Supramolecular networks in (9‐fluoro‐4H‐chromeno[4,3‐c]isoxazol‐3‐yl)methanol and its 9‐chloro analogue at 100 K

The title compounds, (9‐fluoro‐4H‐chromeno4,3‐c]isoxazol‐3‐yl)methanol, C₁₁H₈FNO₃, (I), and (9‐chloro‐4H‐chromeno4,3‐c]isoxazol‐3‐yl)methanol, C₁₁H₈ClNO₃, (II), crystallize in the orthorhombic space group Pbca with Z′ = 1 and the triclinic space group P with Z′ = 6, respectively. The simple replacement of F by Cl in the main molecular scaffold of (I) and (II) results in significant differences in the intermolecular interaction patterns and a corresponding change in the point‐group symmetry from D_2h to C_i = S₂. These striking differences are manifested through the presence of C—H...F and the absence of O—H...O and C—H...O interactions in (I), and the absence of C—H...Cl and the presence of O—H...O and C—H...O interactions in (II). However, the geometry of the synthons formed by the O—H...N and O—H...X (X = F or Cl) interactions observed in the constitution of the supramolecular networks of both (I) and (II) remains similar. Also, C—H...O interactions are not preferred in the presence of F in (I), while they are much preferred in the presence of Cl in (II).