Water of crystallization

In crystallography, water of crystallization or water of hydration or crystallization water is water that occurs in crystals. Water of crystallization is necessary for the maintenance of crystalline properties, but capable of being removed by sufficient heat. ^[1] It is the total weight of water retained by certain salts at a given temperature^[2] and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex but which is not directly bonded to the metal ion.

Upon crystallization from water or moist solvents, many compounds incorporate water molecules in their crystalline frameworks.

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.

Nomenclature

In molecular formulas water of crystallization can be denoted in different ways:

• "hydrous compound⋅nH₂O" or "hydrous compound×nH₂O"
  

This notation is used when the compound only contains lattice water or when the crystal structure is undetermined. For example Calcium chloride: CaCl₂·2H₂O

• "hydrous compound(H₂O)_n"
  

A hydrate with coordinated water. For example Zinc chloride: ZnCl₂(H₂O)₄

• Both notations can be combined as for example in copper(II) sulfate: [Cu(H₂O)₄]SO₄·H₂O

Position in the crystal structure

A salt with associated water of crystallization is known as a hydrate. The structure of hydrates can be quite elaborate, because of the existence of hydrogen bonds that define polymeric structures. ^{[3] [4]} Historically, the structures of many hydrates were unknown, and the dot in the formula of a hydrate was employed to specify the composition without indicating how the water is bound. Examples:

• CuSO₄•5H₂O - copper(II) sulfate pentahydrate
• CoCl₂•6H₂O - cobalt(II) chloride hexahydrate
• SnCl₂•2H₂O - tin(II) (or stannous) chloride dihydrate

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 consist of [Cu(H₂O)₄]²⁺ centers linked to SO₄^2- 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 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 arises from water. Glauber's salt, Na₂SO₄(H₂O)₁₀, is a white crystalline solid with greater than 50% water by weight.

Consider the case of nickel(II) chloride hexahydrate. This species has the formula NiCl₂(H₂O)₆. Crystallographic analysis reveals that the solid consists of [trans-NiCl₂(H₂O)₄] subunits that are hydrogen bonded to each other as well as two additional 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".

Analysis

The water content of most compounds can be determined with a knowledge of its formula. An unknown sample can be determined through thermogravimetric analysis (TGA) where the sample is heated strongly, and the accurate weight of a sample is plotted against the temperature. The amount of water driven off is then divided by the molar mass of water to obtain the number of molecules of water bound to the salt.

Other solvents of crystallization

Water is particularly common solvent to be found in crystals because it is small and polar. But all solvents can be found in some host crystals. Water is noteworthy because it is reactive, whereas other solvents such as benzene are considered to be chemically innocuous. Occasionally more than one solvent is found in a crystal, and often the stoichiometry is variable, reflected in the crystallographic concept of "partial occupancy." It is common and conventional for a chemist to "dry" a sample with a combination of vacuum and heat "to constant weight."

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.

Table of crystallization water in some inorganic halides

In the table below are indicated the number of molecules of water per metal in various salts.^[5]

Formula of hydrated metal halides	Coordination sphere of the metal	equivalents of water of crystallization that are not bound to M	Remarks
VCl3(H2O)6	trans-[VCl2(H2O)4]+	two
VBr3(H2O)6	trans-[VBr2(H2O)4]+	two	bromides and chlorides are usually similar
VI3(H2O)6	[V(H2O)6]3+	none	iodide competes poorly with water
CrCl3(H2O)6	trans-[CrCl2(H2O)4]+	two	dark green isomer
CrCl3(H2O)6	[CrCl(H2O)5]2+	one	blue-green isomer
CrCl2(H2O)4	trans-[CrCl2(H2O)4]	none	molecular
CrCl3(H2O)6	[Cr(H2O)6]3+	none	violet isomer
MnCl2(H2O)6	trans-[MnCl2(H2O)4]	two
MnCl2(H2O)4	cis-[MnCl2(H2O)4]	none	note cis molecular
MnBr2(H2O)4	cis-[MnBr2(H2O)4]	none	note cis molecular
MnCl2(H2O)2	trans-[MnCl4(H2O)2]	none	polymeric with bridging chloride
MnBr2(H2O)2	trans-[MnBr4(H2O)2]	none	polymeric with bridging bromide
FeCl2(H2O)6	trans-[FeCl2(H2O)4]	two
FeCl2(H2O)4	trans-[FeCl2(H2O)4]	none	molecular
FeBr2(H2O)4	trans-[FeBr2(H2O)4]	none	molecular
FeCl2(H2O)2	trans-[FeCl4(H2O)2]	none	polymeric with bridging chloride
CoCl2(H2O)6	trans-[CoCl2(H2O)4]	two
CoBr2(H2O)6	trans-[CoBr2(H2O)4]	two
CoBr2(H2O)4	trans-[CoBr2(H2O)4]	none	molecular
CoCl2(H2O)4	cis-[CoCl2(H2O)4]	none	note: cis molecular
CoCl2(H2O)2	trans-[CoCl4(H2O)2]	none	polymeric with bridging chloride
CoBr2(H2O)2	trans-[CoBr4(H2O)2]	none	polymeric with bridging bromide
NiCl2(H2O)6	trans-[NiCl2(H2O)4]	two
NiCl2(H2O)4	cis-[NiCl2(H2O)4]	none	note: cis molecular
NiBr2(H2O)6	trans-[NiBr2(H2O)4]	two
NiCl2(H2O)2	trans-[NiCl2(H2O)4]	none	polymeric with bridging chloride
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

See also

• Hydrate
• Mineral hydration

References

1. ^ Medical Dictionary: water of crystallization
2. ^ V.P. Sokoloff: Water of Crystallization in Total Solids of Water Analysis Ind. Eng. Chem. Anal. Ed.; 1933, 5 (5), pp 336–337 doi:10.1021/ac50085a023
3. ^ Yonghui Wang et al. Novel Hydrogen-Bonded Three-Dimensional Networks Encapsulating One-Dimensional Covalent Chains: ... Inorg. Chem., 2002, 41 (24), pp 6351–6357. doi:10.1021/ic025915o
4. ^ Carmen R. Maldonadoa, Miguel Quirós and J.M. Salas: Formation of 2D water morphologies in the lattice of the salt... Inorganic Chemistry Communications Volume 13, Issue 3, March 2010, p.399-403; doi:10.1016/j.inoche.2009.12.033
5. ^ K. Waizumi, H. Masuda, H. Ohtaki, "X-ray structural studies of FeBr₂4H₂O, CoBr₂4H₂O, NiCl₂ 4H₂O, and CuBr₂4H₂O. cis/trans Selectivity in transition metal(I1) dihalide Tetrahydrate" Inorganica Chimica Acta, 1992 volume 192, pages 173-181.