Piperazine-1,4-diium bis-(2,4,5-tricarb-oxy-benzoate) dihydrate.

In the title hydrated salt, C4H12N2 (2+)·2C10H5O8 (-)·2H2O, the piperazinediium cation, lying about an inversion center, adopts a chair conformation. The benzene ring of the anion makes dihedral angles of 25.17 (8)° with the carboxyl-ate group and angles of 8.50 (7), 20.07 (7) and 80.86 (8)° with the three carb-oxy-lic acid groups. In the crystal, the cations, anions and water mol-ecules are connected by O-H⋯O and N-H⋯O hydrogen bonds into double layers parallel to (110).

Related literature

For supra­molecular architectures involving benzene-1,2,4,5-tetra­carb­oxy­lic acid and its anions, see: Aghabozorg et al. (2006 ▶, 2008 ▶); Chiwei et al. (2005 ▶); Pasban et al. (2012 ▶); Pasdar et al. (2010 ▶); Smith et al. (2008 ▶); Smith & Wermuth (2010 ▶); Vaidhyanathan et al. (2002 ▶). For proton-transfer systems, see: Aghabozorg et al. (2010 ▶). For inter­molecular inter­actions, see: Janiak (2000 ▶).

Experimental

Crystal data

C4H12N2 2+·2C10H5O8 −·2H2O

M = 630.46

Triclinic,

a = 8.2521 (2) Å

b = 8.4810 (2) Å

c = 9.6369 (2) Å

α = 87.117 (5)°

β = 89.527 (5)°

γ = 70.962 (4)°

V = 636.73 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.14 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.945, T max = 0.985

11108 measured reflections

2234 independent reflections

2061 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.085

S = 1.06

2234 reflections

224 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and DIAMOND (Brandenburg, 2007 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681300723X/yk2086sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300723X/yk2086Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681300723X/yk2086Isup3.cml

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

C4H12N22+·2C10H5O8−·2H2O	Z = 1
Mr = 630.46	F(000) = 328
Triclinic, P1	Dx = 1.644 Mg m−3
Hall symbol: -P 1	Melting point: 560 K
a = 8.2521 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.4810 (2) Å	Cell parameters from 7490 reflections
c = 9.6369 (2) Å	θ = 2.5–33.0°
α = 87.117 (5)°	µ = 0.14 mm−1
β = 89.527 (5)°	T = 293 K
γ = 70.962 (4)°	Block, colourless
V = 636.73 (3) Å3	0.30 × 0.20 × 0.20 mm

Bruker Kappa APEXII CCD diffractometer	2234 independent reflections
Radiation source: fine-focus sealed tube	2061 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω and φ scan	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
Tmin = 0.945, Tmax = 0.985	k = −9→10
11108 measured reflections	l = −11→11

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)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.085	w = 1/[σ2(Fo2) + (0.0431P)2 + 0.2345P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2234 reflections	Δρmax = 0.21 e Å−3
224 parameters	Δρmin = −0.20 e Å−3
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.075 (5)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

	x	y	z	Uiso*/Ueq
C1	0.06597 (16)	0.70913 (15)	0.05612 (13)	0.0202 (3)
C2	0.08629 (16)	0.66166 (16)	−0.08067 (13)	0.0219 (3)
H2	0.0098	0.7264	−0.1480	0.026*
C3	0.21641 (16)	0.52142 (16)	−0.12023 (13)	0.0196 (3)
C4	0.32899 (16)	0.42177 (15)	−0.01920 (13)	0.0198 (3)
C5	0.30804 (16)	0.46709 (16)	0.11737 (13)	0.0212 (3)
H5	0.3824	0.3995	0.1846	0.025*
C6	0.18074 (16)	0.60918 (16)	0.15847 (13)	0.0200 (3)
C7	0.22375 (16)	0.47981 (16)	−0.27035 (13)	0.0217 (3)
C8	0.47247 (16)	0.27185 (16)	−0.05880 (13)	0.0217 (3)
C9	0.18506 (17)	0.63946 (17)	0.31156 (14)	0.0241 (3)
C10	−0.08355 (17)	0.86608 (16)	0.07812 (14)	0.0244 (3)
C11	0.5751 (2)	0.1289 (2)	0.4758 (2)	0.0448 (4)
H11A	0.6750	0.1621	0.4555	0.054*
H11B	0.4771	0.2293	0.4836	0.054*
C12	0.5451 (2)	0.0307 (2)	0.36090 (17)	0.0436 (4)
N1	0.60207 (17)	0.02802 (17)	0.60844 (14)	0.0371 (3)
O1	−0.08934 (13)	0.95103 (12)	0.18574 (11)	0.0337 (3)
H1	−0.0039	0.9062	0.2342	0.051*
O2	−0.19676 (13)	0.91343 (13)	−0.01098 (11)	0.0368 (3)
O3	0.29608 (14)	0.56784 (13)	−0.34862 (10)	0.0327 (3)
H3	0.2974	0.5411	−0.4293	0.049*
O4	0.16086 (14)	0.38163 (14)	−0.31255 (10)	0.0348 (3)
O5	0.50699 (13)	0.24168 (13)	−0.17891 (10)	0.0337 (3)
O6	0.55721 (13)	0.18159 (13)	0.04674 (10)	0.0373 (3)
H6	0.6341	0.1014	0.0187	0.056*
O7	0.25414 (14)	0.51726 (13)	0.39115 (10)	0.0359 (3)
O8	0.12443 (14)	0.78708 (13)	0.35313 (10)	0.0339 (3)
O9	0.10687 (16)	0.23958 (16)	0.41278 (14)	0.0453 (3)
H12B	0.646 (3)	−0.068 (3)	0.352 (2)	0.051 (5)*
H12A	0.518 (3)	0.099 (3)	0.276 (2)	0.061 (6)*
H1A	0.700 (2)	−0.060 (2)	0.605 (2)	0.046 (5)*
H1B	0.615 (3)	0.092 (3)	0.677 (2)	0.064 (6)*
H9A	0.043 (3)	0.224 (4)	0.479 (2)	0.097 (10)*
H9B	0.135 (4)	0.323 (3)	0.421 (3)	0.106 (11)*

	U11	U22	U33	U12	U13	U23
C1	0.0199 (6)	0.0181 (6)	0.0217 (7)	−0.0048 (5)	0.0028 (5)	−0.0015 (5)
C2	0.0211 (6)	0.0216 (6)	0.0193 (6)	−0.0023 (5)	−0.0020 (5)	0.0016 (5)
C3	0.0203 (6)	0.0203 (6)	0.0177 (6)	−0.0061 (5)	0.0017 (5)	−0.0012 (5)
C4	0.0192 (6)	0.0200 (6)	0.0188 (6)	−0.0042 (5)	0.0012 (5)	−0.0016 (5)
C5	0.0216 (6)	0.0216 (6)	0.0172 (6)	−0.0029 (5)	−0.0011 (5)	0.0006 (5)
C6	0.0209 (6)	0.0211 (6)	0.0175 (6)	−0.0062 (5)	0.0021 (5)	−0.0021 (5)
C7	0.0194 (6)	0.0222 (7)	0.0192 (6)	−0.0010 (5)	−0.0010 (5)	−0.0009 (5)
C8	0.0211 (6)	0.0216 (7)	0.0204 (7)	−0.0039 (5)	−0.0003 (5)	−0.0029 (5)
C9	0.0229 (7)	0.0286 (7)	0.0200 (7)	−0.0067 (5)	0.0033 (5)	−0.0047 (5)
C10	0.0233 (7)	0.0205 (7)	0.0262 (7)	−0.0030 (5)	0.0047 (6)	−0.0002 (5)
C11	0.0417 (9)	0.0311 (8)	0.0642 (12)	−0.0163 (7)	−0.0010 (8)	0.0049 (8)
C12	0.0459 (10)	0.0509 (10)	0.0267 (8)	−0.0069 (8)	0.0089 (7)	0.0058 (7)
N1	0.0346 (7)	0.0356 (7)	0.0356 (7)	−0.0016 (6)	−0.0049 (6)	−0.0169 (6)
O1	0.0353 (6)	0.0245 (5)	0.0334 (6)	0.0025 (4)	0.0003 (4)	−0.0098 (4)
O2	0.0298 (6)	0.0326 (6)	0.0350 (6)	0.0084 (4)	−0.0040 (5)	−0.0059 (5)
O3	0.0481 (6)	0.0378 (6)	0.0168 (5)	−0.0202 (5)	0.0040 (4)	−0.0023 (4)
O4	0.0428 (6)	0.0422 (6)	0.0262 (5)	−0.0221 (5)	0.0022 (4)	−0.0100 (4)
O5	0.0354 (6)	0.0339 (6)	0.0210 (5)	0.0042 (4)	0.0023 (4)	−0.0086 (4)
O6	0.0347 (6)	0.0350 (6)	0.0230 (5)	0.0147 (4)	−0.0001 (4)	−0.0012 (4)
O7	0.0478 (7)	0.0342 (6)	0.0168 (5)	−0.0008 (5)	−0.0016 (4)	−0.0016 (4)
O8	0.0418 (6)	0.0303 (6)	0.0258 (5)	−0.0049 (5)	−0.0001 (4)	−0.0127 (4)
O9	0.0401 (7)	0.0411 (7)	0.0463 (8)	−0.0006 (6)	−0.0027 (6)	−0.0112 (6)

C1—C2	1.3906 (18)	C10—O2	1.2269 (17)
C1—C6	1.4127 (18)	C10—O1	1.2841 (17)
C1—C10	1.5138 (17)	C11—N1	1.479 (2)
C2—C3	1.3851 (18)	C11—C12	1.487 (3)
C2—H2	0.9300	C11—H11A	0.9700
C3—C4	1.3947 (18)	C11—H11B	0.9700
C3—C7	1.5024 (17)	C12—N1i	1.478 (2)
C4—C5	1.3833 (18)	C12—H12B	0.98 (2)
C4—C8	1.4911 (17)	C12—H12A	0.96 (2)
C5—C6	1.3885 (18)	N1—C12i	1.478 (2)
C5—H5	0.9300	N1—H1A	0.904 (15)
C6—C9	1.5129 (18)	N1—H1B	0.901 (16)
C7—O4	1.2031 (17)	O1—H1	0.8200
C7—O3	1.3074 (16)	O3—H3	0.8200
C8—O5	1.2096 (16)	O6—H6	0.8200
C8—O6	1.3014 (16)	O9—H9A	0.858 (17)
C9—O7	1.2367 (17)	O9—H9B	0.824 (18)
C9—O8	1.2715 (17)
C2—C1—C6	118.71 (11)	O8—C9—C6	119.92 (12)
C2—C1—C10	114.30 (11)	O2—C10—O1	120.53 (12)
C6—C1—C10	126.99 (12)	O2—C10—C1	118.69 (12)
C3—C2—C1	122.32 (12)	O1—C10—C1	120.74 (12)
C3—C2—H2	118.8	N1—C11—C12	110.21 (13)
C1—C2—H2	118.8	N1—C11—H11A	109.6
C2—C3—C4	119.08 (12)	C12—C11—H11A	109.6
C2—C3—C7	117.76 (11)	N1—C11—H11B	109.6
C4—C3—C7	123.09 (11)	C12—C11—H11B	109.6
C5—C4—C3	118.88 (11)	H11A—C11—H11B	108.1
C5—C4—C8	120.72 (11)	N1i—C12—C11	110.90 (13)
C3—C4—C8	120.38 (11)	N1i—C12—H12B	107.1 (11)
C4—C5—C6	122.85 (12)	C11—C12—H12B	109.1 (12)
C4—C5—H5	118.6	N1i—C12—H12A	106.8 (12)
C6—C5—H5	118.6	C11—C12—H12A	110.4 (13)
C5—C6—C1	118.16 (11)	H12B—C12—H12A	112.5 (17)
C5—C6—C9	114.29 (11)	C12i—N1—C11	110.89 (13)
C1—C6—C9	127.54 (11)	C12i—N1—H1A	110.4 (12)
O4—C7—O3	124.71 (12)	C11—N1—H1A	110.1 (12)
O4—C7—C3	122.38 (12)	C12i—N1—H1B	109.9 (14)
O3—C7—C3	112.81 (11)	C11—N1—H1B	108.3 (14)
O5—C8—O6	124.18 (12)	H1A—N1—H1B	107.1 (19)
O5—C8—C4	121.94 (12)	C10—O1—H1	109.5
O6—C8—C4	113.86 (11)	C7—O3—H3	109.5
O7—C9—O8	122.61 (12)	C8—O6—H6	109.5
O7—C9—C6	117.42 (11)	H9A—O9—H9B	112 (3)
C6—C1—C2—C3	−0.96 (19)	C4—C3—C7—O4	81.46 (17)
C10—C1—C2—C3	179.89 (12)	C2—C3—C7—O3	80.87 (15)
C1—C2—C3—C4	1.5 (2)	C4—C3—C7—O3	−102.12 (14)
C1—C2—C3—C7	178.63 (12)	C5—C4—C8—O5	−170.29 (13)
C2—C3—C4—C5	−0.59 (19)	C3—C4—C8—O5	7.9 (2)
C7—C3—C4—C5	−177.56 (12)	C5—C4—C8—O6	8.07 (18)
C2—C3—C4—C8	−178.79 (11)	C3—C4—C8—O6	−173.75 (12)
C7—C3—C4—C8	4.23 (19)	C5—C6—C9—O7	−24.00 (18)
C3—C4—C5—C6	−0.9 (2)	C1—C6—C9—O7	157.18 (13)
C8—C4—C5—C6	177.35 (12)	C5—C6—C9—O8	153.59 (13)
C4—C5—C6—C1	1.4 (2)	C1—C6—C9—O8	−25.2 (2)
C4—C5—C6—C9	−177.56 (12)	C2—C1—C10—O2	18.28 (18)
C2—C1—C6—C5	−0.46 (18)	C6—C1—C10—O2	−160.79 (13)
C10—C1—C6—C5	178.57 (12)	C2—C1—C10—O1	−159.58 (12)
C2—C1—C6—C9	178.31 (12)	C6—C1—C10—O1	21.4 (2)
C10—C1—C6—C9	−2.7 (2)	N1—C11—C12—N1i	56.82 (19)
C2—C3—C7—O4	−95.55 (16)	C12—C11—N1—C12i	−56.81 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O8	0.82	1.63	2.4225 (15)	161
O3—H3···O7ii	0.82	1.80	2.6100 (13)	167
O6—H6···O2iii	0.82	1.78	2.5884 (13)	170
N1—H1A···O9i	0.90 (2)	1.83 (2)	2.7283 (17)	176 (2)
N1—H1B···O5iv	0.90 (2)	1.94 (2)	2.7420 (16)	147 (2)
O9—H9A···O8v	0.86 (2)	2.14 (2)	2.9904 (18)	174 (3)
O9—H9B···O7	0.82 (2)	2.18 (2)	2.9799 (19)	163 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O8	0.82	1.63	2.4225 (15)	161
O3—H3⋯O7i	0.82	1.80	2.6100 (13)	167
O6—H6⋯O2ii	0.82	1.78	2.5884 (13)	170
N1—H1A⋯O9iii	0.90 (2)	1.83 (2)	2.7283 (17)	176 (2)
N1—H1B⋯O5iv	0.90 (2)	1.94 (2)	2.7420 (16)	147 (2)
O9—H9A⋯O8v	0.86 (2)	2.14 (2)	2.9904 (18)	174 (3)
O9—H9B⋯O7	0.82 (2)	2.18 (2)	2.9799 (19)	163 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .