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Unsaturated Carboxylic Acids—(E)-Hept-2-Enoic Acid and (E)-Oct-2-Enoic Acid

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Unsaturated Carboxylic Acids—(E)-Hept-2-Enoic Acid and (E)-Oct-2-Enoic Acid crystals Article Synthesis and Molecular Structures of the Lowest Melting Odd- and Even-Numbered a,b-Unsaturated Carboxylic Acids—(E)-Hept-2-Enoic Acid and (E)-Oct-2-Enoic Acid Marcel Sonneck, Anke Spannenberg, Sebastian Wohlrab and Tim Peppel * Leibniz Institute for Catalysis at the University of Rostock (LIKAT), Albert-Einstein-Str. 29a, D-18059 Rostock, Germany; [email protected] (M.S.); [email protected] (A.S.); [email protected] (S.W.) * Correspondence: [email protected]; Tel.: +49-381-1281-363 Academic Editor: Helmut Cölfen Received: 13 May 2016; Accepted: 31 May 2016; Published: 3 June 2016 Abstract: The molecular structures of the two lowest melting odd- and even-numbered a,b-unsaturated carboxylic acids—(E)-hept-2-enoic acid (C7) and (E)-oct-2-enoic acid (C8)—are herein reported. The title compounds were crystallized by slow evaporation of ethanolic solutions at ´30 ˝C. C7 crystallizes in the triclinic space group P1 with two molecules in the unit cell and C8 in the monoclinic space group C2/c with eight molecules in the unit cell. The unit cell parameters for C7 are: a = 5.3049(2) Å, b = 6.6322(3) Å, c = 11.1428(5) Å, a = 103.972(3)˝, b = 97.542(3)˝, g = 90.104(3)˝, and V = 376.92(3) Å3 (T = 150(2) K). The unit cell parameters for C8 are: a = 19.032(10) Å, b = 9.368(5) Å, c = 11.520(6) Å, b = 123.033(11)˝, and V = 1721.80(16) Å3 (T = 200(2) K). Keywords: X-ray crystal structure; hydrogen bond; dimer; unsaturated carboxylic acid 1. Introduction Essential fatty acids have attracted much interest in food, health, and nutrition sciences due to their role in biological processes especially for humans [1–4]. Oleic acid, (Z)-octadec-9-enoic acid, and linoleic acid, (9Z,12Z)-9,12-octadecadienoic acid, respectively, can be found, for example, in meat and milk products, nuts, olives, and oils. Increasing the number of double bonds within the alkyl chain leads to a melting point decrease and hence yields liquids at ambient conditions, which is an especially important property of polyunsaturated fatty acids [5]. Derivatives of the title compounds—(E)-hept-2-enoic acid (C7) and (E)-oct-2-enoic acid (C8)—exhibit interesting occurrences and properties. For example, they can be found as active compounds in beetles’ sexual pheromones [6,7], as part of siderophores in bacteria [8,9], as an anti-osteoporotic [10], or as phytotoxic substances [11], respectively. Crystal structure determinations of a,b-unsaturated carboxylic acids have been known from the literature in the cases of acrylic acid (C3)[12–15] and crotonic acid (C4)[16] for more than 40 years, but the crystal structures of other members of a,b-unsaturated carboxylic acids, namely, (E)-pent-2-enoic acid (C5)[17], (E)-hex-2-enoic acid (C6)[18], (E)-non-2-enoic acid (C9), (E)-dec-2-enoic acid (C10)[19], (E)-undec-2-enoic acid (C11)[20], and (E)-dodec-2-enoic acid (C12)[21], respectively, have just recently been reported. In addition, two crystal structure determinations of co-crystals containing C6 are also known [22,23]. In comparison, a complete set of crystal structures of the corresponding saturated carboxylic acids (propionic acid to pentadecanoic acid) is also available from the literature [24–28]. In this contribution, we report on the synthesis, characterization, and crystal structure determinations of the two missing and lowest melting odd- and even-numbered members Crystals 2016, 6, 66; doi:10.3390/cryst6060066 www.mdpi.com/journal/crystals Crystals 2016, 6, 66 2 of 9 Crystals 2016, 6, 66 2 of 9 of the series of a,b-unsaturated carboxylic acids—(E)-hept-2-enoic acid (C7) and (E)-oct-2-enoic acid series of α,β-unsaturated carboxylic acids—(E)-hept-2-enoic acid (C7) and (E)-oct-2-enoic acid (C8)— (C8)—respectively, which complete the series of crystal structure data from C3 to C12. respectively, which complete the series of crystal structure data from C3 to C12. 2. ResultsCrystals 2016 and, 6 Discussion, 66 2 of 9 2. Results and Discussion 2.1. Synthesisseries of α and,β-unsaturated Melting Points carboxylic acids—(E)-hept-2-enoic acid (C7) and (E)-oct-2-enoic acid (C8)— 2.1.respectively, Synthesis and which Melting complete Points the series of crystal structure data from C3 to C12. The synthesis of a,b-unsaturated carboxylic acids has been known for more than 130 years, when The synthesis of α,β-unsaturated carboxylic acids has been known for more than 130 years, when Schneegans2. Results reported and Discussion on the synthesis of nonenoic acid via the reaction of heptanal, sodium acetate, Schneegans reported on the synthesis of nonenoic acid via the reaction of heptanal, sodium acetate, and acetic anhydride in 1885 [29]. More than 20 years later, Harding and Weizmann reported on the and2.1. acetic Synthesis anhydride and Melting in 1885 Points [29]. More than 20 years later, Harding and Weizmann reported on the correctcorrect molecular molecular formula formula of of the the received received ((EE)-non-2-enoic)-non-2-enoic acid acid in in 1910 1910 [3 [0].30 ].The The syntheses syntheses of the of thetwo two a,b-unsaturatedα,β-unsaturatedThe synthesis carboxylic carboxylic of α,β-unsaturated acids acidsC7 C7and and carboxylicC8 C8 werewere acids conducted has been by by known an an adapte adapted for mored condensation condensation than 130 years, reaction reactionwhen of of malonicmalonicSchneegans acid acid and reportedand the appropriatethe onappropriate the synthesis aldehyde aldehyde of nonenoic at room at room temperatureacid viatemperature the reaction in high in of yieldshigh heptanal, yields and sodium puritiesand purities acetate, as depicted as in Schemedepictedand acetic1[ 31in –Schemeanhydride34] (see 1 Experimental[31–34] in 1885 (see[29]. Experimental More Section than for20 Sectionyears details). later, for Hardingdetails). and Weizmann reported on the correct molecular formula of the received (E)-non-2-enoic acid in 1910 [30]. The syntheses of the two α,β-unsaturated carboxylic acids C7 and C8 were conducted by an adapted condensation reaction of malonic acid and the appropriate aldehyde at room temperature in high yields and purities as depicted in Scheme 1 [31–34] (see Experimental Section for details). Scheme 1. Reaction sequence for the synthesis of the two title compounds—C7 and C8. Scheme 1. Reaction sequence for the synthesis of the two title compounds—C7 and C8. The title compounds exhibit low melting points, which lie below room temperature (C7: −11 °C; ˝ C8The: 10title °C). compoundsAs expected, exhibitcrystallographic low melting data points, of these which structures lie below have roomnot yet temperature been reported (C7 to: date´11 C; ˝ Scheme 1. Reaction sequence for the synthesis of the two title compounds—C7 and C8. C8:due 10 toC). difficulties As expected, in crystallizing crystallographic and analyzing. data of theseFrom structuresthe complete have series not of yet trans- beenα,β reported-unsaturated to date duecarboxylic to difficultiesThe titleacids, compounds in a crystallizing melting exhibit point and low altern analyzing.meltingation points, for From even- which the and lie complete odd-numberedbelow room series temperature oftrans- trans-α,βa (-unsaturated,C7b-unsaturated: −11 °C; carboxyliccarboxylicC8: 10 °C). acids, acids As aexpected, meltingfrom C3 crystallographic pointto C16 alternation can be data found of for th even-eseas structuresfor and most odd-numbered havehomologous not yet been chemical trans- reporteda, bseries.-unsaturated to date For carboxyliccomparison,due to acids difficulties in from the C3casein crystallizingto ofC16 saturatedcan beand carboxylic found analyzing. as foracids, From most from the homologous completehexanoic seriesacid chemical to of pentadecanoic trans- series.α,β-unsaturated For acid, comparison, this in theeffectcarboxylic case was of traced saturatedacids, backa melting carboxylic to crystal point acids,density alternation from variatio for hexanoic nseven- [24]. and acidThis odd-numbered tocorrelation pentadecanoic was trans- not acid,α ,detectedβ-unsaturated this effect in the was tracedpresentcarboxylic back case to crystal acidsfor trans- from densityα, βC3-unsaturated variationsto C16 can carboxylic [24 be]. Thisfound acids correlation as forfrom most C3 was tohomologous C16 not. detected chemical in the presentseries. For case for trans-comparison,a,bThe-unsaturated melting in the point carboxyliccase alternation of saturated acids for carboxylic fromthe seriesC3 toacids, ofC16 trans- from. α ,hexanoicβ-unsaturated acid to carboxylic pentadecanoic acids acid,C3 to this C16 basedTheeffect meltingon was melting traced point points back alternation knownto crystal from fordensity the the literatureseries variatio of andns trans- [24]. thisa Thiswork,b-unsaturated correlation is depicted was carboxylicin Figure not detected 1 [17–21,35–40]. acids inC3 theto C16 It presentis clear casethat for C7 trans- has theα,β -unsaturatedlowest melting carboxylic point within acids fromthe series C3 to of C16 odd-numbered. carboxylic acids, based on melting points known from the literature and this work is depicted in Figure1[ 17–21,35–40]. whereasThe C8 melting exhibits point the alternationlowest melting for the point series within of trans- theα series,β-unsaturated of even-numbered carboxylic acidscarboxylic C3 to acids,C16 It is clear that C7 has the lowest melting point within the series of odd-numbered carboxylic acids, respectively.based on melting Crystall pointsographic known density from the of literature C7 is significantly and this work higher is depicted than inthat Figure of C81 [17–21,35–40]., whereas the whereasmeltingIt is C8clear pointexhibits that of C7 C7 thehas is remarkably lowestthe lowest melting meltinglower pointthan point that within within of C8 thethe, which series is of in of odd-numberedcontrast even-numbered to the mostcarboxylic carboxylic homologous acids, acids, respectively.chemicalwhereas series, CrystallographicC8 exhibits e.g., for the sa lowestturated density melting carboxylic of C7 pointis significantlyacids.
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