Water, methane, and carbon monoxide are expected to be among the most abundant molecules besides molecular hydrogen in the hot atmosphere of close-in extrasolar giant planets. Atmospheric models for these planets predict that the strongest spectrophotometric features of those molecules are located at wavelengths ranging from 1 to 10 μm  making this region of particular interest. Consequently, transit observations in the mid-infrared (mid-IR) allow the atmospheric content of transiting planets to be determined. We present new primary transit observations of the hot-Jupiter HD 189733b, obtained simultaneously at 4.5 and 8 μm with the Infrared Array Camera onboard the Spitzer Space Telescope. Together with a new refined analysis of previous observations at 3.6 and 5.8 μm using the same instrument, we are able to derive the system parameters, including planet-to-star radius ratio, impact parameter, scale of the system, and central time of the transit from fits of the transit light curves at these four wavelengths. We measure the four planet-to-star radius ratios, to be (R_p /R )_{3.6 μm} = 0.1545 ± 0.0003, (R_p /R )_{4.5 μm} = 0.1557 ± 0.0003, (R_p /R )_{5.8 μm} = 0.1547 ± 0.0005, and (R_p /R )_{8 μm} = 0.1544 ± 0.0004. The high accuracy of the planet radii measurement allows the search for atmospheric molecular absorbers. Contrary to a previous analysis of the same data set, our study is robust against systematics and reveals that water vapor absorption at 5.8 μm is not detected in this photometric data set. Furthermore, in the band centered around 4.5 μm we find a hint of excess absorption with an apparent planetary radius ΔR_p /R _* = 0.00128 ± 0.00056 larger (2.3σ) than the one measured simultaneously at 8 μm. This value is 4σ above what would be expected for an atmosphere where water vapor is the only absorbing species in the near-IR. This shows that an additional species absorbing around 4.5 μm could be present in the atmosphere. Carbon monoxide (CO) being a strong absorber at this wavelength is a possible candidate and this may suggest a large CO/H₂O ratio between 5 and 60.