Hydrogen bonding in basic copper salts: a spectroscopic study of malachite,Cu2(OH)2CO3, and brochantite,Cu4(OH)6SO4 |
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Authors: | M. Schmidt H. D. Lutz |
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Affiliation: | 1. Universit?t Siegen, Anorganische Chemie I, Postfach 101240, W-5900, Siegen, Germany
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Abstract: | Infrared and Raman spectra of the basic copper salts malachite, Cu2(OH)2CO3, and brochantite, Cu4(OH)6SO4, as well as of deuterated and 13C substituted samples are presented and discussed in terms of group theory and the hydrogen bonds present. The main results are that (i) the hydrogen donor strengths of the OH? ions are strongly increased due to the very great synergetic effect of the copper ions, (ii) the acceptor strengths of the H-bond acceptor groups (SO4 2-, CO3 2-, and OH? ions) are significantly modified by the linkage and coordination of the acceptor atoms — this complicates true assignment of the OH bands observed to the two and six different OH? ions present in malachite and brochantite, respectively -, and (iii) the Cu — O stretching modes at 430–590 cm?1 and 420–520 cm?1 for malachite and brochantite, respectively, exhibit strong, partially covalent Cu — O bonding. |
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