Download citation
Download citation
link to html
A new type of hydrogen-bond pattern for piperidinium p-substituted benzoates is reported; this is found in piperidinium p-nitro­benzoate, C5H12N+·C7H4NO4, (I). In the crystal of (I), the cations and anions are linked by N—H...O hydrogen bonds around a center of symmetry to form a cyclic dimer of the formula unit.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010844/ci6044sup1.cif
Contains datablocks shelxl, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010844/ci6044Isup2.hkl
Contains datablock I

CCDC reference: 170898

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.057
  • wR factor = 0.205
  • Data-to-parameter ratio = 14.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
ABSTM_02 Alert A Test not performed as the _exptl_absorpt_correction_type has not been identified. See test ABSTY_01. ABSTY_01 Alert A The absorption correction should be one of the following * none * analytical * integration * numerical * gaussian * empirical * psi-scan * multi-scan * refdelf * sphere * cylinder
Yellow Alert Alert Level C:
PLAT_353 Alert C Long N-H Bond (0.87A) N(2) - H(6) = 1.03 Ang.
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

We report here a new type of hydrogen-bond pattern in cyclic secondary amine–p-substituted benzoic acid (1/1) system. In piperidinium p-nitrobenzoate, (I), a centrosymmetric dimer of the formula unit is formed through N—H···O hydrogen bonds (Fig. 1 and Table 1).

In most of cryslalline salts formed between cyclic secondary amines and p-substituted benzoic acids, the cations and anions are arranged around a twofold screw axis to form N—H···O hydrogen bonds (Kashino et al., 1972, 1978, 1981; Kashino, 1973). The same type of hydrogen bonding is also found in both pyrrolidinium p-nitrobenzoate and hexamethyleneiminium p-nitrobenzoate (Takeda, 1992). In a few cases, the cations and anions are arranged along a glide plane to form the N—H···O hydrogen bonds (Kashino et al., 1973, 1981).

The possibility of the formation of a cyclic dimer through the N—H···O hydrogen bonds was deduced based on a result of a molecular weight measurement in a benzene solution, combined with a geometrical consideration of the hydrogen-bonded system (Kashino, 1973). However, the formation of cyclic dimer has been found only in one of the dimorphs of hexamethyleneiminium p-bromobenzoate, in which the dimer is formed around a twofold axis (Kashino et al., 1981). The present study established a centrosymmetric type as the fourth pattern of hydrogen bonding possible in salts of cyclic secondary amines and p-substituted benzoic acids.

Experimental top

Stoichiometric amounts of piperidine and p-nitrobenzoic acid were dissolved in benzene at 340 K. After cooling the solution, crystals of (I) were grown by slow evaporation at room temperature.

Refinement top

All H atoms were found from a difference Fourier map. At the final stage of the least-squares refinement, all H atoms except those involved in hydrogen bonds were fixed at the ideal positions, and their isotropic displacement parameters were fixed to 1.2Ueq of the parent atoms.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN for Windows.

Figures top
[Figure 1] Fig. 1. A molecular view of (I) showing the hydrogen-bonding pattern and the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms involved in hydrogen bonds are shown as small spheres of arbitrary radii. Hydrogen bonds are indicated by dashed lines. [Symmetry code: (i) 1 - x, 1 - y, 1 - z.]
Piperidinium p-nitrobenzoate top
Crystal data top
C5H12N+·C7H4NO4Dx = 1.312 Mg m3
Mr = 252.27Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PccnCell parameters from 25 reflections
a = 8.949 (2) Åθ = 10.6–11.4°
b = 22.451 (5) ŵ = 0.10 mm1
c = 12.712 (4) ÅT = 298 K
V = 2554.0 (11) Å3Prismatic, colorless
Z = 80.50 × 0.30 × 0.20 mm
F(000) = 1072
Data collection top
Rigaku AFC5R
diffractometer
1142 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anodeRint = 0.022
Graphite monochromatorθmax = 26.0°, θmin = 1.8°
ω–2θ scansh = 011
Absorption correction: ψ
(North et al., 1968)
k = 027
Tmin = 0.952, Tmax = 0.980l = 015
2875 measured reflections3 standard reflections every 97 reflections
2509 independent reflections intensity decay: 0.6%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.205 w = 1/[σ2(Fo2) + (0.1P)2 + 1.1042P]
where P = (Fo2 + 2Fc2)/3
S = 0.91(Δ/σ)max = 0.002
2509 reflectionsΔρmax = 0.13 e Å3
172 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0059 (14)
Crystal data top
C5H12N+·C7H4NO4V = 2554.0 (11) Å3
Mr = 252.27Z = 8
Orthorhombic, PccnMo Kα radiation
a = 8.949 (2) ŵ = 0.10 mm1
b = 22.451 (5) ÅT = 298 K
c = 12.712 (4) Å0.50 × 0.30 × 0.20 mm
Data collection top
Rigaku AFC5R
diffractometer
1142 reflections with I > 2σ(I)
Absorption correction: ψ
(North et al., 1968)
Rint = 0.022
Tmin = 0.952, Tmax = 0.9803 standard reflections every 97 reflections
2875 measured reflections intensity decay: 0.6%
2509 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.205H atoms treated by a mixture of independent and constrained refinement
S = 0.91Δρmax = 0.13 e Å3
2509 reflectionsΔρmin = 0.18 e Å3
172 parameters
Special details top

Experimental. The scan width was (1.21 + 0.30tanθ)° with an ω scan speed of 4° per minute (up to 2 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

Ratio observed/unique reflections is too low. Although we tried to measure two set of data by using differnt sizes of crystals and scan times, the high ratio was not achieved. This is probably an effect of thermal puckering motions of the piperidinium ring and thermal libration of the nitro group.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

The bond length N2—H6 1.02 (5) Å is longer than the normal. Such elongation is sometimes observed in the N—H bond involved in hydrogen bond, e.g. Kashino et al., (2001). Acta Cryst. C57, 627–631.

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 > σ(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.

The Ueq of N2 is low as compared to neighbors in the piperidinium ion. This is probably because the C atoms in the ring are effected by thermal puckering of the ring, while the thermal mortion of the N2 atom is suppressed by two hydrogen bonds in which the N2 atom is involved.

Precision (0.006 Å) on the C—C bond lengths is low in the piperidinium ring. This may be an effect of large thermal motion of the C atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.6510 (3)0.39431 (15)0.5753 (2)0.0806 (10)
O20.6200 (3)0.43747 (11)0.4196 (2)0.0645 (8)
O31.0833 (4)0.22697 (16)0.1981 (3)0.1061 (13)
O41.1384 (4)0.19333 (14)0.3512 (3)0.0991 (12)
N11.0720 (4)0.22754 (16)0.2936 (3)0.0708 (10)
N20.3792 (4)0.44210 (16)0.6108 (2)0.0526 (8)
C10.7829 (4)0.35452 (15)0.4302 (3)0.0445 (9)
C20.8025 (4)0.35291 (16)0.3220 (3)0.0524 (10)
C30.8971 (4)0.31161 (17)0.2773 (3)0.0561 (10)
C40.9727 (4)0.27250 (16)0.3415 (3)0.0514 (10)
C50.9581 (4)0.27403 (16)0.4494 (3)0.0573 (10)
C60.8614 (4)0.31491 (16)0.4930 (3)0.0524 (10)
C70.6770 (4)0.39926 (17)0.4788 (3)0.0529 (10)
C80.2869 (5)0.4107 (2)0.5319 (3)0.0754 (13)
C90.1310 (5)0.4364 (2)0.5315 (4)0.0807 (14)
C100.0621 (5)0.4307 (2)0.6394 (4)0.0748 (13)
C110.1591 (5)0.4595 (2)0.7215 (3)0.0708 (12)
C120.3153 (4)0.43536 (19)0.7182 (3)0.0639 (11)
H10.75050.38040.27860.063*
H20.90990.31020.20310.067*
H31.01340.24750.49280.069*
H40.84830.31600.56720.063*
H50.480 (5)0.4309 (17)0.605 (3)0.069 (12)*
H60.386 (5)0.487 (2)0.593 (3)0.096 (15)*
H70.33030.41540.46420.090*
H80.28230.36950.54900.090*
H90.13550.47730.51250.097*
H100.07150.41550.48200.097*
H110.03300.44960.63930.090*
H120.05030.38970.65590.090*
H130.16200.50120.70920.085*
H140.11760.45200.78900.085*
H150.31380.39440.73670.077*
H160.37550.45660.76700.077*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.075 (2)0.111 (3)0.0555 (18)0.0372 (18)0.0125 (15)0.0146 (17)
O20.0690 (18)0.0521 (15)0.0725 (18)0.0103 (15)0.0019 (15)0.0147 (14)
O30.127 (3)0.116 (3)0.075 (2)0.038 (2)0.001 (2)0.031 (2)
O40.119 (3)0.076 (2)0.102 (3)0.042 (2)0.005 (2)0.005 (2)
N10.079 (2)0.057 (2)0.076 (3)0.006 (2)0.003 (2)0.013 (2)
N20.047 (2)0.055 (2)0.0559 (19)0.0030 (17)0.0077 (16)0.0026 (17)
C10.0407 (19)0.0418 (19)0.051 (2)0.0079 (17)0.0002 (17)0.0063 (17)
C20.057 (2)0.049 (2)0.051 (2)0.001 (2)0.0024 (18)0.0077 (19)
C30.064 (2)0.056 (2)0.048 (2)0.006 (2)0.001 (2)0.0006 (19)
C40.050 (2)0.046 (2)0.059 (2)0.0025 (18)0.0033 (19)0.0061 (19)
C50.061 (2)0.050 (2)0.060 (3)0.005 (2)0.006 (2)0.0085 (19)
C60.053 (2)0.056 (2)0.048 (2)0.0011 (19)0.0036 (18)0.0067 (18)
C70.0414 (19)0.057 (2)0.060 (2)0.0027 (18)0.0002 (19)0.007 (2)
C80.078 (3)0.086 (3)0.062 (3)0.013 (3)0.010 (2)0.014 (2)
C90.061 (3)0.105 (4)0.076 (3)0.020 (3)0.012 (2)0.010 (3)
C100.049 (2)0.079 (3)0.096 (3)0.009 (2)0.009 (2)0.022 (3)
C110.063 (3)0.083 (3)0.067 (3)0.002 (2)0.022 (2)0.006 (2)
C120.062 (2)0.080 (3)0.050 (2)0.003 (2)0.004 (2)0.014 (2)
Geometric parameters (Å, º) top
O1—C71.253 (4)N2—C121.489 (5)
O2—C71.250 (4)N2—H50.94 (4)
O3—N11.219 (4)N2—H61.02 (5)
O4—N11.216 (4)C8—C91.510 (6)
N1—C41.476 (5)C8—H70.95
C1—C61.386 (5)C8—H80.95
C1—C21.387 (5)C9—C101.509 (6)
C1—C71.513 (5)C9—H90.95
C2—C31.378 (5)C9—H100.95
C2—H10.95C10—C111.502 (6)
C3—C41.377 (5)C10—H110.95
C3—H20.95C10—H120.95
C4—C51.379 (5)C11—C121.500 (6)
C5—C61.378 (5)C11—H130.95
C5—H30.95C11—H140.95
C6—H40.95C12—H150.95
N2—C81.478 (5)C12—H160.95
O4—N1—O3123.6 (4)N2—C8—C9109.6 (4)
O4—N1—C4118.5 (4)N2—C8—H7109
O3—N1—C4117.9 (4)C9—C8—H7109
C6—C1—C2119.4 (3)N2—C8—H8109
C6—C1—C7120.5 (3)C9—C8—H8109
C2—C1—C7120.1 (3)H7—C8—H8110
C3—C2—C1120.3 (3)C10—C9—C8110.0 (4)
C3—C2—H1120C10—C9—H9109
C1—C2—H1120C8—C9—H9109
C4—C3—C2119.1 (3)C10—C9—H10109
C4—C3—H2121C8—C9—H10109
C2—C3—H2120H9—C9—H10110
C3—C4—C5121.8 (4)C11—C10—C9111.0 (3)
C3—C4—N1119.2 (3)C11—C10—H11109
C5—C4—N1119.0 (4)C9—C10—H11109
C6—C5—C4118.5 (3)C11—C10—H12109
C6—C5—H3121C9—C10—H12109
C4—C5—H3121H11—C10—H12110
C5—C6—C1120.9 (3)C12—C11—C10111.4 (4)
C5—C6—H4120C12—C11—H13109
C1—C6—H4120C10—C11—H13109
O2—C7—O1125.0 (4)C12—C11—H14109
O2—C7—C1117.7 (3)C10—C11—H14109
O1—C7—C1117.2 (3)H13—C11—H14110
C8—N2—C12111.1 (3)N2—C12—C11110.3 (3)
C8—N2—H5111 (2)N2—C12—H15109
C12—N2—H5114 (2)C11—C12—H15109
C8—N2—H6110 (2)N2—C12—H16109
C12—N2—H6109 (2)C11—C12—H16109
H5—N2—H6101 (4)H15—C12—H16110
C6—C1—C2—C31.1 (5)C2—C1—C6—C50.1 (5)
C7—C1—C2—C3179.0 (3)C7—C1—C6—C5180.0 (3)
C1—C2—C3—C40.7 (5)C6—C1—C7—O2173.5 (3)
C2—C3—C4—C50.9 (6)C2—C1—C7—O26.4 (5)
C2—C3—C4—N1178.9 (3)C6—C1—C7—O17.9 (5)
O4—N1—C4—C3179.9 (4)C2—C1—C7—O1172.2 (4)
O3—N1—C4—C30.2 (5)C12—N2—C8—C960.4 (5)
O4—N1—C4—C50.3 (5)N2—C8—C9—C1058.5 (5)
O3—N1—C4—C5180.0 (4)C8—C9—C10—C1155.7 (5)
C3—C4—C5—C61.9 (6)C9—C10—C11—C1254.4 (5)
N1—C4—C5—C6177.9 (3)C8—N2—C12—C1158.7 (5)
C4—C5—C6—C11.4 (6)C10—C11—C12—N255.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H5···O10.94 (4)1.78 (4)2.697 (5)165 (4)
N2—H6···O2i1.02 (5)1.71 (5)2.731 (4)171 (4)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC5H12N+·C7H4NO4
Mr252.27
Crystal system, space groupOrthorhombic, Pccn
Temperature (K)298
a, b, c (Å)8.949 (2), 22.451 (5), 12.712 (4)
V3)2554.0 (11)
Z8
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.50 × 0.30 × 0.20
Data collection
DiffractometerRigaku AFC5R
diffractometer
Absorption correctionψ
(North et al., 1968)
Tmin, Tmax0.952, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
2875, 2509, 1142
Rint0.022
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.205, 0.91
No. of reflections2509
No. of parameters172
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.13, 0.18

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1997-1999), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), TEXSAN for Windows.

Selected geometric parameters (Å, º) top
O1—C71.253 (4)C3—C41.377 (5)
O2—C71.250 (4)C4—C51.379 (5)
O3—N11.219 (4)C5—C61.378 (5)
O4—N11.216 (4)N2—C81.478 (5)
N1—C41.476 (5)N2—C121.489 (5)
C1—C61.386 (5)C8—C91.510 (6)
C1—C21.387 (5)C10—C111.502 (6)
C1—C71.513 (5)C11—C121.500 (6)
C2—C31.378 (5)
O4—N1—O3123.6 (4)C6—C5—C4118.5 (3)
O4—N1—C4118.5 (4)C5—C6—C1120.9 (3)
O3—N1—C4117.9 (4)O2—C7—O1125.0 (4)
C6—C1—C2119.4 (3)O2—C7—C1117.7 (3)
C6—C1—C7120.5 (3)O1—C7—C1117.2 (3)
C2—C1—C7120.1 (3)C8—N2—C12111.1 (3)
C3—C2—C1120.3 (3)N2—C8—C9109.6 (4)
C4—C3—C2119.1 (3)C10—C9—C8110.0 (4)
C3—C4—C5121.8 (4)C11—C10—C9111.0 (3)
C3—C4—N1119.2 (3)C12—C11—C10111.4 (4)
C5—C4—N1119.0 (4)N2—C12—C11110.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H5···O10.94 (4)1.78 (4)2.697 (5)165 (4)
N2—H6···O2i1.02 (5)1.71 (5)2.731 (4)171 (4)
Symmetry code: (i) x+1, y+1, z+1.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds