Aravindhan

G. Chakkaravarthi

N. Swarna Sowmya

Nagapandiselvi

Parthiban

R. Mohan Kumar

S. Sampathkrishnan

S. Sudhahar

Sankar

Sheldrick

Spek

Acta Crystallographica Section E

In the title molecular salt, C5H12N+·C6H4NO3−, the piperidine ring adopts a chair conformation and the cation is protonated at the N atom. In the anion, the nitro group is twisted at an angle of 10.30 (11)° with respect to the attached benzene ring. In the crystal, N—H...O hydrogen bonds link adjacent anions and cations into infinite chains propagating along [100]. The chains are linked by C—H...π interactions, forming sheets lying parallel to (001).</jats:p

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research communicationsActa Cryst. (2014). E70, 559–561 doi:10.1107/S1600536814025306 559Received 13 November 2014Accepted 18 November 2014Edited by H. Stoeckli-Evans, University ofNeuchaˆtel, Switzerland†Keywords: crystal structure; molecular salt;piperidinium; 4-nitrophenol; hydrogen bonding;C—H   interactionsCCDC reference: 1034875Supporting information: this article hassupporting information at journals.iucr.org/eCrystal structure of piperidinium 4-nitrophenolateN. Swarna Sowmya,a S. Sampathkrishnan,a S. Sudhahar,b G. Chakkaravarthic* andR. Mohan KumarbaDepartment of Applied Physics, Sri Venkateswara College of Engineering, Chennai 602 117, India, bDepartment ofPhysics, Presidency College, Chennai 600 005, India, and cDepartment of Physics, CPCL Polytechnic College, Chennai600 068, India. *Correspondence e-mail: chakkaravarthi_2005@yahoo.com,mohan66@hotmail.comIn the title molecular salt, C5H12N+C6H4NO3, the piperidine ring adopts achair conformation and the cation is protonated at the N atom. In the anion, thenitro group is twisted at an angle of 10.30 (11) with respect to the attachedbenzene ring. In the crystal, N—H  O hydrogen bonds link adjacent anions andcations into infinite chains propagating along [100]. The chains are linked by C—H   interactions, forming sheets lying parallel to (001).1. Chemical contextPiperidine derivatives exhibit a broad-spectrum of biologicalactivities such as anti-bacterial and anti-cancer (Parthiban etal., 2005). Nitro-aromatics are widely used either as materialsor as intermediates in explosives, dyestuffs, pesticides andorganic synthesis (Yan et al., 2006). We report herein on thesynthesis and crystal structure of the title molecular salt,prepared by mixing piperidine with 4-nitrophenol.2. Structural commentaryThe molecular structure of the title compound is illustrated inFig. 1. The geometric parameters are close to those reportedfor similar structures viz. 1-acetyl-c-3,t-3-dimethyl-r-2,c-6-di-phenylpiperidin-4-one (Aravindhan et al., 2009), 4-nitro-phenol-piperazine (2/1) (Nagapandiselvi et al., 2013) and2-carboxylatopyridinium-4-nitrophenol (1/1) (Sankar et al.,2014). The piperidine ring (C8–C11/N2/C12) adopts a chairconformation with puckering parameters of Q =0.5601 (17) A˚,  = 1.80 (17) and ’ = 19 (10). The nitro group(N1/O2/O3) is twisted at an angle of 10.30 (11) with respect tothe attached benzene ring (C1–C6).ISSN 1600-53683. Supramolecular featuresIn the crystal, adjacent cations and anions are linked by theN—H  O hydrogen bonds, which generate infinite chainsalong [100] (see Table 1 and Fig. 2). The chains are linked byC—H   interactions, forming sheets lying parallel to the abplane (Table 1).4. Synthesis and crystallizationPiperidine (0.85 g) and 4-nitrophenol (1.39) in an equimolar(1:1) ratio were added to methanol as solvent and the mixturewas stirred for 2 h, giving a clear solution. The solution wasfiltered into a beaker and sealed with parafilm and keptat room temperature for one week. Colourless crystalssuitable for X-ray diffraction analysis were obtained after oneweek.5. RefinementCrystal data, data collection and structure refinement detailsare summarized in Table 2. The N-bound and C-bound Hatoms were positioned geometrically and refined using ariding model: N—H = 0.90, C—H = 0.93 and 0.97 A˚ for CHand CH2 H atoms, respectively, and with Uiso(H) =1.2Ueq(N,C).AcknowledgementsThe authors wish to acknowledge the SAIF, IIT, Madras, forthe data collection.ReferencesAravindhan, S., Ponnuswamy, S., Jamesh, M., Ramesh, P. &Ponnuswamy, M. N. (2009). Acta Cryst. E65, o1974.Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison,Wisconsin, USA.560 Sowmya et al.  C5H12N+C6H4NO3 Acta Cryst. (2014). E70, 559–561research communicationsTable 1Hydrogen-bond geometry (A˚, ).Cg1 is the centroid of the C1–C6 ring.D—H  A D—H H  A D  A D—H  AN2—H2A  O1i 0.90 1.92 2.788 (2) 161N2—H2B  O1ii 0.90 1.80 2.6985 (15) 175C6—H6  Cg1iii 0.93 2.75 3.428 (3) 130Symmetry codes: (i) x; y 12;zþ 12; (ii) xþ 12;yþ 1; zþ 12; (iii)x þ 12;yþ 12;z.Figure 2The crystal packing of the title salt, viewed along the b axis. Hydrogenbonds are shown as dashed lines (see Table 1 for details; H atoms notinvolved in hydrogen bonding have been omitted for clarity).Table 2Experimental details.Crystal dataChemical formula C5H12N+C6H4NO3Mr 224.26Crystal system, space group Orthorhombic, P212121Temperature (K) 295a, b, c (A˚) 6.867 (5), 10.121 (4), 16.497 (6)V (A˚3) 1146.6 (10)Z 4Radiation type Mo K (mm1) 0.10Crystal size (mm) 0.26  0.22  0.20Data collectionDiffractometer Bruker Kappa APEXII CCDAbsorption correction Multi-scan (SADABS; Sheldrick,1996)Tmin, Tmax 0.976, 0.981No. of measured, independent andobserved [I > 2(I)] reflections6505, 2908, 2612Rint 0.017(sin /)max (A˚1) 0.673RefinementR[F 2 > 2(F 2)], wR(F 2), S 0.035, 0.091, 1.04No. of reflections 2908No. of parameters 146H-atom treatment H-atom parameters constrainedmax, min (e A˚3) 0.13, 0.16Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97(Sheldrick, 2008) and PLATON (Spek, 2009).Figure 1The molecular structure of the title salt, showing the atom labelling.Displacement ellipsoids are drawn at the 30% probability level.Nagapandiselvi, P., Muralidharan, S., Srinivasan, T., Goplalakrishnan,R. & Velmurugan, D. (2013). Acta Cryst. E69, o1044.Parthiban, P., Balasubramanian, S., Aridoss, G. & Kabilan, S. (2005).Med. Chem. Res. 14, 523–538.Sankar, A., Ambalatharasu, S., Peramaiyan, G., Chakkaravarthi, G. &Kanagadurai, R. (2014). Acta Cryst. E70, o450.Sheldrick, G. M. (1996). SADABS. University of Go¨ttingen,Germany.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Spek, A. L. (2009). Acta Cryst. D65, 148–155.Yan, X. F., Xiao, H. M., Gong, X. D. & Ju, X. H. (2006). J. Mol. Struct.Theochem, 764, 141–148.research communicationsActa Cryst. (2014). E70, 559–561 Sowmya et al.  C5H12N+C6H4NO3 561supporting informationsup-1Acta Cryst. (2014). E70, 559-561    supporting informationActa Cryst. (2014). E70, 559-561    [doi:10.1107/S1600536814025306]Crystal structure of piperidinium 4-nitrophenolateN. Swarna Sowmya, S. Sampathkrishnan, S. Sudhahar, G. Chakkaravarthi and R. Mohan KumarComputing details Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Piperidinium 4-nitrophenolate Crystal data C5H12N+·C6H4NO3−Mr = 224.26Orthorhombic, P212121Hall symbol: P 2ac 2aba = 6.867 (5) Åb = 10.121 (4) Åc = 16.497 (6) ÅV = 1146.6 (10) Å3Z = 4F(000) = 480Dx = 1.299 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 658 reflectionsθ = 2.4–28.6°µ = 0.10 mm−1T = 295 KBlock, colourless0.26 × 0.22 × 0.20 mmData collection Bruker Kappa APEXII CCD diffractometerRadiation source: fine-focus sealed tubeGraphite monochromatorω and φ scanAbsorption correction: multi-scan (SADABS; Sheldrick, 1996)Tmin = 0.976, Tmax = 0.9816505 measured reflections2908 independent reflections2612 reflections with I > 2σ(I)Rint = 0.017θmax = 28.6°, θmin = 2.4°h = −6→9k = −11→13l = −22→10Refinement Refinement on F2Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.035wR(F2) = 0.091S = 1.042908 reflections146 parameters0 restraintsPrimary atom site location: structure-invariant direct methodsSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[σ2(Fo2) + (0.0452P)2 + 0.1138P] where P = (Fo2 + 2Fc2)/3(Δ/σ)max < 0.001Δρmax = 0.13 e Å−3Δρmin = −0.16 e Å−3Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4Extinction coefficient: 0.119 (6)supporting informationsup-2Acta Cryst. (2014). E70, 559-561    Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) x y z Uiso*/UeqC1 0.08265 (18) 0.22326 (12) 0.09031 (7) 0.0380 (3)C2 0.0102 (2) 0.31257 (12) 0.14583 (7) 0.0404 (3)H2 −0.0220 0.2848 0.1979 0.049*C3 −0.0144 (2) 0.44223 (12) 0.12419 (7) 0.0403 (3)H3 −0.0638 0.5014 0.1621 0.048*C4 0.03355 (18) 0.48874 (11) 0.04556 (7) 0.0373 (3)C5 0.1115 (2) 0.39408 (13) −0.00839 (8) 0.0474 (3)H5 0.1491 0.4211 −0.0600 0.057*C6 0.1336 (2) 0.26352 (13) 0.01258 (8) 0.0465 (3)H6 0.1820 0.2029 −0.0247 0.056*C8 0.6387 (2) 0.21154 (17) 0.33603 (10) 0.0570 (4)H8A 0.7057 0.2749 0.3702 0.068*H8B 0.7348 0.1503 0.3149 0.068*C9 0.5422 (3) 0.28329 (19) 0.26652 (10) 0.0626 (4)H9A 0.6386 0.3342 0.2371 0.075*H9B 0.4854 0.2197 0.2294 0.075*C10 0.3854 (3) 0.37423 (16) 0.29817 (10) 0.0545 (4)H10A 0.4442 0.4428 0.3312 0.065*H10B 0.3199 0.4164 0.2530 0.065*C11 0.2391 (2) 0.29893 (14) 0.34801 (9) 0.0480 (3)H11A 0.1444 0.3601 0.3703 0.058*H11B 0.1703 0.2370 0.3135 0.058*C12 0.4907 (2) 0.13639 (13) 0.38617 (9) 0.0488 (3)H12A 0.4341 0.0663 0.3537 0.059*H12B 0.5549 0.0963 0.4324 0.059*N1 0.10251 (18) 0.08685 (11) 0.11247 (8) 0.0487 (3)N2 0.33415 (17) 0.22610 (10) 0.41493 (6) 0.0405 (3)H2A 0.2438 0.1784 0.4415 0.049*H2B 0.3851 0.2845 0.4502 0.049*O1 0.00554 (15) 0.61052 (8) 0.02564 (6) 0.0458 (2)O2 0.1387 (2) 0.00445 (11) 0.06015 (8) 0.0730 (4)O3 0.0795 (2) 0.05548 (12) 0.18390 (7) 0.0771 (4)supporting informationsup-3Acta Cryst. (2014). E70, 559-561    Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23C1 0.0355 (6) 0.0359 (5) 0.0427 (6) 0.0007 (5) −0.0004 (5) 0.0057 (5)C2 0.0423 (6) 0.0453 (6) 0.0337 (5) −0.0013 (6) −0.0019 (5) 0.0049 (5)C3 0.0434 (7) 0.0414 (6) 0.0361 (6) 0.0028 (5) 0.0005 (5) −0.0033 (5)C4 0.0324 (6) 0.0364 (6) 0.0431 (6) −0.0006 (5) 0.0018 (5) 0.0030 (5)C5 0.0545 (8) 0.0445 (7) 0.0432 (7) 0.0065 (6) 0.0179 (6) 0.0089 (5)C6 0.0517 (8) 0.0412 (6) 0.0466 (7) 0.0096 (6) 0.0155 (6) 0.0019 (5)C8 0.0425 (7) 0.0574 (8) 0.0710 (10) 0.0055 (7) 0.0071 (7) −0.0019 (7)C9 0.0635 (10) 0.0723 (10) 0.0520 (8) −0.0044 (9) 0.0162 (8) 0.0073 (8)C10 0.0568 (9) 0.0489 (8) 0.0577 (8) −0.0017 (7) −0.0023 (7) 0.0146 (7)C11 0.0388 (7) 0.0459 (7) 0.0594 (8) 0.0031 (6) −0.0029 (6) 0.0053 (6)C12 0.0495 (8) 0.0408 (6) 0.0559 (7) 0.0053 (6) −0.0015 (7) 0.0016 (6)N1 0.0516 (7) 0.0396 (6) 0.0547 (7) −0.0015 (5) 0.0013 (6) 0.0090 (5)N2 0.0433 (6) 0.0377 (5) 0.0406 (5) −0.0053 (4) 0.0014 (4) −0.0029 (4)O1 0.0494 (5) 0.0346 (4) 0.0535 (5) 0.0023 (4) 0.0079 (5) 0.0061 (4)O2 0.1004 (10) 0.0403 (5) 0.0782 (8) 0.0118 (6) 0.0251 (7) 0.0021 (5)O3 0.1256 (13) 0.0504 (6) 0.0554 (6) −0.0028 (7) −0.0012 (7) 0.0188 (5)Geometric parameters (Å, º) C1—C2 1.3798 (18) C9—C10 1.510 (2)C1—C6 1.3902 (18) C9—H9A 0.9700C1—N1 1.4347 (17) C9—H9B 0.9700C2—C3 1.3703 (18) C10—C11 1.506 (2)C2—H2 0.9300 C10—H10A 0.9700C3—C4 1.4187 (17) C10—H10B 0.9700C3—H3 0.9300 C11—N2 1.4793 (18)C4—O1 1.2900 (15) C11—H11A 0.9700C4—C5 1.4129 (18) C11—H11B 0.9700C5—C6 1.374 (2) C12—N2 1.4848 (19)C5—H5 0.9300 C12—H12A 0.9700C6—H6 0.9300 C12—H12B 0.9700C8—C9 1.511 (2) N1—O2 1.2257 (17)C8—C12 1.516 (2) N1—O3 1.2306 (16)C8—H8A 0.9700 N2—H2A 0.9000C8—H8B 0.9700 N2—H2B 0.9000C2—C1—C6 120.73 (12) H9A—C9—H9B 108.2C2—C1—N1 119.70 (11) C11—C10—C9 110.87 (13)C6—C1—N1 119.55 (12) C11—C10—H10A 109.5C3—C2—C1 119.92 (11) C9—C10—H10A 109.5C3—C2—H2 120.0 C11—C10—H10B 109.5C1—C2—H2 120.0 C9—C10—H10B 109.5C2—C3—C4 121.83 (12) H10A—C10—H10B 108.1C2—C3—H3 119.1 N2—C11—C10 111.42 (13)C4—C3—H3 119.1 N2—C11—H11A 109.3supporting informationsup-4Acta Cryst. (2014). E70, 559-561    O1—C4—C5 122.95 (11) C10—C11—H11A 109.3O1—C4—C3 121.02 (11) N2—C11—H11B 109.3C5—C4—C3 116.03 (11) C10—C11—H11B 109.3C6—C5—C4 122.36 (12) H11A—C11—H11B 108.0C6—C5—H5 118.8 N2—C12—C8 110.68 (12)C4—C5—H5 118.8 N2—C12—H12A 109.5C5—C6—C1 119.09 (12) C8—C12—H12A 109.5C5—C6—H6 120.5 N2—C12—H12B 109.5C1—C6—H6 120.5 C8—C12—H12B 109.5C9—C8—C12 111.16 (14) H12A—C12—H12B 108.1C9—C8—H8A 109.4 O2—N1—O3 121.66 (13)C12—C8—H8A 109.4 O2—N1—C1 119.64 (12)C9—C8—H8B 109.4 O3—N1—C1 118.70 (12)C12—C8—H8B 109.4 C11—N2—C12 112.69 (11)H8A—C8—H8B 108.0 C11—N2—H2A 109.1C10—C9—C8 110.09 (13) C12—N2—H2A 109.1C10—C9—H9A 109.6 C11—N2—H2B 109.1C8—C9—H9A 109.6 C12—N2—H2B 109.1C10—C9—H9B 109.6 H2A—N2—H2B 107.8C8—C9—H9B 109.6C6—C1—C2—C3 0.8 (2) C12—C8—C9—C10 56.35 (18)N1—C1—C2—C3 −178.12 (12) C8—C9—C10—C11 −56.27 (19)C1—C2—C3—C4 −0.2 (2) C9—C10—C11—N2 55.67 (18)C2—C3—C4—O1 178.45 (13) C9—C8—C12—N2 −55.31 (17)C2—C3—C4—C5 −1.21 (19) C2—C1—N1—O2 169.09 (14)O1—C4—C5—C6 −177.44 (14) C6—C1—N1—O2 −9.8 (2)C3—C4—C5—C6 2.2 (2) C2—C1—N1—O3 −9.8 (2)C4—C5—C6—C1 −1.8 (2) C6—C1—N1—O3 171.33 (14)C2—C1—C6—C5 0.2 (2) C10—C11—N2—C12 −55.30 (16)N1—C1—C6—C5 179.09 (14) C8—C12—N2—C11 54.81 (16)Hydrogen-bond geometry (Å, º) Cg1 is the centroid of the C1–C6 ring.D—H···A D—H H···A D···A D—H···AN2—H2A···O1i 0.90 1.92 2.788 (2) 161N2—H2B···O1ii 0.90 1.80 2.6985 (15) 175C6—H6···Cg1iii 0.93 2.75 3.428 (3) 130Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1/2, −y+1, z+1/2; (iii) x+1/2, −y+1/2, −z.

Acta Crystallographica Section E Structure Reports Online

Crystal structure of piperidinium 4-nitrophenolate

http://journals.iucr.org/e/issues/2014/12/00/su5022/su5022.pdf

Crystal structure of piperidinium 4-nitrophenolate

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