(18-Crown-6)(trifluoromethanesulfonato)sodium (original) (raw)
Bis[tris(3,5-dimethyl-1H-pyrazol-1-yl-κN2)methyl]sodium trifluoromethanesulfonate
Acta Crystallographica Section E Structure Reports Online, 2012
In the title salt, [Na(C 16 H 22 N 6) 2 ]CF 3 SO 3 , the Na + cation is coordinated by six N atoms from two tridentate tris(3,5dimethylpyrazol-1-yl)methane ligands in a distorted octahedral geometry. The Na-N distances range from 2.427 (3) to 2.507 (3) Å , intra-ligand N-Na-N angles range from 74.71 (8) to 79.31 (9) , and adjacent inter-ligand N-Na-N angles range between 100.42 (9) and 104.97 (9). The structure is twinned by inversion [occupancy factors = 0.50 (9)] and the trifluoromethanesulfonate anion is disordered, with two endover-end orientations of unequal occupancy [0.781 (3) and 0.219 (3)]. Related literature For ligand synthesis details, see: Reger et al. (2000). For structural, spectroscopic and angular overlap studies of tris-(pyrazol-1-yl)methane complexes, see: Astley et al. (1993). For details of the refinement strategy for twinned and disordered structures, see: Parkin (2000); Spek (2009). Experimental Crystal data [Na(C 16 H 22 N 6) 2 ]CF 3 O 3 S M r = 768.85 Monoclinic, Pc a = 9.0579 (1) Å b = 12.5733 (1) Å c = 16.4386 (2) Å = 90.5917 (4) V = 1872.05 (3) Å 3 Z = 2 Mo K radiation = 0.17 mm À1 T = 90 K 0.22 Â 0.18 Â 0.12 mm Data collection Nonius KappaCCD diffractometer Absorption correction: multi-scan [SCALEPACK (Otwinowski & Minor, 1997) and XABS2 (Parkin et al. 1995)] T min = 0.965, T max = 0.981 47745 measured reflections 8385 independent reflections 7036 reflections with I > 2(I) R int = 0.043 Refinement R[F 2 > 2(F 2)] = 0.041 wR(F 2) = 0.112 S = 1.09 8385 reflections 516 parameters 59 restraints H-atom parameters constrained Á max = 0.26 e Å À3 Á min = À0.27 e Å À3
Bis[tris(3,5-dimethyl-1H-pyrazol-1-yl-κN2)methyl]sodium trifluoromethanesulfonate
Acta Crystallographica Section E-structure Reports Online, 2012
In the title salt, [Na(C 16 H 22 N 6) 2 ]CF 3 SO 3 , the Na + cation is coordinated by six N atoms from two tridentate tris(3,5dimethylpyrazol-1-yl)methane ligands in a distorted octahedral geometry. The Na-N distances range from 2.427 (3) to 2.507 (3) Å , intra-ligand N-Na-N angles range from 74.71 (8) to 79.31 (9) , and adjacent inter-ligand N-Na-N angles range between 100.42 (9) and 104.97 (9). The structure is twinned by inversion [occupancy factors = 0.50 (9)] and the trifluoromethanesulfonate anion is disordered, with two endover-end orientations of unequal occupancy [0.781 (3) and 0.219 (3)]. Related literature For ligand synthesis details, see: Reger et al. (2000). For structural, spectroscopic and angular overlap studies of tris-(pyrazol-1-yl)methane complexes, see: Astley et al. (1993). For details of the refinement strategy for twinned and disordered structures, see: Parkin (2000); Spek (2009). Experimental Crystal data [Na(C 16 H 22 N 6) 2 ]CF 3 O 3 S M r = 768.85 Monoclinic, Pc a = 9.0579 (1) Å b = 12.5733 (1) Å c = 16.4386 (2) Å = 90.5917 (4) V = 1872.05 (3) Å 3 Z = 2 Mo K radiation = 0.17 mm À1 T = 90 K 0.22 Â 0.18 Â 0.12 mm Data collection Nonius KappaCCD diffractometer Absorption correction: multi-scan [SCALEPACK (Otwinowski & Minor, 1997) and XABS2 (Parkin et al. 1995)] T min = 0.965, T max = 0.981 47745 measured reflections 8385 independent reflections 7036 reflections with I > 2(I) R int = 0.043 Refinement R[F 2 > 2(F 2)] = 0.041 wR(F 2) = 0.112 S = 1.09 8385 reflections 516 parameters 59 restraints H-atom parameters constrained Á max = 0.26 e Å À3 Á min = À0.27 e Å À3
Crystalline complexes of 18-crown-6 with methyl sulfonates
Canadian Journal of Chemistry, 1993
ROBERT CRENEVERT, RENE GAGNON, DANIEL CHAMBERLAND, and MICHEL SIMARD. Can. J. Chem. 71, 1225Chem. 71, (1993. The macrocyclic polyether 18-crown-6 forms crystalline complexes with methyl sulfonates. Most complexes have a 2: 1 (su1fonate:crown) stoichiometry whereas small aliphatic sulfonates give a 1 : 1 ratio. In the 2: 1 ratio complexes, the guest molecules are coordinated above and below the crown in such a way that the dipoles are compensated. In the 1 : 1 ratio complexes, there is a polymeric type association with the two ends of the sulfonate interacting with different crown molecules. A crystal structure is reported for each type of complex. The complex 18-crown-6. CH3S03CH3 crystallizes in the monoclinic system, space group P2,/c with Z = 4. The unit cell dimensions are as follows: a = 8.525(4), b = 16.401(7), c = 15.071(6) A, P = 113.92(3)". Final R,,, = 0.064 for 3650 reflections. The complex 18-crown 6 . (C6H5S03Me)2 (I) crystallizes in the monoclinic systemo, space group P2,/c with Z = 2. The unit cell dimensions are as follows: a = 8.101(3), b = 17.136(5), c = 12.990(5) A, P = 121.30(3)". Final R,, = 0.048 for 2913 reflections. ROBERT CHENEVERT, RENE GAGNON, DANIEL CHAMBERLAND et MICHEL SIMARD. Can. J. Chem. 71, 1225 (1993).
Journal of the Chemical Society, Dalton Transactions, 1994
Reaction of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) with potassium thiocyanate in liquid sulfur dioxide gives, on recrystallisation from diethyl ether-sulfur dioxide, yellow crystals of the complex [K(18-crown-6)] + [NCS-SO,]in 98% yield. Vibrational spectroscopy points to the formation of a weak donor-acceptor complex anion [ NCS=SO,]-, and this was confirmed by X-ray crystallography: triclinic, P i (no. 2). a=7.635(2), b=9.595(2), c=8.171(1) A, a=102.95(2), P=95.68(2),y=111.91(2)", 2 = 1. The centrosymmetric [K(18-crown-6)] + cations are centred on special positions on the corners of the unit cell, and the complex anion is disordered about the inversion centre at (+G,+). The nature of the disorder makes it difficult to locate the positions of some light atoms in the [NCS*SO,]anion, although the S-S bond length, 2.736(9) A, is consistent with the lability of the complex. Dissociation pressure measurements at different temperatures were used to determine a binding energy for gaseous [NCS-SO,]of 66 kJ mot-', a value which is compared with those of related sulfite complexes in relation to Pearson's concept of 'absolute hardness'.