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1.  4-Formyl-2-nitro­phenyl 3-nitro-2-methyl­benzoate 
In the title formyl nitro aryl benzoate derivative, C15H10N2O7, the benzene rings form a dihedral angle of 4.96 (3)°. The mean plane of the central ester group, C—O—C–(=O)—C (r.m.s. deviation = 0.0484 Å), is twisted away from the formyl nitro aryl and benzoate rings by 46.61 (5) and 49.93 (5)°, respectively. In the crystal, the mol­ecules are packed forming C—H⋯O inter­actions in chains which propagate along [010]. Edge-fused R 3 3(15) rings are generated along this direction.
doi:10.1107/S1600536813032583
PMCID: PMC3914067  PMID: 24526968
2.  2,4,6-Tri­nitro­phenyl furan-2-carboxyl­ate 
In the title carboxyl­ate derivative, C11H5N3O9, the picryl ring forms an angle of 75.79 (7)° with the ester fragment, indicating a near perpendicular disposition. The nitro substituents are variously oriented with respect to the picryl ring [dihedral angles = 3.22 (10), 16.03 (12) and 36.63 (10)°]. In the crystal, mol­ecules form helical chains sustained by C—H⋯O inter­actions along [010]. The furanyl residue is disordered, having two coplanar slightly displaced orientations [major component = 0.730 (9)].
doi:10.1107/S1600536813028274
PMCID: PMC3884337  PMID: 24454113
3.  N-(2-Nitro­phen­yl)furan-2-carboxamide 
In the title furan­carboxamide derivative, C11H8N2O4, the benzene and furan rings are rotated from the mean plane of the central fragment by 2.68 (5) and 7.03 (4)°, respectively. The nitro group forms a dihedral angle of 10.15 (5)° with the adjacent benzene ring. In the crystal, mol­ecules are linked by weak C—H⋯O inter­actions, forming helical chains running along [010].
doi:10.1107/S1600536813026202
PMCID: PMC3790447  PMID: 24098266
5.  Structural Tracking of the Potassium-Mediated Magnesiation of Anisole 
doi:10.1002/chem.200901897
PMCID: PMC3784043  PMID: 19746488
crystal structure; magnesiation; metalation; NMR spectroscopy; potassium
6.  Structurally Defined Potassium-Mediated Zincation of Pyridine and 4-R-Substituted Pyridines (R=Et, iPr, tBu, Ph, and Me2N) by Using Dialkyl–TMP–Zincate Bases 
Abstract
Two potassium–dialkyl–TMP–zincate bases [(pmdeta)K(μ-Et)(μ-tmp)Zn(Et)] (1) (PMDETA=N,N,N′,N′′,N′′-pentamethyldiethylenetriamine, TMP=2,2,6,6-tetramethylpiperidide), and [(pmdeta)K(μ-nBu)(μ-tmp)Zn(nBu)] (2), have been synthesized by a simple co-complexation procedure. Treatment of 1 with a series of substituted 4-R-pyridines (R=Me2N, H, Et, iPr, tBu, and Ph) gave 2-zincated products of the general formula [{2-Zn(Et)2-μ-4-R-C5H3N}2⋅2{K(pmdeta)}] (3–8, respectively) in isolated crystalline yields of 53, 16, 7, 23, 67, and 51%, respectively; the treatment of 2 with 4-tBu-pyridine gave [{2-Zn(nBu)2-μ-4-tBu-C5H3N}2⋅2{K(pmdeta)}] (9) in an isolated crystalline yield of 58%. Single-crystal X-ray crystallographic and NMR spectroscopic characterization of 3–9 revealed a novel structural motif consisting of a dianionic dihydroanthracene-like tricyclic ring system with a central diazadicarbadizinca (ZnCN)2 ring, face-capped on either side by PMDETA-wrapped K+ cations. All the new metalated pyridine complexes share this dimeric arrangement. As determined by NMR spectroscopic investigations of the reaction filtrates, those solutions producing 3, 7, 8, and 9 appear to be essentially clean reactions, in contrast to those producing 4, 5, and 6, which also contain laterally zincated coproducts. In all of these metalation reactions, the potassium–zincate base acts as an amido transfer agent with a subsequent ligand-exchange mechanism (amido replacing alkyl) inhibited by the coordinative saturation, and thus, low Lewis acidity of the 4-coordinate Zn centers in these dimeric molecules. Studies on analogous trialkyl–zincate reagents in the absence and presence of stoichiometric or substoichiometric amounts of TMP(H) established the importance of Zn–N bonds for efficient zincation.
doi:10.1002/chem.200900549
PMCID: PMC3784044  PMID: 19533716
alkali metals; metalation; potassium; pyridine; zincation
7.  12-(2-Hy­droxy-6-oxo­cyclo­hex-1-en­yl)-9,10-di­hydro-8H-benzo[a]xanthen-11(12H)-one 
In the xanthenone system of the title compound, C23H20O4, the pyran ring has a maximum deviation of 0.111 (1) Å from planarity and the outer cyclo­hexene ring exhibits a puckered conformation. The three methyl­ene C atoms of the cyclo­hexene ring bonded to the pyran unit are disordered over two sets of sites [occupancies = 0.570 (3) and 0.430 (3)]. In the crystal, mol­ecules are linked by C—H⋯O and O—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (110). A C—H⋯π inter­action occurs between these networks.
doi:10.1107/S1600536813025324
PMCID: PMC3790420  PMID: 24098239
8.  Developing a Hetero-Alkali-Metal Chemistry of 2,2,6,6-Tetramethyl-piperidide (TMP): Stoichiometric and Structural Diversity within a Series of Lithium/Sodium, Lithium/Potassium and Sodium/Potassium TMP Compounds 
Studied extensively in solution and in the solid state, Li(TMP) (TMP=2,2,6,6-tetramethylpiperidide) is an important utility reagent popular as a strongly basic, weakly nucleophilic tool for C–H metallation. Recently, there has been a surge in interest in mixed metal derivatives containing the bulky TMP anion. Herein, we start to develop hetero (alkali metal) TMP chemistry by reporting the N,N,N′,N′-tetramethylethylenediamine (TMEDA)-hemisolvated sodium–lithium cycloheterodimer [(tmeda)Na(μ-tmp)2Li], and its TMEDA-free variant [{Na(μ-tmp)Li(μ-tmp)}∞], which provides a rare example of a crystallographically authenticated polymeric alkali metal amide. Experimental observations suggest that the former is a kinetic intermediate en route to the latter thermodynamic product. Furthermore, a third modification, the mixed potassium–lithium-rich cycloheterotrimer [(tmeda)K(μ-tmp)Li(μ-tmp)Li(μ-tmp)], has also been synthesised and crystallographically characterised. On moving to the bulkier tridentate donor N,N,N′,N′′,N′′-pentamethyldiethylenediamine (PMDETA), the additional ligation forces the sodium–lithium and potassium–dilithium ring species to open giving the acyclic arc-shaped complexes [(pmdeta)Na(μ-tmp)Li(tmp)] and [(pmdeta)K(μ-tmp)Li(μ-tmp)Li(tmp)], respectively. Completing the series, the potassium–lithium and potassium–sodium derivatives [(pmdeta)K(μ-tmp)2M] (M=Li, Na) have also been isolated as closed structures with a distinctly asymmetric central MN2K ring. Collectively, these seven new bimetallic compounds display five distinct structural motifs, four of which have never hitherto been witnessed in TMP chemistry and three of which are unprecedented in the vast structural library of alkali metal amide chemistry.
doi:10.1002/chem.201101167
PMCID: PMC3761191  PMID: 21766365
aggregation; alkali metals; amides; heterometallic complexes; X-ray diffraction
9.  1-{(E)-[(2-Fluoro-5-nitro­phen­yl)imino]­meth­yl}naphthalen-2-ol 
The title mol­ecule, C17H11FN2O3, is nearly planar [maximum deviation = 0.197 (1) Å] and the mol­ecular conformation is stabilized by an N—H⋯O hydrogen bond forming an S(6) ring motif. The H atom of the intra­molecular hydrogen bond was found to be disordered over two sites and thus both the hy­droxy and keto tautomers are simultaneously present in the solid. Refinement of the occupancy of this site suggests that the hy­droxy form is the major component [occupancy refined to 0.59 (3):0.41 (3)]. Bond lengths are also largely consistent with dominance of the hy­droxy form. In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds, forming layers parallel to (101). π–π stacking inter­actions [centroid–centroid distances = 3.5649 (9) and 3.7579 (9) Å] inter-connect these layers.
doi:10.1107/S1600536813012099
PMCID: PMC3684934  PMID: 23795036
10.  14-Bromo-12-chloro-2,16-dioxa­penta­cyclo­[7.7.5.01,21.03,8.010,15]henicosa-3(8),10,12,14-tetra­ene-7,20-dione 
In the title compound, C19H16BrClO4, both the fused xanthene rings and one of the cyclo­hexane rings adopt envelope conformations, while the other cyclo­hexane ring is in a chair conformation. In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds, forming infinite chains running along [10-1] incorporating R 2 2(16) ring motifs. In addition, C—H⋯π inter­actions and weak π–π stacking inter­actions [centroid–centroid distance = 3.768 (3) Å] help to consolidate the packing.
doi:10.1107/S1600536813010374
PMCID: PMC3648294  PMID: 23723914
11.  3-Amino-1-phenyl-1H-benzo[f]chromene-2-carbonitrile 
In the title compound, C20H14N2O, the phenyl ring is almost normal to the naphthalene ring system with a dihedral angle of 86.72 (9)°. The 4H-pyran ring fused with the naphthalene ring system has a boat conformation. In the crystal, mol­ecules are linked into a helical supra­molecular chain along the b axis via N—H⋯N hydrogen bonds. The chains are consolidated into a three-dimensional architecture by C—H⋯π inter­actions.
doi:10.1107/S1600536813004376
PMCID: PMC3588429  PMID: 23476583
12.  2,4,6-Trinitro­phenyl benzoate 
In the title mol­ecule, C13H7N3O8, the phenyl and benzene rings are rotated from the mean plane of the central ester group by 18.41 (9) and 81.80 (5)°, respectively. The dihedral angle between the rings is 80.12 (14)°. In the crystal, mol­ecules are linked by weak C—H⋯O inter­actions, forming helical chains along [010].
doi:10.1107/S1600536812048362
PMCID: PMC3589064  PMID: 23476300
13.  4-Phenyl-1H-1,5-benzodiazepin-2(3H)-one 
In the title compound, C15H12N2O, the phenyl ring makes a dihedral angle of 32.45 (9)° with the benzene ring of the 1,5-benzodiazepin-2-one unit. The seven-membered ring adopts a boat conformation with the methyl­ene group as the prow and the fused benzene-ring C atoms as the stern. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R 2 2(8) loops. The dimers are further linked by C—H⋯O hydrogen bonds, so forming a column along the a-axis direction.
doi:10.1107/S160053681204651X
PMCID: PMC3588955  PMID: 23476191
14.  catena-Poly[sodium-μ2-(N,N,N′,N′-tetra­methyl­ethane-1,2-diamine)-κ2 N:N′-sodium-bis­[μ2-bis­(trimethyl­sil­yl)aza­nido-κ2 N:N]] 
The title compound, [Na2(C6H18NSi2)2(C6H16N2)]n, was found to consist of dimeric [Na(NSiMe3)2] units with crystallographically imposed centrosymmetry based upon four-membered NaNNaN rings. The dimers are bridged by N,N,N′,N′-tetra­methyl­ethylenediamine ligands, which act in an unusual extended non-chelating coordination mode. This gives a one-dimensional coordination polymer that extends parallel to the a-axis direction.
doi:10.1107/S1600536812045126
PMCID: PMC3588730  PMID: 23468695
15.  Diethyl 3,4-dimethyl­thieno[2,3-b]thio­phene-2,5-dicarboxyl­ate 
In the title compound, C14H16O4S2, the thieno[2,3-b]thio­phene ring systems are planar [maximum deviation = 0.008 (2) Å]. The mol­ecular conformation is stabilized by intra­molecular C—H⋯O hydrogen bonds, while the crystal packing is stabilized by C—H⋯O, C—H⋯π and π–π stacking [centroid–centroid distance = 3.6605 (14) Å] inter­actions, which lead to supra­molecular layers in the ab plane.
doi:10.1107/S160053681204593X
PMCID: PMC3588935  PMID: 23476171
16.  4-Bromo-2-[(E)-{[4-nitro-2-(trifluoro­meth­yl)phen­yl]imino}­meth­yl]phenol 
Except two F atoms of the –CF3 group, the title compound, C14H8BrF3N2O3, has an almost planar conformation, the dihedral angle between the aromatic rings being 3.60 (16)°. The mol­ecule adopts the enol–imine tautomeric form, with an intra­molecular O—H⋯N hydrogen bond, which generates an S(6) ring motif. In the crystal, face-to-face π–π stacking [centroid–centroid distances = 3.669 (2) and 3.732 (2) Å] between the aromatic rings of the mol­ecules, which lie in sheets parallel to (202), help to establish the packing.
doi:10.1107/S1600536812042262
PMCID: PMC3515262  PMID: 23284482
17.  1-Benzyl­piperidin-4-one O-(2-bromo­benz­yl)oxime 
In the title mol­ecule, C19H21BrN2O, the piperidone ring adopts a chair conformation with a total puckering amplitude Q T of 0.554 (2) Å. The dihedral angle between the benzene rings is 64.10 (7)°. There are no significant inter­molecular inter­actions.
doi:10.1107/S1600536812040263
PMCID: PMC3470391  PMID: 23125804
18.  2-Amino­ethanaminium iodide 
The title salt, [NH3CH2CH2NH2]+·I−, has an array structure based on strong inter­molecular N—H⋯N hydrogen bonding formed between the ammonium and amine groups of adjacent cations. This inter­action gives a helical chain of cations that runs parallel to the b axis. The four remaining NH group H atoms all form hydrogen bonds to the iodide anion, and these iodide anions lie in channels parallel to the cation–cation chains.
doi:10.1107/S160053681202065X
PMCID: PMC3379320  PMID: 22719518
19.  (E)-Benzaldehyde O-{[3-(pyridin-3-yl)isoxazol-5-yl]meth­yl}oxime 
The asymmetric unit of the title compound, C16H13N3O2, contains two independent mol­ecules in which the pyridine and benzene rings form dihedral angles of 81.7 (2) and 79.8 (2)°, indicating the twist in the mol­ecules. In the crystal, weak C—H⋯N inter­actions link mol­ecules into chains along [100].
doi:10.1107/S1600536812010732
PMCID: PMC3344035  PMID: 22589944
20.  1,4-Dimethyl­piperazin-1-ium 3-hy­droxy-2-naphtho­ate 
The reaction of 1,4-dimethyl­piperazine and 3-hy­droxy-2-naphthoic acid gives the title 1:1 salt, C6H15N2 +·C11H7O3 −, with a singly protonated piperazinium cation. In the crystal, a single N—H⋯O hydrogen bond links the cations and anions into discrete pairs and the aromatic anions stack along the crystallographic a-axis direction. This results in layers of cations and anions alternating along the crystallographic c-axis direction. An intra­molecular O—H⋯O hydrogen bond is also present.
doi:10.1107/S1600536812005375
PMCID: PMC3297856  PMID: 22412659
21.  2-Bromo-N-(4-chloro­phen­yl)-2-methyl­propanamide 
In the title mol­ecule, C10H11BrClNO, there is a twist between the mean plane of the amide group and the benzene ring [C(=O)—N—C—C torsion angle = −27.1 (3)°]. In the crystal, inter­molecular N—H⋯O and weak C—H⋯O hydrogen bonds link the mol­ecules into chains along [010].
doi:10.1107/S1600536811035562
PMCID: PMC3201238  PMID: 22064690
22.  2-Bromo-N-(2-hy­droxy-5-methyl­phen­yl)-2-methyl­propanamide 
In the title mol­ecule, C11H14BrNO2, there is twist between the mean plane of the amide group and the benzene ring [the C—N—C—C torsion angle is −172.1 (2)°]. The amide H atom forms an intra­molecular hydrogen bond with the Br atom. In the crystal, inter­molecular O—H⋯O and weak C—H⋯O hydrogen bonds link mol­ecules into a chain along [100].
doi:10.1107/S1600536811033150
PMCID: PMC3200793  PMID: 22065656
23.  catena-Poly[[(nitrito-κ2 O,O′)silver(I)]-μ-1,2-bis­[1-(pyridin-4-yl)ethyl­idene]hydrazine-κ2 N:N′] 
The asymmetric unit of the title compound, [Ag(NO2)(C14H14N4)]n, contains half of the repeating formula unit (Z′ = 1/2). The AgI ion lies on a twofold rotation axis. The primary structure consists of a one-dimensional coordination polymer formed by the AgI ions and the bipyridyl azine ligand in which there is an inversion center at the mid-point of the N—N bond. The nitrite anion inter­acts with the AgI ion through a chelating μ2 inter­action involving both O atoms. In the crystal, the coordination chains are parallel and inter­act through Ag⋯π [3.220 (2) Å] and π–π [3.489 (3) Å] inter­actions.
doi:10.1107/S1600536811028546
PMCID: PMC3212196  PMID: 22090898
24.  2-Bromo-2-methyl-N-p-tolyl­propanamide 
In the title mol­ecule, C11H14BrNO, there is twist between the mean plane of the amide group and the benzene ring [C(=O)—N—C C torsion angle = −31.2 (5)°]. In the crystal, inter­molecular N—H⋯O and weak C—H⋯O hydrogen bonds link mol­ecules into chains along [100]. The methyl group H atoms are disordered over two sets of sites with equal occupancy.
doi:10.1107/S1600536811019337
PMCID: PMC3120290  PMID: 21754902
25.  5,7,7,12,14,14-Hexamethyl-4,8-diaza-1,11-diazo­niocyclotetra­deca-4,11-diene diiodide dihydrate 
The asymmetric unit of the title compound, C16H34N4 2+·2I−·2H2O, contains one half-cation, one iodide anion and one water mol­ecule. The cation has crystallographically imposed centrosymmetric symmetry. Despite some differences in the unit-cell dimensions, packing analysis on a cluster of 15 cations and a comparison of the hydrogen bonding suggests that this compound is isostructural with its bromide analogue. Inter­molecular hydrogen bonding forms eight-membered [H—O—H⋯I]2 and [H—N—H⋯I]2 rings and creates a sheet structure.
doi:10.1107/S1600536811005848
PMCID: PMC3052064  PMID: 21522429

Results 1-25 (48)