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

Tseng, F.-S.; Lin, C.-H.

doi:10.1107/S1600536809042901

organic compounds

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Volume 65| Part 11| November 2009| Page o2822

https://doi.org/10.1107/S1600536809042901

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

Feng-Shuen Tseng ^a and Chia-Her Lin ^a ^*

^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 ).

Experimental

Crystal data

C₁₃H₂₈N₂²⁺·C₈H₄O₄²⁻
M_r = 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 ) 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[F² > 2σ(F²)] = 0.046
wR(F²) = 0.095
S = 0.82
2286 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus; 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).

Supporting information

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042901/nc2162sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042901/nc2162Isup2.hkl

checkCIF report

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.

Structure description top

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

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⁺·C₈H₄O₄²⁻	F(000) = 816
M_r = 376.49	D_x = 1.295 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2292 reflections
a = 20.2902 (18) Å	θ = 3.0–26.1°
b = 8.4534 (8) Å	µ = 0.09 mm⁻¹
c = 11.8815 (9) Å	T = 295 K
β = 108.610 (3)°	Columnar, colourless
V = 1931.4 (3) Å³	0.25 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2286 independent reflections
Radiation source: fine-focus sealed tube	1073 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.114
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.3°, θ_min = 2.1°
φ and ω scans	h = −25→26
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −11→9
T_min = 0.978, T_max = 0.982	l = −10→14
9090 measured reflections

Refinement top

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0287P)²] where P = (F_o² + 2F_c²)/3
S = 0.82	(Δ/σ)_max < 0.001
2286 reflections	Δρ_max = 0.18 e Å⁻³
124 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (5)

Crystal data top

C₁₃H₂₈N₂²⁺·C₈H₄O₄²⁻	V = 1931.4 (3) Å³
M_r = 376.49	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.2902 (18) Å	µ = 0.09 mm⁻¹
b = 8.4534 (8) Å	T = 295 K
c = 11.8815 (9) Å	0.25 × 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)
T_min = 0.978, T_max = 0.982	R_int = 0.114
9090 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 0.82	Δρ_max = 0.18 e Å⁻³
2286 reflections	Δρ_min = −0.20 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N1	−0.28726 (7)	0.06898 (17)	−0.42869 (12)	0.0323 (4)
H1N1	−0.3055	0.1498	−0.4782	0.039*
H2N1	−0.2517	0.0285	−0.4493	0.039*
C4	−0.38067 (9)	0.0846 (2)	−0.28506 (14)	0.0280 (4)
H4A	−0.3658	−0.0015	−0.2272	0.034*
C5	−0.44100 (9)	0.1711 (2)	−0.26231 (15)	0.0308 (5)
H5A	−0.4226	0.2327	−0.1902	0.037*
H5B	−0.4601	0.2450	−0.3269	0.037*
C7	−0.5000	0.0702 (3)	−0.2500	0.0322 (7)
H7A	−0.4829	0.0036	−0.1814	0.039*
C8	−0.34100 (9)	−0.0545 (2)	−0.44141 (16)	0.0343 (5)
H8A	−0.3213	−0.1429	−0.3896	0.041*
H8B	−0.3569	−0.0929	−0.5226	0.041*
C9	−0.26075 (9)	0.1290 (2)	−0.30457 (15)	0.0379 (5)
H9A	−0.2259	0.2099	−0.2988	0.045*
H9B	−0.2390	0.0432	−0.2515	0.045*
C10	−0.40175 (9)	0.0137 (2)	−0.40950 (15)	0.0310 (5)
H10A	−0.4357	−0.0692	−0.4152	0.037*
H10B	−0.4238	0.0950	−0.4667	0.037*
C13	−0.31977 (9)	0.1974 (2)	−0.26785 (16)	0.0354 (5)
H13A	−0.3364	0.2927	−0.3136	0.042*
H13B	−0.3020	0.2274	−0.1848	0.042*
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	−0.6131	0.041*
C14	−0.00395 (10)	0.1067 (2)	−0.41537 (15)	0.0345 (5)
H14A	−0.0062	0.1796	−0.3580	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0262 (9)	0.0356 (10)	0.0398 (10)	0.0020 (7)	0.0173 (7)	0.0003 (7)
C4	0.0246 (10)	0.0315 (11)	0.0309 (11)	−0.0002 (9)	0.0130 (8)	0.0033 (8)
C5	0.0279 (11)	0.0354 (12)	0.0339 (11)	−0.0001 (9)	0.0164 (8)	−0.0012 (8)
C7	0.0281 (15)	0.0353 (17)	0.0388 (16)	0.000	0.0186 (12)	0.000
C8	0.0299 (11)	0.0354 (12)	0.0406 (12)	−0.0022 (9)	0.0154 (9)	−0.0048 (9)
C9	0.0271 (11)	0.0500 (13)	0.0378 (12)	−0.0074 (10)	0.0121 (9)	−0.0076 (9)
C10	0.0233 (10)	0.0347 (12)	0.0371 (11)	−0.0039 (9)	0.0125 (8)	−0.0012 (9)
C13	0.0305 (12)	0.0445 (13)	0.0342 (11)	−0.0034 (10)	0.0148 (9)	−0.0055 (9)
O1	0.0409 (9)	0.0385 (9)	0.0579 (9)	0.0085 (7)	0.0281 (7)	0.0027 (7)
O2	0.0315 (9)	0.0544 (10)	0.0797 (11)	−0.0039 (8)	0.0303 (7)	−0.0104 (8)
C6	0.0255 (11)	0.0287 (11)	0.0377 (11)	0.0039 (9)	0.0170 (8)	0.0077 (9)
C11	0.0306 (12)	0.0374 (13)	0.0417 (12)	0.0074 (11)	0.0199 (9)	0.0108 (10)
C12	0.0265 (11)	0.0358 (13)	0.0421 (12)	0.0002 (9)	0.0123 (9)	−0.0004 (9)
C14	0.0355 (12)	0.0336 (13)	0.0382 (12)	0.0044 (10)	0.0173 (9)	−0.0007 (9)

Geometric parameters (Å, º) top

N1—C8	1.482 (2)	C9—C13	1.514 (2)
N1—C9	1.488 (2)	C9—H9A	0.9700
N1—H1N1	0.9000	C9—H9B	0.9700
N1—H2N1	0.9000	C10—H10A	0.9700
C4—C13	1.522 (2)	C10—H10B	0.9700
C4—C5	1.522 (2)	C13—H13A	0.9700
C4—C10	1.525 (2)	C13—H13B	0.9700
C4—H4A	0.9800	O1—C11	1.261 (2)
C5—C7	1.515 (2)	O2—C11	1.255 (2)
C5—H5A	0.9700	C6—C12	1.383 (2)
C5—H5B	0.9700	C6—C14	1.384 (2)
C7—C5ⁱ	1.514 (2)	C6—C11	1.506 (2)
C7—H7A	0.9598	C12—C14ⁱⁱ	1.379 (2)
C8—C10	1.514 (2)	C12—H12A	0.9300
C8—H8A	0.9700	C14—C12ⁱⁱ	1.379 (2)
C8—H8B	0.9700	C14—H14A	0.9300

C8—N1—C9	111.26 (13)	C13—C9—H9A	109.6
C8—N1—H1N1	109.4	N1—C9—H9B	109.6
C9—N1—H1N1	109.4	C13—C9—H9B	109.6
C8—N1—H2N1	109.4	H9A—C9—H9B	108.1
C9—N1—H2N1	109.4	C8—C10—C4	113.16 (14)
H1N1—N1—H2N1	108.0	C8—C10—H10A	108.9
C13—C4—C5	109.83 (14)	C4—C10—H10A	108.9
C13—C4—C10	109.95 (14)	C8—C10—H10B	108.9
C5—C4—C10	111.61 (14)	C4—C10—H10B	108.9
C13—C4—H4A	108.5	H10A—C10—H10B	107.8
C5—C4—H4A	108.5	C9—C13—C4	113.86 (15)
C10—C4—H4A	108.5	C9—C13—H13A	108.8
C7—C5—C4	116.86 (15)	C4—C13—H13A	108.8
C7—C5—H5A	108.1	C9—C13—H13B	108.8
C4—C5—H5A	108.1	C4—C13—H13B	108.8
C7—C5—H5B	108.1	H13A—C13—H13B	107.7
C4—C5—H5B	108.1	C12—C6—C14	118.11 (16)
H5A—C5—H5B	107.3	C12—C6—C11	121.05 (17)
C5ⁱ—C7—C5	111.4 (2)	C14—C6—C11	120.80 (17)
C5ⁱ—C7—H7A	109.3	O2—C11—O1	124.56 (18)
C5—C7—H7A	109.3	O2—C11—C6	117.75 (18)
N1—C8—C10	109.74 (15)	O1—C11—C6	117.67 (18)
N1—C8—H8A	109.7	C14ⁱⁱ—C12—C6	120.88 (17)
C10—C8—H8A	109.7	C14ⁱⁱ—C12—H12A	119.6
N1—C8—H8B	109.7	C6—C12—H12A	119.6
C10—C8—H8B	109.7	C12ⁱⁱ—C14—C6	121.00 (17)
H8A—C8—H8B	108.2	C12ⁱⁱ—C14—H14A	119.5
N1—C9—C13	110.28 (14)	C6—C14—H14A	119.5
N1—C9—H9A	109.6

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱⁱⁱ	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: (iii) −x−1/2, −y+1/2, −z−1.

Experimental details

Crystal data
Chemical formula	C₁₃H₂₈N₂²⁺·C₈H₄O₄²⁻
M_r	376.49
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	20.2902 (18), 8.4534 (8), 11.8815 (9)
β (°)	108.610 (3)
V (Å³)	1931.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.978, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	9090, 2286, 1073
R_int	0.114
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.095, 0.82
No. of reflections	2286
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.90	1.91	2.7958 (19)	168.9
N1—H2N1···O2	0.90	1.82	2.7213 (18)	174.2
N1—H2N1···O1	0.90	2.61	3.1528 (19)	119.8

Symmetry code: (i) −x−1/2, −y+1/2, −z−1.

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

Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar