Structures and magnetic properties of trinuclear copper(II) halide salts

Todd E. Grigereit, B. L. Ramakrishna, Helen Place, Roger D. Willett, Gian Carlo Pellacani, Tiziano Manfredini, Ledi Menabue, Anna Bonamartini-Corradi, Luigi Pietro Battaglia

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Abstract

The crystal structures of a series of trinuclear copper(II) halide salts have been determined. These all contain pseudoplanar, symmetrically bibridged Cu3X8 2- (Ia) or Cu3X7L- (Ib) anions. A2Cu3Cl8 or A2Cu3Cl8 salts are formed with A being the (Chemical Equation Presented) N-methylpiperazinium (NMPZ), 3-methyl-2-aminopyridinium (3MAP), and 5-methyl-2-aminopyridinium (5MAP) cations. A Cu3Br8 3- analogue is found with the 5-bromo-6-methyl-2-aminopyridinium (5B6MAP) cation. With the methylphenethylammonium (NMPH) cation, a (NMPH)Cu3Cl7·EtOH salt is isolated. The salts are all monoclinic with the following space group and lattice constants: NMPZ, C5H14N2Cu3Cl8, P21/c, a = 6.840 (3) Å, b = 14.321 (9) Å, c = 9.890 (5) Å, β = 102.90 (5)°, Z = 4; 3MAP, C12H18N4Cu3Cl8, C2/c, a = 26.05 (1) Å, b = 13.687 (4) Å, c = 7.099 (3) Å, β = 117.95 (3)°, Z = 4; NMPH, C11H20NOC3Cl7, P21/n, a = 11.843 (4) Å, b = 7.626 (3) Å, c = 23.840 (10) Å, β = 79.61 (3)°, Z = 4; 5B6MAP, C12N10N4-Cu3Br10, P21/n, a = 13.216 (3) Å, b = 4.076 (1) Å, c = 24.614 (6) Å, β = 91.65 (2)°, Z = 2. Each copper ion extends its primary coordination by formation of two semicoordinate bonds to halide ions in adjacent oligomers, yielding the familiar 4+2 coordination geometry for copper(II) complexes. These additional linkages cause the oligomers to aggregate into stacks, yielding stacking patterns of type IIa (NMPZ, 3MAP salts) or type IIb (NMPH, 5MAP, and 5B6MAP). Cu-X distances are approximately 2.3 (Figure Presented) Å (Cl) or 2.4 Å (Br) within the oligomers and 2.7-3.3 Å (Cl) or 3.2-3.3 Å (Br) between oligomers. The bridging Cu-X-Cu angles within the trimer average near 94°. Magnetic susceptibility measurements have been made on the NMPZ, NMPH, 3MAP, and 5MAP chloride salts. In addition, measurements were performed on Cu3Cl6(CH3CN)2, which contains neutral trinuclear oligomers. All compounds have doublet ground states arising from antiferromagnetic exchange coupling between neighboring copper(II) ions. The value of J/k is typically -20 to -35 K, consistent with the structural characteristics of the trimeric species.

Original languageEnglish (US)
Pages (from-to)2235-2243
Number of pages9
JournalInorganic Chemistry
Volume26
Issue number14
StatePublished - 1987

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halides
Copper
Magnetic properties
oligomers
Oligomers
Salts
magnetic properties
salts
copper
Cations
Ions
cations
Exchange coupling
ions
trimers
Magnetic susceptibility
linkages
Ground state
Lattice constants
Anions

ASJC Scopus subject areas

  • Inorganic Chemistry

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Grigereit, T. E., Ramakrishna, B. L., Place, H., Willett, R. D., Pellacani, G. C., Manfredini, T., ... Battaglia, L. P. (1987). Structures and magnetic properties of trinuclear copper(II) halide salts. Inorganic Chemistry, 26(14), 2235-2243.

Structures and magnetic properties of trinuclear copper(II) halide salts. / Grigereit, Todd E.; Ramakrishna, B. L.; Place, Helen; Willett, Roger D.; Pellacani, Gian Carlo; Manfredini, Tiziano; Menabue, Ledi; Bonamartini-Corradi, Anna; Battaglia, Luigi Pietro.

In: Inorganic Chemistry, Vol. 26, No. 14, 1987, p. 2235-2243.

Research output: Contribution to journalArticle

Grigereit, TE, Ramakrishna, BL, Place, H, Willett, RD, Pellacani, GC, Manfredini, T, Menabue, L, Bonamartini-Corradi, A & Battaglia, LP 1987, 'Structures and magnetic properties of trinuclear copper(II) halide salts', Inorganic Chemistry, vol. 26, no. 14, pp. 2235-2243.
Grigereit TE, Ramakrishna BL, Place H, Willett RD, Pellacani GC, Manfredini T et al. Structures and magnetic properties of trinuclear copper(II) halide salts. Inorganic Chemistry. 1987;26(14):2235-2243.
Grigereit, Todd E. ; Ramakrishna, B. L. ; Place, Helen ; Willett, Roger D. ; Pellacani, Gian Carlo ; Manfredini, Tiziano ; Menabue, Ledi ; Bonamartini-Corradi, Anna ; Battaglia, Luigi Pietro. / Structures and magnetic properties of trinuclear copper(II) halide salts. In: Inorganic Chemistry. 1987 ; Vol. 26, No. 14. pp. 2235-2243.
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title = "Structures and magnetic properties of trinuclear copper(II) halide salts",
abstract = "The crystal structures of a series of trinuclear copper(II) halide salts have been determined. These all contain pseudoplanar, symmetrically bibridged Cu3X8 2- (Ia) or Cu3X7L- (Ib) anions. A2Cu3Cl8 or A2Cu3Cl8 salts are formed with A being the (Chemical Equation Presented) N-methylpiperazinium (NMPZ), 3-methyl-2-aminopyridinium (3MAP), and 5-methyl-2-aminopyridinium (5MAP) cations. A Cu3Br8 3- analogue is found with the 5-bromo-6-methyl-2-aminopyridinium (5B6MAP) cation. With the methylphenethylammonium (NMPH) cation, a (NMPH)Cu3Cl7·EtOH salt is isolated. The salts are all monoclinic with the following space group and lattice constants: NMPZ, C5H14N2Cu3Cl8, P21/c, a = 6.840 (3) {\AA}, b = 14.321 (9) {\AA}, c = 9.890 (5) {\AA}, β = 102.90 (5)°, Z = 4; 3MAP, C12H18N4Cu3Cl8, C2/c, a = 26.05 (1) {\AA}, b = 13.687 (4) {\AA}, c = 7.099 (3) {\AA}, β = 117.95 (3)°, Z = 4; NMPH, C11H20NOC3Cl7, P21/n, a = 11.843 (4) {\AA}, b = 7.626 (3) {\AA}, c = 23.840 (10) {\AA}, β = 79.61 (3)°, Z = 4; 5B6MAP, C12N10N4-Cu3Br10, P21/n, a = 13.216 (3) {\AA}, b = 4.076 (1) {\AA}, c = 24.614 (6) {\AA}, β = 91.65 (2)°, Z = 2. Each copper ion extends its primary coordination by formation of two semicoordinate bonds to halide ions in adjacent oligomers, yielding the familiar 4+2 coordination geometry for copper(II) complexes. These additional linkages cause the oligomers to aggregate into stacks, yielding stacking patterns of type IIa (NMPZ, 3MAP salts) or type IIb (NMPH, 5MAP, and 5B6MAP). Cu-X distances are approximately 2.3 (Figure Presented) {\AA} (Cl) or 2.4 {\AA} (Br) within the oligomers and 2.7-3.3 {\AA} (Cl) or 3.2-3.3 {\AA} (Br) between oligomers. The bridging Cu-X-Cu angles within the trimer average near 94°. Magnetic susceptibility measurements have been made on the NMPZ, NMPH, 3MAP, and 5MAP chloride salts. In addition, measurements were performed on Cu3Cl6(CH3CN)2, which contains neutral trinuclear oligomers. All compounds have doublet ground states arising from antiferromagnetic exchange coupling between neighboring copper(II) ions. The value of J/k is typically -20 to -35 K, consistent with the structural characteristics of the trimeric species.",
author = "Grigereit, {Todd E.} and Ramakrishna, {B. L.} and Helen Place and Willett, {Roger D.} and Pellacani, {Gian Carlo} and Tiziano Manfredini and Ledi Menabue and Anna Bonamartini-Corradi and Battaglia, {Luigi Pietro}",
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journal = "Inorganic Chemistry",
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TY - JOUR

T1 - Structures and magnetic properties of trinuclear copper(II) halide salts

AU - Grigereit, Todd E.

AU - Ramakrishna, B. L.

AU - Place, Helen

AU - Willett, Roger D.

AU - Pellacani, Gian Carlo

AU - Manfredini, Tiziano

AU - Menabue, Ledi

AU - Bonamartini-Corradi, Anna

AU - Battaglia, Luigi Pietro

PY - 1987

Y1 - 1987

N2 - The crystal structures of a series of trinuclear copper(II) halide salts have been determined. These all contain pseudoplanar, symmetrically bibridged Cu3X8 2- (Ia) or Cu3X7L- (Ib) anions. A2Cu3Cl8 or A2Cu3Cl8 salts are formed with A being the (Chemical Equation Presented) N-methylpiperazinium (NMPZ), 3-methyl-2-aminopyridinium (3MAP), and 5-methyl-2-aminopyridinium (5MAP) cations. A Cu3Br8 3- analogue is found with the 5-bromo-6-methyl-2-aminopyridinium (5B6MAP) cation. With the methylphenethylammonium (NMPH) cation, a (NMPH)Cu3Cl7·EtOH salt is isolated. The salts are all monoclinic with the following space group and lattice constants: NMPZ, C5H14N2Cu3Cl8, P21/c, a = 6.840 (3) Å, b = 14.321 (9) Å, c = 9.890 (5) Å, β = 102.90 (5)°, Z = 4; 3MAP, C12H18N4Cu3Cl8, C2/c, a = 26.05 (1) Å, b = 13.687 (4) Å, c = 7.099 (3) Å, β = 117.95 (3)°, Z = 4; NMPH, C11H20NOC3Cl7, P21/n, a = 11.843 (4) Å, b = 7.626 (3) Å, c = 23.840 (10) Å, β = 79.61 (3)°, Z = 4; 5B6MAP, C12N10N4-Cu3Br10, P21/n, a = 13.216 (3) Å, b = 4.076 (1) Å, c = 24.614 (6) Å, β = 91.65 (2)°, Z = 2. Each copper ion extends its primary coordination by formation of two semicoordinate bonds to halide ions in adjacent oligomers, yielding the familiar 4+2 coordination geometry for copper(II) complexes. These additional linkages cause the oligomers to aggregate into stacks, yielding stacking patterns of type IIa (NMPZ, 3MAP salts) or type IIb (NMPH, 5MAP, and 5B6MAP). Cu-X distances are approximately 2.3 (Figure Presented) Å (Cl) or 2.4 Å (Br) within the oligomers and 2.7-3.3 Å (Cl) or 3.2-3.3 Å (Br) between oligomers. The bridging Cu-X-Cu angles within the trimer average near 94°. Magnetic susceptibility measurements have been made on the NMPZ, NMPH, 3MAP, and 5MAP chloride salts. In addition, measurements were performed on Cu3Cl6(CH3CN)2, which contains neutral trinuclear oligomers. All compounds have doublet ground states arising from antiferromagnetic exchange coupling between neighboring copper(II) ions. The value of J/k is typically -20 to -35 K, consistent with the structural characteristics of the trimeric species.

AB - The crystal structures of a series of trinuclear copper(II) halide salts have been determined. These all contain pseudoplanar, symmetrically bibridged Cu3X8 2- (Ia) or Cu3X7L- (Ib) anions. A2Cu3Cl8 or A2Cu3Cl8 salts are formed with A being the (Chemical Equation Presented) N-methylpiperazinium (NMPZ), 3-methyl-2-aminopyridinium (3MAP), and 5-methyl-2-aminopyridinium (5MAP) cations. A Cu3Br8 3- analogue is found with the 5-bromo-6-methyl-2-aminopyridinium (5B6MAP) cation. With the methylphenethylammonium (NMPH) cation, a (NMPH)Cu3Cl7·EtOH salt is isolated. The salts are all monoclinic with the following space group and lattice constants: NMPZ, C5H14N2Cu3Cl8, P21/c, a = 6.840 (3) Å, b = 14.321 (9) Å, c = 9.890 (5) Å, β = 102.90 (5)°, Z = 4; 3MAP, C12H18N4Cu3Cl8, C2/c, a = 26.05 (1) Å, b = 13.687 (4) Å, c = 7.099 (3) Å, β = 117.95 (3)°, Z = 4; NMPH, C11H20NOC3Cl7, P21/n, a = 11.843 (4) Å, b = 7.626 (3) Å, c = 23.840 (10) Å, β = 79.61 (3)°, Z = 4; 5B6MAP, C12N10N4-Cu3Br10, P21/n, a = 13.216 (3) Å, b = 4.076 (1) Å, c = 24.614 (6) Å, β = 91.65 (2)°, Z = 2. Each copper ion extends its primary coordination by formation of two semicoordinate bonds to halide ions in adjacent oligomers, yielding the familiar 4+2 coordination geometry for copper(II) complexes. These additional linkages cause the oligomers to aggregate into stacks, yielding stacking patterns of type IIa (NMPZ, 3MAP salts) or type IIb (NMPH, 5MAP, and 5B6MAP). Cu-X distances are approximately 2.3 (Figure Presented) Å (Cl) or 2.4 Å (Br) within the oligomers and 2.7-3.3 Å (Cl) or 3.2-3.3 Å (Br) between oligomers. The bridging Cu-X-Cu angles within the trimer average near 94°. Magnetic susceptibility measurements have been made on the NMPZ, NMPH, 3MAP, and 5MAP chloride salts. In addition, measurements were performed on Cu3Cl6(CH3CN)2, which contains neutral trinuclear oligomers. All compounds have doublet ground states arising from antiferromagnetic exchange coupling between neighboring copper(II) ions. The value of J/k is typically -20 to -35 K, consistent with the structural characteristics of the trimeric species.

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JF - Inorganic Chemistry

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