Tetra-imidazolium piperazinediium bis-(benzene-1,3,5-tricarboxyl-ate) dihydrate.

During the crystallization of the title compound, 4C(3)H(5)N(2) (+)·C(4)H(12)N(2) (+)·2C(9)H(3)O(6) (3-)·2H(2)O, the acidic protons were transferred to the imidazole and piperazine N atoms, forming the final 4:1:2:2 hydrated mixed salt. The mean planes of the three carboxyl-ate groups in the anion are twisted with respect to the the central benzene ring, making dihedral angles of 13.5 (1), 14.5 (1) and 16.9 (1)°. In the crystal, the component ions are linked into a three-dimensional network by a combination of inter-molecular N-H⋯O, O-H⋯O and weak C-H⋯O hydrogen bonds. Further stabilization is provided by π-π stacking inter-actions with centroid-centroid distances of 3.393 (2) Å and weak C=O⋯π inter-actions [O-centroid = 3.363 (2) Å].

Related literature

For applications of multi-component piperazine compounds, see: Jacobs et al. (2009 ▶); Oswald et al. (2002 ▶); Wang & Jia (2008 ▶). For examples of compounds containing weak anion–π inter­actions, see: Schottel et al. (2008 ▶); Gao et al. (2009 ▶).

Experimental

Crystal data

4C3H5N2 +·C4H12N2 +·2C9H3O6 3−·2H2O

M = 814.78

Triclinic,

a = 7.1548 (4) Å

b = 9.9424 (5) Å

c = 13.3567 (7) Å

α = 96.895 (1)°

β = 95.201 (1)°

γ = 101.439 (2)°

V = 918.11 (8) Å3

Z = 1

Mo Kα radiation

μ = 0.12 mm−1

T = 298 K

0.20 × 0.13 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.967, T max = 0.989

10341 measured reflections

3925 independent reflections

2757 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.122

S = 1.04

3925 reflections

286 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810041310/lh5148sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041310/lh5148Isup2.hkl

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

4C3H5N2+·C4H12N2+·2C9H3O63−·2H2O	Z = 1
Mr = 814.78	F(000) = 428
Triclinic, P1	Dx = 1.474 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1548 (4) Å	Cell parameters from 2102 reflections
b = 9.9424 (5) Å	θ = 2.4–23.2°
c = 13.3567 (7) Å	µ = 0.12 mm−1
α = 96.895 (1)°	T = 298 K
β = 95.201 (1)°	Block, colorless
γ = 101.439 (2)°	0.20 × 0.13 × 0.10 mm
V = 918.11 (8) Å3

Bruker SMART APEX CCD area-detector diffractometer	3925 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2757 reflections with I > 2σ(I)
graphite	Rint = 0.029
0.3° wide ω scans	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
Tmin = 0.967, Tmax = 0.989	k = −11→12
10341 measured reflections	l = −17→17

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0631P)2 + 0.0369P] where P = (Fo2 + 2Fc2)/3
3925 reflections	(Δ/σ)max = 0.001
286 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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	0.2128 (2)	−0.05764 (17)	0.89657 (11)	0.0263 (4)
C2	0.1004 (2)	−0.17749 (17)	0.84080 (11)	0.0263 (4)
H2	0.0409	−0.2481	0.8743	0.032*
C3	0.0756 (2)	−0.19338 (17)	0.73487 (11)	0.0274 (4)
C4	0.1609 (2)	−0.08588 (18)	0.68651 (12)	0.0295 (4)
H4	0.1465	−0.0964	0.6159	0.035*
C5	0.2676 (2)	0.03761 (17)	0.74101 (12)	0.0267 (4)
C6	0.2947 (2)	0.04896 (17)	0.84640 (12)	0.0274 (4)
H6	0.3694	0.1297	0.8838	0.033*
C7	0.2458 (2)	−0.04026 (18)	1.01134 (12)	0.0297 (4)
C8	−0.0459 (2)	−0.32408 (19)	0.67241 (12)	0.0332 (4)
C9	0.3502 (2)	0.15651 (19)	0.68720 (13)	0.0310 (4)
C10	0.2728 (3)	−0.0067 (2)	1.32738 (13)	0.0391 (5)
H10	0.3430	0.0790	1.3175	0.047*
C11	0.1114 (3)	−0.2190 (2)	1.29964 (14)	0.0432 (5)
H11	0.0505	−0.3063	1.2661	0.052*
C12	0.1222 (3)	−0.1753 (2)	1.39965 (13)	0.0421 (5)
H12	0.0702	−0.2261	1.4484	0.051*
C13	0.2479 (3)	0.3752 (2)	0.99158 (14)	0.0401 (5)
H13	0.2379	0.2876	1.0111	0.048*
C14	0.2247 (3)	0.4896 (2)	1.04845 (14)	0.0396 (5)
H14	0.1949	0.4961	1.1150	0.048*
C15	0.2920 (3)	0.5449 (2)	0.90127 (14)	0.0400 (5)
H15	0.3176	0.5954	0.8480	0.048*
C16	0.3894 (3)	0.4987 (2)	0.58396 (13)	0.0422 (5)
H16A	0.3773	0.5318	0.6539	0.051*
H16B	0.2710	0.4341	0.5557	0.051*
C17	0.5803 (3)	0.3814 (2)	0.47501 (14)	0.0462 (5)
H17A	0.4688	0.3126	0.4428	0.055*
H17B	0.6910	0.3387	0.4747	0.055*
N1	0.2057 (2)	−0.11215 (17)	1.25638 (11)	0.0396 (4)
H1A	0.217 (3)	−0.111 (2)	1.1923 (16)	0.048*
N2	0.2245 (2)	−0.04171 (17)	1.41557 (11)	0.0389 (4)
H2A	0.265 (3)	0.014 (2)	1.4745 (16)	0.047*
N3	0.2891 (2)	0.41179 (16)	0.89917 (12)	0.0374 (4)
H3A	0.320 (3)	0.355 (2)	0.8468 (14)	0.045*
N4	0.2528 (2)	0.59528 (17)	0.99092 (11)	0.0361 (4)
H4A	0.240 (3)	0.686 (2)	1.0107 (14)	0.043*
N5	0.5516 (2)	0.42669 (17)	0.58090 (11)	0.0388 (4)
H5A	0.667 (3)	0.486 (2)	0.6204 (14)	0.047*
H5B	0.520 (3)	0.350 (2)	0.6120 (15)	0.047*
O1	0.3047 (2)	0.07841 (13)	1.05718 (9)	0.0488 (4)
O2	0.21058 (18)	−0.14867 (12)	1.05409 (8)	0.0379 (3)
O3	−0.15144 (18)	−0.40803 (13)	0.71833 (9)	0.0450 (4)
O4	−0.0363 (2)	−0.34118 (16)	0.58017 (9)	0.0617 (5)
O5	0.3573 (2)	0.13542 (13)	0.59351 (9)	0.0436 (3)
O6	0.41142 (19)	0.27435 (12)	0.73950 (9)	0.0415 (3)
O7	0.4407 (2)	0.26393 (16)	1.22724 (10)	0.0498 (4)
H7A	0.407 (3)	0.201 (3)	1.1749 (19)	0.075*
H7B	0.342 (3)	0.306 (3)	1.2364 (18)	0.075*

	U11	U22	U33	U12	U13	U23
C1	0.0326 (9)	0.0259 (9)	0.0207 (8)	0.0069 (7)	0.0028 (6)	0.0045 (6)
C2	0.0329 (9)	0.0236 (9)	0.0223 (8)	0.0025 (7)	0.0046 (6)	0.0073 (6)
C3	0.0293 (8)	0.0277 (10)	0.0243 (8)	0.0042 (7)	0.0023 (6)	0.0038 (7)
C4	0.0368 (9)	0.0330 (10)	0.0186 (7)	0.0064 (8)	0.0040 (6)	0.0047 (7)
C5	0.0301 (9)	0.0256 (9)	0.0265 (8)	0.0071 (7)	0.0068 (6)	0.0069 (7)
C6	0.0330 (9)	0.0218 (9)	0.0261 (8)	0.0036 (7)	0.0025 (7)	0.0027 (7)
C7	0.0397 (10)	0.0282 (10)	0.0213 (8)	0.0080 (8)	0.0034 (7)	0.0026 (7)
C8	0.0360 (9)	0.0336 (11)	0.0256 (8)	0.0009 (8)	−0.0006 (7)	0.0013 (7)
C9	0.0357 (9)	0.0301 (10)	0.0307 (9)	0.0095 (8)	0.0088 (7)	0.0103 (7)
C10	0.0498 (11)	0.0398 (12)	0.0308 (9)	0.0124 (9)	0.0099 (8)	0.0090 (8)
C11	0.0501 (11)	0.0425 (12)	0.0332 (10)	0.0025 (9)	0.0019 (8)	0.0040 (9)
C12	0.0477 (11)	0.0478 (13)	0.0322 (10)	0.0064 (10)	0.0094 (8)	0.0140 (9)
C13	0.0473 (11)	0.0327 (11)	0.0427 (10)	0.0080 (9)	0.0089 (8)	0.0128 (9)
C14	0.0465 (11)	0.0394 (12)	0.0352 (10)	0.0105 (9)	0.0087 (8)	0.0086 (8)
C15	0.0500 (11)	0.0342 (12)	0.0376 (10)	0.0081 (9)	0.0112 (8)	0.0097 (8)
C16	0.0441 (11)	0.0506 (13)	0.0269 (9)	−0.0014 (9)	0.0040 (8)	0.0040 (8)
C17	0.0566 (12)	0.0361 (12)	0.0432 (11)	0.0085 (10)	−0.0001 (9)	0.0013 (9)
N1	0.0508 (10)	0.0500 (11)	0.0216 (7)	0.0155 (8)	0.0074 (7)	0.0090 (7)
N2	0.0487 (9)	0.0454 (11)	0.0233 (7)	0.0121 (8)	0.0055 (7)	0.0035 (7)
N3	0.0446 (9)	0.0289 (9)	0.0390 (9)	0.0081 (7)	0.0091 (7)	0.0020 (7)
N4	0.0434 (9)	0.0264 (9)	0.0391 (8)	0.0086 (7)	0.0076 (7)	0.0037 (7)
N5	0.0455 (10)	0.0309 (9)	0.0344 (8)	−0.0067 (8)	−0.0049 (7)	0.0143 (7)
O1	0.0874 (11)	0.0259 (7)	0.0268 (6)	0.0060 (7)	−0.0025 (6)	−0.0047 (5)
O2	0.0642 (9)	0.0285 (7)	0.0213 (6)	0.0072 (6)	0.0072 (5)	0.0076 (5)
O3	0.0521 (8)	0.0360 (8)	0.0371 (7)	−0.0124 (6)	0.0057 (6)	0.0016 (6)
O4	0.0783 (11)	0.0614 (10)	0.0263 (7)	−0.0223 (8)	0.0034 (7)	−0.0059 (6)
O5	0.0648 (9)	0.0375 (8)	0.0297 (7)	0.0058 (6)	0.0163 (6)	0.0107 (5)
O6	0.0592 (8)	0.0252 (7)	0.0393 (7)	0.0009 (6)	0.0146 (6)	0.0079 (6)
O7	0.0637 (10)	0.0433 (9)	0.0349 (7)	−0.0004 (7)	0.0066 (7)	−0.0058 (6)

C1—C6	1.382 (2)	C12—H12	0.9300
C1—C2	1.385 (2)	C13—C14	1.337 (3)
C1—C7	1.513 (2)	C13—N3	1.369 (2)
C2—C3	1.396 (2)	C13—H13	0.9300
C2—H2	0.9300	C14—N4	1.369 (2)
C3—C4	1.382 (2)	C14—H14	0.9300
C3—C8	1.517 (2)	C15—N3	1.317 (2)
C4—C5	1.390 (2)	C15—N4	1.318 (2)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.391 (2)	C16—N5	1.481 (3)
C5—C9	1.506 (2)	C16—C17i	1.497 (3)
C6—H6	0.9300	C16—H16A	0.9700
C7—O1	1.236 (2)	C16—H16B	0.9700
C7—O2	1.272 (2)	C17—N5	1.477 (2)
C8—O4	1.233 (2)	C17—C16i	1.497 (3)
C8—O3	1.265 (2)	C17—H17A	0.9700
C9—O5	1.251 (2)	C17—H17B	0.9700
C9—O6	1.264 (2)	N1—H1A	0.87 (2)
C10—N1	1.307 (2)	N2—H2A	0.90 (2)
C10—N2	1.324 (2)	N3—H3A	0.915 (19)
C10—H10	0.9300	N4—H4A	0.93 (2)
C11—C12	1.345 (3)	N5—H5A	0.98 (2)
C11—N1	1.361 (2)	N5—H5B	0.91 (2)
C11—H11	0.9300	O7—H7A	0.86 (3)
C12—N2	1.365 (2)	O7—H7B	0.90 (3)
C6—C1—C2	119.32 (14)	N3—C13—H13	126.6
C6—C1—C7	119.29 (14)	C13—C14—N4	107.51 (16)
C2—C1—C7	121.39 (15)	C13—C14—H14	126.2
C1—C2—C3	120.66 (15)	N4—C14—H14	126.2
C1—C2—H2	119.7	N3—C15—N4	109.13 (17)
C3—C2—H2	119.7	N3—C15—H15	125.4
C4—C3—C2	118.85 (14)	N4—C15—H15	125.4
C4—C3—C8	119.66 (14)	N5—C16—C17i	110.90 (16)
C2—C3—C8	121.48 (15)	N5—C16—H16A	109.5
C3—C4—C5	121.49 (14)	C17i—C16—H16A	109.5
C3—C4—H4	119.3	N5—C16—H16B	109.5
C5—C4—H4	119.3	C17i—C16—H16B	109.5
C4—C5—C6	118.38 (15)	H16A—C16—H16B	108.0
C4—C5—C9	120.74 (14)	N5—C17—C16i	111.07 (16)
C6—C5—C9	120.88 (15)	N5—C17—H17A	109.4
C1—C6—C5	121.22 (15)	C16i—C17—H17A	109.4
C1—C6—H6	119.4	N5—C17—H17B	109.4
C5—C6—H6	119.4	C16i—C17—H17B	109.4
O1—C7—O2	124.44 (15)	H17A—C17—H17B	108.0
O1—C7—C1	117.75 (16)	C10—N1—C11	108.59 (15)
O2—C7—C1	117.81 (14)	C10—N1—H1A	124.3 (14)
O4—C8—O3	124.28 (16)	C11—N1—H1A	127.1 (14)
O4—C8—C3	117.93 (16)	C10—N2—C12	108.49 (16)
O3—C8—C3	117.79 (14)	C10—N2—H2A	122.6 (13)
O5—C9—O6	122.58 (16)	C12—N2—H2A	128.7 (13)
O5—C9—C5	119.37 (16)	C15—N3—C13	108.45 (16)
O6—C9—C5	118.05 (14)	C15—N3—H3A	125.6 (13)
N1—C10—N2	108.95 (18)	C13—N3—H3A	125.7 (12)
N1—C10—H10	125.5	C15—N4—C14	108.03 (16)
N2—C10—H10	125.5	C15—N4—H4A	126.1 (12)
C12—C11—N1	107.52 (17)	C14—N4—H4A	125.8 (12)
C12—C11—H11	126.2	C17—N5—C16	110.82 (14)
N1—C11—H11	126.2	C17—N5—H5A	113.0 (11)
C11—C12—N2	106.45 (17)	C16—N5—H5A	110.0 (11)
C11—C12—H12	126.8	C17—N5—H5B	108.4 (13)
N2—C12—H12	126.8	C16—N5—H5B	107.1 (13)
C14—C13—N3	106.88 (17)	H5A—N5—H5B	107.3 (16)
C14—C13—H13	126.6	H7A—O7—H7B	108 (2)
C6—C1—C2—C3	2.5 (2)	C4—C3—C8—O3	−166.35 (16)
C7—C1—C2—C3	−178.26 (15)	C2—C3—C8—O3	12.2 (3)
C1—C2—C3—C4	−1.7 (3)	C4—C5—C9—O5	−14.7 (3)
C1—C2—C3—C8	179.66 (15)	C6—C5—C9—O5	165.86 (16)
C2—C3—C4—C5	−1.0 (3)	C4—C5—C9—O6	165.85 (16)
C8—C3—C4—C5	177.65 (15)	C6—C5—C9—O6	−13.6 (2)
C3—C4—C5—C6	2.9 (3)	N1—C11—C12—N2	−0.3 (2)
C3—C4—C5—C9	−176.58 (15)	N3—C13—C14—N4	−0.3 (2)
C2—C1—C6—C5	−0.5 (2)	N2—C10—N1—C11	−0.1 (2)
C7—C1—C6—C5	−179.78 (15)	C12—C11—N1—C10	0.3 (2)
C4—C5—C6—C1	−2.1 (2)	N1—C10—N2—C12	0.0 (2)
C9—C5—C6—C1	177.32 (15)	C11—C12—N2—C10	0.2 (2)
C6—C1—C7—O1	17.1 (2)	N4—C15—N3—C13	−0.5 (2)
C2—C1—C7—O1	−162.20 (16)	C14—C13—N3—C15	0.5 (2)
C6—C1—C7—O2	−163.16 (15)	N3—C15—N4—C14	0.3 (2)
C2—C1—C7—O2	17.6 (2)	C13—C14—N4—C15	0.0 (2)
C4—C3—C8—O4	13.2 (3)	C16i—C17—N5—C16	56.2 (2)
C2—C3—C8—O4	−168.22 (17)	C17i—C16—N5—C17	−56.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.87 (2)	1.83 (2)	2.6870 (18)	166.9 (19)
N2—H2A···O5ii	0.90 (2)	1.86 (2)	2.7522 (19)	177.4 (19)
N3—H3A···O6	0.915 (19)	1.80 (2)	2.701 (2)	168.8 (18)
N4—H4A···O2iii	0.93 (2)	1.74 (2)	2.668 (2)	176.6 (18)
N5—H5A···O3iv	0.98 (2)	1.83 (2)	2.7872 (19)	166.7 (17)
N5—H5A···O4iv	0.98 (2)	2.60 (2)	3.366 (2)	135.7 (14)
N5—H5B···O5	0.91 (2)	2.19 (2)	2.985 (2)	145.2 (16)
N5—H5B···O6	0.91 (2)	2.10 (2)	2.888 (2)	145.1 (18)
O7—H7A···O1	0.86 (3)	1.86 (3)	2.7184 (17)	171 (2)
O7—H7B···O3v	0.90 (3)	1.95 (3)	2.840 (2)	169 (2)
C10—H10···O7	0.93	2.35	3.217 (3)	156
C12—H12···O4ii	0.93	2.32	3.244 (2)	175
C13—H13···O1	0.93	2.36	3.267 (2)	164
C14—H14···O3v	0.93	2.51	3.372 (2)	154
C15—H15···O7vi	0.93	2.38	3.186 (2)	145
C16—H16B···O4vii	0.97	2.32	3.200 (2)	150
C16—H16A···O7vi	0.97	2.48	3.207 (2)	132

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.87 (2)	1.83 (2)	2.6870 (18)	166.9 (19)
N2—H2A⋯O5i	0.90 (2)	1.86 (2)	2.7522 (19)	177.4 (19)
N3—H3A⋯O6	0.915 (19)	1.80 (2)	2.701 (2)	168.8 (18)
N4—H4A⋯O2ii	0.93 (2)	1.74 (2)	2.668 (2)	176.6 (18)
N5—H5A⋯O3iii	0.98 (2)	1.83 (2)	2.7872 (19)	166.7 (17)
N5—H5A⋯O4iii	0.98 (2)	2.60 (2)	3.366 (2)	135.7 (14)
N5—H5B⋯O5	0.91 (2)	2.19 (2)	2.985 (2)	145.2 (16)
N5—H5B⋯O6	0.91 (2)	2.10 (2)	2.888 (2)	145.1 (18)
O7—H7A⋯O1	0.86 (3)	1.86 (3)	2.7184 (17)	171 (2)
O7—H7B⋯O3iv	0.90 (3)	1.95 (3)	2.840 (2)	169 (2)
C10—H10⋯O7	0.93	2.35	3.217 (3)	156
C12—H12⋯O4i	0.93	2.32	3.244 (2)	175
C13—H13⋯O1	0.93	2.36	3.267 (2)	164
C14—H14⋯O3iv	0.93	2.51	3.372 (2)	154
C15—H15⋯O7v	0.93	2.38	3.186 (2)	145
C16—H16B⋯O4vi	0.97	2.32	3.200 (2)	150
C16—H16A⋯O7v	0.97	2.48	3.207 (2)	132

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