Hydrogen Bonding of CHCl<sub>3</sub> to Coordinated Nitric Oxide in a Binuclear Metallomacrocycle and the Crystal Structures of <i>anti-</i>[Mo(NO){HB(3,5-Me<sub>2</sub>C<sub>3</sub>HN<sub>2</sub>)<sub>3</sub>}(2,7-O<sub>2</sub>C<sub>10</sub>H<sub>6</sub>)]<sub>2</sub>·2CHCl<sub>3</sub>·CH<sub>2</sub>Cl<sub>2</sub>, <i>syn-</i>[Mo(NO){HB(3,5-Me<sub>2</sub>C<sub>3</sub>HN<sub>2</sub>)<sub>3</sub>}(2,7-O<sub>2</sub>C<sub>10</sub>H<sub>6</sub>)]<sub>2</sub>·0.67CHCl<sub>3</sub>·2.7H<sub>2</sub>O, and <i>syn-</i>[Mo(NO){HB(3,5-Me<sub>2</sub>C<sub>3</sub>HN<sub>2</sub>)<sub>3</sub>}(2,7-O<sub>2</sub>C<sub>10</sub>H<sub>6</sub>)]<sub>2</sub>·3(CH<sub>3</sub>)<sub>2</sub>CO
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The reaction between [Mo(NO)(Tp*)I2] {Tp*- = hydrotris(3,5-dimethylpyrazol-1-yl)borate} and 2,7-dihydroxynaphthalene affords, as its major product, the binuclear complex [Mo(NO)(Tp*)(2,7-O2C10H6)]2. The reaction appears to proceed under kinetic control so that shorter reaction times afford the syn-isomer (47% yield after 40 min) while longer reaction times allow the anti-isomer (43% yield after 48 h) to be obtained. The molecular structures of anti-[Mo(NO){HB(3,5-Me2C3HN2)3}(2,7-O2C10H6)]2·2CHCl3·CH2Cl2 (1), syn-[Mo(NO){HB(3,5-Me2C3HN2)3}(2,7-O2C10H6)]2·0.67CHCl3·2.7H2O (2) and syn-[Mo(NO){HB(3,5-Me2C3HN2)3}(2,7-O2C10H6)]2·3(CH3)2CO (3) have been determined crystallographically: (1) C50H56B2N14O6Mo2·2CHCl3·CH2Cl2, triclinic, space group P1̄, a = 11.535(2) Å, b = 14.032(3) Å, c = 11.247(3) Å, α = 94.70(1)°, β = 102.30(2)°, γ = 110.31(2)°, Z = 1; (2) C50H56B2N14O6Mo2·0.67CHCl3·2.7H2O, monoclinic space group P21/m, a = 23.770(7) Å, b = 26.600(10) Å, c = 11.334(4) Å, β = 99.86(2)°, Z = 4; (3) C50H56B2N14O6Mo2.3C3H6O, triclinic, space group P1̄, a = 16.929(3) Å, b = 17.465(4) Å, c = 12.739(2) Å, α = 100.06(1)°, β = 94.93(2)°, γ = 114.13(1)°, Z = 2. In 1 each nitric oxide ligand is hydrogen bonded [C−H 0.98, H···O 2.26, C···O 3.13(2) Å, C−H···O 147°} to a chloroform molecule which lies within a cavity in the molecule having as its base a bridging 2,7-naphthalenediyl fragment and as its sides a part of each HB(3,5-Me2C3HN2)3 ligand. No hydrogen bonding interactions with nitric oxide are apparent in the structures of 2 or 3.
