Piperazine-1,4-diium bis­(3,5-dicarboxy­benzoate)

Dong, G.-Y.; Fan, L.-H.; Yang, L.-X.; Khan, I.U.

doi:10.1107/S1600536810013140

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1097

https://doi.org/10.1107/S1600536810013140

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Piperazine-1,4-diium bis(3,5-dicarboxybenzoate)

Gui-Ying Dong,^a Li-Hua Fan,^a Li-Xia Yang ^a and Islam Ullah Khan ^b ^*

^aCollege of Chemical Engineering and Biotechnology, Hebei Polytechnic University, Tangshan 063009, People's Republic of China, and ^bMaterials Chemistry Laboratory, Department of Chemistry, Government College University, Lahore 54000, Pakistan
^*Correspondence e-mail: iukhangcu@126.com

(Received 5 April 2010; accepted 9 April 2010; online 17 April 2010)

The asymmetric unit of the title salt, C₄H₁₂N₂²⁺·2C₉H₅O₆⁻, comprises one half of the piperazine-1,4-diium dication lying on an inversion centre and one 3,5-dicarboxybenzoate anion. In the crystal, the ions are linked into a two-dimensional framework parallel to (101) by N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For related structures, see: Divya et al. (2003 ); Sharma & Zaworotko et al. (1996 ).

Experimental

Crystal data

C₄H₁₂N₂²⁺·2C₉H₅O₆⁻
M_r = 506.42
Triclinic, $[P \overline 1]$
a = 7.3029 (15) Å
b = 8.6758 (17) Å
c = 9.0422 (18) Å
α = 87.04 (3)°
β = 69.94 (3)°
γ = 83.76 (3)°
V = 534.9 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 295 K
0.22 × 0.21 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.968, T_max = 0.971
5586 measured reflections
2443 independent reflections
1563 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.219
S = 1.00
2443 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.90	1.85	2.725 (4)	165
N1—H1B⋯O6ⁱⁱ	0.90	1.92	2.751 (4)	153
O2—H2⋯O4ⁱⁱⁱ	0.82	1.87	2.612 (4)	149
O5—H5⋯O3^iv	0.82	1.79	2.584 (4)	164
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z; (iii) x, y+1, z; (iv) x-1, y, z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810013140/ci5078sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810013140/ci5078Isup2.hkl

checkCIF report

Comment top

1,3,5-Benzenetricarboxylic acid is an important building block in crystal engineering due to its predictable honeycomb formation in the crystal lattice. It has six potential donor sites in the three carboxylic acid group, and it can form mono-, di- and trianionic ligand species through deprotonation. The adduct of 4,4'-bipyridyl with trimesic acid (1,3,5-benzenetricarboxylic acid) is of 2:3 stoichiometry and it forms a two-dimensional network (Sharma & Zaworotko, 1996). We report here the crystal structure of the title compound, (I).

The asymmetric unit of the compound (I) comprises one-half of a piperazine-1,4-diium cation which lies on an inversion centre and one 3,5-dicarboxy benzoate anion (Fig. 1). Bond distances and angles in (I) are normal (Divya et al., 2003).

In the crystal structure, the cations and anions are interlinked by N—H···O and O—H···O hydrogen bonds (Table 1) producing a two-dimensional hydrogen-bonded framework structure parallel to the (101) [Fig. 2].

Related literature top

For related structures, see: Divya et al. (2003); Sharma & Zaworotko et al. (1996).

Experimental top

1,3,5-Benzenetricarboxylic acid (1.06 g, 5 mmol) and piperazine (0.43 g, 5 mmol) were dissolved in warm water (30 ml). Single crystals of the title compound were obtained by slow evaporation of this solution.

Structure description top

For related structures, see: Divya et al. (2003); Sharma & Zaworotko et al. (1996).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, showing the atomic numbering and 30% probability displacement ellipsoids. Atoms labelled with the suffix A are generated by the symmetry operation (1-x, 1-y, 1-z).
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines

Piperazine-1,4-diium bis(3,5-dicarboxybenzoate) top

Crystal data top

C₄H₁₂N₂²⁺·2C₉H₅O₆⁻	Z = 1
M_r = 506.42	F(000) = 264
Triclinic, P1	D_x = 1.572 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3029 (15) Å	Cell parameters from 2886 reflections
b = 8.6758 (17) Å	θ = 4.1–23.7°
c = 9.0422 (18) Å	µ = 0.13 mm⁻¹
α = 87.04 (3)°	T = 295 K
β = 69.94 (3)°	Prism, colourless
γ = 83.76 (3)°	0.22 × 0.21 × 0.20 mm
V = 534.9 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2443 independent reflections
Radiation source: fine-focus sealed tube	1563 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
φ and ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.968, T_max = 0.971	k = −11→11
5586 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.219	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1021P)² + 0.7768P] where P = (F_o² + 2F_c²)/3
2443 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₄H₁₂N₂²⁺·2C₉H₅O₆⁻	γ = 83.76 (3)°
M_r = 506.42	V = 534.9 (2) Å³
Triclinic, P1	Z = 1
a = 7.3029 (15) Å	Mo Kα radiation
b = 8.6758 (17) Å	µ = 0.13 mm⁻¹
c = 9.0422 (18) Å	T = 295 K
α = 87.04 (3)°	0.22 × 0.21 × 0.20 mm
β = 69.94 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2443 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1563 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.971	R_int = 0.048
5586 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.219	H-atom parameters constrained
S = 1.00	Δρ_max = 0.35 e Å⁻³
2443 reflections	Δρ_min = −0.22 e Å⁻³
165 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
O3	0.5054 (4)	−0.0789 (3)	−0.2891 (3)	0.0327 (7)
O4	0.3840 (4)	−0.2898 (3)	−0.1607 (3)	0.0351 (7)
O5	−0.2059 (4)	0.0124 (3)	0.4770 (3)	0.0299 (6)
H5	−0.2853	−0.0331	0.5479	0.045*
O6	−0.0820 (4)	−0.2283 (3)	0.3989 (3)	0.0401 (8)
C6	0.0627 (5)	0.1419 (4)	0.2228 (4)	0.0244 (8)
H6	−0.0104	0.2046	0.3073	0.029*
O2	0.3069 (5)	0.4294 (3)	−0.0579 (3)	0.0507 (9)
H2	0.3110	0.5232	−0.0547	0.076*
C2	0.2932 (5)	0.1130 (4)	−0.0401 (4)	0.0213 (7)
H2A	0.3740	0.1567	−0.1322	0.026*
C3	0.2797 (5)	−0.0471 (4)	−0.0306 (4)	0.0200 (7)
C5	0.0477 (5)	−0.0166 (4)	0.2327 (4)	0.0220 (7)
C1	0.1875 (5)	0.2071 (4)	0.0863 (4)	0.0238 (8)
C4	0.1576 (5)	−0.1116 (4)	0.1067 (4)	0.0231 (8)
H4	0.1490	−0.2181	0.1146	0.028*
C8	0.3998 (5)	−0.1456 (4)	−0.1710 (4)	0.0221 (7)
O1	0.1355 (6)	0.4589 (3)	0.1961 (4)	0.0588 (10)
C9	−0.0858 (5)	−0.0890 (4)	0.3773 (4)	0.0243 (8)
C7	0.2045 (6)	0.3776 (4)	0.0825 (4)	0.0324 (9)
N1	0.6111 (5)	0.5988 (3)	0.5510 (3)	0.0294 (7)
H1A	0.5332	0.6181	0.6509	0.035*
H1B	0.7184	0.6495	0.5311	0.035*
C11	0.5066 (7)	0.6562 (4)	0.4430 (5)	0.0375 (10)
H11A	0.5946	0.6439	0.3352	0.045*
H11B	0.4656	0.7659	0.4602	0.045*
C10	0.3299 (6)	0.5704 (4)	0.4671 (5)	0.0385 (10)
H10A	0.2357	0.5906	0.5716	0.046*
H10B	0.2682	0.6068	0.3907	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0350 (14)	0.0304 (14)	0.0214 (13)	−0.0079 (11)	0.0066 (11)	−0.0010 (10)
O4	0.0490 (17)	0.0175 (13)	0.0256 (14)	−0.0037 (12)	0.0047 (12)	−0.0024 (10)
O5	0.0265 (14)	0.0288 (14)	0.0223 (13)	−0.0038 (11)	0.0074 (10)	0.0010 (10)
O6	0.0459 (17)	0.0261 (14)	0.0318 (15)	−0.0108 (12)	0.0099 (13)	0.0006 (11)
C6	0.0257 (18)	0.0196 (16)	0.0219 (17)	−0.0002 (14)	−0.0002 (14)	−0.0049 (13)
O2	0.085 (2)	0.0214 (14)	0.0282 (15)	−0.0164 (15)	0.0054 (15)	0.0018 (11)
C2	0.0253 (18)	0.0196 (16)	0.0157 (15)	−0.0037 (14)	−0.0025 (13)	0.0021 (13)
C3	0.0183 (16)	0.0200 (16)	0.0189 (16)	−0.0021 (13)	−0.0027 (13)	−0.0005 (12)
C5	0.0229 (17)	0.0230 (17)	0.0162 (16)	−0.0035 (14)	−0.0015 (13)	0.0003 (13)
C1	0.0280 (18)	0.0199 (17)	0.0224 (17)	−0.0043 (14)	−0.0064 (14)	0.0000 (13)
C4	0.0268 (18)	0.0203 (16)	0.0207 (17)	−0.0048 (14)	−0.0052 (14)	−0.0014 (13)
C8	0.0220 (17)	0.0220 (17)	0.0198 (16)	−0.0035 (14)	−0.0034 (14)	−0.0008 (13)
O1	0.091 (3)	0.0257 (15)	0.0370 (17)	−0.0137 (16)	0.0105 (17)	−0.0093 (13)
C9	0.0232 (17)	0.0249 (18)	0.0208 (17)	−0.0078 (15)	−0.0010 (14)	0.0005 (14)
C7	0.041 (2)	0.0224 (18)	0.0285 (19)	−0.0098 (17)	−0.0025 (17)	0.0000 (15)
N1	0.0306 (17)	0.0261 (16)	0.0255 (16)	−0.0069 (13)	0.0001 (13)	−0.0063 (13)
C11	0.058 (3)	0.0202 (18)	0.033 (2)	−0.0037 (18)	−0.0124 (19)	−0.0006 (15)
C10	0.038 (2)	0.033 (2)	0.044 (2)	0.0074 (18)	−0.0150 (19)	−0.0115 (18)

Geometric parameters (Å, º) top

O3—C8	1.240 (4)	C5—C4	1.396 (5)
O4—C8	1.265 (4)	C5—C9	1.493 (4)
O5—C9	1.314 (4)	C1—C7	1.496 (5)
O5—H5	0.82	C4—H4	0.93
O6—C9	1.213 (4)	O1—C7	1.204 (5)
C6—C5	1.387 (5)	N1—C11	1.471 (5)
C6—C1	1.394 (5)	N1—C10ⁱ	1.485 (5)
C6—H6	0.93	N1—H1A	0.90
O2—C7	1.318 (4)	N1—H1B	0.90
O2—H2	0.8200	C11—C10	1.505 (6)
C2—C1	1.387 (5)	C11—H11A	0.97
C2—C3	1.399 (4)	C11—H11B	0.97
C2—H2A	0.93	C10—N1ⁱ	1.485 (5)
C3—C4	1.388 (5)	C10—H10A	0.97
C3—C8	1.516 (5)	C10—H10B	0.97

C9—O5—H5	109.5	O6—C9—C5	122.5 (3)
C5—C6—C1	120.0 (3)	O5—C9—C5	113.5 (3)
C5—C6—H6	120.0	O1—C7—O2	123.3 (3)
C1—C6—H6	120.0	O1—C7—C1	123.8 (3)
C7—O2—H2	109.5	O2—C7—C1	112.9 (3)
C1—C2—C3	120.7 (3)	C11—N1—C10ⁱ	111.1 (3)
C1—C2—H2A	119.6	C11—N1—H1A	109.4
C3—C2—H2A	119.6	C10ⁱ—N1—H1A	109.4
C4—C3—C2	119.4 (3)	C11—N1—H1B	109.4
C4—C3—C8	121.7 (3)	C10ⁱ—N1—H1B	109.4
C2—C3—C8	118.9 (3)	H1A—N1—H1B	108.0
C6—C5—C4	120.3 (3)	N1—C11—C10	111.5 (3)
C6—C5—C9	121.0 (3)	N1—C11—H11A	109.3
C4—C5—C9	118.7 (3)	C10—C11—H11A	109.3
C2—C1—C6	119.6 (3)	N1—C11—H11B	109.3
C2—C1—C7	122.1 (3)	C10—C11—H11B	109.3
C6—C1—C7	118.3 (3)	H11A—C11—H11B	108.0
C3—C4—C5	119.9 (3)	N1ⁱ—C10—C11	110.1 (3)
C3—C4—H4	120.0	N1ⁱ—C10—H10A	109.6
C5—C4—H4	120.0	C11—C10—H10A	109.6
O3—C8—O4	124.4 (3)	N1ⁱ—C10—H10B	109.6
O3—C8—C3	117.7 (3)	C11—C10—H10B	109.6
O4—C8—C3	117.9 (3)	H10A—C10—H10B	108.2
O6—C9—O5	124.0 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱⁱ	0.90	1.85	2.725 (4)	165
N1—H1B···O6ⁱⁱⁱ	0.90	1.92	2.751 (4)	153
O2—H2···O4^iv	0.82	1.87	2.612 (4)	149
O5—H5···O3^v	0.82	1.79	2.584 (4)	164

Symmetry codes: (ii) x, y+1, z+1; (iii) x+1, y+1, z; (iv) x, y+1, z; (v) x−1, y, z+1.

Experimental details

Crystal data
Chemical formula	C₄H₁₂N₂²⁺·2C₉H₅O₆⁻
M_r	506.42
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	7.3029 (15), 8.6758 (17), 9.0422 (18)
α, β, γ (°)	87.04 (3), 69.94 (3), 83.76 (3)
V (Å³)	534.9 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.22 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.968, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	5586, 2443, 1563
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.219, 1.00
No. of reflections	2443
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.22

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.90	1.85	2.725 (4)	165
N1—H1B···O6ⁱⁱ	0.90	1.92	2.751 (4)	153
O2—H2···O4ⁱⁱⁱ	0.82	1.87	2.612 (4)	149
O5—H5···O3^iv	0.82	1.79	2.584 (4)	164

Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z; (iii) x, y+1, z; (iv) x−1, y, z+1.

Acknowledgements

The authors thank Hebei Polytechnic University and Government College University for support this work.

References

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