Natural gas hydrates recovered from the Congo- Angola basin and Nigerian margins are analyzed by synchrotron X- ray powder diffraction. Biogenic methane is the most abundant gas trapped in the samples and others minor components (CO2, H2S) are co-clathrated in a type I cubic lattice structure. The refinement for the type I structure gives lattice parameters of a = 11.8646 ( 39) angstrom and a = 11.8619 ( 23) angstrom for specimens from Congo- Angola and Nigerian margins respectively at 90 K. These values, intermediate between the lattice constant of less pure methane specimens and pure artificial methane hydrates, indicate that lattice constants can be affected by the presence of encaged CO2, H2S and other gas molecules, even in small amounts. Thermal expansion is also presented for Congo- Angola hydrate in the temperature range 90 - 200 K. The coefficients are comparable with values reported for synthetic hydrates at low temperature and tend to approach thermal expansion of ice at higher temperature.