Hydrogen Bonding of CHCl(3) to Coordinated Nitric Oxide in a Binuclear Metallomacrocycle and the Crystal Structures of anti-[Mo(NO){HB(3,5-Me(2)C(3)HN(2))(3)}(2,7-O(2)C(10)H(6))](2).2CHCl(3).CH(2)Cl(2), syn-[Mo(NO){HB(3,5-Me(2)C(3)HN(2))(3)}(2,7-O(2)C(10)H(6))](2).0.67CHCl(3).2.7H(2)O, and syn-[Mo(NO){HB(3,5-Me(2)C(3)HN(2))(3)}(2,7-O(2)C(10)H(6))](2).3(CH(3))(2)CO.
The reaction between [Mo(NO)(Tp)I(2)] {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-O(2)C(10)H(6))](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-Me(2)C(3)HN(2))(3)}(2,7-O(2)C(10)H(6))](2).2CHCl(3).CH(2)Cl(2) (1)(,) syn-[Mo(NO){HB(3,5-Me(2)C(3)HN(2))(3)}(2,7-O(2)C(10)H(6))](2).0.67CHCl(3).2.7H(2)O (2) and syn-[Mo(NO){HB(3,5-Me(2)C(3)HN(2))(3)}(2,7-O(2)C(10)H(6))](2).3(CH(3))(2)CO (3) have been determined crystallographically: (1) C(50)H(56)B(2)N(14)O(6)Mo(2).2CHCl(3).CH(2)Cl(2), triclinic, space group P&onemacr;, a = 11.535(2) Å, b = 14.032(3) Å, c = 11.247(3) Å, alpha = 94.70(1) degrees, beta = 102.30(2) degrees, gamma = 110.31(2) degrees, Z = 1; (2) C(50)H(56)B(2)N(14)O(6)Mo(2).0.67CHCl(3).2.7H(2)O, monoclinic space group P2(1)/m, a = 23.770(7) Å, b = 26.600(10) Å, c = 11.334(4) Å, beta = 99.86(2) degrees, Z = 4; (3) C(50)H(56)B(2)N(14)O(6)Mo(2).3C(3)H(6)O, triclinic, space group P&onemacr;, a = 16.929(3) Å, b = 17.465(4) Å, c = 12.739(2) Å, alpha = 100.06(1) degrees, beta = 94.93(2) degrees, gamma = 114.13(1) degrees, 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 degrees } 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-Me(2)C(3)HN(2))(3) ligand. No hydrogen bonding interactions with nitric oxide are apparent in the structures of 2 or 3.
McQuillan
Ferida S.
FS
School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, U.K.
Chen
Hongli
H
Hamor
Thomas A.
TA
Jones
Christopher J.
CJ
Paxton
Keith
K