Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. IV [Acid Salts] of the 4-Nitrophenoxides of Group 1

1998 ◽  
Vol 51 (8) ◽  
pp. 747 ◽  
Author(s):  
Jack M. Harrowfield ◽  
Raj Pal Sharma ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Hydrogen Atom ◽  
Metal Ions ◽  
Room Temperature ◽  
Closed Shell ◽  
X Ray ◽  
Salt Structure ◽  
Group 1 ◽  
Parent Ligand ◽  
Oxygen Atoms ◽  
Acid Salts

Room-temperature single-crystal X-ray studies are recorded for a number of ‘acid salts’ formed between Group 1 salts of 4-nitrophenol, M(4-np), and the parent ligand 4-npH, variously hydrated. The 1 : 1 salts M(4-np)(4-npH).x H2O are found for all of M = Li, Na, K, Rb and Cs. The lithium adduct (tetrahydrate) is monoclinic, C2/c, a 19·438(4), b 11·207(2), c 7·421(2) Å, β 91·38(2)°, Z = 4, conventional R on |F| being 0·043 for 1369 independent ‘observed’ (I > 3σ(I)) diffractometer reflections. The sodium adduct (dihydrate) is monoclinic, C2, a 2·174(3), b 3·674(2), c 10·358(1) Å, β 117·21(1)°, Z = 2, R 0·035 for No 1092; the potassium adduct (monohydrate) is monoclinic, C 2/c, a 22·10(1), b 3·798(3), c 21·270(6) Å, β 120·97(4)°, Z = 4, R 0·050 for No 1065. The isomorphous rubidium and caesium monohydrates are triclinic, P-1, a ≈ 11·9, b ≈ 10·2,c ≈ 6·3 Å, α ≈ 90, β ≈ 92, γ ≈ 112°, Z = 2, R 0·042, 0·028 for No 2340, 3053 respectively. For M = Rb, a 1 : 3 adduct Rb(4-np).3(4-npH) is also obtained (with an isomorphous thallium counterpart recorded elsewhere): a 12·143(5), b 11·50(1), c 11·36(1) Å, α 114·38(9), β 110·54(6), γ 96·73(6)°, Z = 2, R 0·034 for No 3945. The lithium salt may be represented as [Li(OH2)4]+ (4-npH.4-np)½-. The cation lies disposed about a crystallographic 2 axis; the anion, close to an axis, confronts its rotational image, with the associated hydrogen atom modelled as disordered between them, rather than located on the 2 axis. The sodium salt is a sheet structure, the six-coordinate sodium atoms being disposed on a crystallographic 2 axis and linked up that axis ... Na(µ-O)2Na(µ-O)2Na ... by bridging water molecule oxygen atoms, while symmetry-related trans O-nitrophenoxide moieties are bridged by confronting phenoxide oxygen atoms about an associated hydrogen atom provisionally disposed on a 2 axis also. The potassium salt structure is developed from this array, modelled with disordered potassium atoms, now lying off the 2 axis, 0·922(2) Å apart. In the rubidium/caesium structure, columns of oxygen-bridged metal ions are disposed about c, crosslinked by O-nitro-bonded phenoxide moieties, with confronting phenoxide oxygen atoms about a shared associated hydrogen.

Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. I 2-Nitrophenoxides of Group 1

1998 ◽  
Vol 51 (8) ◽  
pp. 707 ◽  
Author(s):  
Jack M. Harrowfield ◽  
Raj Pal Sharma ◽  
Todd M. Shand ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Room Temperature ◽  
Closed Shell ◽  
Aromatic Rings ◽  
X Ray ◽  
Metal Atoms ◽  
Metal Derivatives ◽  
Derivatives Of ◽  
Fourth Coordination ◽  
Group 1 ◽  
Oxygen Atoms

Room-temperature, single-crystal X-ray studies are recorded for the variously hydrated Group 1 metal derivatives of 2-nitrophenol (2-npH = C6H5NO3). A provisional determination is reported for Li(2-np).½H2O, set as monoclinic, P21/c, a 3·535(3), b 15·06(1), c 24·42(2) Å, β 91·7(1)°, Z = 8, conventional R on F currently 0·18 for No 875 ‘observed’ (I > 3σ(I)) reflections. Na(2-np).H2O is monoclinic, C2/c, a 34 ·23(2), b 3·624(4), c 35·48(2) Å, β 91·24(4)°, Z = 24, R 0·060 for No 1371. Rb(2-np).½ H2O is monoclinic, C2/c (isomorphous with the previously determined potassium analogue), a 25·269(9), b 5·381(5), c 12·010(3) Å, β 105·35(3)°, Z = 8, R 0·046 for No 1380. Cs(2-np).½H2O is monoclinic, P21/n, a 7·648(3), b 26·19(1), c 8·713(6) Å, β 111·75(2)°, Z = 8, R 0·061 for No 2347. All compounds except the lithium derivative are two-dimensional polymeric sheets in which the aromatic rings project to either side of a core of metal atoms coordinated by a web of 2-nitrophenoxide oxygen atoms in various bridging functionalities. The lithium compound is a novel ‘stair’ polymer with two crystallographically independent lithium atoms at successive independent Li–O crossbars, the oxygen atoms of which are phenoxide-Oof each of the two independent ligands. The lithium atoms are alternately four- and five-coordinate, the fourth coordination site of the first being occupied by the water molecule oxygen atom, while the fourth and fifth sites of the second are occupied by the cis-2-nitro oxygen atoms of the two ligands

Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. VII Acid Salts of the 4-Nitrophenoxides of Group 2

1998 ◽  
Vol 51 (8) ◽  
pp. 785 ◽  
Author(s):  
Jack M. Harrowfield ◽  
Raj Pal Sharma ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Room Temperature ◽  
Calcium Salt ◽  
Three Dimensional ◽  
Closed Shell ◽  
The Other ◽  
X Ray ◽  
C 23 ◽  
Structure Determinations ◽  
Group 2 ◽  
Acid Salts

Room-temperature single-crystal X-ray structure determinations are recorded for a number of Group 2 4-nitrophenoxide acid salts, variously hydrated M(4-np)2.x(4-npH).yH2O. Ca(4-np)2.2(4-npH).8H2O is monoclinic, P 21/n, a 30·52(1), b 10·027(1), c 23·65(2) Å, β 116·3(5)°, Z = 8, conventional R on |F| being 0·058 for No 5092 independent ‘observed’ (I > 3s(I)) reflections. Sr(4-np)2.2(4-npH).8H2O, based on a subcell of the former, is monoclinic, P 21/c, a 15·576(5), b10·081(6), c 24·20(2) Å, β 117·99(5)° , Z = 4, R 0·054 for No 2908. Ba(4-np)2.2(4-npH).4H2O is orthorhombic, Fdd2, a 28·01(1), b 19·90(1), c 10·692(7)Å, Z = 8, R 0·028 for No 1967. The strontium array (and that of the calcium salt developed from it) may be represented as [(H2O)6Sr(4-npH.4-np)] (4-npH.4-np), a neutral ligand being unsymmetrically chelated to the strontium through the nitro group, with a quasi-parallel counter ion hydrogen-bonded to it by phenoxide confrontation. The other two 4-np residues make up a similar phenoxide-confronting pair (4-npH.4-np), the hydrogen being more intimately associated with one moiety. The barium salt is also an interesting array: the 10-coordinate barium lies on a crystallographic 2 axis, in an environment of two pairs of symmetry-related nitro-chelating ligand anions, and a pair of nitro-O coordinating neutral 4-npH ligands; the whole [(H2O)4Ba(4-np)2(4-npH)2] array may be envisaged as a single neutral (super)molecule. Hydrogen bonds between confronting phenoxides of the neutral 4-npH components of the parent and the 4-np- components of neighbouring molecules link the whole into a three-dimensional array.

Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. V 2-Nitrophenoxides of Group 2

1998 ◽  
Vol 51 (8) ◽  
pp. 761 ◽  
Author(s):  
Jack M. Harrowfield ◽  
Raj Pal Sharma ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Water Molecule ◽  
Metal Ions ◽  
Single Crystal ◽  
Room Temperature ◽  
Closed Shell ◽  
Magnesium Salt ◽  
Water Molecules ◽  
One Dimensional ◽  
X Ray ◽  
Group 2

Room-temperature single-crystal X-ray studies are recorded for 2-nitrophenoxide salts of Group 2 metals, variously hydrated M(2-np)2.xH2O, M = Mg, Ca, Sr; the structure of the barium analogue has been previously recorded. Mg(2-np)2.2H2O is monoclinic, P21/a, a 7·377(1), b 7·518(1), c 12·877(3) Å, β 106·58(2)°, Z = 2; conventional R on |F| 0·13 for No 508 independent ‘observed’ (I > 3σ(I)) reflections. Ca(2-np)2.H2O is monoclinic, C2, a 25·92(1), b 7·176(3), c 3·660(4) Å, β 93·66(5)°, Z = 2, R 0·061 for No 541. M(2-np)2.4H2O, M = Ca, Sr, are isomorphous, monoclinic, C2/c, a ≈ 31·3, b ≈ 8·1, c ≈ 12·8 Å, β 103°, Z = 8; R was 0·056, 0·055 forNo 1988, 1744 respectively. The magnesium salt is a discrete molecular array disposed about a crystallographic inversion centre with chelating phenoxide ligands: trans-[Mg(2-np)2(OH2)2]. The calcium monohydrate salt is a novel one-dimensional polymer with a ... Ca(µ-O)2Ca(µ-O)2Ca ... spine, the ligand pairs chelating the calcium with phenoxide-O additionally bridging. The seven-coordinate calcium atoms lie on the crystallographic 2 axis with the water molecule, also on that axis, making up a seven-coordinate environment. The tetrahydrate is also a one-dimensional polymer with a similar spine, the bridging oxygen atoms derivative of water molecules. A chelating ligand and two further water molecules make up an eight-coordinate metal environment, with the free anions interleaving stacks of coordinated anions up c.

Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. III 2/4-Nitrophenoxides of Univalent Heavy Metals

1998 ◽  
Vol 51 (8) ◽  
pp. 735 ◽  
Author(s):  
Jack M. Harrowfield ◽  
Raj Pal Sharma ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Room Temperature ◽  
Three Dimensional ◽  
Closed Shell ◽  
Two Dimensional ◽  
Nitrogen Base ◽  
Coinage Metal ◽  
Aromatic Carbon ◽  
X Ray ◽  
Dimensional Network ◽  
Oxygen Atoms

Room-temperature single-crystal X-ray studies are recorded for 2- and 4-nitrophenoxide salts of silver(I) and thallium(I), M(2-np) and Tl(4-np) (anhydrous), and Ag(4-np).H2O. Ag(2-np) is monoclinic, P21/c, a 9·012(4), b 5·743(5), c 12·594(5) Å, β 104·34(4)°, Z = 4; conventional R on |F| was 0·042 for No 1378 independent ‘observed’ (I > 3σ(I)) reflections. Tl(2-np) is monoclinic, C2/c, a 27·250(3), b 3·712(1), c 15·147(3) Å, β 114·41(1)°, Z = 8, R 0·025 for No 1346. Ag(4-np).H2O is monoclinic, P21/a, a 5·613(6), b 13·191(7), c 9·844(5) Å, β 92·50(6)°, Z = 4, R 0 ·033 for No 622. Tl(4-np) is tetragonal, I 41/a, a 18·037(8), c 8·979(8) Å, Z = 16, R 0·043 for No 924. An acid salt of the latter, Tl(4-np).(4-npH)3, triclinic, P-1, a 11·861(8), b 11·45(1), c 11· 423(1) Å, α 114·00(6), β 109·78(5), γ 96·87(7)°, Z = 2, R 0·042 for No 3814, is isomorphous with its rubidium analogue. These comprise a novel array of structures: although the structures of the silver(I) complexes are two-dimensional sheets with familiar head-tail connecting ligands, a strong silver-aromatic carbon interaction is found in Ag(2-np) (Ag–C 2·496(5) Å). Tl(2-np) and Tl(4-np) both present unusual forms related to the stair-polymer and cubane adducts found in 1 : 1 coinage metal(I)/halide-unidentate nitrogen base adducts; Tl(2-np) is a double-stranded stair-polymer array, with the phenoxide oxygen atoms incorporated in the stair and the nitro oxygen atoms linking successive thallium atoms. The structure of Tl(4-np) is based on a tetranuclear cubane motif of -4 symmetry, [Tl(O-phenoxide)]4, these being linked into a three-dimensional network by further Tl · · · O-nitro interactions from adjacent units. The structure of silver(I) picrate monohydrate, isomorphous with its sodium counterpart, is also recorded: monoclinic, C 2/m, a 12·818(7), b 20·208(8), c 3· 741(1) Å, β 88·25(3)°, Z = 4, R 0·047 for No 1042, void of any significant Ag · · · C contacts.

Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. II 4-Nitrophenoxides of Group 1

1998 ◽  
Vol 51 (8) ◽  
pp. 723 ◽  
Author(s):  
Jack M. Harrowfield ◽  
Raj Pal Sharma ◽  
Brian W. Skelton ◽  
Allan H. White
Keyword(s):  
Single Crystal ◽  
Molecular Complex ◽  
Room Temperature ◽  
Three Dimensional ◽  
Closed Shell ◽  
The Other ◽  
Monoclinic Space Group ◽  
X Ray ◽  
Metal Atoms ◽  
Group 1

Room-temperature single-crystal X-ray studies are recorded for 4-nitrophenoxide (4-np¯) salts, variously hydrated, of the Group 1 metals, M(4-np-).χH2O, for M = Li, Na (redetermination), K (already recorded), Rb and Cs. Li(4-np).3H2O is monoclinic, space group Pc, a 11·359(3), b 7·518(3), c 10·855(4) Å, β 90·56(3)°, Z = 4; conventional R on |F| was 0·056 for No 2098 independent `observed" (I > 3σ(I)) reflections. Na(4-np).2H2O is orthorhombic, Ima2, a 6·888(6), b 19·699(8), c 6·436(8) Å, Z = 4, R 0·031 for No 664. Rb(4-np).H2O is orthorhombic, Pbca, a 11·82(3), b 19·724(7), c 7·199(1) Å, Z = 8, R 0·036 for No 1465. Cs(4-np).3H2O is monoclinic, P 21/c, a 13·337(2), b 12·770(5), c 6·311(2) Å, β 100·56(3)°, Z = 4, R 0·031 for No 2636. Whereas the lithium compound is essentially a discrete mononuclear neutral molecular complex [(4-np-O)Li(OH2)3] with four-coordinate lithium, the other compounds exhibit two- or three-dimensional sheet polymer structures with 4-nitrophenoxide moieties providing O-C6H4-NO2 head-tail connecting motifs between successive metal atoms.

Structural Systematics of 2/4-Nitrophenoxide Complexes of Closed-Shell Metal Ions. VI 4-Nitrophenoxides of Group 2

1998 ◽  
Vol 51 (8) ◽  
pp. 775 ◽  
Author(s):  
Jack M. Harrowfield ◽  
Raj Pal Sharma ◽  
Brian W. Skelton ◽  
Paloth Venugopalam ◽  
Allan H. White
Keyword(s):  
Metal Ions ◽  
Closed Shell ◽  
Water Molecules ◽  
One Dimensional ◽  
Phenolic Oxygen ◽  
C 23 ◽  
Structure Determinations ◽  
Group 2 ◽  
Coordinated Water ◽  
Oxygen Atoms

Room-temperature single-crystal X-ray structure determinations are recorded for 4-nitrophenolate (4-np-) salts of Group 2 metal ions, variously hydrated, M(4-np)2.xH2O, M = Mg, Ca, Sr, Ba. Mg(4-np)2.8H2 O is monoclinic, P21/c, a 12·402(3), b 6·673(7), c 11·833(6) Å, β 93·70(3)°, Z = 2; conventional R on |F| was 0·041 for No 1995 independent ‘observed’ (I > 3σ(I)) reflections. Ca(4-np)2.4H2O is monoclinic, P21/c, a 13·109(8), b 3·644(1), c 21·181(8) Å, β 125·55(3)°, Z= 2, R 0·050 for No 1371. Sr(4-np)2.8H2O is monoclinic, P21/n, a 7·934(1), b 10·658(1), c 23·602(2) Å, β 91·36(1)°, Z = 4, R 0·038 for No 2050. Ba(4-np)2.8H2O is monoclinic P21/c, a 15·990(8), b 6·337(3), c 25·634(8) Å, β 126·1(3)°, Z = 4, R 0·021 for No 3115. The magnesium salt is ionic with [Mg(OH2)6]2+ cations and interleaved anion stacks up b. The calcium salt is a one-dimensional polymer with ... Ca(µ-O)2Ca(µ-O)2Ca ... spine, the bridges being phenolic oxygen atoms.trans-Coordinated water molecules make up six-coordination about the calcium, the anion planes stacking at the b spacing. The strontium adduct is also a one-dimensional polymer with a similar spine, but with water molecule oxygen atoms bridging, the nine-coordinate strontium environment being made up by a chelating nitro group and three unidentate water molecules. Coordinated anions stacked up a are interleaved by free anions. The barium salt is simply [Ba(4-np)(OH2)8]+ (4-np-), the ligand anion (semi)chelated through the nitro pair of oxygen atoms, again with interleaving anion/ligand stacking.

Lewis-Base Adducts of Main Group 1 Metal Compounds. VI. Novel Hydrogen Bonding and a Novel Binuclear Aquated Lithium Cation in [(H2O)2Li(OH2)2Li(OH2)2]2+.2Cl-.6L (L = 2,6-Dimethylpyridine)

1988 ◽  
Vol 41 (3) ◽  
pp. 413 ◽  
Author(s):  
CL Raston ◽  
CR Whitaker ◽  
AH White
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Atom ◽  
Lewis Base ◽  
Lithium Cation ◽  
Water Molecules ◽  
The Novel ◽  
Metal Compounds ◽  
X Ray ◽  
The Subject ◽  
Group 1

The title compound, isolated as an artefact of the recrystallization of lithium chloride from 2,6-dimethylpyridine, and the subject of a single-crystal X-ray study (R = 0.063 for 1200 'observed' reflections), contains the novel centrosymmetric [(H2O)2Li(OH2)2Li(OH2)2]2+ cation. Li- O(bridging) are 2.05(2), 2.00(2)Ǻ; Li-O (terminal) are 1.88(2), 1.88(2)Ǻ. Li-O-Li is 89.1(7) and O-Li-O′ (core) is 90.9(8)°. The angle between the terminal water oxygens at the lithium is 122.6(11)° and O(terminal)-Li-O(bridge) range from 101.7(7) to 123.0(10)°. An elegant hydrogen bonding scheme is found, one hydrogen atom from each of the water molecules being associated with the chloride counterion at 2.0- 2.2 Ǻ; the other hydrogen atom of each water is directed towards the nitrogen atom of one of each of the base molecules, H…N ~ 1.6-2.1 Ǻ.

Room-Temperature Structure of Ammonia Borane

2007 ◽  
Vol 60 (3) ◽  
pp. 149 ◽  
Author(s):  
Mark E. Bowden ◽  
Graeme J. Gainsford ◽  
Ward T. Robinson
Keyword(s):  
Hydrogen Atom ◽  
Single Crystal ◽  
Room Temperature ◽  
Ammonia Borane ◽  
Temperature Structure ◽  
Orthorhombic Structure ◽  
Tetrahedral Geometry ◽  
New Model ◽  
X Ray ◽  
Diffraction Peaks

Structural determinations of ammonia borane (BH3NH3) have been carried out for the orthorhombic (at 90 K) and tetragonal (at 298 K) modifications using single-crystal X-ray data. The orthorhombic structure (space group Pmn21) agreed with a previously published neutron determination, while the tetragonal structure (I4mm) exhibited halos of hydrogen atom occupancy around both the nitrogen and boron atoms. The bond angles to the regions of hydrogen occupancy are consistent with the expected tetrahedral geometry for –BH3 and –NH3 groups. A new model for tetragonal BH3NH3 was constructed which accounts for the hydrogen disorder in the I4mm structure while introducing only weak new diffraction peaks. These peaks could not be found, however, and it is likely that the hydrogen disorder in tetragonal BH3NH3 arises from either rotations of higher than 3-fold order, or from random orientations of hydrogen-containing groups.

Structural Characterization of a Calix[4]arene Constrained to a 1,3-Alternate Conformation by Polyether Bridging

1994 ◽  
Vol 47 (4) ◽  
pp. 757 ◽  
Author(s):  
Z Asfari ◽  
JM Harrowfield ◽  
AN Sobolev ◽  
J Vicens
Keyword(s):  
Alkali Metal ◽  
Metal Ions ◽  
Single Crystal ◽  
Structural Characterization ◽  
Room Temperature ◽  
Free Ligand ◽  
Tetraethylene Glycol ◽  
Space Group ◽  
X Ray

Despite evidence of coordinative interactions with alkali metal picrates in solution, attempts to crystallize Li+, Na+, K+, Rb+ or Cs+ complexes of a 'doubly crowned' calix [4] arene (obtained by reaction of tetraethylene glycol ditosylate with p-t- butylcalix [4] arene ) have resulted only in the deposition of crystals of the free ligand . A room-temperature single-crystal X-ray study has shown the crystals to be hexagonal, space group P6422, a (= b) 17.092(5), c 20.147(7) Ǻ, V 5097(5) Ǻ3, Z 3, conventional R (on |F|) 0.082 for 1397 'observed' reflections [I > 3σ(I)]. The highly symmetrical oblate-globular shape of this doublecrowncalix allows the enclosure of an extended narrow cavity possibly better suited to the binding of two small metal ions rather than one large.

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