We synthesized a linear alkane, K35DA, with a main-chain carbon number n = 33 and three functional groups, a carbonyl group in the middle and carboxyl groups at both ends, and studied influences of the functional groups as well as chain length on morphologies of samples prepared by solution-grown and bulk crystallization methods (SG-K35DA and BK-K35DA) from differential scanning calorimetry (DSC), X-ray diffraction, and IR absorption measurements. Data analyses reveal that at room temperature an orthorhombic crystal of type P2(1)2(1)2(1), together with a considerable amount ofamorphous fraction, is predominantly realized in BK-K35DA due to the van der Waals force between neighboring long methylene sequences, whereas a monoclinic type of crystal belonging to the same space group (P2(1)/c) as reported for linear dicarboxylic acid crystals with odd carbon numbers is coexistent for SG-K35DA. The crystalline structures appear to be distorted with increasing temperature, as the dipole-dipole interaction between the carbonyl groups tends to be weakened, and both orthorhombic and monoclinic crystals undergo the solid-solid phase transition to the hexagonal crystalline structure at a temperature about 10 K below their respective T(m)s, which can be regarded as a new example of the Brill transition.