Hydrogen bonding in basic copper salts: a spectroscopic study of malachite,Cu2(OH)2CO3, and brochantite,Cu4(OH)6SO4

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.