Single‐ <i>vs</i> Double‐Decker Copper 12‐MC‐4 Metallacrown Using the Coordination Flexibility of a Soft Donor Ligand

2-Methylmercaptobenzohydroxamic acid (mmbHA) has been synthesized and used to form {CuIICl2(MeOH)[12-MCCu(II)N(mmbHA)-4]}2 ⋅ 4MeOH (1) {CuII(μ2-ClO4)(MeOH)2(py)4[12-MCCu(II)N(mmbHA)-4]}ClO4 (2), a copper(II) based double-decker discrete metallacrown (MC) system, respectively. While 1 forms in the absence of coordinating co-ligand, presence pyridine (Py) leads change coordination mode mmbHA MC 2 is formed. Both compounds have structurally magnetically characterized. The magnetic susceptibility measured from 2–300 K shows overall antiferromagnetic exchange coupling within both crown structures obtained constants are J1=−88.0(1) cm−1and J2=−64.7(3) cm−1 for J1=−90.0(5) J2=−31.1(1) 2. However, ratio parameters highly affected by structural change.