The influence of functional group orientation on the structure of zinc 1,1,4-trimethylthiosemicarbazide dicarboxylates: Probing the limits of crystal engineering strategies

A D Burrows, R W Harrington, M F Mahon, S J Teat

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Abstract

The reaction of [Zn(tmtsc)(2)](NO3)(2) [tmtsc = 1,1,4-trimethylthiosemicarbazide, MeNHC(S)NHNMe2] with a range of sodium dicarboxylates has been shown to lie on the borderline between commonly used crystal engineering strategies. The products exhibit a wide range of structural diversity with the main driving force being the relative orientation of the carboxylate groups. Thus, fumarate leads to the hydrogen-bonded aggregate [Zn(tmtsc)(2)(OH2)][fumarate] (2) in which cations and anions are linked by hydrogen bond donor-donor acceptor-acceptor (DD:AA) interactions, whereas isophthalate and (+)-camphorate lead to coordination polymers [Zn(tmtsc)(mu-isophthalate)] (3a) and [Zn(tmtsc)(mu-camphorate)] (4) with the metal centres linked by bridging dicarboxylate ligands. In the case of isophthalate, a hydrated product [Zn(tmtsc)(mu-isophthalate)].H2O (3b) was also characterised, although microanalysis and powder X-ray diffraction revealed this to be a minor product. Incorporation of water was shown to lead to a change in carboxylate coordination mode from eta(1) in 3a to 112 in 3b. Use of terephthalate leads to the compound [{Zn(tmtsc)(OH2)}(2)(mu-terephthalate)]-[terephthalate].2H(2)O (5), in which half of the terephthalates bridge metal centres, to form dimers, and the remainder link the dimeric cations through DD:AA hydrogen bond interactions. Homophthalate leads to discrete dimers [Zn(tmtsc)(mu-homophthalate)12 (6), whereas acetylenedicarboxylate yields the unexpected compound [Zn(tmtsc)(2)(OH2)][O2CCH= CC(O)N(Me)C(=NNMe2)S](2).H2O (7) in which the dicarboxylate has reacted with tmtsc to give a 2-hydrazono-4-oxo1,3-thiazolidineacetate, which is subsequently trapped in the solid state by DDAA hydrogen bonding interactions with [Zn(tMtSO(2)(OH2)](2+). All products were characterised by single crystal X-ray crystallography, and the representational nature of these crystal structures to the bulk materials was confirmed by microanalysis and powder diffraction. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Original languageEnglish
Pages (from-to)766-776
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Issue number4
Publication statusPublished - 2003

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Crystal engineering
Functional groups
Zinc
Hydrogen bonds
Fumarates
Dimers
Cations
Metals
X ray crystallography
X ray powder diffraction
Anions
Hydrogen
Polymers
Crystal structure
Sodium
Single crystals
Ligands
terephthalic acid
isophthalate
Water

Cite this

@article{a46300e92fb0480cb70591ed00058a86,
title = "The influence of functional group orientation on the structure of zinc 1,1,4-trimethylthiosemicarbazide dicarboxylates: Probing the limits of crystal engineering strategies",
abstract = "The reaction of [Zn(tmtsc)(2)](NO3)(2) [tmtsc = 1,1,4-trimethylthiosemicarbazide, MeNHC(S)NHNMe2] with a range of sodium dicarboxylates has been shown to lie on the borderline between commonly used crystal engineering strategies. The products exhibit a wide range of structural diversity with the main driving force being the relative orientation of the carboxylate groups. Thus, fumarate leads to the hydrogen-bonded aggregate [Zn(tmtsc)(2)(OH2)][fumarate] (2) in which cations and anions are linked by hydrogen bond donor-donor acceptor-acceptor (DD:AA) interactions, whereas isophthalate and (+)-camphorate lead to coordination polymers [Zn(tmtsc)(mu-isophthalate)] (3a) and [Zn(tmtsc)(mu-camphorate)] (4) with the metal centres linked by bridging dicarboxylate ligands. In the case of isophthalate, a hydrated product [Zn(tmtsc)(mu-isophthalate)].H2O (3b) was also characterised, although microanalysis and powder X-ray diffraction revealed this to be a minor product. Incorporation of water was shown to lead to a change in carboxylate coordination mode from eta(1) in 3a to 112 in 3b. Use of terephthalate leads to the compound [{Zn(tmtsc)(OH2)}(2)(mu-terephthalate)]-[terephthalate].2H(2)O (5), in which half of the terephthalates bridge metal centres, to form dimers, and the remainder link the dimeric cations through DD:AA hydrogen bond interactions. Homophthalate leads to discrete dimers [Zn(tmtsc)(mu-homophthalate)12 (6), whereas acetylenedicarboxylate yields the unexpected compound [Zn(tmtsc)(2)(OH2)][O2CCH= CC(O)N(Me)C(=NNMe2)S](2).H2O (7) in which the dicarboxylate has reacted with tmtsc to give a 2-hydrazono-4-oxo1,3-thiazolidineacetate, which is subsequently trapped in the solid state by DDAA hydrogen bonding interactions with [Zn(tMtSO(2)(OH2)](2+). All products were characterised by single crystal X-ray crystallography, and the representational nature of these crystal structures to the bulk materials was confirmed by microanalysis and powder diffraction. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.",
author = "Burrows, {A D} and Harrington, {R W} and Mahon, {M F} and Teat, {S J}",
note = "ID number: ISI:000181151300026",
year = "2003",
language = "English",
pages = "766--776",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag",
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}

TY - JOUR

T1 - The influence of functional group orientation on the structure of zinc 1,1,4-trimethylthiosemicarbazide dicarboxylates: Probing the limits of crystal engineering strategies

AU - Burrows, A D

AU - Harrington, R W

AU - Mahon, M F

AU - Teat, S J

N1 - ID number: ISI:000181151300026

PY - 2003

Y1 - 2003

N2 - The reaction of [Zn(tmtsc)(2)](NO3)(2) [tmtsc = 1,1,4-trimethylthiosemicarbazide, MeNHC(S)NHNMe2] with a range of sodium dicarboxylates has been shown to lie on the borderline between commonly used crystal engineering strategies. The products exhibit a wide range of structural diversity with the main driving force being the relative orientation of the carboxylate groups. Thus, fumarate leads to the hydrogen-bonded aggregate [Zn(tmtsc)(2)(OH2)][fumarate] (2) in which cations and anions are linked by hydrogen bond donor-donor acceptor-acceptor (DD:AA) interactions, whereas isophthalate and (+)-camphorate lead to coordination polymers [Zn(tmtsc)(mu-isophthalate)] (3a) and [Zn(tmtsc)(mu-camphorate)] (4) with the metal centres linked by bridging dicarboxylate ligands. In the case of isophthalate, a hydrated product [Zn(tmtsc)(mu-isophthalate)].H2O (3b) was also characterised, although microanalysis and powder X-ray diffraction revealed this to be a minor product. Incorporation of water was shown to lead to a change in carboxylate coordination mode from eta(1) in 3a to 112 in 3b. Use of terephthalate leads to the compound [{Zn(tmtsc)(OH2)}(2)(mu-terephthalate)]-[terephthalate].2H(2)O (5), in which half of the terephthalates bridge metal centres, to form dimers, and the remainder link the dimeric cations through DD:AA hydrogen bond interactions. Homophthalate leads to discrete dimers [Zn(tmtsc)(mu-homophthalate)12 (6), whereas acetylenedicarboxylate yields the unexpected compound [Zn(tmtsc)(2)(OH2)][O2CCH= CC(O)N(Me)C(=NNMe2)S](2).H2O (7) in which the dicarboxylate has reacted with tmtsc to give a 2-hydrazono-4-oxo1,3-thiazolidineacetate, which is subsequently trapped in the solid state by DDAA hydrogen bonding interactions with [Zn(tMtSO(2)(OH2)](2+). All products were characterised by single crystal X-ray crystallography, and the representational nature of these crystal structures to the bulk materials was confirmed by microanalysis and powder diffraction. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

AB - The reaction of [Zn(tmtsc)(2)](NO3)(2) [tmtsc = 1,1,4-trimethylthiosemicarbazide, MeNHC(S)NHNMe2] with a range of sodium dicarboxylates has been shown to lie on the borderline between commonly used crystal engineering strategies. The products exhibit a wide range of structural diversity with the main driving force being the relative orientation of the carboxylate groups. Thus, fumarate leads to the hydrogen-bonded aggregate [Zn(tmtsc)(2)(OH2)][fumarate] (2) in which cations and anions are linked by hydrogen bond donor-donor acceptor-acceptor (DD:AA) interactions, whereas isophthalate and (+)-camphorate lead to coordination polymers [Zn(tmtsc)(mu-isophthalate)] (3a) and [Zn(tmtsc)(mu-camphorate)] (4) with the metal centres linked by bridging dicarboxylate ligands. In the case of isophthalate, a hydrated product [Zn(tmtsc)(mu-isophthalate)].H2O (3b) was also characterised, although microanalysis and powder X-ray diffraction revealed this to be a minor product. Incorporation of water was shown to lead to a change in carboxylate coordination mode from eta(1) in 3a to 112 in 3b. Use of terephthalate leads to the compound [{Zn(tmtsc)(OH2)}(2)(mu-terephthalate)]-[terephthalate].2H(2)O (5), in which half of the terephthalates bridge metal centres, to form dimers, and the remainder link the dimeric cations through DD:AA hydrogen bond interactions. Homophthalate leads to discrete dimers [Zn(tmtsc)(mu-homophthalate)12 (6), whereas acetylenedicarboxylate yields the unexpected compound [Zn(tmtsc)(2)(OH2)][O2CCH= CC(O)N(Me)C(=NNMe2)S](2).H2O (7) in which the dicarboxylate has reacted with tmtsc to give a 2-hydrazono-4-oxo1,3-thiazolidineacetate, which is subsequently trapped in the solid state by DDAA hydrogen bonding interactions with [Zn(tMtSO(2)(OH2)](2+). All products were characterised by single crystal X-ray crystallography, and the representational nature of these crystal structures to the bulk materials was confirmed by microanalysis and powder diffraction. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

M3 - Article

SP - 766

EP - 776

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 4

ER -