Local coordination numbers can be estimated from liquid structure factors by a number of routes. Here, we keep as close as possible to the liquid structure factor S(q) data, determined by diffraction experiments. For the expanded fluid heavy alkali metals along the liquid-vapour coexistence curve towards the critical point, the coordination number varies lineary with number density. Here attention is focused also on the melting curve of Rb under pressure, the results being compared and contrasted with the predictions of the one-component plasma model. Such liquid alkali metal behaviour is then compared and contrasted with that of some highly directionally bonded fluids including B, C and Si, in the latter two of which liquid-liquid phase transition occur in very different regimes of thermodynamic state. Finally, some structural integrals involving pair potentials and the pair correlation functions they generate are used to define a characteristics "structural length". In turn, this is compared with a "thermodynamic length" which is defined as the ratio of surface tension to the deviation of the pressure P from its perfect gas value rho kappa_BT. Some numerical results are given utilizing pair potentials and corresponding structure factors for Be and B.

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