organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

aDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li 320, Taiwan
*Correspondence e-mail: chiaher@cycu.edu.tw

(Received 10 October 2009; accepted 19 October 2009; online 23 October 2009)

The hydro­thermal reaction of benzene-1,4-dicarboxylic acid and 4,4′-trimethyl­ene dipiperidine leads to the formation of the title compound, C13H28N22+·C8H4O42−. 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[Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629-1659.]).

[Scheme 1]

Experimental

Crystal data
  • C13H28N22+·C8H4O42−

  • Mr = 376.49

  • Monoclinic, C 2/c

  • 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[Bruker (2008). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.978, Tmax = 0.982

  • 9090 measured reflections

  • 2286 independent reflections

  • 1073 reflections with I > 2σ(I)

  • Rint = 0.114

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1N1⋯O1i 0.90 1.91 2.7958 (19) 169
N1—H2N1⋯O2 0.90 1.82 2.7213 (18) 174
N1—H2N1⋯O1 0.90 2.61 3.1528 (19) 120
Symmetry code: (i) [-x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z-1].

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2008[Bruker (2008). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2009[Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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).

Structure description top

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).

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

Computing details top

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

Figures top
[Figure 1] 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.].
4,4'-Trimethylenedipiperidiniumbenzene-1,4-dicarboxylate top
Crystal data top
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 top
Bruker APEXII CCD
diffractometer
2286 independent reflections
Radiation source: fine-focus sealed tube1073 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.114
Detector resolution: 8.3333 pixels mm-1θmax = 28.3°, θmin = 2.1°
φ and ω scansh = 2526
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
k = 119
Tmin = 0.978, Tmax = 0.982l = 1014
9090 measured reflections
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)] = 0.046H-atom parameters constrained
wR(F2) = 0.095 w = 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)
Crystal data top
C13H28N22+·C8H4O42V = 1931.4 (3) Å3
Mr = 376.49Z = 4
Monoclinic, C2/cMo Kα radiation
a = 20.2902 (18) ŵ = 0.09 mm1
b = 8.4534 (8) ÅT = 295 K
c = 11.8815 (9) Å0.25 × 0.20 × 0.20 mm
β = 108.610 (3)°
Data collection top
Bruker APEXII CCD
diffractometer
2286 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
1073 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.982Rint = 0.114
9090 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 0.82Δρmax = 0.18 e Å3
2286 reflectionsΔρmin = 0.20 e Å3
124 parameters
Special details top

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) top
xyzUiso*/Ueq
N10.28726 (7)0.06898 (17)0.42869 (12)0.0323 (4)
H1N10.30550.14980.47820.039*
H2N10.25170.02850.44930.039*
C40.38067 (9)0.0846 (2)0.28506 (14)0.0280 (4)
H4A0.36580.00150.22720.034*
C50.44100 (9)0.1711 (2)0.26231 (15)0.0308 (5)
H5A0.42260.23270.19020.037*
H5B0.46010.24500.32690.037*
C70.50000.0702 (3)0.25000.0322 (7)
H7A0.48290.00360.18140.039*
C80.34100 (9)0.0545 (2)0.44141 (16)0.0343 (5)
H8A0.32130.14290.38960.041*
H8B0.35690.09290.52260.041*
C90.26075 (9)0.1290 (2)0.30457 (15)0.0379 (5)
H9A0.22590.20990.29880.045*
H9B0.23900.04320.25150.045*
C100.40175 (9)0.0137 (2)0.40950 (15)0.0310 (5)
H10A0.43570.06920.41520.037*
H10B0.42380.09500.46670.037*
C130.31977 (9)0.1974 (2)0.26785 (16)0.0354 (5)
H13A0.33640.29270.31360.042*
H13B0.30200.22740.18480.042*
O10.13904 (7)0.19495 (16)0.41743 (12)0.0428 (4)
O20.18035 (7)0.03599 (17)0.50059 (12)0.0522 (4)
C60.06382 (9)0.0291 (2)0.48175 (15)0.0290 (4)
C110.13273 (10)0.0646 (2)0.46455 (16)0.0346 (5)
C120.05893 (10)0.0776 (2)0.56701 (16)0.0345 (5)
H12A0.09860.13040.61310.041*
C140.00395 (10)0.1067 (2)0.41537 (15)0.0345 (5)
H14A0.00620.17960.35800.041*
Atomic displacement parameters (Å2) top
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, º) top
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) x1, y, z1/2; (ii) x, y, z1.
Hydrogen-bond geometry (Å, º) top
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 code: (iii) x1/2, y+1/2, z1.

Experimental details

Crystal data
Chemical formulaC13H28N22+·C8H4O42
Mr376.49
Crystal system, space groupMonoclinic, C2/c
Temperature (K)295
a, b, c (Å)20.2902 (18), 8.4534 (8), 11.8815 (9)
β (°) 108.610 (3)
V3)1931.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.25 × 0.20 × 0.20
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.978, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
9090, 2286, 1073
Rint0.114
(sin θ/λ)max1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.095, 0.82
No. of reflections2286
No. of parameters124
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.20

Computer programs: APEX2 (Bruker, 2008), SAINT-Plus (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N1···O1i0.901.912.7958 (19)168.9
N1—H2N1···O20.901.822.7213 (18)174.2
N1—H2N1···O10.902.613.1528 (19)119.8
Symmetry code: (i) x1/2, y+1/2, z1.
 

Acknowledgements

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.

References

First citationBrandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2008). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationMoulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1659.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
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