In 2,4-dihydroxybenzaldehyde 2,4-dinitrophenylhydrazone N,N-dimethylformamide solvate (or 4-[(2,4-dinitrophenyl)-hydrazonomethyl]benzene-1,3-diol N,N-dimethylformamide solvat

Baughman, Russell G.

Martin, Kenneth L.

Singh, Rajendra K.

Stoffer, James O.

English

Missouri University of Science and Technology (Missouri S&T): Scholars' Mine

Missouri University of Science and Technology Scholars' Mine Chemistry Faculty Research & Creative Works Chemistry 01 Jan 2004 2,4-Dinitrophenylhydrazones of 2,4-dihydroxybenzaldehyde, 2,4-dihydroxyacetophenone and 2,4-dihydroxybenzophenone Russell G. Baughman Kenneth L. Martin Rajendra K. Singh James O. Stoffer Missouri University of Science and Technology, jstoffer@mst.edu Follow this and additional works at: https://scholarsmine.mst.edu/chem_facwork  Part of the Chemistry Commons Recommended Citation R. G. Baughman et al., "2,4-Dinitrophenylhydrazones of 2,4-dihydroxybenzaldehyde, 2,4-dihydroxyacetophenone and 2,4-dihydroxybenzophenone," Acta Crystallographica Section C: Crystal Structure Communications, International Union of Crystallography (IUCr), Jan 2004. The definitive version is available at https://doi.org/10.1107/S0108270103027197 This Article - Journal is brought to you for free and open access by Scholars' Mine. It has been accepted for inclusion in Chemistry Faculty Research & Creative Works by an authorized administrator of Scholars' Mine. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact scholarsmine@mst.edu. 2,4-Dinitrophenylhydrazones of2,4-dihydroxybenzaldehyde,2,4-dihydroxyacetophenone and2,4-dihydroxybenzophenoneRussell G. Baughman,a* Kenneth L. Martin,a² Rajendra K.Singhb³ and James O. StofferbaDivision of Science, Truman State University, Kirksville, MO 63501-4221, USA,and bDepartment of Chemistry, University of Missouri±Rolla, Rolla, MO 65409, USACorrespondence e-mail: baughman@truman.eduReceived 7 August 2003Accepted 26 November 2003Online 10 January 2004In 2,4-dihydroxybenzaldehyde 2,4-dinitrophenylhydrazoneN,N-dimethylformamide solvate {or 4-[(2,4-dinitrophenyl)-hydrazonomethyl]benzene-1,3-diol N,N-dimethylformamidesolvate}, C13H10N4O6C3H7NO, (X), 2,4-dihydroxyaceto-phenone 2,4-dinitrophenylhydrazone N,N-dimethylformam-ide solvate (or 4-{1-[(2,4-dinitrophenyl)hydrazono]ethyl}-benzene-1,3-diol N,N-dimethylformamide solvate), C14H12-N4O6C3H7NO, (XI), and 2,4-dihydroxybenzophenone 2,4-di-nitrophenylhydrazone N,N-dimethylacetamide solvate (or4-{[(2,4-dinitrophenyl)hydrazono]phenylmethyl}benzene-1,3-diol N,N-dimethylacetamide solvate), C19H14N4O6C4H9NO,(XII), the molecules all lack a center of symmetry, crystallizein centrosymmetric space groups and have been observed toexhibit non-linear optical activity. In each case, the hydrazoneskeleton is fairly planar, facilitated by the presence of twointramolecular hydrogen bonds and some partial NÐNdouble-bond character. Each molecule is hydrogen bondedto one solvent molecule.CommentHydrazone derivatives are an attractive class of non-linearoptical (NLO) crystalline materials because of their largemolecular non-linearities and their remarkable propensity toform non-centrosymmetric crystal systems (Serbutoviez et al.,1995). The current approach to the development of practicalNLO materials has focused on the use of a dihydroxy-func-tionalized hydrazone chromophore that can be easilysynthesized and subsequently incorporated into a commercialepoxy polymer system. The preliminary goal was to providefor a systematic variation of the chromophore structure tostudy the resulting structure±property relationships. To thisend, three hydrazones were synthesized by coupling 2,4-di-nitrophenylhydrazine (2,4-DNPH) with three carbonylcompounds, namely, 2,4-dihydroxybenzaldehyde, 2,4-di-hydroxyacetophenone and 2,4-dihydroxybenzophenone, toyield hydrazones (X), (XI) and (XII), respectively.To con®rm the structures of these three hydrazones, whichare part of a series of related compounds currently underinvestigation [including compounds (I)±(IX), which are still inprogress], the single-crystal data for these compounds arereported here. While each of the three compounds demon-strates NLO properties, it should be noted that each crystal-lizes in a centrosymmetric space group and that each moleculelacks a center of symmetry.As seen in Figs. 1±3, all three compounds crystallize in a 1:1ratio with solvent molecules [N,N-dimethylformamide (DMF)for (X) and (XI), and N,N-dimethylacetamide (DMAc) for(XII)], which accept a hydrogen bond at atom O7 from atomH1A of the para-hydroxy group of the hydrazone. In eachcase, across the C7 N1 bond, N2 is E to C4; simultaneously,each R substituent at C7 is Z to N2. In each molecule, twointramolecular hydrogen bonds, H2A  N1 and H2B  O3,help to facilitate the planarity of each hydrazone.The 23-atom hydrazone skeleton [atoms O1±O6, N1±N4and C1±C13, plus atom C14 for (XI) and (XII)] of (X) is themost planar of the three compounds, as it has an r.m.s.deviation of 0.061 AÊ , with atoms O2 and C5 having the largestdeviations [0.137 (3) and 0.117 (3) AÊ , respectively] from theplane. On the other hand, (XI) and (XII) display somebuckling. They have larger r.m.s. deviations (0.190 and0.122 AÊ , respectively), in part due to atoms with largerdeviations from the plane of the skeleton. For example, in(XI), atoms O2 and O6 have deviations of 0.488 (2) and0.491 (2) AÊ , respectively, while in (XII), atoms O5 and C5have deviations of 0.330 (3) and 0.180 (3) AÊ , respectively,from the 23-atom plane of the skeleton.Acta Cryst. (2004). C60, o103±o106 DOI: 10.1107/S0108270103027197 # 2004 International Union of Crystallography o103organic compoundsActa Crystallographica Section CCrystal StructureCommunicationsISSN 0108-2701² Current address: Department of Chemistry, Berry College, Mt Berry,GA 30149, USA.³ Current address: General Electric Co., Lexan Technology, One Lexan Lane,Mt Vernon, IN 47620, USA.organic compoundso104 Russell G. Baughman et al.  Three 2,4-dinitrophenylhydrazones Acta Cryst. (2004). C60, o103±o106In the case of compound (X), even the solvent molecule iscoplanar with the plane of the hydrazone molecule; the r.m.s.deviation for all non-H atoms is 0.081 AÊ . However, neithersolvent molecule in compounds (XI) and (XII) is coplanarwith the hydrazone molecule (Figs. 2 and 3; Tables 3 and 5).The phenyl substituent (C14±C19) in compound (XII) isnearly perpendicular (Table 5) to the plane of the hydrazoneskeleton, likely due in large part to steric problems around C7.While the intramolecular hydrogen bonding minimizes therotational freedom about the C4ÐC7 and N2ÐC8 bonds,rotation about N1ÐN2 is also reduced. The average of theC7 N1 bond lengths (Table 6) is3 longer than the averageof 13 C N bond lengths (in PhC NH coordinationcompounds) gleaned from the Cambridge Structural Database(CSD, Version 5.23; Allen, 2002). Similarly, the average of theN1ÐN2 bond lengths (Table 6) is 20 shorter than theaverage of ®ve NÐN bond lengths in hydrazine-solvatedcompounds in the CSD. This likely implies some N1ÐN2double-bond character, thus reducing rotational mobility. Theextent of this character changes as substituents vary on C7.The variation of C7 N1 bond lengths is 0.020 AÊ (7), whilethat for N1ÐN2 is 0.015 AÊ (5).As seen in Table 6, some bond lengths near C7 are affectedsigni®cantly (3) by changes in the R substituent on C7.Speci®cally, increases in bond lengths are noted for C7 N1,C4ÐC7 and C4. . .C5, concomitant with decreases in the N1ÐN2 and O2ÐC3 bond lengths as the R substituent changesfrom ±H to ±CH3 to ±Ph. The effect of going from H to alkyl toaromatic groups is felt as much as three bonds away from theC7ÐR bond.ExperimentalThe three title hydrazones were synthesized according to a knownprocedure (Vogel, 1989) by mixing a solution of 2,4-DNPH in anethanol±tetrahydrofuran solvent mixture [1:1 for (X), 3:1 for (XI),and 2:1 for (XII)] with the three dihydroxy±carbonyl compounds in a1:1.05 molar ratio, with concentrated HCl as catalyst. The decom-position points (>523 K for each of the three hydrazones) weredetermined on a Thermal Analysis differential scanning calorimeterat a heating rate of 10 K minÿ1. Crystals suitable for diffractionanalysis were grown by slow evaporation of a saturated solution inDMF for hydrazones (X) and (XI), and in DMAc for hydrazone(XII). Each crystal was placed into a capillary and sealed with motherliquor.Compound (X)Crystal dataC13H10N4O6C3H7NOMr = 391.35Monoclinic, P21=ca = 19.697 (4) AÊb = 7.152 (1) AÊc = 12.949 (3) AÊ = 100.34 (2)V = 1794.5 (6) AÊ 3Z = 4Dx = 1.448 Mg mÿ3Mo K radiationCell parameters from 49re¯ections = 7.8±17.5 = 0.12 mmÿ1T = 293 (2) KBlock cut from a larger crystal,red±orange0.50  0.39  0.13 mmFigure 1A view of the asymmetric unit of (X), showing the atom-labeling scheme.Displacement ellipsoids are drawn at the 50% probability level, andsigni®cant H atoms are labeled and drawn as small spheres of arbitraryradii.Figure 2A view of the asymmetric unit of (XI), showing the atom-labeling scheme.Displacement ellipsoids are drawn at the 50% probability level, andsigni®cant H atoms are labeled and drawn as small spheres of arbitraryradii.Figure 3A view of the asymmetric unit of (XII), showing the atom-labelingscheme. Displacement ellipsoids are drawn at the 50% probability level,and signi®cant H atoms are labeled and drawn as small spheres ofarbitrary radii.Data collectionSiemens P4 diffractometer/2 scans3504 measured re¯ections3119 independent re¯ections1774 re¯ections with I > 2(I)Rint = 0.013max = 25.0h = ÿ23! 23k = ÿ8! 2l = 0! 153 standard re¯ectionsevery 50 re¯ectionsintensity decay: 2.3%Re®nementRe®nement on F 2R[F 2 > 2(F 2)] = 0.051wR(F 2) = 0.137S = 1.013110 re¯ections258 parametersH-atom parameters constrainedw = 1/[2(Fo2) + (0.0658P)2]where P = (Fo2 + 2Fc2)/3(/)max < 0.001max = 0.21 e AÊÿ3min = ÿ0.16 e AÊ ÿ3Extinction correction: SHELXL97(Sheldrick, 1997)Extinction coef®cient: 0.0059 (11)Compound (XI)Crystal dataC14H12N4O6C3H7NOMr = 405.37Triclinic, P1a = 7.928 (1) AÊb = 9.146 (1) AÊc = 14.362 (2) AÊ = 104.45 (1) = 91.04 (1) = 108.80 (1)V = 949.1 (2) AÊ 3Z = 2Dx = 1.418 Mg mÿ3Mo K radiationCell parameters from 50re¯ections = 9.6±18.8 = 0.11 mmÿ1T = 293 (2) KBlock cut from a larger crystal,red±orange0.54  0.43  0.31 mmData collectionSiemens P4 diffractometer/2 scans4336 measured re¯ections3310 independent re¯ections2207 re¯ections with I > 2(I)Rint = 0.011max = 25.1h = ÿ3! 9k = ÿ10! 10l = ÿ17! 173 standard re¯ectionsevery 50 re¯ectionsintensity decay: 1.5%Re®nementRe®nement on F 2R[F 2 > 2(F 2)] = 0.047wR(F 2) = 0.142S = 1.013298 re¯ections268 parametersH-atom parameters constrainedw = 1/[2(Fo2) + (0.0747P)2+ 0.1707P]where P = (Fo2 + 2Fc2)/3(/)max < 0.001max = 0.18 e AÊÿ3min = ÿ0.16 e AÊ ÿ3Extinction correction: SHELXL97(Sheldrick, 1997)Extinction coef®cient: 0.026 (4)Compound (XII)Crystal dataC19H14N4O6C4H9NOMr = 481.46Triclinic, P1a = 7.8155 (9) AÊb = 11.549 (2) AÊc = 13.904 (2) AÊ = 100.38 (1) = 95.80 (1) = 102.74 (1)V = 1191.0 (3) AÊ 3Z = 2Dx = 1.343 Mg mÿ3Mo K radiationCell parameters from 50re¯ections = 6.3±20.7 = 0.10 mmÿ1T = 293 (2) KParallelepiped, red±orange0.50  0.38  0.38 mmData collectionSiemens P4 diffractometer/2 scans5472 measured re¯ections4175 independent re¯ections2517 re¯ections with I > 2(I)Rint = 0.013max = 25.1h = ÿ1! 9k = ÿ13! 13l = ÿ16! 163 standard re¯ectionsevery 50 re¯ectionsintensity decay: 1.7%Re®nementRe®nement on F 2R[F 2 > 2(F 2)] = 0.057wR(F 2) = 0.171S = 1.044153 re¯ections322 parametersH-atom parameters constrainedw = 1/[2(Fo2) + (0.0921P)2+ 0.1171P]where P = (Fo2 + 2Fc2)/3(/)max < 0.001max = 0.51 e AÊÿ3min = ÿ0.25 e AÊ ÿ3Extinction correction: SHELXL97(Sheldrick, 1997)Extinction coef®cient: 0.025 (4)Acta Cryst. (2004). C60, o103±o106 Russell G. Baughman et al.  Three 2,4-dinitrophenylhydrazones o105organic compoundsTable 1Hydrogen-bonding geometry (AÊ , ) for (X).DÐH  A DÐH H  A D  A DÐH  AO1ÐH1A  O7 0.82 1.83 2.626 (3) 163O2ÐH2A  N1 0.82 1.97 2.691 (3) 146N2ÐH2B  O3 0.86 1.96 2.603 (3) 131Table 2Hydrogen-bonding geometry (AÊ , ) for (XI).DÐH  A DÐH H  A D  A DÐH  AO1ÐH1A  O7 0.82 1.86 2.677 (3) 175O2ÐH2A  N1 0.82 1.88 2.590 (2) 146N2ÐH2B  O3 0.86 1.94 2.590 (2) 131Table 3Selected r.m.s. deviations (AÊ ) and dihedral angle () for (XI).Plane 1 r.m.s. deviation Plane 2 r.m.s. deviation AngleHydrazone 0.194Hydrazone + C14 0.190 DMF 0.004 85.3 (1)Table 4Hydrogen-bonding geometry (AÊ , ) for (XII).DÐH  A DÐH H  A D  A DÐH  AO1ÐH1A  O7 0.82 1.82 2.630 (3) 172O2ÐH2A  N1 0.82 1.90 2.623 (3) 146N2ÐH2B  O3 0.86 1.95 2.600 (3) 131Table 5Selected r.m.s. deviations (AÊ ) and dihedral angles () for (XII).Plane 1 r.m.s. deviation Plane 2 r.m.s. deviation AngleHydrazone 0.109 C14±C19 0.002 84.04 (7)Hydrazone 0.109 DMAc 0.031 44.7 (1)Hydrazone + C14 0.122organic compoundso106 Russell G. Baughman et al.  Three 2,4-dinitrophenylhydrazones Acta Cryst. (2004). C60, o103±o106In all three cases, the approximate positions of the two hydroxy Hatoms were ®rst obtained from a difference map. These atoms werethen placed in `ideal' positions and re®ned as a rotating group. Bondlengths were constrained (AFIX 43) at 0.93 AÊ for aromatic CÐH,0.96 AÊ (AFIX 137) for methyl CÐH, 0.86 AÊ (AFIX 43) for NÐHand 0.82 AÊ (AFIX 147) for OÐH. Uiso(H) values were ®xed at 1.5Ueqfor OH and methyl H atoms, and 1.2Ueq for all other H atoms. In the®nal stages of re®nement for all three compounds, a few very small ornegative Fo values were deemed to be in strong disagreement withtheir Fc values. The corresponding nine, 12, and 22 re¯ections for (X),(XI), and (XII), respectively, were eliminated from the ®nal re®ne-ment. The percentage decay of the three standards was calculated asthe average of their (I) values.For all three compounds, data collection: P3/P4-PC DiffractometerProgram (Siemens, 1991); cell re®nement: P3/P4-PC DiffractometerProgram; data reduction: XDISK (Siemens, 1991); program(s) usedto solve structure: SHELXS86 (Sheldrick, 1990a); program(s) used tore®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:SHELXTL/PC (Sheldrick, 1990b); software used to prepare materialfor publication: SHELXTL/PC and SHELXL97.David B. Hall, Northwestern University, Evanston, IL,USA, is thanked for NLO analyses.Supplementary data for this paper are available from the IUCr electronicarchives (Reference: LN1175). Services for accessing these data aredescribed at the back of the journal.ReferencesAllen, F. H. (2002). Acta Cryst. B58, 380±388.Serbutoviez, C., Bosshard, C., Knop¯e, G., Wyss, P., Pretre, P., Gunter, P.,Schenk, K., Solari, E. & Chapuis, G. (1995). Chem. Mater. 7, 1198±1206.Sheldrick, G. M. (1990a). Acta Cryst. A46, 467±473.Sheldrick, G. M. (1990b). SHELXTL/PC. Release 4.1. Siemens AnalyticalX-ray Instruments Inc., Madison, Wisconsin, USA.Sheldrick, G. M. (1997). SHELXL97. University of GoÈ ttingen, Germany.Siemens (1991). P3/P4-PC Diffractometer Program (Version 4.23) and XDISK(Version 4.20.2PC). Siemens Analytical X-ray Instruments Inc., Madison,Wisconsin, USA.Vogel, A. I. (1989). Vogel's Textbook of Practical Organic Chemistry, 5th ed.,revised by B. S. Furniss, A. J. Hannaford, P. W. G. Smith & A. R. Tatchell,pp. 1257±1258. New York: John Wiley & Sons Inc.Table 6Selected interatomic distances (AÊ ) for compounds (X)±(XII); the effectsof changing R at C7 from ±H to ±CH3 to ±Ph.Bond (X) (XI) (XII) Change², (AÊ )/s.u.(X)³ Range§,R (AÊ )R/s.u.(X)³O1ÐC1 1.358 (3) 1.358 (3) 1.352 (3) ÿ0.006 2.0 0.006 2.0O2ÐC3 1.362 (3) 1.347 (3) 1.351 (3) ÿ0.009 3.0 0.015 5.0C3. . .C4 1.408 (3) 1.415 (3) 1.414 (4) 0.006 2.0 0.007 2.3C4. . .C5 1.386 (3) 1.397 (3) 1.396 (3) 0.010 3.3 0.011 3.7C4ÐC7 1.439 (3) 1.469 (3) 1.462 (3) 0.023 7.7 0.030 10.0C7ÐC14 1.496 (3) 1.502 (3) 0.006} 2.0²² 0.006 2.0C7 N1 1.283 (3) 1.303 (3) 1.302 (3) 0.019 6.3 0.020 6.7N1ÐN2 1.386 (3) 1.372 (2) 1.371 (3) ÿ0.015 5.0 0.015 5.0N2ÐC8 1.343 (3) 1.354 (3) 1.348 (3) 0.005 1.7 0.011 3.7N3ÐC13 1.447 (3) 1.450 (3) 1.447 (3) ÿ0.000 0.0 0.003 1.0N4ÐC11 1.459 (4) 1.452 (3) 1.461 (4) 0.002 0.5 0.009 2.3²  for (XII)ÿ(X) }  for (XII)ÿ(XI) ²² /s.u.(XI) ³ s.u.(X) is the s.u. in thebond length for (X) § Range = maximum value ÿ minimum value.

2,4-Dinitrophenylhydrazones of 2,4-dihydroxybenzaldehyde, 2,4-dihydroxyacetophenone and 2,4-dihydroxybenzophenone

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2,4-Dinitrophenylhydrazones of 2,4-dihydroxybenzaldehyde, 2,4-dihydroxyacetophenone and 2,4-dihydroxybenzophenone

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