Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010844/ci6044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010844/ci6044Isup2.hkl |
CCDC reference: 170898
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.
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.
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.
C5H12N+·C7H4NO4− | Dx = 1.312 Mg m−3 |
Mr = 252.27 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pccn | Cell parameters from 25 reflections |
a = 8.949 (2) Å | θ = 10.6–11.4° |
b = 22.451 (5) Å | µ = 0.10 mm−1 |
c = 12.712 (4) Å | T = 298 K |
V = 2554.0 (11) Å3 | Prismatic, colorless |
Z = 8 | 0.50 × 0.30 × 0.20 mm |
F(000) = 1072 |
Rigaku AFC5R diffractometer | 1142 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.022 |
Graphite monochromator | θmax = 26.0°, θmin = 1.8° |
ω–2θ scans | h = 0→11 |
Absorption correction: ψ (North et al., 1968) | k = 0→27 |
Tmin = 0.952, Tmax = 0.980 | l = 0→15 |
2875 measured reflections | 3 standard reflections every 97 reflections |
2509 independent reflections | intensity decay: 0.6% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.057 | H 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 reflections | Δρmax = 0.13 e Å−3 |
172 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0059 (14) |
C5H12N+·C7H4NO4− | V = 2554.0 (11) Å3 |
Mr = 252.27 | Z = 8 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 8.949 (2) Å | µ = 0.10 mm−1 |
b = 22.451 (5) Å | T = 298 K |
c = 12.712 (4) Å | 0.50 × 0.30 × 0.20 mm |
Rigaku AFC5R diffractometer | 1142 reflections with I > 2σ(I) |
Absorption correction: ψ (North et al., 1968) | Rint = 0.022 |
Tmin = 0.952, Tmax = 0.980 | 3 standard reflections every 97 reflections |
2875 measured reflections | intensity decay: 0.6% |
2509 independent reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.205 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | Δρmax = 0.13 e Å−3 |
2509 reflections | Δρmin = −0.18 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.6510 (3) | 0.39431 (15) | 0.5753 (2) | 0.0806 (10) | |
O2 | 0.6200 (3) | 0.43747 (11) | 0.4196 (2) | 0.0645 (8) | |
O3 | 1.0833 (4) | 0.22697 (16) | 0.1981 (3) | 0.1061 (13) | |
O4 | 1.1384 (4) | 0.19333 (14) | 0.3512 (3) | 0.0991 (12) | |
N1 | 1.0720 (4) | 0.22754 (16) | 0.2936 (3) | 0.0708 (10) | |
N2 | 0.3792 (4) | 0.44210 (16) | 0.6108 (2) | 0.0526 (8) | |
C1 | 0.7829 (4) | 0.35452 (15) | 0.4302 (3) | 0.0445 (9) | |
C2 | 0.8025 (4) | 0.35291 (16) | 0.3220 (3) | 0.0524 (10) | |
C3 | 0.8971 (4) | 0.31161 (17) | 0.2773 (3) | 0.0561 (10) | |
C4 | 0.9727 (4) | 0.27250 (16) | 0.3415 (3) | 0.0514 (10) | |
C5 | 0.9581 (4) | 0.27403 (16) | 0.4494 (3) | 0.0573 (10) | |
C6 | 0.8614 (4) | 0.31491 (16) | 0.4930 (3) | 0.0524 (10) | |
C7 | 0.6770 (4) | 0.39926 (17) | 0.4788 (3) | 0.0529 (10) | |
C8 | 0.2869 (5) | 0.4107 (2) | 0.5319 (3) | 0.0754 (13) | |
C9 | 0.1310 (5) | 0.4364 (2) | 0.5315 (4) | 0.0807 (14) | |
C10 | 0.0621 (5) | 0.4307 (2) | 0.6394 (4) | 0.0748 (13) | |
C11 | 0.1591 (5) | 0.4595 (2) | 0.7215 (3) | 0.0708 (12) | |
C12 | 0.3153 (4) | 0.43536 (19) | 0.7182 (3) | 0.0639 (11) | |
H1 | 0.7505 | 0.3804 | 0.2786 | 0.063* | |
H2 | 0.9099 | 0.3102 | 0.2031 | 0.067* | |
H3 | 1.0134 | 0.2475 | 0.4928 | 0.069* | |
H4 | 0.8483 | 0.3160 | 0.5672 | 0.063* | |
H5 | 0.480 (5) | 0.4309 (17) | 0.605 (3) | 0.069 (12)* | |
H6 | 0.386 (5) | 0.487 (2) | 0.593 (3) | 0.096 (15)* | |
H7 | 0.3303 | 0.4154 | 0.4642 | 0.090* | |
H8 | 0.2823 | 0.3695 | 0.5490 | 0.090* | |
H9 | 0.1355 | 0.4773 | 0.5125 | 0.097* | |
H10 | 0.0715 | 0.4155 | 0.4820 | 0.097* | |
H11 | −0.0330 | 0.4496 | 0.6393 | 0.090* | |
H12 | 0.0503 | 0.3897 | 0.6559 | 0.090* | |
H13 | 0.1620 | 0.5012 | 0.7092 | 0.085* | |
H14 | 0.1176 | 0.4520 | 0.7890 | 0.085* | |
H15 | 0.3138 | 0.3944 | 0.7367 | 0.077* | |
H16 | 0.3755 | 0.4566 | 0.7670 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.075 (2) | 0.111 (3) | 0.0555 (18) | 0.0372 (18) | 0.0125 (15) | 0.0146 (17) |
O2 | 0.0690 (18) | 0.0521 (15) | 0.0725 (18) | 0.0103 (15) | 0.0019 (15) | 0.0147 (14) |
O3 | 0.127 (3) | 0.116 (3) | 0.075 (2) | 0.038 (2) | 0.001 (2) | −0.031 (2) |
O4 | 0.119 (3) | 0.076 (2) | 0.102 (3) | 0.042 (2) | 0.005 (2) | 0.005 (2) |
N1 | 0.079 (2) | 0.057 (2) | 0.076 (3) | 0.006 (2) | −0.003 (2) | −0.013 (2) |
N2 | 0.047 (2) | 0.055 (2) | 0.0559 (19) | 0.0030 (17) | 0.0077 (16) | 0.0026 (17) |
C1 | 0.0407 (19) | 0.0418 (19) | 0.051 (2) | −0.0079 (17) | −0.0002 (17) | 0.0063 (17) |
C2 | 0.057 (2) | 0.049 (2) | 0.051 (2) | 0.001 (2) | −0.0024 (18) | 0.0077 (19) |
C3 | 0.064 (2) | 0.056 (2) | 0.048 (2) | −0.006 (2) | −0.001 (2) | −0.0006 (19) |
C4 | 0.050 (2) | 0.046 (2) | 0.059 (2) | −0.0025 (18) | −0.0033 (19) | −0.0061 (19) |
C5 | 0.061 (2) | 0.050 (2) | 0.060 (3) | 0.005 (2) | −0.006 (2) | 0.0085 (19) |
C6 | 0.053 (2) | 0.056 (2) | 0.048 (2) | 0.0011 (19) | −0.0036 (18) | 0.0067 (18) |
C7 | 0.0414 (19) | 0.057 (2) | 0.060 (2) | −0.0027 (18) | 0.0002 (19) | 0.007 (2) |
C8 | 0.078 (3) | 0.086 (3) | 0.062 (3) | −0.013 (3) | 0.010 (2) | −0.014 (2) |
C9 | 0.061 (3) | 0.105 (4) | 0.076 (3) | −0.020 (3) | −0.012 (2) | 0.010 (3) |
C10 | 0.049 (2) | 0.079 (3) | 0.096 (3) | −0.009 (2) | 0.009 (2) | 0.022 (3) |
C11 | 0.063 (3) | 0.083 (3) | 0.067 (3) | 0.002 (2) | 0.022 (2) | 0.006 (2) |
C12 | 0.062 (2) | 0.080 (3) | 0.050 (2) | −0.003 (2) | 0.004 (2) | 0.014 (2) |
O1—C7 | 1.253 (4) | N2—C12 | 1.489 (5) |
O2—C7 | 1.250 (4) | N2—H5 | 0.94 (4) |
O3—N1 | 1.219 (4) | N2—H6 | 1.02 (5) |
O4—N1 | 1.216 (4) | C8—C9 | 1.510 (6) |
N1—C4 | 1.476 (5) | C8—H7 | 0.95 |
C1—C6 | 1.386 (5) | C8—H8 | 0.95 |
C1—C2 | 1.387 (5) | C9—C10 | 1.509 (6) |
C1—C7 | 1.513 (5) | C9—H9 | 0.95 |
C2—C3 | 1.378 (5) | C9—H10 | 0.95 |
C2—H1 | 0.95 | C10—C11 | 1.502 (6) |
C3—C4 | 1.377 (5) | C10—H11 | 0.95 |
C3—H2 | 0.95 | C10—H12 | 0.95 |
C4—C5 | 1.379 (5) | C11—C12 | 1.500 (6) |
C5—C6 | 1.378 (5) | C11—H13 | 0.95 |
C5—H3 | 0.95 | C11—H14 | 0.95 |
C6—H4 | 0.95 | C12—H15 | 0.95 |
N2—C8 | 1.478 (5) | C12—H16 | 0.95 |
O4—N1—O3 | 123.6 (4) | N2—C8—C9 | 109.6 (4) |
O4—N1—C4 | 118.5 (4) | N2—C8—H7 | 109 |
O3—N1—C4 | 117.9 (4) | C9—C8—H7 | 109 |
C6—C1—C2 | 119.4 (3) | N2—C8—H8 | 109 |
C6—C1—C7 | 120.5 (3) | C9—C8—H8 | 109 |
C2—C1—C7 | 120.1 (3) | H7—C8—H8 | 110 |
C3—C2—C1 | 120.3 (3) | C10—C9—C8 | 110.0 (4) |
C3—C2—H1 | 120 | C10—C9—H9 | 109 |
C1—C2—H1 | 120 | C8—C9—H9 | 109 |
C4—C3—C2 | 119.1 (3) | C10—C9—H10 | 109 |
C4—C3—H2 | 121 | C8—C9—H10 | 109 |
C2—C3—H2 | 120 | H9—C9—H10 | 110 |
C3—C4—C5 | 121.8 (4) | C11—C10—C9 | 111.0 (3) |
C3—C4—N1 | 119.2 (3) | C11—C10—H11 | 109 |
C5—C4—N1 | 119.0 (4) | C9—C10—H11 | 109 |
C6—C5—C4 | 118.5 (3) | C11—C10—H12 | 109 |
C6—C5—H3 | 121 | C9—C10—H12 | 109 |
C4—C5—H3 | 121 | H11—C10—H12 | 110 |
C5—C6—C1 | 120.9 (3) | C12—C11—C10 | 111.4 (4) |
C5—C6—H4 | 120 | C12—C11—H13 | 109 |
C1—C6—H4 | 120 | C10—C11—H13 | 109 |
O2—C7—O1 | 125.0 (4) | C12—C11—H14 | 109 |
O2—C7—C1 | 117.7 (3) | C10—C11—H14 | 109 |
O1—C7—C1 | 117.2 (3) | H13—C11—H14 | 110 |
C8—N2—C12 | 111.1 (3) | N2—C12—C11 | 110.3 (3) |
C8—N2—H5 | 111 (2) | N2—C12—H15 | 109 |
C12—N2—H5 | 114 (2) | C11—C12—H15 | 109 |
C8—N2—H6 | 110 (2) | N2—C12—H16 | 109 |
C12—N2—H6 | 109 (2) | C11—C12—H16 | 109 |
H5—N2—H6 | 101 (4) | H15—C12—H16 | 110 |
C6—C1—C2—C3 | 1.1 (5) | C2—C1—C6—C5 | −0.1 (5) |
C7—C1—C2—C3 | −179.0 (3) | C7—C1—C6—C5 | −180.0 (3) |
C1—C2—C3—C4 | −0.7 (5) | C6—C1—C7—O2 | 173.5 (3) |
C2—C3—C4—C5 | −0.9 (6) | C2—C1—C7—O2 | −6.4 (5) |
C2—C3—C4—N1 | 178.9 (3) | C6—C1—C7—O1 | −7.9 (5) |
O4—N1—C4—C3 | 179.9 (4) | C2—C1—C7—O1 | 172.2 (4) |
O3—N1—C4—C3 | 0.2 (5) | C12—N2—C8—C9 | 60.4 (5) |
O4—N1—C4—C5 | −0.3 (5) | N2—C8—C9—C10 | −58.5 (5) |
O3—N1—C4—C5 | 180.0 (4) | C8—C9—C10—C11 | 55.7 (5) |
C3—C4—C5—C6 | 1.9 (6) | C9—C10—C11—C12 | −54.4 (5) |
N1—C4—C5—C6 | −177.9 (3) | C8—N2—C12—C11 | −58.7 (5) |
C4—C5—C6—C1 | −1.4 (6) | C10—C11—C12—N2 | 55.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H5···O1 | 0.94 (4) | 1.78 (4) | 2.697 (5) | 165 (4) |
N2—H6···O2i | 1.02 (5) | 1.71 (5) | 2.731 (4) | 171 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C5H12N+·C7H4NO4− |
Mr | 252.27 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 298 |
a, b, c (Å) | 8.949 (2), 22.451 (5), 12.712 (4) |
V (Å3) | 2554.0 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.50 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC5R diffractometer |
Absorption correction | ψ (North et al., 1968) |
Tmin, Tmax | 0.952, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2875, 2509, 1142 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.205, 0.91 |
No. of reflections | 2509 |
No. of parameters | 172 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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.
O1—C7 | 1.253 (4) | C3—C4 | 1.377 (5) |
O2—C7 | 1.250 (4) | C4—C5 | 1.379 (5) |
O3—N1 | 1.219 (4) | C5—C6 | 1.378 (5) |
O4—N1 | 1.216 (4) | N2—C8 | 1.478 (5) |
N1—C4 | 1.476 (5) | N2—C12 | 1.489 (5) |
C1—C6 | 1.386 (5) | C8—C9 | 1.510 (6) |
C1—C2 | 1.387 (5) | C10—C11 | 1.502 (6) |
C1—C7 | 1.513 (5) | C11—C12 | 1.500 (6) |
C2—C3 | 1.378 (5) | ||
O4—N1—O3 | 123.6 (4) | C6—C5—C4 | 118.5 (3) |
O4—N1—C4 | 118.5 (4) | C5—C6—C1 | 120.9 (3) |
O3—N1—C4 | 117.9 (4) | O2—C7—O1 | 125.0 (4) |
C6—C1—C2 | 119.4 (3) | O2—C7—C1 | 117.7 (3) |
C6—C1—C7 | 120.5 (3) | O1—C7—C1 | 117.2 (3) |
C2—C1—C7 | 120.1 (3) | C8—N2—C12 | 111.1 (3) |
C3—C2—C1 | 120.3 (3) | N2—C8—C9 | 109.6 (4) |
C4—C3—C2 | 119.1 (3) | C10—C9—C8 | 110.0 (4) |
C3—C4—C5 | 121.8 (4) | C11—C10—C9 | 111.0 (3) |
C3—C4—N1 | 119.2 (3) | C12—C11—C10 | 111.4 (4) |
C5—C4—N1 | 119.0 (4) | N2—C12—C11 | 110.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H5···O1 | 0.94 (4) | 1.78 (4) | 2.697 (5) | 165 (4) |
N2—H6···O2i | 1.02 (5) | 1.71 (5) | 2.731 (4) | 171 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
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.