The goal in growing crystals for a single crystal X-ray diffraction experiment is to grow single crystals (obviously) of suitable size. The optimum size for a crystal is one which has dimensions of 0.2 - 0.4 mm in at least two of the three dimensions. Most potential structure determinations are thwarted by a lack of suitable crystals.
The factors during crystal growth which affect the size of the crystals are, solubility of compound in the solvent chosen for recrystallization, the number of nucleation sites, mechanical agitation to the system, and time.
Solvent. Choose a solvent in which your compound is moderately soluble. If the solute is too soluble, this will result in small crystal size.
Avoid solvents in which your compound forms supersaturated solutions. supersatuated solutions tend to give crystals which are too small in size
PS. This is contradictory to above finding.
Nucleation. The fewer sites at which crystals begin to grow will result in fewer crystals each of larger size. This is desirable. Conversely, many nucleation sites results in a smaller average crystal size, and is not desirable. In many recrystallizations ambient dust in the laboratory provide sites of nucleation. It is important to minimize dust or other extraneous particulate matter in the crystal growing vessel.
Mechanics. Mechanical disturbance of the crystal growing vessel results in smaller crystals. Let the crystals grow with a minimum of disturbance. This means: Don't try to grow crystals next to your vacuum pump, and don't pick up the vessel everyday to check on how your crystals are growing. Set up the crystal growing attempt, in a quiet, out of the way place and forget about it (if possible!) for a week.
Time. This is related to mechanics. Crystals fully recognize that patience is a virtue and will reward those who practice it.
Crystal growing is an art, and there are as many variations to the basic crystal growing recipes as there are crystallographers. The recipes given below are ones which I have either tried or I have read about and sound reasonable. The techniques chosen will largely depend on the chemical properties of the compound of interest: Is the compound air sensitive, moisture sensitive? Is it hygroscopic? etc. etc.
Slow Evaporation. This is the simplest way to grow crystals and works best for compounds which are not sensitive to ambient conditions in the laboratory. Prepare a solution of the compound in a suitable solvent. The solution should be saturated or nearly saturated. Transfer the solution to a CLEAN crystal growing dish and cover. The covering for the container should not be air tight. Aluminium foil with some holes poked in it works well, or a flat piece of glass with microscope slides used as a spacer also will do the trick. Place the container in a quiet out of the way place and let it evaporate. This method works best where there is enough material to saturate at least a few milliliters of solvent.
Slow Cooling. This is good for solute-solvent systems which are less than moderately soluble and the solvent's boiling point is less than 100 deg C. Prepare a saturated solution of the compound where is the solvent is heated to just it's boiling point or a just below it. Transfer the solution to a CLEAN large test tube and stopper. Transfer the test tube to a Dewar flask in which hot water (heated to a temperature of a couple of degrees below the solvent boiling point). The water level should exceed the solvent level in the test tube, but should not exceed the height of the test tube. Stopper the Dewar flask with a cork stopper and let the vessel sit for a week. A more elaborate version of this involves a thermostated oven rather than a Dewar flask.
Variations on Slow Evaporation and Slow Cooling. If the above two techniques do yield suitable crystals from single solvent systems, one may expand these techniques to binary or tertiary solvent systems. The basic rationale for this is by varying the solvent composition one may inhibit growth of certain crystal faces and promote the growth of other faces, yielding crystals of suitable morphology and size. If you choose this route for growing crystals, it absolutely necessary to record the solvent composition you use! If crystal growing is an art, growing crystals from binary or tertiary solvent mixtures is that much more imprecise. Remember reproducibility is paramount in science.
Vapor Diffusion. (excerpted and paraphrased from Stout and Jensen p. 65). This method is good for milligram amounts of material. A solution of the substance is prepared using solvent S1 and placed in test tube T. A second solvent, S2, is placed in a closed beaker, B. S2 is chosen such that when mixed with S1 the solute will become less soluble. The test tube containing S1 is then placed in the beaker and the beaker is sealed. Slow diffusion of S2 into T and S1 out of T will cause crystals to form. If S2 is more volatile than S1 the solvent level will increase and prevent microcrystalline crusts from forming on the sides of T.
Last edited by Mustafa Umut Sarac; 10-27-2013 at 03:09 AM. Click to view previous post history.