Classically, "water of crystallization" refers to water that is found in a crystalline framework of a metal complex but that is not directly bonded to the metal ion. Obviously the "water of crystallization" is bound or interacting with some other atoms and ions or it would not be included in the crystalline framework. Consider the case of nickel(II) chloride hexahydrate. This species has the formula NiCl2(H2O)6. Examination of its molecular structure reveals that the crystal consists of [trans-NiCl2(H2O)4] subunits that are hydrogen bonded to each other and two isolated molecules of H2O. Thus 1/3 of the water molecules in the crystal are not directly bonded to Ni2+, and these might be termed "water of crystallization".
Compared to inorganic salts, proteins crystallize with unusually large amounts of water in the crystal lattice. A water content of 50 % is not uncommon. The extended hydration shell is what allows the protein crystallographer to argue that the conformation in the crystal is not too far from the native conformation in solution.
Since the latter part of the 20th century, the structures of most common hydrates have been determined by crystallography, so the dot formalism is increasingly obsolete. Another reason for using the dot formalism is simplicity. For many salts, the exact bonding of the water is unimportant because the water molecules are labilized upon dissolution. For example, an aqueous solution prepared from CuSO4•5H2O and anhydrous CuSO4 behave identically. Therefore, knowledge of the degree of hydration is important only for determining the equivalent weight: one mole of CuSO4•5H2O weighs more than one mole of CuSO4. In some cases, the degree of hydration can be critical to the resulting chemical properties. For example, anhydrous RhCl3 is not soluble in water and is relatively useless in organometallic chemistry whereas RhCl3•3H2O is versatile. Similarly, hydrated AlCl3 is a poor Lewis acid and thus inactive as a catalyst for Friedel-Crafts reactions. Samples of AlCl3 must therefore be protected from atmospheric moisture to preclude the formation of hydrates.
Crystals of the aforementioned hydrated copper sulfate consists of [Cu(H2O)4]2+ centers linked to SO42- ions. Copper is surrounded by six oxygen atoms, provided by two different sulfate groups and four molecules of water. A fifth water resides elsewhere in the framework but does not bind directly to copper. The cobalt iodide mentioned above occurs as [Co(H2O)6]2+ and I-. In the tin chloride, each Sn(II) center is pyramidal (mean O/Cl-Sn-O/Cl angle is 83°) being bound to two chloride ions and one water. The second water in the formula unit is hydrogen-bonded to the chloride and to the coordinated water molecule. Water of crystallization is stabilized by electrostatic attractions, consequently hydrates are common for salts that contain +2 and +3 cations as well as -2 anions. In some cases, the majority of the weight of a compound can arises from water. Glauber's salt, a white crystalline solid Na2SO4(H2O)10 is >50% water by weight.
A serious complication to the thermal analysis for the presence of water of hydration is that compounds that contain hydrogen and oxygen will release water when heated, regardless of whether they contained water molecules. Thus, the release of water upon heating, especially to high temperatures, is insufficient criterion for the presence of water in the sample prior to heating. For example, if one heats a carboxylic acid, RCO2H, one obtains H2O. No water was present in the starting carboxylic acid.
| Formula of|
hydrated metal halides
sphere of the metal
| equivalentsof water of|
are not bound to M
|VBr3(H2O)6||trans-[VBr2(H2O)4]+||two|| bromides and|
chlorides are usually
|VI3(H2O)6||[V(H2O)6]3+||none|| iodide competes|
poorly with water
|CrCl3(H2O)6||trans-[CrCl2(H2O)4]+||two||dark green isomer|
|MnCl2(H2O)4||cis-[MnCl2(H2O)4]||none|| note cis|
|MnBr2(H2O)4||cis-[MnBr2(H2O)4]||none|| note cis|
|MnCl2(H2O)2||trans-[MnCl4(H2O)2]||none|| polymeric with|
|MnBr2(H2O)2||trans-[MnBr4(H2O)2]||none|| polymeric with|
|FeCl2(H2O)2||trans-[FeCl4(H2O)2]||none|| polymeric with|
|CoCl2(H2O)4||cis-[CoCl2(H2O)4]||none|| note: cis|
|CoCl2(H2O)2||trans-[CoCl4(H2O)2]||none|| polymeric with|
|CoBr2(H2O)2||trans-[CoBr4(H2O)2]||none|| polymeric with|
|NiCl2(H2O)4||cis-[NiCl2(H2O)4]||none|| note: cis|
|NiCl2(H2O)2||trans-[NiCl4(H2O)2]||none|| polymeric with|
|CuCl2(H2O)2||[CuCl4(H2O)2]2||none|| tetragonally distorted|
two long Cu-Cl distances
|CuBr2(H2O)4||[CuBr4(H2O)2]n||two|| tetragonally distorted|
two long Cu-Br distances
For other solvents of crystallization, analysis is conveniently accomplished by dissolving the sample in a deuterated solvent and analyzing the sample for solvent signals by NMR spectroscopy. Single crystal X-ray crystallography is often able to detect the presence of these solvents of crystallization as well.