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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2822.
Published online 2009 October 23. doi:  10.1107/S1600536809042901
PMCID: PMC2970973

4,4′-Trimethyl­enedipiperidiniumbenzene-1,4-dicarboxyl­ate

Abstract

The hydro­thermal reaction of benzene-1,4-dicarboxylic acid and 4,4′-trimethyl­ene dipiperidine leads to the formation of the title compound, C13H28N2 2+·C8H4O4 2−. The anion is located on a center of inversion whereas the cation is positioned on a twofold rotation axis. In the crystal structure, the anions and cations are linked by N—H(...)O and N—H(...)(O,O) hydrogen bonds.

Related literature

For general background, see: Moulton & Zaworotko (2001 [triangle]).

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Object name is e-65-o2822-scheme1.jpg

Experimental

Crystal data

  • C13H28N2 2+·C8H4O4 2−
  • M r = 376.49
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2822-efi2.jpg
  • a = 20.2902 (18) Å
  • b = 8.4534 (8) Å
  • c = 11.8815 (9) Å
  • β = 108.610 (3)°
  • V = 1931.4 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 295 K
  • 0.25 × 0.20 × 0.20 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2008 [triangle]) T min = 0.978, T max = 0.982
  • 9090 measured reflections
  • 2286 independent reflections
  • 1073 reflections with I > 2σ(I)
  • R int = 0.114

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.095
  • S = 0.82
  • 2286 reflections
  • 124 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT-Plus (Bruker, 2008 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2009 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536809042901/nc2162sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809042901/nc2162Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This research project was supported by the National Science Council of Taiwan (NSC97–2113-M-033–003-MY2) and by the project of specific research fields of Chung Yuan Christian University, Taiwan, under grant CYCU-98-CR—CH.

supplementary crystallographic information

Comment

Crystals of the title compound were obtained by accident during our studies on the synthesis and structural characterization of coordination polymers. For their identification the crystal structure was determined.

The asymmetric unit consists of benzene-1,4-dicarboxylate anions and 4,4'-trimethylene dipiperidine cations each of them located in special positions. The anions are positioned on centers of inversion, whereas the cations are located on a 2-fold rotation axis which goes through the central C atom C7.

In the crystal structure the anions and cations are connected via N-H···O hydrogen bonding between the amino H atoms and the carboxylate oxygen atoms (Table 1).

Experimental

The title compound was prepared by the reaction of 4,4'-trimethylenedipiperidine (0.0840 g, 0.4 mmol) and benzene-1,4-dicarboxylic acid (0.1661 g, 2.0 mmol) in H2O (1.0 ml) and CH3CN (5.0 ml). The mixture was heated to 393 K for 2 days in a Teflon-lined autoclave with an internal volume of 23 ml followed by slow cooling at 6 K/h to room temperature. The title compound was obtained as colorless crystals.

Refinement

All hydrogen atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93, 0.96, and 0.97 Å and Uiso(H) = 1.2 Ueq(C) and N—H = 0.90 Å and Uiso(H) = 1.2 Ueq(N).

Figures

Fig. 1.
Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level for non-H atoms. The hydrogen bonding is indicated as a dashed line. Symmetry codes: (i) -1 - x, y, -1/2 - z; (ii) -x, -y, -1 - z.].

Crystal data

C13H28N22+·C8H4O42F(000) = 816
Mr = 376.49Dx = 1.295 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2292 reflections
a = 20.2902 (18) Åθ = 3.0–26.1°
b = 8.4534 (8) ŵ = 0.09 mm1
c = 11.8815 (9) ÅT = 295 K
β = 108.610 (3)°Columnar, colourless
V = 1931.4 (3) Å30.25 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer2286 independent reflections
Radiation source: fine-focus sealed tube1073 reflections with I > 2σ(I)
graphiteRint = 0.114
Detector resolution: 8.3333 pixels mm-1θmax = 28.3°, θmin = 2.1°
[var phi] and ω scansh = −25→26
Absorption correction: multi-scan (SADABS; Bruker, 2008)k = −11→9
Tmin = 0.978, Tmax = 0.982l = −10→14
9090 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.095w = 1/[σ2(Fo2) + (0.0287P)2] where P = (Fo2 + 2Fc2)/3
S = 0.82(Δ/σ)max < 0.001
2286 reflectionsΔρmax = 0.18 e Å3
124 parametersΔρmin = −0.20 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0026 (5)

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)

xyzUiso*/Ueq
N1−0.28726 (7)0.06898 (17)−0.42869 (12)0.0323 (4)
H1N1−0.30550.1498−0.47820.039*
H2N1−0.25170.0285−0.44930.039*
C4−0.38067 (9)0.0846 (2)−0.28506 (14)0.0280 (4)
H4A−0.3658−0.0015−0.22720.034*
C5−0.44100 (9)0.1711 (2)−0.26231 (15)0.0308 (5)
H5A−0.42260.2327−0.19020.037*
H5B−0.46010.2450−0.32690.037*
C7−0.50000.0702 (3)−0.25000.0322 (7)
H7A−0.48290.0036−0.18140.039*
C8−0.34100 (9)−0.0545 (2)−0.44141 (16)0.0343 (5)
H8A−0.3213−0.1429−0.38960.041*
H8B−0.3569−0.0929−0.52260.041*
C9−0.26075 (9)0.1290 (2)−0.30457 (15)0.0379 (5)
H9A−0.22590.2099−0.29880.045*
H9B−0.23900.0432−0.25150.045*
C10−0.40175 (9)0.0137 (2)−0.40950 (15)0.0310 (5)
H10A−0.4357−0.0692−0.41520.037*
H10B−0.42380.0950−0.46670.037*
C13−0.31977 (9)0.1974 (2)−0.26785 (16)0.0354 (5)
H13A−0.33640.2927−0.31360.042*
H13B−0.30200.2274−0.18480.042*
O1−0.13904 (7)0.19495 (16)−0.41743 (12)0.0428 (4)
O2−0.18035 (7)−0.03599 (17)−0.50059 (12)0.0522 (4)
C6−0.06382 (9)0.0291 (2)−0.48175 (15)0.0290 (4)
C11−0.13273 (10)0.0646 (2)−0.46455 (16)0.0346 (5)
C12−0.05893 (10)−0.0776 (2)−0.56701 (16)0.0345 (5)
H12A−0.0986−0.1304−0.61310.041*
C14−0.00395 (10)0.1067 (2)−0.41537 (15)0.0345 (5)
H14A−0.00620.1796−0.35800.041*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0262 (9)0.0356 (10)0.0398 (10)0.0020 (7)0.0173 (7)0.0003 (7)
C40.0246 (10)0.0315 (11)0.0309 (11)−0.0002 (9)0.0130 (8)0.0033 (8)
C50.0279 (11)0.0354 (12)0.0339 (11)−0.0001 (9)0.0164 (8)−0.0012 (8)
C70.0281 (15)0.0353 (17)0.0388 (16)0.0000.0186 (12)0.000
C80.0299 (11)0.0354 (12)0.0406 (12)−0.0022 (9)0.0154 (9)−0.0048 (9)
C90.0271 (11)0.0500 (13)0.0378 (12)−0.0074 (10)0.0121 (9)−0.0076 (9)
C100.0233 (10)0.0347 (12)0.0371 (11)−0.0039 (9)0.0125 (8)−0.0012 (9)
C130.0305 (12)0.0445 (13)0.0342 (11)−0.0034 (10)0.0148 (9)−0.0055 (9)
O10.0409 (9)0.0385 (9)0.0579 (9)0.0085 (7)0.0281 (7)0.0027 (7)
O20.0315 (9)0.0544 (10)0.0797 (11)−0.0039 (8)0.0303 (7)−0.0104 (8)
C60.0255 (11)0.0287 (11)0.0377 (11)0.0039 (9)0.0170 (8)0.0077 (9)
C110.0306 (12)0.0374 (13)0.0417 (12)0.0074 (11)0.0199 (9)0.0108 (10)
C120.0265 (11)0.0358 (13)0.0421 (12)0.0002 (9)0.0123 (9)−0.0004 (9)
C140.0355 (12)0.0336 (13)0.0382 (12)0.0044 (10)0.0173 (9)−0.0007 (9)

Geometric parameters (Å, °)

N1—C81.482 (2)C9—C131.514 (2)
N1—C91.488 (2)C9—H9A0.9700
N1—H1N10.9000C9—H9B0.9700
N1—H2N10.9000C10—H10A0.9700
C4—C131.522 (2)C10—H10B0.9700
C4—C51.522 (2)C13—H13A0.9700
C4—C101.525 (2)C13—H13B0.9700
C4—H4A0.9800O1—C111.261 (2)
C5—C71.515 (2)O2—C111.255 (2)
C5—H5A0.9700C6—C121.383 (2)
C5—H5B0.9700C6—C141.384 (2)
C7—C5i1.514 (2)C6—C111.506 (2)
C7—H7A0.9598C12—C14ii1.379 (2)
C8—C101.514 (2)C12—H12A0.9300
C8—H8A0.9700C14—C12ii1.379 (2)
C8—H8B0.9700C14—H14A0.9300
C8—N1—C9111.26 (13)C13—C9—H9A109.6
C8—N1—H1N1109.4N1—C9—H9B109.6
C9—N1—H1N1109.4C13—C9—H9B109.6
C8—N1—H2N1109.4H9A—C9—H9B108.1
C9—N1—H2N1109.4C8—C10—C4113.16 (14)
H1N1—N1—H2N1108.0C8—C10—H10A108.9
C13—C4—C5109.83 (14)C4—C10—H10A108.9
C13—C4—C10109.95 (14)C8—C10—H10B108.9
C5—C4—C10111.61 (14)C4—C10—H10B108.9
C13—C4—H4A108.5H10A—C10—H10B107.8
C5—C4—H4A108.5C9—C13—C4113.86 (15)
C10—C4—H4A108.5C9—C13—H13A108.8
C7—C5—C4116.86 (15)C4—C13—H13A108.8
C7—C5—H5A108.1C9—C13—H13B108.8
C4—C5—H5A108.1C4—C13—H13B108.8
C7—C5—H5B108.1H13A—C13—H13B107.7
C4—C5—H5B108.1C12—C6—C14118.11 (16)
H5A—C5—H5B107.3C12—C6—C11121.05 (17)
C5i—C7—C5111.4 (2)C14—C6—C11120.80 (17)
C5i—C7—H7A109.3O2—C11—O1124.56 (18)
C5—C7—H7A109.3O2—C11—C6117.75 (18)
N1—C8—C10109.74 (15)O1—C11—C6117.67 (18)
N1—C8—H8A109.7C14ii—C12—C6120.88 (17)
C10—C8—H8A109.7C14ii—C12—H12A119.6
N1—C8—H8B109.7C6—C12—H12A119.6
C10—C8—H8B109.7C12ii—C14—C6121.00 (17)
H8A—C8—H8B108.2C12ii—C14—H14A119.5
N1—C9—C13110.28 (14)C6—C14—H14A119.5
N1—C9—H9A109.6

Symmetry codes: (i) −x−1, y, −z−1/2; (ii) −x, −y, −z−1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N1···O1iii0.901.912.7958 (19)169
N1—H2N1···O20.901.822.7213 (18)174
N1—H2N1···O10.902.613.1528 (19)120

Symmetry codes: (iii) −x−1/2, −y+1/2, −z−1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2162).

References

  • Brandenburg, K. (2009). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2008). APEX2, SADABS and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev 101, 1629–1659. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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