Piperazine-1,4-diium bis­(3-carb­oxy-2,3-di­hydroxy­propano­ate)

Asserar, F.; Guenoun, F.; Sekkat, C.; Labrim, H.; Marah, H.; Zouihri, H.; Yamni, K.

doi:10.1107/S2414314617002498

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170249

https://doi.org/10.1107/S2414314617002498

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Piperazine-1,4-diium bis(3-carboxy-2,3-dihydroxypropanoate)

Fatima Asserar,^a Farhate Guenoun,^a Chakib Sekkat,^a Hicham Labrim,^b Hamid Marah,^b Hafid Zouihri ^c and Khalid Yamni ^c ^*

^aEquipe de Chimie Moléculaire et Molécules Bioactifs, Département de Chimie, Faculté des Sciences, Université Moulay Ismail, Meknès, Morocco, ^bCentre National de l'Energie, des Sciences et des Techniques Nucléaires, (CNESTEN), Rabat, Morocco, and ^cLaboratoire de Chimie des Matériaux et Biotechnologie des Produits Naturels, E.Ma.Me.P.S, Université Moulay Ismail, Faculté des Sciences, Meknès, Morocco
^*Correspondence e-mail: kyamni@hotmail.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 6 February 2017; accepted 13 February 2017; online 17 February 2017)

The asymmetric unit of the title salt, C₄H₁₂N₂²⁺·2C₄H₅O₆⁻, comprises one half of the piperazine-1,4-diium dication lying on a twofold rotation axis and one 3-carboxy-2,3-dihydroxypropanoate anion. In the crystal, the ions are linked into a three-dimensional network by N—H⋯O, C—H⋯O and O—H⋯O hydrogen bonds.

Keywords: crystal structure; organic salt; hydrogen bonds; three-dimensional network.

CCDC reference: 1532469

Structure description

The asymmetric unit of the title compound comprises one-half of a piperazine-1,4-diium cation, which lies on a twofold rotation axis, and one 3-carboxy-2,3-dihydroxypropanoate anion (Fig. 1). The N—C and C—C bond lengths of this cation are comparable with the values observed in related piperazine-1,4-diium adducts or co-crystals piperazine-1, 4-diium bis(2,4,5-tricarboxybenzoate) dihydrate (Narayanam et al., 2013 ), piperazine-1,4-diium bis(3,5-dicarboxybenzoate) (Dong et al., 2010 ) and piperazine-1,4-diium 2-(carboxymethyl)-2-hydroxybutanedioate monohydrate (Liu et al., 2010 ). In addition, the C—C, C—O and C=O bond lengths of the dihydroxypropanoate anion are similar to those in the related compounds 2-amino-4-methylpyridin-1-ium (2R,3R)-3-carboxy-2,3-dihydroxypropanoate monohydrate (Jovita et al., 2014 ), (R)-doxylaminium (R,R)-tartrate (Dayananda et al., 2012 ) and 2-(1H-imidazol-2-yl)-1H-imidazol-3-ium 3-carboxy-2,3-dihydroxypropanoate hemihydrate (Gao et al., 2014 ).

Figure 1
The molecular structure of the title compound, showing the atomic numbering and 30% probability displacement ellipsoids. In the cation, the atoms labelled with the suffix a are generated by the twofold axis (symmetry operation y, x, 2 − z).

In the crystal, the cations and anions are linked by N—H⋯O, C—H⋯O and O—H⋯O hydrogen bonds (Table 1, Fig. 2), forming a three-dimensional network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.89	2.02	2.8118 (10)	147
N1—H1B⋯O5ⁱⁱ	0.89	1.98	2.8167 (10)	155
O3—H3A⋯O2	0.82	2.17	2.6525 (9)	118
O3—H3A⋯O4ⁱⁱⁱ	0.82	2.14	2.8581 (9)	146
O4—H4⋯O1ⁱⁱⁱ	0.82	1.94	2.7225 (9)	160
O6—H6⋯O2^iv	0.82	1.67	2.4810 (9)	172
C2—H2⋯O1^v	0.98	2.60	3.3740 (9)	136
C5—H5A⋯O6^vi	0.97	2.45	3.1555 (11)	129
C5—H5B⋯O5^vii	0.97	2.51	3.2553 (11)	133
C5—H5A⋯O6^vi	0.97	2.45	3.1555 (11)	129
Symmetry codes: (i) y+1, x, -z+1; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{5\over 4}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 4}}]$ ; (iv) x+1, y, z; (v) y, x, -z; (vi) x, y, z+1; (vii) $[y+{\script{1\over 2}}, -x+{\script{3\over 2}}, z+{\script{3\over 4}}]$ .

Figure 2
A partial packing diagram of the title compound. The O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds are shown as dotted lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Synthesis and crystallization

At room temperature, a solution of tartaric acid in acetone and propionic acid (as co-solvent), was gradually added with stirring to a solution of piperazine in acetone (in an equimolar ratio). After one day, the supernatant layer was separated and the residue was recrystallized by slow evaporation from a mixture of ethanol–water (1:1).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	0.5C₄H₁₂N₂²⁺·C₄H₅O₆⁻
M_r	193.16
Crystal system, space group	Tetragonal, P4₁2₁2
Temperature (K)	293
a, c (Å)	7.5446 (1), 27.6498 (5)
V (Å³)	1573.85 (5)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.15
Crystal size (mm)	0.26 × 0.23 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD detector
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.962, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	45806, 7781, 6025
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	1.058

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.117, 1.12
No. of reflections	7781
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.22
Absolute structure	Flack x determined using 2104 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013 )
Absolute structure parameter	−0.17 (14)
Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1532469

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002498/bt4039sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002498/bt4039Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617002498/bt4039Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Piperazine-1,4-diium bis(3-carboxy-2,3-dihydroxypropanoate) top

Crystal data top

0.5C₄H₁₂N₂²⁺·C₄H₅O₆⁻	D_x = 1.630 Mg m⁻³
M_r = 193.16	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₁2₁2	Cell parameters from 245 reflections
a = 7.5446 (1) Å	θ = 1.6–31°
c = 27.6498 (5) Å	µ = 0.15 mm⁻¹
V = 1573.85 (5) Å³	T = 293 K
Z = 8	Prism, colourless
F(000) = 816	0.26 × 0.23 × 0.15 mm

Data collection top

Bruker APEXII CCD detector diffractometer	7781 independent reflections
Radiation source: fine-focus sealed tube	6025 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and φ scans	θ_max = 48.8°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −14→14
T_min = 0.962, T_max = 0.978	k = −10→15
45806 measured reflections	l = −54→58

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0642P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.117	(Δ/σ)_max = 0.001
S = 1.12	Δρ_max = 0.37 e Å⁻³
7781 reflections	Δρ_min = −0.22 e Å⁻³
120 parameters	Absolute structure: Flack x determined using 2104 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.17 (14)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C3	0.46028 (9)	0.27973 (9)	0.10854 (2)	0.01701 (10)
H3	0.4637	0.4083	0.1035	0.020*
C2	0.36287 (8)	0.19808 (9)	0.06515 (2)	0.01647 (9)
H2	0.4216	0.2397	0.0357	0.020*
C4	0.65177 (9)	0.21412 (10)	0.10980 (2)	0.01791 (10)
O6	0.74013 (8)	0.24921 (10)	0.07049 (2)	0.02337 (11)
H6	0.8415	0.2113	0.0731	0.035*
O3	0.37612 (8)	0.01095 (8)	0.06619 (3)	0.02293 (11)
H3A	0.2772	−0.0321	0.0698	0.034*
O4	0.37208 (9)	0.24868 (9)	0.15256 (2)	0.02348 (11)
H4	0.3843	0.1445	0.1603	0.035*
C1	0.17119 (9)	0.26428 (10)	0.06395 (2)	0.01868 (10)
O1	0.14690 (9)	0.42374 (9)	0.05493 (2)	0.02666 (12)
O2	0.05315 (8)	0.14850 (10)	0.07153 (3)	0.03266 (15)
O5	0.71328 (10)	0.13485 (12)	0.14444 (2)	0.03238 (16)
N1	0.84578 (10)	0.57964 (12)	1.00611 (3)	0.02954 (15)
H1A	0.9225	0.5023	0.9937	0.035*
H1B	0.8509	0.5714	1.0382	0.035*
C5	0.66484 (13)	0.53461 (11)	0.98963 (3)	0.02630 (15)
H5A	0.6346	0.4156	1.0001	0.032*
H5B	0.6598	0.5380	0.9546	0.032*
C6	0.89681 (13)	0.76223 (15)	0.99109 (3)	0.03121 (18)
H6A	0.9043	0.7678	0.9561	0.037*
H6B	1.0126	0.7907	1.0042	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.0156 (2)	0.0172 (2)	0.0182 (2)	0.00126 (18)	0.00116 (17)	−0.00002 (18)
C2	0.0125 (2)	0.0185 (2)	0.0184 (2)	0.00121 (17)	0.00160 (17)	−0.00001 (17)
C4	0.0157 (2)	0.0196 (3)	0.0185 (2)	0.00035 (18)	−0.00220 (17)	0.00026 (18)
O6	0.01428 (19)	0.0316 (3)	0.0242 (2)	0.00292 (19)	0.00191 (16)	0.00567 (19)
O3	0.0161 (2)	0.0178 (2)	0.0349 (3)	0.00112 (16)	0.00423 (19)	−0.00378 (19)
O4	0.0273 (3)	0.0229 (2)	0.02022 (19)	0.0026 (2)	0.00757 (18)	−0.00030 (18)
C1	0.0138 (2)	0.0211 (3)	0.0212 (2)	0.00295 (18)	−0.00028 (17)	−0.0001 (2)
O1	0.0257 (3)	0.0220 (3)	0.0323 (3)	0.0067 (2)	−0.0034 (2)	0.0011 (2)
O2	0.0125 (2)	0.0270 (3)	0.0584 (5)	0.00103 (19)	0.0027 (2)	0.0043 (3)
O5	0.0265 (3)	0.0464 (4)	0.0243 (3)	0.0081 (3)	−0.0039 (2)	0.0110 (3)
N1	0.0238 (3)	0.0354 (4)	0.0293 (3)	0.0142 (3)	−0.0004 (2)	0.0020 (3)
C5	0.0335 (4)	0.0183 (3)	0.0270 (3)	0.0018 (3)	−0.0036 (3)	0.0019 (2)
C6	0.0218 (3)	0.0437 (5)	0.0281 (3)	−0.0046 (3)	0.0024 (3)	0.0014 (3)

Geometric parameters (Å, º) top

C3—O4	1.4068 (9)	C1—O1	1.2422 (10)
C3—C4	1.5276 (10)	C1—O2	1.2649 (10)
C3—C2	1.5359 (9)	N1—C5	1.4786 (13)
C3—H3	0.9800	N1—C6	1.4894 (15)
C2—O3	1.4157 (9)	N1—H1A	0.8900
C2—C1	1.5304 (9)	N1—H1B	0.8900
C2—H2	0.9800	C5—C5ⁱ	1.5032 (18)
C4—O5	1.2209 (9)	C5—H5A	0.9700
C4—O6	1.3022 (9)	C5—H5B	0.9700
O6—H6	0.8200	C6—C6ⁱ	1.518 (2)
O3—H3A	0.8200	C6—H6A	0.9700
O4—H4	0.8200	C6—H6B	0.9700

O4—C3—C4	111.94 (6)	O2—C1—C2	115.87 (7)
O4—C3—C2	112.50 (6)	C5—N1—C6	111.42 (7)
C4—C3—C2	109.90 (5)	C5—N1—H1A	109.3
O4—C3—H3	107.4	C6—N1—H1A	109.3
C4—C3—H3	107.4	C5—N1—H1B	109.3
C2—C3—H3	107.4	C6—N1—H1B	109.3
O3—C2—C1	113.12 (6)	H1A—N1—H1B	108.0
O3—C2—C3	110.51 (6)	N1—C5—C5ⁱ	109.62 (6)
C1—C2—C3	109.77 (5)	N1—C5—H5A	109.7
O3—C2—H2	107.7	C5ⁱ—C5—H5A	109.7
C1—C2—H2	107.7	N1—C5—H5B	109.7
C3—C2—H2	107.7	C5ⁱ—C5—H5B	109.7
O5—C4—O6	124.04 (7)	H5A—C5—H5B	108.2
O5—C4—C3	122.42 (7)	N1—C6—C6ⁱ	110.81 (6)
O6—C4—C3	113.53 (6)	N1—C6—H6A	109.5
C4—O6—H6	109.5	C6ⁱ—C6—H6A	109.5
C2—O3—H3A	109.5	N1—C6—H6B	109.5
C3—O4—H4	109.5	C6ⁱ—C6—H6B	109.5
O1—C1—O2	126.74 (7)	H6A—C6—H6B	108.1
O1—C1—C2	117.37 (7)

Symmetry code: (i) y, x, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱⁱ	0.89	2.02	2.8118 (10)	147
N1—H1B···O5ⁱⁱⁱ	0.89	1.98	2.8167 (10)	155
O3—H3A···O2	0.82	2.17	2.6525 (9)	118
O3—H3A···O4^iv	0.82	2.14	2.8581 (9)	146
O4—H4···O1^iv	0.82	1.94	2.7225 (9)	160
O6—H6···O2^v	0.82	1.67	2.4810 (9)	172
C2—H2···O1^vi	0.98	2.60	3.3740 (9)	136
C5—H5A···O6^vii	0.97	2.45	3.1555 (11)	129
C5—H5B···O5^viii	0.97	2.51	3.2553 (11)	133
C5—H5A···O6^vii	0.97	2.45	3.1555 (11)	129

Symmetry codes: (ii) y+1, x, −z+1; (iii) −x+3/2, y+1/2, −z+5/4; (iv) −x+1/2, y−1/2, −z+1/4; (v) x+1, y, z; (vi) y, x, −z; (vii) x, y, z+1; (viii) y+1/2, −x+3/2, z+3/4.

Acknowledgements

F. Asserar thanks the CNRST of Morocco for a doctoral Bursary.

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