Bleaching the Record: After 200 Years, Single Crystal X-Ray Crystallography Reveals the Structure and Hydrogen-Bonding Properties of Hypochlorite and Hypobromite Ions in the Solid State

<div>We report the first single crystal structures of hypochlorite and hypobromite salts, including hydrated sodium hypochlorite - a ubiquitous bleaching and disinfection agent in use for almost 200 years. The structures represent the first characterization of fundamentally important hypochlorite and hypobromite anions in the solid state, by X-ray crystallography and are supported by Raman spectroscopy on individual crystals. The structural analysis provides insight into supramolecular chemistry of the hypohalite ions in the hydrated environment of the NaOCl<sup>.</sup>5H<sub>2</sub>O and NaOBr<sup>.</sup>5H<sub>2</sub>O solid salts, and reveals measured Cl-O and Br-O bond lengths of 1.69 A and 1.82 A, respectively, which are significantly longer than those for corresponding higher-valence oxoanions, and in agreement with the values spectroscopically determined for hypohalous acids and corresponding oxides in the gas phase.<br></div>

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Synthesis and structural characterization of a magnesium phthalocyanine(3–) anion

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424611004440 ◽

2012 ◽

Vol 16 (01) ◽

pp. 154-162 ◽

Cited By ~ 24

Author(s):

Edwin W.Y. Wong ◽

Daniel B. Leznoff

Keyword(s):

Absorption Spectrum ◽

Solid State ◽

Single Crystal ◽

Structural Characterization ◽

Heterometallic Complex ◽

State Structure ◽

Solid State Structure ◽

X Ray ◽

X Ray Crystallography

The reduction of magnesium phthalocyanine (MgPc) with 2.2 equivalents of potassium graphite in 1,2-dimethoxyethane (DME) gives [K2(DME)4]PcMg(OH)(1) in 67% yield. Compound 1 was structurally characterized using single crystal X-ray crystallography and was found to be a monomeric, heterometallic complex consisting of a μ3-OH ligand that bridges a [MgIIPc3-]- anion to two potassium cations solvated by four DME molecules. An absorption spectrum of 1 confirms the Pc ligand is singly reduced and has a 3–charge. The solid-state structure of 1 does not indicate breaking of the aromaticity of the Pc ligand. Compound 1 is only the second Pc3- complex and the first reduced MgPc to be isolated and structurally characterized.

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Synthesis and characterization of the binuclear diamido titanium chalcogenides [(Ar)NCH2CH2CH2N(Ar)]2Ti(µ-E)2 (E = Se, Te)

Canadian Journal of Chemistry ◽

10.1139/v02-052 ◽

2002 ◽

Vol 80 (11) ◽

pp. 1524-1529 ◽

Cited By ~ 2

Author(s):

Tianle Zhang ◽

Warren E Piers ◽

Masood Parvez

Keyword(s):

Solid State ◽

Key Words ◽

Synthesis And Characterization ◽

Catalyst Precursor ◽

Tellurium Atom ◽

Titanium Complex ◽

X Ray ◽

X Ray Crystallography ◽

Atom Source

Reaction of McConville's chelating amido titanium complex [(Ar)NCH2CH2CH2N(Ar)]Ti(CH3)2 (Ar = 2,6-i-Pr2C6H3) with either elemental Se or the tellurium atom source Te=PBu3 resulted in the formation of bis-µ-chalcogenido dimers [(Ar)NCH2CH2CH2N(Ar)]2Ti(µ-E)2 (E = Se, 2; Te, 3) with concommitant loss of EMe2. The dimers 2 and 3 were characterized spectroscopically and via X-ray crystallography. The two compounds are isostructural in the solid state. The tellurido dimer 3 may also be synthesized by reduction of the diamido dichloride [(Ar)NCH2CH2CH2N(Ar)]2TiCl2 with NaHg amalgam followed by treatment with Te=PBu3. This dimer is unreactive toward further Te=PBu3 or stannanes such as HSnBu3. Unlike decamethyltitanocene derivatives, the diamido complex is not an effective catalyst precursor for the heterohydrodecoupling of Te=PBu3 and HSnBu3.Key words: diamido titanium complexes, selenides, tellurides.

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The Synthesis and Characterization of a Novel One-Dimensional Bismuth (III) Coordination Polymer as a Precursor for the Production of Bismuth (III) Oxide Nanorods

Crystals ◽

10.3390/cryst12010113 ◽

2022 ◽

Vol 12 (1) ◽

pp. 113

Author(s):

Younes Hanifehpour ◽

Babak Mirtamizdoust ◽

Jaber Dadashi ◽

Ruiyao Wang ◽

Mahboube Rezaei ◽

...

Keyword(s):

Single Crystal ◽

Coordination Compound ◽

Organic Ligand ◽

One Dimensional ◽

X Ray ◽

X Ray Crystallography ◽

Oxide Nanorods ◽

Pure Phase ◽

3D Framework

A novel Bi (III) coordination compound, [Bi(HQ)(Cl)4]n ((Q = pyridine-4-carbaldehyde thiosemicarbazone), was prepared in this research using a sonochemical technique. SEM, infrared spectroscopy (IR), XRD, and single-crystal X-ray analysis were utilized to analyze the Bi(III) coordination compound. The structure determined using single-crystal X-ray crystallography indicates that the coordination compound is a 1D polymer in solid state and that the coordination number of bismuth (III) ions is six, (BiSCl5), with one S donor from the organic ligand and five Cl donors from anions. It is equipped with a hemidirectional coordination sphere. It is interesting that the ligand has been protonated in the course of the reaction with a Cl- ion balancing the charge. This compound’s supramolecular properties are directed and regulated by weak directional intermolecular interactions. Through π–π stacking interactions, the chains interact with one another, forming a 3D framework. Thermolysis of the compound at 170 °C with oleic acid resulted in the formation of pure phase nanosized Bi (III) oxide. SEM technique was used to examine the morphology and size of the bismuth (III) oxide product produced.

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The structure of 1-formyl-3-phenyl-Δ2-pyrazoline in the gas phase (DFT calculations), in solution (NMR) and in the solid state (X-ray crystallography)

Journal of Molecular Structure ◽

10.1016/j.molstruc.2003.10.041 ◽

2004 ◽

Vol 689 (3) ◽

pp. 251-254 ◽

Cited By ~ 14

Author(s):

I. Alkorta ◽

J. Elguero ◽

A. Fruchier ◽

N. Jagerovic ◽

G.P.A. Yap

Keyword(s):

Solid State ◽

Dft Calculations ◽

Gas Phase ◽

Solution Nmr ◽

X Ray ◽

X Ray Crystallography

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1-[N-Methyl-N-(Phenyl)amino]-3- (4-Methylphenyl)Thiourea

Molbank ◽

10.3390/m1052 ◽

2019 ◽

Vol 2019 (1) ◽

pp. M1052 ◽

Cited By ~ 1

Author(s):

Chien Yeo ◽

Edward Tiekink

Keyword(s):

Hydrogen Bond ◽

Solid State ◽

Hydrogen Bonds ◽

Single Crystal ◽

Elemental Analysis ◽

Title Compound ◽

Molecular Conformation ◽

Phenyl Hydrazine ◽

X Ray ◽

X Ray Crystallography

The title compound, 1-[N-methyl-N-(phenyl)amino]-3-(4-methylphenyl)thiourea (1), was synthesized by the reaction of 1-methyl-1-phenyl hydrazine and 4-tolyl isothiocyanate, and was characterized by spectroscopy (1H and 13C{1H} NMR, IR, and UV), elemental analysis as well as by single crystal X-ray crystallography. In the solid state, the molecule exists as the thioamide tautomer and features an anti-disposition of the thioamide–N–H atoms; an intramolecular N–H⋯N hydrogen bond is noted. The molecular conformation resembles that of the letter L. In the molecular packing, thioamide-N1–H⋯S1(thione) hydrogen bonds lead to centrosymmetric eight-membered {⋯HNCS}2 synthons. The dimers are assembled into a supramolecular layer in the bc-plane by phenyl- and methyl-C–H⋯π(phenyl) interactions.

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Switching the Conformation of 3,2′:6′,3″-tpy Domains in 4′-(4-n-Alkyloxyphenyl)-3,2′:6′,3″-Terpyridines

Molecules ◽

10.3390/molecules25143162 ◽

2020 ◽

Vol 25 (14) ◽

pp. 3162 ◽

Cited By ~ 2

Author(s):

Dalila Rocco ◽

Alessandro Prescimone ◽

Edwin C. Constable ◽

Catherine E. Housecroft

Keyword(s):

Solid State ◽

Single Crystal ◽

Crystal Structures ◽

Dominant Role ◽

Van Der Waals Interactions ◽

Single Crystal Structures ◽

Solid State Structures ◽

Packing Interactions ◽

Adjacent Sheet

The preparation and characterization of 4′-(4-n-octyloxyphenyl)-3,2′:6′,3″-terpyridine (8) and 4′-(4-n-nonyloxyphenyl)-3,2′:6′,3″-terpyridine (9) are reported. The single crystal structures of 4′-(4-n-hexyloxyphenyl)-3,2′:6′,3″-terpyridine (6), 4′-(4-n-heptyloxyphenyl)-3,2′:6′,3″-terpyridine (7), and compounds 8 and 9 have been determined. The conformation of the 3,2′:6′,3″-tpy unit is trans,trans in 6 and 7, but switches to cis,trans in 8 and 9. This is associated with significant changes in the packing interactions with a more dominant role for van der Waals interactions between adjacent n-alkyloxy chains and C–Hmethylene... π interactions in 8 and 9. The solid-state structures of 6 and 7 with the n-hexyloxy and n-heptyloxy chains feature interwoven sheets of supramolecular assemblies of molecules, with pairs of n-alkyloxy chains threaded through cavities in an adjacent sheet.

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The Role of Percent Volume Buried in the Characterization of Copper(I) Complexes for Lighting Purposes

Molecules ◽

10.3390/molecules25112647 ◽

2020 ◽

Vol 25 (11) ◽

pp. 2647 ◽

Cited By ~ 1

Author(s):

Murat Alkan-Zambada ◽

Edwin C. Constable ◽

Catherine E. Housecroft

Keyword(s):

Solid State ◽

Single Crystal ◽

Quantum Yields ◽

X Ray ◽

Photophysical Behavior

The usefulness of percent volume buried (%Vbur) as a readily quantifiable property is investigated with regard to [Cu(NN)(PP)]+ complexes of interest for lighting purposes. Photoluminescence quantum yields (PLQYs) and single crystal X-ray structures of 100 reported compounds were assembled, %Vbur of the ligand systems were calculated and analyzed for correlations. We found that increased shielding of the central Cu(I) cation relying on shared contributions of both (NN) and (PP) ligand systems led to increased PLQYs. These findings are of relevance for future characterizations of Cu(I)-based complexes and their photophysical behavior in the solid-state.

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