Croconic acid
   HOME

TheInfoList



OR:

Croconic acid or 4,5-dihydroxycyclopentenetrione is a
chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
with formula or . It has a
cyclopentene Cyclopentene is a chemical compound with the formula . It is a colorless liquid with a petrol-like odor. It has few applications, and thus is mainly used as a minor component of gasoline, present in concentrations of less than 1%. It is one of t ...
backbone with two
hydroxyl In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydroxy ...
groups adjacent to the double bond and three
ketone In organic chemistry, a ketone is a functional group with the structure R–C(=O)–R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group –C(=O)– (which contains a carbon-oxygen double bo ...
groups on the remaining
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
atoms. It is sensitive to light, soluble in water and
ethanol Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an Alcohol (chemistry), alcohol with the chemical formula . Its formula can be also written as or (an ethyl ...
and forms yellow crystals that decompose at 212 °C. The compound is acidic and loses the
proton A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
s from the
hydroxyl In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydroxy ...
groups (p''K''a1 = and p''K''a2 = at 25 °C). The resulting
anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s, hydrogencroconate and croconate are also quite stable. The croconate ion, in particular, is
aromatic In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...
and symmetric, as the double bond and the negative charges become delocalized over the five CO units (with two electrons,
Hückel's rule In organic chemistry, Hückel's rule predicts that a planar ring molecule will have aromatic properties if it has 4''n'' + 2 π electrons, where ''n'' is a non-negative integer. The quantum mechanical basis for its formulation was ...
means this is an aromatic configuration). The
lithium Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid el ...
,
sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...
and
potassium Potassium is the chemical element with the symbol K (from Neo-Latin ''kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmosphe ...
croconates crystallize from water as dihydrates but the orange potassium salt can be dehydrated to form a
monohydrate In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was underst ...
. The croconates of
ammonium The ammonium cation is a positively-charged polyatomic ion with the chemical formula or . It is formed by the protonation of ammonia (). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary a ...
,
rubidium Rubidium is the chemical element with the symbol Rb and atomic number 37. It is a very soft, whitish-grey solid in the alkali metal group, similar to potassium and caesium. Rubidium is the first alkali metal in the group to have a density higher ...
and
caesium Caesium (IUPAC spelling) (or cesium in American English) is a chemical element with the symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of , which makes it one of only five elemental metals that a ...
crystallize in the anhydrous form. Salts of
barium Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
,
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
,
silver Silver is a chemical element with the Symbol (chemistry), symbol Ag (from the Latin ', derived from the Proto-Indo-European wikt:Reconstruction:Proto-Indo-European/h₂erǵ-, ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, whi ...
, and others are also known. Croconic acid also forms
ether In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again be c ...
s such as
dimethyl croconate Ethane ( , ) is an organic chemical compound with chemical formula . At standard temperature and pressure, ethane is a colorless, odorless gas. Like many hydrocarbons, ethane is isolated on an industrial scale from natural gas and as a petr ...
where the hydrogen atom of the hydroxyl group is substituted with an
alkyl In organic chemistry, an alkyl group is an alkane missing one hydrogen. The term ''alkyl'' is intentionally unspecific to include many possible substitutions. An acyclic alkyl has the general formula of . A cycloalkyl is derived from a cycloalk ...
group.


History

Croconic acid and potassium croconate dihydrate were discovered by
Leopold Gmelin Leopold Gmelin (2 August 1788 – 13 April 1853) was a German chemist. Gmelin was a professor at the University of Heidelberg He worked on the red prussiate and created Gmelin's test, and wrote his ''Handbook of Chemistry'', which over successiv ...
in 1825, who named the compounds from Greek meaning "
crocus ''Crocus'' (; plural: crocuses or croci) is a genus of seasonal flowering plants in the family Iridaceae (iris family) comprising about 100 species of perennials growing from corms. They are low growing plants, whose flower stems remain undergro ...
" or "egg yolk". The structure of ammonium croconate was determined by Baenziger et al. in 1964. The structure of was determined by Dunitz in 2001.


Structure

In the solid state, croconic acid has a peculiar structure consisting of pleated strips, each "page" of the strip being a planar ring of 4 molecules of held together by
hydrogen bond In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing a ...
s. In
dioxane 1,4-Dioxane () is a heterocyclic organic compound, classified as an ether. It is a colorless liquid with a faint sweet odor similar to that of diethyl ether. The compound is often called simply dioxane because the other dioxane isomers ( 1,2- ...
it has a large dipole moment of 9–10  D, while the free molecule is estimated to have a dipole of 7–7.5 D. The solid is
ferroelectric Ferroelectricity is a characteristic of certain materials that have a spontaneous electric polarization that can be reversed by the application of an external electric field. All ferroelectrics are also piezoelectric and pyroelectric, with the ad ...
with a
Curie point In physics and materials science, the Curie temperature (''T''C), or Curie point, is the temperature above which certain materials lose their permanent magnetic properties, which can (in most cases) be replaced by induced magnetism. The Cur ...
above , indeed the organic crystal with the highest spontaneous polarization (about 20 μC/cm2). This is due to proton transfer between adjacent molecules in each pleated sheet, rather than molecular rotation. In the solid
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
salts, the croconate anions and the alkali cations form parallel columns. In the mixed salt , which formally contains both one croconate dianion and one hydrogencroconate monoanion (), the hydrogen is shared equally by two adjacent croconate units. Salts of the croconate anion and its derivatives are of interest in
supramolecular chemistry Supramolecular chemistry refers to the branch of chemistry concerning chemical systems composed of a discrete number of molecules. The strength of the forces responsible for spatial organization of the system range from weak intermolecular forces ...
research because of their potential for π-stacking effects, where the delocalized electrons of two stacked croconate anions interact. Infrared and Raman assignments indicate that the equalization of the carbon–carbon bond lengths, thus the electronic delocalization, follows with an increase in counter-ion size for salts. This result leads to a further interpretation that the degree of aromaticity is enhanced for salts as a function of the size of the counter-ion. The same study provided quantum mechanical DFT calculations for the optimized structures and vibrational spectra which were in agreement with experimental findings. The values for calculated theoretical indices of aromaticity also increased with counterion size. The croconate anion forms
hydrate In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
d crystalline
coordination compound A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...
s with divalent
cation An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s of
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
s, with general formula ; where M stands for
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...
(yielding a brown solid),
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...
(dark purple),
zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
(yellow),
nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to ...
(green),
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
(dark green), or
cobalt Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, pr ...
(purple). These complexes all have the same
orthorombic In crystallography, the orthorhombic crystal system is one of the 7 crystal systems. Orthorhombic lattices result from stretching a cubic lattice along two of its orthogonal pairs by two different factors, resulting in a rectangular prism with a ...
crystal structure, consisting of chains of alternating croconate and metal ions. Each croconate is bound to the preceding metal by one
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
atom, and to the next metal through its two opposite oxygens, leaving two oxygens unbound. Each metal is bound to three croconate oxygens and to one water molecule.
Calcium Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to ...
also forms a compound with the same formula (yellow) but the structure appears to be different. The croconate anion also forms compounds with trivalent cations such as
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
(yellow),
chromium Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium metal is valued for its high corrosion resistance and hardne ...
(brown), and iron (purple). These compounds also include hydroxyl groups as well as hydration water and have a more complicated crystal structure. No indication was found of sandwich-type bonds between the delocalized electrons and the metal (as are seen in
ferrocene Ferrocene is an organometallic compound with the formula . The molecule is a complex consisting of two cyclopentadienyl rings bound to a central iron atom. It is an orange solid with a camphor-like odor, that sublimes above room temperature, a ...
, for example), but the anion can form metal complexes with a large variety of bonding patterns, involving from only one to all five of its oxygen atoms.


See also

*
Croconate violet Croconate violet or 1,3-bis(dicyanomethylene)croconate is a divalent anion with chemical formula or ((N≡C−)2C=)2(C5O3)2−. It is one of the pseudo-oxocarbon anions, as it can be described as a derivative of the croconate oxocarbon anion ...
*
Croconate blue Croconate blue or 1,2,3-tris(dicyanomethylene)croconate is a divalent anion with chemical formula or ((N≡C−)2C=)3(C5O2)2−. It is one of the pseudo-oxocarbon anions, as it can be described as a derivative of the croconate oxocarbon anio ...
*
Rhodizonic acid Rhodizonic acid is a chemical compound with formula or . It can be seen as a twofold enol and fourfold ketone of cyclohexene, more precisely 5,6-dihydroxycyclohex-5-ene-1,2,3,4-tetrone. Rhodizonic acid is usually obtained in the form of a dihyd ...
*
Squaric acid Squaric acid, also called quadratic acid because its four carbon atoms approximately form a square, is a diprotic organic acid with the chemical formula C4O2(OH)2. The conjugate base of squaric acid is the hydrogensquarate anion ; and the conjug ...
*
Deltic acid Deltic acid or dihydroxycyclopropenone is a chemical substance with the chemical formula C3O(OH)2. It can be viewed as a ketone and double Alcohol (chemistry), alcohol of cyclopropene. At room temperature, it is a stable white solid, soluble in d ...
*
Cyclopentanepentone Cyclopentanepentone, also known as leuconic acid, is a hypothetical organic compound with formula C5O5, the fivefold ketone of cyclopentane. It would be an oxide of carbon (an oxocarbon), indeed a pentamer of carbon monoxide. As of 2000, the co ...
(leuconic acid)


References


External links

* {{DEFAULTSORT:Croconic Acid Cyclopentenes Triketones Enediols Organic acids