrich

Tchougréeff

et al. 2012

Zeitschrift Für Naturforschung B

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The two isotypic compounds Cr(NCNH 2 ) 4 Cl 2 and Mn(NCNH 2 ) 4 Cl 2 have been synthesized and characterized by X-ray diffraction. They crystallize in the cubic space group Im3m (Z = 6) with a = 12.643(2)Å for Cr(NCNH 2 ) 4 Cl 2 and a = 12.821(1)Å for Mn(NCNH 2 ) 4 Cl 2 . The divalent transition metal ions are octahedrally coordinated by four H 2 NCN molecules in equatorial and two chloride ions in axial positions. The magnetic susceptibility data of the four Curie-paramagnetic compounds Cr(NCNH 2 ) 4 Cl 2 , Mn(NCNH 2 ) 4 Cl 2 , Co(NCNH 2 ) 4 Cl 2 , and Ni(NCNH 2 ) 4 Cl 2 have been analyzed in greater detail, including many-body quantum theory.

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Section: Resultssupporting

confidence: 68%

Syntheses, Crystal Structures and Magnetic Properties of Cr(NCNH₂)₄Cl₂ and Mn(NCNH₂)₄Cl₂

Tang

Speldrich

Tchougréeff

et al. 2012

Zeitschrift Für Naturforschung B

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“…These planar chain structures of CrCl 2 units are the basic building blocks of the a-CrCl 2 phase in the solid state. [31,61,62] In the solid, every Cr atom is in a ligand field of an elongated and distorted octahedron of Cl atoms. [61,62] However, four Cl atoms form a close rectangle with the Cr atom in its centre, resulting in CrCl 2 chains along the crystallographic c-axis.…”

Section: Resultsmentioning

confidence: 99%

“…[31,61,62] In the solid, every Cr atom is in a ligand field of an elongated and distorted octahedron of Cl atoms. [61,62] However, four Cl atoms form a close rectangle with the Cr atom in its centre, resulting in CrCl 2 chains along the crystallographic c-axis. The global minima of the dimers, trimers, and tetramers (D 1, T 1, and Q 1, respectively) as shown in Figures 4-6 are the basic units of these chains.…”

Section: Resultsmentioning

confidence: 99%

“…[56] Chromium dichloride, with its d 4 electronic configuration, is an interesting system in that it is subject to both the JahnTeller and the Renner-Teller effects; the former in its crystals and the latter in the gas phase. The chromium atom in the crystal of a-CrCl 2 has a distorted (elongated) octahedral coordination according to both its X-ray diffraction [62] and computational [31] Small clusters of CrCl 2 from dimers to tetramers have been investigated. It was found that they all consist of antiferromagnetically coupled chains of CrCl 2 molecules, forming four-membered rings, closely resembling the solid-state structure of a-CrCl 2 .…”

Section: Discussionmentioning

confidence: 99%

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The Elusive Structure of CrCl₂—A Combined Computational and Gas‐Phase Electron‐Diffraction Study

Vest

Varga

Hargittai

et al. 2008

Chemistry A European J

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Chromium dichloride poses a challenge to the structural chemist. Its different forms of aggregation and association display all well-known structural distortions induced by vibronic interactions. The monomeric molecule has a Renner-Teller distorted bent geometry, the crystal exhibits strong Jahn-Teller distortion, and the oligomers have slightly distorted four-membered-ring structures due to the pseudo-Jahn-Teller effect. In this paper we report on the low-energy structures of the monomer and its clusters, Cr(2)Cl(4), Cr(3)Cl(6), and Cr(4)Cl(8), from unrestricted Kohn-Sham (broken-symmetry) density functional calculations. CrCl(2) was also investigated at higher level, including coupled-cluster and state-average CASSCF computations. The global minima of the gas-phase clusters consist of two-dimensional, antiferromagnetically coupled chains of CrCl(2) units forming four-membered, doubly bridged Cr(2)Cl(2) rings, closely resembling the solid-state structure of alpha-CrCl(2). Each Cr atom in these chains has spin quantum number S=2. This suggests that the CrCl(2) nucleation starts very early on the structural chain motif found in the solid. There is only a very small change in energy from the antiferromagnetically to the ferromagnetically coupled Cr atoms, which indicates little spin-coupling between the metal centers. There is an approximately constant change in energy, about 50 kcal mol(-1), with every new CrCl(2) unit during cluster formation. Information about the structure of these clusters was used in the re-analysis of high-temperature electron-diffraction data. The vapor at 1170 K contained about 77 % monomeric molecules, 19 % dimers, and a small amount of trimers. Monomeric CrCl(2) was found to be bent with a bond angle of 149(10) degrees, in good agreement with our computations, which resulted in a Renner-Teller distortion of the lowest-energy (5)Pi(g) electronic state into the bent (5)B(2) ground state. The vibrational spectrum of chromium dichloride is discussed and the thermodynamics of cluster formation from 1000-2000 K is examined.

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“…We found around Cr(1) two long and four short Cr-C1 distances and around Cr(2) two short and four long Cr-C1 distances (Table 4). For comparison the average Cr-C1 distances in CrC12 (Tracey, 1961), Rb2CrC14 (Fair, Gregson, Day & Hutchings, 1977) and CSECrC14 (Hutchings, Gregson, Day & Leech, 1974) are 2.57, 2.54 and 2.53/~ respectively. This implies that the structure consists of chains of face-sharing alternating elongated and compressed 'D4n' octahedra.…”

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confidence: 99%

The cooperative Jahn–Teller distorted structures of rubidium chromium(II) trichloride and caesium chromium(II) trichloride

Crama¹,

Maaskant²,

Verschoor³

1978

Acta Crystallogr Sect B

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The crystal structure of chromium(II) chloride

Cited by 38 publications

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Syntheses, Crystal Structures and Magnetic Properties of Cr(NCNH₂)₄Cl₂ and Mn(NCNH₂)₄Cl₂

Syntheses, Crystal Structures and Magnetic Properties of Cr(NCNH₂)₄Cl₂ and Mn(NCNH₂)₄Cl₂

The Elusive Structure of CrCl₂—A Combined Computational and Gas‐Phase Electron‐Diffraction Study

The cooperative Jahn–Teller distorted structures of rubidium chromium(II) trichloride and caesium chromium(II) trichloride

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The crystal structure of chromium(II) chloride

Cited by 38 publications

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Syntheses, Crystal Structures and Magnetic Properties of Cr(NCNH2)4Cl2 and Mn(NCNH2)4Cl2

Syntheses, Crystal Structures and Magnetic Properties of Cr(NCNH2)4Cl2 and Mn(NCNH2)4Cl2

The Elusive Structure of CrCl2—A Combined Computational and Gas‐Phase Electron‐Diffraction Study

The cooperative Jahn–Teller distorted structures of rubidium chromium(II) trichloride and caesium chromium(II) trichloride

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Syntheses, Crystal Structures and Magnetic Properties of Cr(NCNH₂)₄Cl₂ and Mn(NCNH₂)₄Cl₂

Syntheses, Crystal Structures and Magnetic Properties of Cr(NCNH₂)₄Cl₂ and Mn(NCNH₂)₄Cl₂

The Elusive Structure of CrCl₂—A Combined Computational and Gas‐Phase Electron‐Diffraction Study