We investigate the serendipitous X-ray source population revealed in XMM-Newton observations targeted in the Galactic Plane within the region 315<l<45 and |b|<2.5 deg. Our study focuses on a sample of 2204 X-ray sources at intermediate to faint fluxes, which were detected in a total of 116 XMM fields and are listed in the 2XMMi catalogue. We characterise each source as spectrally soft or hard on the basis of whether the bulk of the recorded counts have energies below or above 2 keV and find that the sample divides roughly equally (56%:44%) into these soft and hard categories. The X-ray spectral form underlying the soft sources may be represented as either a power-law continuum with Gamma~2.5 or a thermal spectrum with kT~0.5 keV, with N_H ranging from 10^{20-22} cm^{-2}. For the hard sources, a significantly harder continuum form is likely, i.e., Gamma~1 with N_H=10^{22-24} cm^{-2}. For ~50% of the hard sources, the inferred column density is commensurate with the total Galactic line-of-sight value; many of these sources will be located at significant distances across the Galaxy implying a hard band luminosity L_X>10^{32} erg/s, whereas some will be extragalactic interlopers. >90% of the soft sources have potential NIR (2MASS and/or UKIDSS) counterparts inside their error circles, consistent with the dominant soft X-ray source population being relatively nearby coronally-active stars. These stellar counterparts are generally brighter than J=16, a brightness cutoff which corresponds to the saturation of the X-ray coronal emission at L_X=10^{-3} L_{bol}. In contrast, the success rate in finding likely IR counterparts to the hard X-ray sample is no more than ~15% down to J=16 and ~25% down to J=20, set against a rapidly rising chance coincidence rate. The make-up of the hard X-ray source population, in terms of the known classes of accreting and non-accreting systems, remains uncertain.
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