Position the flash above the tank, pointing down and slightly toward the back of the aquarium. This will create a more natural look since sunlight filters down from above in underwater settings. Also, firing the flash from above will prevent any unwanted reflections from the front or rear glass panels.
The water in the tank will act as a natural diffuser, giving the light a less artificial quality.
As an added precaution against reflections from the front glass panel, place the lens as close as possible to the glass surface and use a lens hood to block ambient light. The lens hood can in fact be placed right up against the glass.
Also, ensure that the lens is as nearly perpendicular to the glass surface as possible. Obviously, the glass used in aquariums is not of the same quality as that found in your camera gear. The glass will not be perfectly flat, and keeping your lens perpendicular to it will minimize any distortions which may be introduced.
Choose a subject you wish to photography, but while you are composing the shot keep in mind that you want to avoid any distracting elements in your photo, such as a dark rock or filter tube in the background. This can be tricky, particularly with a moving subject, but patience will pay off, and you will be rewarded with a superior image.
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