Acta Crystallographica Section C

Crystal Structure Communications

Volume 69, Part 2 (February 2013)

metal-organic compounds

eg3103 scheme

Acta Cryst. (2013). C69, 127-137    [ doi:10.1107/S0108270113000322 ]

Chiral one- and two-dimensional silver(I)-biotin coordination polymers

M. Altaf and H. Stoeckli-Evans

Abstract: Reaction of biotin {C10H16N2O3S, HL; systematic name: 5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoic acid} with silver acetate and a few drops of aqueous ammonia leads to the deprotonation of the carboxylic acid group and the formation of a neutral chiral two-dimensional polymer network, poly[[{[mu]3-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}silver(I)] trihydrate], {[Ag(C10H15N2O3S)]·3H2O}n or {[Ag(L)]·3H2O}n, (I). Here, the AgI cations are pentacoordinate, coordinated by four biotin anions via two S atoms and a ureido O atom, and by two carboxylate O atoms of the same molecule. The reaction of biotin with silver salts of potentially coordinating anions, viz. nitrate and perchlorate, leads to the formation of the chiral one-dimensional coordination polymers catena-poly[[bis[nitratosilver(I)]-bis{[mu]3-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}] monohydrate], {[Ag2(NO3)2(C10H16N2O3S)2]·H2O}n or {[Ag2(NO3)2(HL)2]·H2O}n, (II), and catena-poly[bis[perchloratosilver(I)]-bis{[mu]3-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}], [Ag2(ClO4)2(C10H16N2O3S)2]n or [Ag2(ClO4)2(HL)2]n, (III), respectively. In (II), the AgI cations are again pentacoordinated by three biotin molecules via two S atoms and a ureido O atom, and by two O atoms of a nitrate anion. In (I), (II) and (III), the AgI cations are bridged by an S atom and are coordinated by the ureido O atom and the O atoms of the anions. The reaction of biotin with silver salts of noncoordinating anions, viz. hexafluoridophosphate (PF6-) and hexafluoridoantimonate (SbF6-), gave the chiral double-stranded helical structures catena-poly[[silver(I)-bis{[mu]2-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}] hexafluoridophosphate], {[Ag(C10H16N2O3S)2](PF6)}n or {[Ag(HL)2](PF6)}n, (IV), and catena-poly[[[{5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}silver(I)]-[mu]2-{5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}] hexafluoridoantimonate], {[Ag(C10H16N2O3S)2](SbF6)}n or {[Ag(HL)2](SbF6)}n, (V), respectively. In (IV), the AgI cations have a tetrahedral coordination environment, coordinated by four biotin molecules via two S atoms, and by two carboxy O atoms of two different molecules. In (V), however, the AgI cations have a trigonal coordination environment, coordinated by three biotin molecules via two S atoms and one carboxy O atom. In (IV) and (V), neither the ureido O atom nor the F atoms of the anion are involved in coordination. Hence, the coordination environment of the AgI cations varies from AgS2O trigonal to AgS2O2 tetrahedral to AgS2O3 square-pyramidal. The conformation of the valeric acid side chain varies from extended to twisted and this, together with the various anions present, has an influence on the solid-state structures of the resulting compounds. The various O-H...O and N-H...O hydrogen bonds present result in the formation of chiral two- and three-dimensional networks, which are further stabilized by C-H...X (X = O, F, S) interactions, and by N-H...F interactions for (IV) and (V). Biotin itself has a twisted valeric acid side chain which is involved in an intramolecular C-H...S hydrogen bond. The tetrahydrothiophene ring has an envelope conformation with the S atom as the flap. It is displaced from the mean plane of the four C atoms (plane B) by 0.8789 (6) Å, towards the ureido ring (plane A). Planes A and B are inclined to one another by 58.89 (14)°. In the crystal, molecules are linked via O-H...O and N-H...O hydrogen bonds, enclosing R22(8) loops, forming zigzag chains propagating along [001]. These chains are linked via N-H...O hydrogen bonds, and C-H...S and C-H...O interactions forming a three-dimensional network. The absolute configurations of biotin and complexes (I), (II), (IV) and (V) were confirmed crystallographically by resonant scattering.

Formula: C10H16N2O3S, [Ag(C10H15N2O3S)]·3H2O and analogues

hkldisplay filedownload file

Structure factor file (CIF format) (103.4 kbytes)
[ doi:10.1107/S0108270113000322/eg3103HLsup2.hkl ]
Contains datablock HL

hkldisplay filedownload file

Structure factor file (CIF format) (187.6 kbytes)
[ doi:10.1107/S0108270113000322/eg3103Isup3.hkl ]
Contains datablock I

hkldisplay filedownload file

Structure factor file (CIF format) (384.6 kbytes)
[ doi:10.1107/S0108270113000322/eg3103IIsup4.hkl ]
Contains datablock II

hkldisplay filedownload file

Structure factor file (CIF format) (718.6 kbytes)
[ doi:10.1107/S0108270113000322/eg3103IVsup5.hkl ]
Contains datablock IV

hkldisplay filedownload file

Structure factor file (CIF format) (289.5 kbytes)
[ doi:10.1107/S0108270113000322/eg3103Vsup6.hkl ]
Contains datablock V


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