Context. This paper is part of a study of the apsidal motion in close eccentric massive binary systems, which aims to constrain the internal structure of the stars. We focus on the binary CPD-41° 7742 and briefly revisit the case of HD 152218. Aims. Independent studies of CPD-41° 7742 in the past showed large discrepancies in the longitude of periastron of the orbit, hinting at the presence of apsidal motion. We here perform a consistent analysis of all observational data, explicitly accounting for the rate of change of the longitude of periastron. Methods. We make use of the extensive set of spectroscopic and photometric observations of CPD-41° 7742 to infer values for the fundamental parameters of the stars and of the binary. Applying a disentangling method to the spectra allows us to simultaneously derive the radial velocities (RVs) at the times of observation and reconstruct the individual spectra of the stars. The spectra are analysed by means of the CMFGEN model atmosphere code to determine the stellar properties. We determine the apsidal motion rate in two ways: First, we complement our RVs with those reported in the literature, and, second, we use the phase shifts between the primary and secondary eclipses. The light curves are further analysed by means of the Nightfall code to constrain the orbital inclination and, thereby, the stellar masses. Stellar structure and evolution models are then constructed with the Clés code for the two stars with the constraints provided by the observations. Different prescriptions for the mixing inside the stars are adopted in the models. Newly available photometric data of HD 152218 are analysed, and stellar structure and evolution models are built for the system as for CPD-41° 7742. Results. The binary system CPD-41° 7742, made of an O9.5 V primary (MP = 17.8 ± 0.5 M⊙, RP = 7.57 ± 0.09 R⊙, Teff, P = 31 800 ± 1000 K, Lbol,P = 5.28−0.68+0.67 × 104 L⊙) and a B1–2 V secondary (MS = 10.0 ± 0.3 M⊙, RS = 4.29−0.06+0.04 R⊙, Teff, S = 24 098 ± 1000 K, Lbol,S = 5.58−0.94+0.93 × 103 L⊙), displays apsidal motion at a rate of 15.°38−0.51+0.42 yr−1. Initial masses of 18.0 ± 0.5 M⊙ and 9.9 ± 0.3 M⊙ are deduced for the primary and secondary stars, respectively, and the binary’s age is estimated to be 6.8 ± 1.4 Myr. Regarding HD 152218, initial masses of 20.6 ± 1.5 and 15.5 ± 1.1 M⊙ are deduced for the primary and secondary stars, respectively, and the binary’s age of 5.2 ± 0.8 Myr is inferred. Conclusions. Our analysis of the observational data of CPD-41° 7742 that explicitly accounts for the apsidal motion allows us to explain the discrepancy in periastron longitudes pointed out in past studies of this binary system. The age estimates are in good agreement with estimates obtained for other massive binaries in NGC 6231. This study confirms the need for enhanced mixing in the stellar evolution models of the most massive stars to reproduce the observational stellar properties; this points towards larger convective cores than usually considered.
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