Literature DB >> 24940287

4-Acetyl-piperazinium picrate.

Channappa N Kavitha1, Manpreet Kaur1, Jerry P Jasinski2, Hemmige S Yathirajan1.   

Abstract

In the title salt, C6H13N2O(+)·C6H2N3O7 (-) (systematic name: 4-acetyl-piperazin-1-ium 2,4,6-tri-nitro-phenolate), the piperazin-1-ium ring has a slightly distorted chair conformation. In the picrate anion, the mean planes of the two o-NO2 and p-NO2 groups are twisted with respect to the benzene ring by 15.0 (2), 68.9 (4) and 4.4 (3)°, respectively. In the crystal, N-H⋯O hydrogen bonds are observed, linking the ions into an infinite chain along [010]. In addition, weak cation-anion C-H⋯O inter-molecular inter-actions and a weak π-π stacking inter-action between the benzene rings of the anions, with an inter-centroid distance of 3.771 (8) Å, help to stabilize the crystal packing, giving an overall sheet structure lying parallel to (100). Disorder was modelled for one of the O atoms in one of the o-NO2 groups over two sites with an occupancy ratio of 0.57 (6):0.43 (6).

Entities:  

Year:  2014        PMID： 24940287      PMCID： PMC4051097          DOI： 10.1107/S1600536814011726

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

Piperazines and substituted piperazines are important pharmacophores that can be found in many biologically active compounds across a number of different therapeutic areas, see: Berkheij (2005 ▶); Choudhary et al. (2006 ▶); Kharb et al. (2012 ▶); Upadhayaya et al. (2004 ▶). For picric acid salts, see: Hundal et al. (1997 ▶); Szumna et al. (2000 ▶); Colquhoun et al. (1986 ▶). For related structures, see: Kavitha et al. (2013 ▶, 2014 ▶); Loughlin et al. (2003 ▶); Wang & Jia (2008 ▶); Song et al. (2012 ▶). For puckering parameters, see Cremer & Pople (1975 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C6H13N2O+·C6H2N3O7 − M = 357.29 Monoclinic, a = 6.6843 (7) Å b = 11.5971 (12) Å c = 20.131 (2) Å β = 90.000 (4)° V = 1560.5 (3) Å3 Z = 4 Cu Kα radiation μ = 1.12 mm−1 T = 173 K 0.32 × 0.28 × 0.06 mm

Data collection

Agilent Eos Gemini diffractometer Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ▶) T min = 0.631, T max = 1.000 9739 measured reflections 2993 independent reflections 2690 reflections with I > 2σ(I) R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.045 wR(F 2) = 0.126 S = 1.10 2993 reflections 238 parameters H-atom parameters constrained Δρmax = 0.27 e Å−3 Δρmin = −0.20 e Å−3 Data collection: CrysAlis PRO (Agilent, 2014 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2. Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814011726/zs2300sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814011726/zs2300Isup2.hkl Click here for additional data file. Supporting information file. DOI: 10.1107/S1600536814011726/zs2300Isup3.cml CCDC reference: 1004370 Additional supporting information: crystallographic information; 3D view; checkCIF report
C6H13N2O+·C6H2N3O7−Dx = 1.521 Mg m−3
Mr = 357.29Melting point = 443–448 K
Monoclinic, P21/nCu Kα radiation, λ = 1.54184 Å
a = 6.6843 (7) ÅCell parameters from 4582 reflections
b = 11.5971 (12) Åθ = 4.4–71.6°
c = 20.131 (2) ŵ = 1.12 mm−1
β = 90.000 (4)°T = 173 K
V = 1560.5 (3) Å3Block, yellow
Z = 40.32 × 0.28 × 0.06 mm
F(000) = 744
Agilent Eos Gemini diffractometer2993 independent reflections
Radiation source: Enhance (Cu) X-ray Source2690 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm-1Rint = 0.036
ω scansθmax = 72.0°, θmin = 4.4°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)h = −8→7
Tmin = 0.631, Tmax = 1.000k = −14→11
9739 measured reflectionsl = −24→24
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045w = 1/[σ2(Fo2) + (0.0624P)2 + 0.6066P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.126(Δ/σ)max < 0.001
S = 1.10Δρmax = 0.27 e Å−3
2993 reflectionsΔρmin = −0.20 e Å−3
238 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0018 (3)
Primary atom site location: structure-invariant direct methods
Experimental. Absorption correction: CrysAlis PRO (Agilent, 2014), Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
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.
xyzUiso*/UeqOcc. (<1)
O1B0.10430 (19)0.26818 (11)0.61927 (6)0.0352 (3)
O2B0.175 (7)0.1019 (8)0.7106 (4)0.076 (5)0.57 (6)
O2BA0.082 (4)0.0947 (14)0.7071 (7)0.051 (4)0.43 (6)
O3B0.1631 (3)−0.07329 (14)0.67738 (7)0.0541 (4)
O4B0.3371 (2)−0.17212 (11)0.45759 (7)0.0395 (3)
O5B0.3065 (2)−0.04833 (12)0.37818 (6)0.0434 (3)
O6B−0.0003 (2)0.34623 (15)0.45462 (9)0.0573 (4)
O7B0.2665 (3)0.39977 (12)0.50421 (8)0.0551 (4)
N1B0.1575 (2)0.02945 (14)0.66573 (7)0.0378 (4)
N2B0.3023 (2)−0.07436 (12)0.43751 (7)0.0291 (3)
N3B0.1445 (2)0.32723 (12)0.48878 (7)0.0304 (3)
C1B0.1524 (2)0.18809 (14)0.58083 (8)0.0255 (3)
C2B0.1827 (2)0.06833 (15)0.59752 (8)0.0274 (4)
C3B0.2322 (2)−0.01538 (14)0.55123 (8)0.0259 (3)
H3B0.2513−0.09130.56460.031*
C4B0.2531 (2)0.01431 (14)0.48536 (8)0.0247 (3)
C5B0.2228 (2)0.12757 (14)0.46350 (7)0.0249 (3)
H5B0.23320.14690.41880.030*
C6B0.1776 (2)0.20831 (13)0.51029 (8)0.0244 (3)
O1A0.31825 (19)0.29011 (10)0.33233 (6)0.0341 (3)
N1A0.3133 (2)0.48149 (12)0.34934 (7)0.0290 (3)
N2A0.1899 (2)0.69006 (13)0.28906 (7)0.0359 (4)
H2AA0.19230.74220.25140.043*
H2AB0.10460.72370.32290.043*
C1A0.4034 (2)0.37845 (14)0.35166 (8)0.0282 (4)
C2A0.1095 (3)0.49259 (15)0.32500 (9)0.0328 (4)
H2AC0.02310.51960.36050.039*
H2AD0.06090.41800.31030.039*
C3A0.1047 (3)0.57715 (17)0.26784 (9)0.0389 (4)
H3AA0.18160.54680.23090.047*
H3AB−0.03220.58780.25310.047*
C4A0.3952 (3)0.67764 (15)0.31576 (9)0.0365 (4)
H4AA0.44250.75160.33180.044*
H4AB0.48450.65200.28080.044*
C5A0.3959 (3)0.59116 (15)0.37192 (9)0.0361 (4)
H5AA0.53180.57970.38750.043*
H5AB0.31680.62040.40860.043*
C6A0.6101 (3)0.37046 (19)0.37903 (12)0.0475 (5)
H6AA0.61050.39670.42420.071*
H6AB0.69840.41770.35310.071*
H6AC0.65450.29180.37740.071*
U11U22U33U12U13U23
O1B0.0435 (7)0.0337 (7)0.0286 (6)0.0049 (5)0.0062 (5)−0.0059 (5)
O2B0.143 (15)0.062 (3)0.0223 (16)−0.009 (4)−0.002 (4)−0.0016 (14)
O2BA0.089 (9)0.044 (4)0.021 (3)0.014 (3)0.014 (3)0.002 (2)
O3B0.0824 (11)0.0453 (9)0.0347 (7)0.0073 (7)0.0086 (7)0.0161 (6)
O4B0.0513 (8)0.0266 (6)0.0406 (7)0.0050 (5)0.0031 (6)−0.0035 (5)
O5B0.0643 (9)0.0419 (7)0.0241 (6)0.0098 (6)0.0067 (6)−0.0033 (5)
O6B0.0440 (8)0.0534 (9)0.0744 (11)0.0097 (7)−0.0153 (7)0.0236 (8)
O7B0.0842 (11)0.0311 (7)0.0501 (9)−0.0127 (7)−0.0205 (8)0.0036 (6)
N1B0.0489 (9)0.0413 (9)0.0232 (7)0.0041 (7)0.0007 (6)0.0058 (6)
N2B0.0293 (7)0.0285 (7)0.0295 (7)0.0008 (5)0.0022 (5)−0.0038 (6)
N3B0.0381 (8)0.0290 (7)0.0240 (7)0.0052 (6)0.0020 (6)0.0007 (5)
C1B0.0222 (7)0.0325 (8)0.0218 (7)0.0007 (6)−0.0001 (5)−0.0021 (6)
C2B0.0287 (8)0.0327 (9)0.0206 (8)−0.0008 (6)0.0002 (6)0.0029 (6)
C3B0.0238 (7)0.0260 (8)0.0280 (8)0.0007 (6)−0.0008 (6)0.0035 (6)
C4B0.0213 (7)0.0276 (8)0.0252 (8)0.0005 (6)0.0013 (6)−0.0022 (6)
C5B0.0248 (7)0.0295 (8)0.0206 (7)0.0000 (6)−0.0001 (5)0.0014 (6)
C6B0.0229 (7)0.0257 (8)0.0244 (8)0.0014 (6)−0.0007 (5)0.0016 (6)
O1A0.0473 (7)0.0235 (6)0.0315 (6)−0.0022 (5)0.0039 (5)−0.0024 (5)
N1A0.0326 (7)0.0235 (7)0.0308 (7)−0.0001 (5)−0.0057 (6)−0.0032 (5)
N2A0.0523 (9)0.0291 (7)0.0263 (7)0.0109 (6)0.0108 (6)0.0039 (6)
C1A0.0353 (9)0.0263 (8)0.0229 (7)0.0008 (6)0.0029 (6)0.0005 (6)
C2A0.0310 (8)0.0300 (8)0.0375 (9)0.0006 (6)−0.0050 (7)−0.0014 (7)
C3A0.0435 (10)0.0408 (10)0.0323 (9)0.0081 (8)−0.0078 (7)−0.0026 (7)
C4A0.0464 (10)0.0240 (8)0.0391 (10)−0.0024 (7)0.0085 (8)−0.0068 (7)
C5A0.0462 (10)0.0276 (9)0.0345 (9)−0.0033 (7)−0.0084 (7)−0.0076 (7)
C6A0.0388 (11)0.0455 (11)0.0582 (13)0.0096 (8)−0.0082 (9)−0.0002 (9)
O1B—C1B1.251 (2)N1A—C2A1.453 (2)
O2B—N1B1.239 (7)N1A—C5A1.459 (2)
O2BA—N1B1.231 (10)N2A—H2AA0.9700
O3B—N1B1.215 (2)N2A—H2AB0.9700
O4B—N2B1.2260 (19)N2A—C3A1.490 (2)
O5B—N2B1.232 (2)N2A—C4A1.481 (3)
O6B—N3B1.208 (2)C1A—C6A1.490 (3)
O7B—N3B1.212 (2)C2A—H2AC0.9700
N1B—C2B1.455 (2)C2A—H2AD0.9700
N2B—C4B1.447 (2)C2A—C3A1.512 (3)
N3B—C6B1.462 (2)C3A—H3AA0.9700
C1B—C2B1.443 (2)C3A—H3AB0.9700
C1B—C6B1.449 (2)C4A—H4AA0.9700
C2B—C3B1.386 (2)C4A—H4AB0.9700
C3B—H3B0.9300C4A—C5A1.511 (3)
C3B—C4B1.377 (2)C5A—H5AA0.9700
C4B—C5B1.400 (2)C5A—H5AB0.9700
C5B—H5B0.9300C6A—H6AA0.9600
C5B—C6B1.362 (2)C6A—H6AB0.9600
O1A—C1A1.235 (2)C6A—H6AC0.9600
N1A—C1A1.339 (2)
O2B—N1B—C2B117.9 (5)C4A—N2A—H2AB109.2
O2BA—N1B—C2B119.6 (4)C4A—N2A—C3A111.88 (13)
O3B—N1B—O2B121.4 (4)O1A—C1A—N1A121.49 (15)
O3B—N1B—O2BA119.0 (6)O1A—C1A—C6A119.48 (16)
O3B—N1B—C2B118.85 (15)N1A—C1A—C6A119.03 (16)
O4B—N2B—O5B122.81 (14)N1A—C2A—H2AC109.8
O4B—N2B—C4B118.74 (14)N1A—C2A—H2AD109.8
O5B—N2B—C4B118.45 (14)N1A—C2A—C3A109.51 (15)
O6B—N3B—O7B123.95 (16)H2AC—C2A—H2AD108.2
O6B—N3B—C6B117.50 (15)C3A—C2A—H2AC109.8
O7B—N3B—C6B118.50 (14)C3A—C2A—H2AD109.8
O1B—C1B—C2B127.34 (15)N2A—C3A—C2A110.09 (15)
O1B—C1B—C6B121.06 (15)N2A—C3A—H3AA109.6
C2B—C1B—C6B111.57 (14)N2A—C3A—H3AB109.6
C1B—C2B—N1B120.12 (14)C2A—C3A—H3AA109.6
C3B—C2B—N1B116.43 (15)C2A—C3A—H3AB109.6
C3B—C2B—C1B123.44 (14)H3AA—C3A—H3AB108.2
C2B—C3B—H3B120.1N2A—C4A—H4AA109.7
C4B—C3B—C2B119.78 (15)N2A—C4A—H4AB109.7
C4B—C3B—H3B120.1N2A—C4A—C5A109.82 (15)
C3B—C4B—N2B119.11 (14)H4AA—C4A—H4AB108.2
C3B—C4B—C5B121.50 (14)C5A—C4A—H4AA109.7
C5B—C4B—N2B119.36 (14)C5A—C4A—H4AB109.7
C4B—C5B—H5B121.3N1A—C5A—C4A110.13 (14)
C6B—C5B—C4B117.37 (14)N1A—C5A—H5AA109.6
C6B—C5B—H5B121.3N1A—C5A—H5AB109.6
C1B—C6B—N3B115.17 (13)C4A—C5A—H5AA109.6
C5B—C6B—N3B118.50 (14)C4A—C5A—H5AB109.6
C5B—C6B—C1B126.31 (15)H5AA—C5A—H5AB108.1
C1A—N1A—C2A120.82 (14)C1A—C6A—H6AA109.5
C1A—N1A—C5A126.65 (14)C1A—C6A—H6AB109.5
C2A—N1A—C5A112.49 (14)C1A—C6A—H6AC109.5
H2AA—N2A—H2AB107.9H6AA—C6A—H6AB109.5
C3A—N2A—H2AA109.2H6AA—C6A—H6AC109.5
C3A—N2A—H2AB109.2H6AB—C6A—H6AC109.5
C4A—N2A—H2AA109.2
O1B—C1B—C2B—N1B0.0 (3)C2B—C1B—C6B—N3B178.55 (13)
O1B—C1B—C2B—C3B178.68 (15)C2B—C1B—C6B—C5B0.4 (2)
O1B—C1B—C6B—N3B0.5 (2)C2B—C3B—C4B—N2B−179.20 (13)
O1B—C1B—C6B—C5B−177.66 (15)C2B—C3B—C4B—C5B−0.9 (2)
O2B—N1B—C2B—C1B−23 (2)C3B—C4B—C5B—C6B1.9 (2)
O2B—N1B—C2B—C3B158 (2)C4B—C5B—C6B—N3B−179.80 (13)
O2BA—N1B—C2B—C1B10.6 (19)C4B—C5B—C6B—C1B−1.7 (2)
O2BA—N1B—C2B—C3B−168.2 (18)C6B—C1B—C2B—N1B−177.95 (14)
O3B—N1B—C2B—C1B172.35 (17)C6B—C1B—C2B—C3B0.8 (2)
O3B—N1B—C2B—C3B−6.5 (2)N1A—C2A—C3A—N2A−56.25 (19)
O4B—N2B—C4B—C3B−4.8 (2)N2A—C4A—C5A—N1A55.87 (19)
O4B—N2B—C4B—C5B176.84 (14)C1A—N1A—C2A—C3A−123.25 (17)
O5B—N2B—C4B—C3B174.87 (15)C1A—N1A—C5A—C4A123.37 (18)
O5B—N2B—C4B—C5B−3.5 (2)C2A—N1A—C1A—O1A1.2 (2)
O6B—N3B—C6B—C1B−111.79 (18)C2A—N1A—C1A—C6A−178.04 (17)
O6B—N3B—C6B—C5B66.5 (2)C2A—N1A—C5A—C4A−59.09 (19)
O7B—N3B—C6B—C1B70.6 (2)C3A—N2A—C4A—C5A−55.55 (18)
O7B—N3B—C6B—C5B−111.05 (18)C4A—N2A—C3A—C2A56.01 (19)
N1B—C2B—C3B—C4B178.21 (14)C5A—N1A—C1A—O1A178.54 (16)
N2B—C4B—C5B—C6B−179.75 (13)C5A—N1A—C1A—C6A−0.7 (3)
C1B—C2B—C3B—C4B−0.5 (2)C5A—N1A—C2A—C3A59.05 (19)
D—H···AD—HH···AD···AD—H···A
N2A—H2AA···O1Ai0.971.782.7057 (19)159
N2A—H2AB···O1Bii0.971.822.7401 (19)157
C3A—H3AA···O5Bi0.972.463.333 (2)150
C3A—H3AB···O3Biii0.972.553.469 (3)158
C5A—H5AA···O7Biv0.972.573.365 (2)139
C5B—H5B···O1A0.932.473.307 (2)149
C5A—H5AB···O4Bv0.972.603.266 (2)126
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A D—HH⋯A D⋯A D—H⋯A
N2A—H2AA⋯O1A i 0.971.782.7057 (19)159
N2A—H2AB⋯O1B ii 0.971.822.7401 (19)157
C3A—H3AA⋯O5B i 0.972.463.333 (2)150
C3A—H3AB⋯O3B iii 0.972.553.469 (3)158
C5A—H5AA⋯O7B iv 0.972.573.365 (2)139
C5B—H5B⋯O1A 0.932.473.307 (2)149

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

  6 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  Optically active antifungal azoles: synthesis and antifungal activity of (2R,3S)-2-(2,4-difluorophenyl)-3-(5-[2-[4-aryl-piperazin-1-yl]-ethyl]-tetrazol-2-yl/1-yl)-1-[1,2,4]-triazol-1-yl-butan-2-ol.

Authors:  Ram Shankar Upadhayaya; Neelima Sinha; Sanjay Jain; Nawal Kishore; Ramesh Chandra; Sudershan K Arora
Journal:  Bioorg Med Chem       Date:  2004-05-01       Impact factor: 3.641

3.  Three-dimensional network in piper-azine-1,4-diium-picrate-piperazine (1/2/1).

Authors:  Zhong-Long Wang; Li-Hui Jia
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2008-03-05

4.  Cinnarizinium picrate.

Authors:  Yanxi Song; C S Chidan Kumar; G B Nethravathi; S Naveen; Hongqi Li
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2012-05-16

5.  1-Piperonylpiperazinium picrate.

Authors:  Channappa N Kavitha; Manpreet Kaur; Brian J Anderson; Jerry P Jasinski; H S Yathirajan
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2014-01-29

6.  1-[4-(4-Hy-droxy-phen-yl)piperazin-1-yl]ethanone.

Authors:  Channappa N Kavitha; Jerry P Jasinski; Brian J Anderson; H S Yathirajan; Manpreet Kaur
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2013-10-19
  6 in total

北京卡尤迪生物科技股份有限公司 © 2022-2023.