Poly­sulfonyl­amines. CXLV.

The prominent features in the molecular structure of the title compound (alternative name: 2‐diethyl­carbamoyl‐1,1,3,3‐tetraoxo‐1,3,2‐benzodi­thia­zole), C₁₁H₁₄N₂O₅S₂, arise in the urea moiety S₂N—C(O)—N′C₂: the sum of the angles at N is 332.3 (1)°, the N—C(O)—N′C₂ unit is planar, and distances N—C(O) = 1.494 (3) Å, N′—C(O) = 1.325 (2) Å and C—O = 1.215 (2) Å. The mol­ecules are associated via five C—H?O hydrogen bonds to form layers parallel to the yz plane. This compound and its di­methyl homologue, which were synthesized by treating the silver salt of o‐benzene­disulfon­imide with carbamoyl chlorides, are prone to rapid hydro­lysis at the weak N—C(O) bond. For both mol­ecules, the rotational barrier about the partial N′—C(O) double bond is ca 50 kJ mol^?1 at 250 K (from dynamic ¹H NMR experiments).     

Azole. 45.

The three title compounds, namely (Z)‐1‐(4,5‐di­nitro­imidazol‐1‐yl)‐3‐morpholinopropan‐2‐one 2,4‐di­nitro­phenyl­hydrazone, C₁₆H₁₇N₉O₉, (IV), (Z)‐3‐morpholino‐1‐(4‐morpholino‐5‐nitro­imidazol‐1‐yl)propan‐2‐one 2,4‐di­nitro­phenyl­hydrazone, C₂₀H₂₅N₉O₈, (Va), and (E)‐3‐morpholino‐1‐(4‐morpholino‐5‐nitro­imidazol‐1‐yl)propan‐2‐one 2,4‐di­nitro­phenylhydra­zone tetra­hydro­furan solvate, C₂₀H₂₅N₉O₈·C₄H₈O, (Vb), have been prepared and their structures determined. In (IV), the C‐4 nitro group is nearly perpendicular to the imidazole ring and the C‐4—NO₂ bond length is comparable to the value for a normal single Csp²—NO₂ bond. In (IV), (Va) and (Vb), the C‐­5 nitro group deviates insignificantly from the imidazole plane and the C‐5—NO₂ bond length is far shorter in all three compounds than C‐4—NO₂ in (IV). In consequence, the C‐4 nitro group in (IV) is easily replaced by morpholine, while the C‐5 nitro group in (IV), (Va) and (Vb) shows an extraordinary stability on treatment with the amine. The E configuration in (Vb) is stabilized by a three‐centre hydrogen bond.     

4‐Fluoro‐2‐(phospho­no­methyl)­benzene­sulfonic acid monohydrate

The title compound, C₇H₈FO₆PS·H₂O, contains both phospho­nic and sulfonic acid functionalities. An extensive network of O—H?O hydrogen bonds is present in the crystal structure. The three acidic protons are associated with the phospho­nate group. Two protons experience typical hydrogen‐bond contacts with the sulfonate‐O atoms, while the third has a longer covalent bond of 1.05 (3) Å to the phospho­nate‐O atom and a short hydrogen‐bond contact of 1.38 (3) Å to the water O atom (all O—H?O angles are in the range 162–175°). The sulfonate group is positioned so that one S—O bond is nearly coplanar with the phenyl ring [torsion angle O—S—C—C ?8.6 (2)°]. The phospho­nate group is oriented approximately perpendicular to the ring [torsion angle P—C—C—C 99.2 (2)°] with one P—O bond anti to the benzyl C—C bond. The mol­ecules pack in layers in the b–c plane with the water mol­ecules in between adjacent pairs of inverted layers.     

The dimeric mixed‐ligand titana­carborane sandwich [1‐(Cp)‐1‐Ti‐2‐(Me)‐3‐(SiMe3)‐2,3‐C2B4H4]2

The title dimer, bis­[1‐cyclo­penta­dienyl‐2‐methyl‐1‐titana‐3‐tri­methylsilyl‐2,3‐dicarba‐closo‐hexaborane(6)], [Ti(C₅H₅)(C₆­H₁₆­B₄Si)]₂, reveals that the centrosymmetric mol­ecule consists of two bent‐sandwich titanacarboranes bridged by the B—H—Ti bonds. The average bond distances are Ti—B 2.445 (3), Ti—C(cage) 2.334 (2) and Ti—C(Cp) 2.376 (3) Å, and the corresponding bond angles are Cp—Ti—Cp 163.2 (1) and Cp—Ti—Cb (Cb = C₂B₃ face) 139.9 (1)°; the Ti—H separations are 2.10 (2) and 2.19 (2) Å.     

cis‐Bis(3,6‐di­hydro‐2H‐1,2‐oxazine‐N)­di­iodo­platinum(II) and cis‐bis(3,4,5,6‐tetra­hydro‐2H‐1,2‐oxazine‐N)­di­iodo­platinum(II)

The title complexes, [Pt(C₄H₇NO)₂I₂], (I), and [Pt(C₄H₉NO)₂I₂], (II), possess similar square‐planar coordination geometries with modest distortions from ideality. For (I), the cis‐L—Pt—L angles are in the range 87.0 (4)–94.2 (3)°, while the trans angles are 174.4 (3) and 176.4 (3)°. For (II), cis‐L—Pt—L are 86.1 (8)–94.2 (6)° and trans‐L—Pt—L are 174.4 (6) and 177.4 (5)°. One 3,6‐di­hydro‐2H‐1,2‐oxazine ligand in (I) is rotated so that the N—O bond is out of the square plane by approximately 70°, while the N—C bond is only ca 20° out of the plane. The other oxazine ligand is rotated so that the N—C bond is about 80° out of the plane, while the N—O bond is out of the plane by approximately 24°. In (II), the 3,4,5,6‐tetra­hydro‐2H‐1,2‐oxazine ligands are also positioned with one having the N—O bond further out of the plane and the other having the N—C bond positioned in that fashion. Both ligands, however, are rotated approximately 90° compared with their positions in (I). In both complexes, this results in an unsymmetrical distortion of the I—Pt—N bond angles in which one is expanded and the other contracted. These features are compared to those of reported cis‐di­amine­di­iodo­platinum(II) complexes.     

A mol­ecule with a C1‐homobasketane framework

The title compound, 6‐(1,3‐benzodi­thiol‐2‐yl­idene)‐5,7‐di­methyl‐1,2‐di­phenylpenta­cyclo­[5.4.0.0^2,5.0^3,11.0^4,8]­un­decane, C₃₂H₂₈S₂, with a C₁‐homobasketane framework, crystallizes in the P space group with one mol­ecule in the asymmetric unit. The two cyclo­butane rings in the cage are in a puckered conformation. Due to the enhanced through‐bond interaction of the phenyl π systems involving a strained σ bond, the (Ph—­)C—C(—Ph) bond length is significantly extended, to 1.610 (3) Å.     

Three N2‐benzoyl­oxybenz­amidines: sheet structures built from hard and soft hydrogen bonds and aromatic π–π stacking interactions

Molecules of the title compounds N²‐(benzoyl­oxy)­benz­ami­dine, C₁₄H₁₂N₂O₂, (I), N²‐(2‐hydroxy­benzoyl­oxy)­benz­ami­dine, C₁₄H₁₂N₂O₃, (II), and N²‐benzoyloxy‐2‐hydroxybenzamidine, C₁₄H₁₂N₂O₃, (III), all have extended chain conformations, with the aryl groups remote from one another. In (I), the mol­ecules are linked into chains by a single N—H⋯N hydrogen bond [H⋯N = 2.15 Å, N⋯N = 3.029 (2) Å and N—H⋯N = 153°] and these chains are linked into sheets by means of aromatic π–π stacking interactions. There is one intramolecular O—H⋯O hydrogen bond in (II), and a combination of one three‐centre N—H⋯(N,O) hydrogen bond [H⋯N = 2.46 Å, H⋯O = 2.31 Å, N⋯N = 3.190 (2) Å, N⋯O = 3.146 (2) Å, N—H⋯N = 138° and N—H⋯O = 154°] and one two‐centre C—H⋯O hydrogen bond [H⋯O = 2.46 Å, C⋯O = 3.405 (2) Å and C—H⋯O = 173°] links the mol­ecules into sheets. In (III), an intramolecular O—H⋯N hydrogen bond and two N—H⋯O hydrogen bonds [H⋯O = 2.26 and 2.10 Å, N⋯O = 2.975 (2) and 2.954 (2) Å, and N—H⋯O = 138 and 163°] link the molecules into sheets.     

Dichloro[1,1′‐(5,9‐dithia‐2,12‐diazoniatrideca‐1,12‐diene‐1,13‐diyl)dinaphthalen‐2‐olato‐κ2O,O′]dimethyltin(IV) acetonitrile solvate

Reaction of the potentially hexadentate ligand 1,9‐bis(2‐hydroxy‐1‐naphthalene­methyl­imino)‐3,7‐di­thia­nonane with di­methyl­tin chloride gave the title 1:1 adduct, in which the long ligand wraps around the SnCl₂Me₂ unit and in which the stereochemistry is fully trans. This compound crystallizes from aceto­nitrile as the 1:1 solvate [Sn(CH₃)₂(C₂₉H₃₀N₂­O₂S₂)Cl₂]·­C₂H₃N. During the reaction, the hydroxyl protons move to the N atoms. Most of the chemically equivalent bond lengths agree to within experimental uncertainty, but the Sn—Cl bond that is inside the ligand pocket is substantially longer than the Sn—Cl bond that points away from the long ligand [2.668 (1) versus 2.528 (1) Å]. The O—Sn—O angle is 166.0 (1)°. Comparison of the Sn—O, C—O and aryl C—C bond lengths with those of related compounds shows that the most important resonance forms for the Schiff base aryl­oxide ligand are double zwitterions, but that the uncharged resonance forms having carbonyl groups also contribute significantly.     

The centrosymmetric dimer of di­chloro­(tri­methyl­siloxy)­aluminium

The title mol­ecule is dimeric, i.e. di‐μ‐tri­methyl­siloxy‐bis­(di­chloro­aluminium), [Al₂Cl₄(C₃H₉Si)₂], and possesses exact crystallographic inversion symmetry. The O atoms of the tri­methyl­siloxy groups bridge the two Al atoms to form a four‐membered ring. The Si—O bond distance [1.711 (3) Å], the Al—O mean bond distance [1.806 (4) Å] and the mean Si—C bond distance [1.875 (6) Å] appear to agree well with standard data. Mean values for C—Si—C, O—Si—C, and Si—O—Al angles are 112.9 (3), 105.8 (2), and 131.8 (2)° repectively. The two ring angles O—Al—O and Al—O—Al are 84.43 (16) and 95.57 (16)°, respectively.     

The seven‐membered nickelacycle [NiBr{o‐CH=C(CF3)C6H4CH2PPh2‐κ2C,P}{PPh(CH2Ph)2}]

The crystal and molecular structures of the title compound, 3‐bromo‐3‐(di­benzyl­phenyl­phospho­nio)‐2,2‐di­phenyl‐5‐trifluoromethyl‐1H‐benzo­[e][1,2]­phosphanickelepine, [NiBr(C₂₂H₁₇F₃P)(C₂₀H₁₉P)], which was obtained as the major regioisomer from insertion of HCCCF₃ into the Ni—C bond of the five‐membered phosphanickelacycle [NiBr(o‐C₆H₄CH₂PPh₂‐κ²C,P){PPh(CH₂Ph)₂}], have been determined. Principal geometric data include the Ni—X bond lengths Ni—Br 2.3343 (4) Å, Ni—P 2.1867 (7) and 2.2094 (7) Å, and Ni—C 1.882 (3) Å, and the two trans angles P—Ni—P 171.55 (3)° and Br—Ni—C 176.88 (9)°.     

2,2′‐[2,3‐Di­hydro‐2‐(prop‐2‐enyl)‐1H‐isoindole‐1,3‐diyl­idene]bis(propane­di­nitrile)–tetra­thia­fulvalene (1/1), TCPI–TTF

The title complex, C₁₇H₉N₅·C₆H₄S₄, contains π‐deficient bis(di­nitrile) and TTF mol­ecules stacked alternately in columns along the a‐axis direction; the interplanar angle between the TTF molecule and the isoindolinyl C₄N[C(CN)₂]₂ moiety is 1.21 (4)°. The N‐allyl moiety in the TCPI mol­ecule is oriented at an angle of 87.10 (10)° with respect to the five‐membered C₄N ring, and the four C[triple‐bond]N bond lengths range from 1.134 (3) to 1.142 (3) Å, with C—C[triple‐bond]N angles in the range 174.3 (3)–176.9 (2)°. In the TTF system, the S—C bond lengths are 1.726 (3)–1.740 (3) and 1.751 (2)–1.763 (2) Å for the external S—C(H) and internal S—C(S) bonds, respectively.     

(E)‐2‐[2‐(1‐Naphthyl)­vinyl]‐3‐tosyl‐2,3‐di­hydro‐1,3‐benzo­thia­zole

The title compound, C₂₆H₂₁NO₂S₂, which consists of a benzo­thia­zole skeleton with α‐naphthyl­vinyl and tosyl groups at positions 2 and 3, respectively, was prepared by palladium–copper‐catalyzed heteroannulation. The E configuration of the mol­ecule about the vinyl C=C bond is established by the benzothiazole–naphthyl C—C—C—C torsion angle of 177.5 (4)°. The five‐membered heterocyclic ring adopts an envelope conformation with the Csp³ atom 0.380 (6) Å from the C₂NS plane. The two S—C [1.751 (4) and 1.838 (4) Å] and two N—C [1.426 (5) and 1.482 (5) Å] bond lengths in the thia­zole ring differ significantly.     

7‐Vinyl‐8‐aza‐7‐de­aza‐2′‐deoxy­adenosine monohydrate

In the title compound, 4‐amino‐1‐(2‐deoxy‐β‐d ‐eythro‐pento­furan­osyl)‐3‐vinyl‐1H‐pyrazolo­[3,4‐d]­pyrimidine monohydrate, C₁₂H₁₅N₅O₃·H₂O, the conformation of the gly­cosyl bond is anti. The furan­ose moiety is in an S conformation with an unsymmetrical twist, and the conformation at the exocyclic C—C(OH) bond is +sc (gauche, gauche). The vinyl side chain is bent out of the heterocyclic ring plane by 147.5 (5)°. The three‐dimensional packing is stabilized by O—H·O, O—H·N and N—H·O hydrogen bonds.     

2‐Amino‐7‐chloro‐2′‐deoxy­tubercidin

In 4‐chloro‐7‐(2‐de­oxy‐β‐d ‐erythro‐pento­furanos­yl)‐7H‐pyr­rolo­[2,3‐d]­pyrimidine‐2,4‐diamine, C₁₁H₁₄ClN₅O₃, the conformation of the N‐glycosylic bond is between anti and high‐anti [χ = −102.5 (6)°]. The 2′‐deoxy­ribofuranosyl unit adopts the C3′‐endo‐C4′‐exo (³T₄) sugar pucker (N‐type) with P = 19.6° and τ_m = 32.9° [terminology: Saenger (1989). Landolt‐Börnstein New Series, Vol. 1, Nucleic Acids, Subvol. a, edited by O. Madelung, pp. 1–21. Berlin: Springer‐Verlag]. The orientation of the exocyclic C4′—C5′ bond is +ap (trans) with a torsion angle γ = 171.5 (4)°. The compound forms a three‐dimensional network that is stabilized by four inter­molecular hydrogen bonds (N—H⋯O and O—H⋯N) and one intra­molecular hydrogen bond (N—H⋯Cl).     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

2′‐Deoxy‐7‐propynyl‐7‐deaza­adenosine: a DNA duplex‐stabilizing nucleoside

In the title compound, 2′‐deoxy‐7‐propynyl‐7‐deaza­adenosine, C₁₄H₁₆N₄O₃, the torsion angle of the N‐glycosylic bond is anti [χ = −130.7 (2)°]. The sugar pucker of the 2′‐deoxy­ribo­furanosyl moiety is C2′‐endo–C3′‐exo, ²T₃ (S‐type), with P = 185.9 (2)° and τ_m = 39.1 (1)°, and the orientation of the exocyclic C4′—C5′ bond is −ap (trans). The 7‐substituted propynyl group is nearly coplanar with the heterocyclic base moiety. Mol­ecules of the nucleoside form a layered network in which the heterocyclic bases are stacked head‐to‐tail with a closest distance of 3.197 (1) Å. The crystal structure of the nucleoside is stabilized by three inter­molecular hydrogen bonds of types N—H⋯ O, O—H⋯ N and O—H⋯ O.     

A hydrogen‐bonded heterodimer of 1‐(4‐hexyloxyphenyl)pyridin‐4(1H)‐one with 4‐cyano­benzoic acid

The two components of the title heterodimer, C₁₇H₂₁NO₂·C₈H₅NO₂, are linked end‐to‐end via O—H⋯O(=C) and C—H⋯O(=C) hydrogen‐bond inter­actions. Additional lateral C—H⋯O inter­actions link the dimers in a side‐by‐side fashion to produce wide infinite mol­ecular ribbons. Adjacent ribbons are inter­connected viaπ–π stacking and C—H⋯π(arene) inter­actions. This structure represents the first evidence of robust hydrogen‐bond formation between the moieties of pyridin‐4(1H)‐one and benzoic acid.     

Pentacarbonyl(4‐phenylpyridine)­tungsten(0) and pentacarbonyl(2‐phenylpyridine)chromium(0)

In penta­carbonyl(4‐phenyl­pyridine)­tungsten(0), [W­(C₁₁H₉N)(CO)₅], the mol­ecules have mm site symmetry and the pyridine ligand, with m symmetry, is completely planar. In penta­carbonyl(2‐phenyl­pyridine)­chromium(0), [Cr(C₁₁­H₉N)(CO)₅], the mol­ecules are in general positions and the phenyl and pyridine rings of the ligand are twisted by 67.7 (3)° with respect to one another by rotation about the C—C bond joining them. In both compounds, the axial M—C_carbonyl bond trans to the M—N_ligand bond is significantly shorter than the equatorial M—C_carbonyl bonds.     

rac‐ and meso‐3,3′‐Bis(3,5‐di­methyl­phenyl)‐3H,3′H‐2,2′‐biindenyl­idene‐1,1′(2H,2′H)‐dione

In the rac isomer of the title compound, C₃₄H₂₈O₂, the two C—Ph_{di­methyl­phenyl} bond axes make an angle of 58.7 (1)°. There is no short contact between the two 3,5‐di­methyl­phenyl rings, although the dihedral angle between them is 4.93 (7)°. The meso isomer has a center of symmetry at the middle of the C=C bond, and the two C—Ph_{di­methyl­phenyl} bond axes are antiparallel to one another.     

Ferrocene compounds. XXXVIII. Di­methyl ferrocene‐1,1′‐di­carboxyl­ate

In the title compound, [Fe(C₇H₇O₂)₂], the cyclo­penta­dienyl rings and the two attached methoxy­carbonyl groups, in an anti arrangement, form an extended π‐conjugated system. The Fe—C distances range from 2.035 (3) to 2.061 (3) Å and the average value of the C—C bond lengths in the two cyclo­penta­dienyl rings is 1.419 (5) Å. The rings are almost parallel to one another [1.0 (2)°] and are mutually twisted from an eclipsed conformation by only 1.8 (3)° (average value). The methoxy­carbonyl groups are twisted out of the plane of the cyclo­penta­dienyl rings by 6.5 (4) and 15.7 (4)°, respectively. The mol­ecules are joined into dimers by intermolecular C—H⃛O hydrogen bonds that form ten‐membered rings. The same types of hydrogen bonds form eight‐membered rings and infinite chains along the b axis.