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In the title compound, C4H12N22+·2C7H5O5·2H2O, the cation lies on a centre of symmetry. The crystal structure is stabilized by various inter­molecular O—H...O and N—H...O hydrogen bonds, and by inter­molecular aromatic π–π inter­actions, with a centroid-to-centroid distance of 3.348 (2) Å between the benzene rings of neighbouring anions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053020/lx2020sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053020/lx2020Isup2.hkl
Contains datablock I

CCDC reference: 672792

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.039
  • wR factor = 0.107
  • Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 200 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 4
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Gallic acid (3, 4, 5-trihydroxybenzoic acid) is one of the main endogenous phenolic acids found in plants as a free or esterified form, and a large amount of them is present in tea, being present at about 5% of the dry weight (Harbowy & Ballentine 1997). Significantly, it has been found that gallic acid and its derivatives are pharmacologically active, and possess antioxidative (Fukumoto & Mazza, 2000), antimutagenic, anticarcinogenic (Akao et al., 2001; Saeki et al., 2000; Stich & Rosin, 1984), antiinflammatory (Kawada et al., 1992), and hepatoprotective activities (Anand et al., 1997). In the earlier work, acetic anhydride had been used to protect hydroxyl group (Li & Guo, 2007). Herein we report the molecular and crystal structure of the title compound (Fig. 1)

The title compound (Fig. 1) was obtained from the solution of 3,4,5-trihydroxybenzoic acid monohydrate and piperazine. The bond distances and angles in the title compound are normal. The molecular packing (Fig. 2) is stabilized by hydrogen bonds of all H atoms in the O and N atoms (Table 1). The molecular packing (Fig. 2) is further stabilized by ππ stacking interactions between the benzene rings of adjacent molecules. The Cg···Cgv distance is 3.348 (2) Å (Cg is the centroid of the C2—C7 ring; symmetry code as in Fig.2).

Related literature top

For related literature, see: Akao et al. (2001); Anand et al. (1997); Fukumoto & Mazza (2000); Harbowy & Ballentine (1997); Kawada et al. (1992); Li & Guo (2007); Saeki et al. (2000); Sartori et al. (2004); Stich & Rosin (1984).

Experimental top

Gallic acid monohydrate (3.76 g, 20 mmol) and piperazine (0.86 g, 10 mmol) were loaded into a 100 ml roundbottom flask, and then 50 ml H2O were droped into above mixture. After reaction the solid gallic acid and piperazine dissolved into solution under heater. Crystals of the title compound were obtained by slow evaporation of deionic H2O solution.

Refinement top

The H atoms of the water molecule and the hydrogen atoms on the N atom were positioned in a different Fourier maps, there the parameters were freely refined. All other H atoms were positioned geometrically and refined using a riding model, with O—H = 0.82 Å for hydroxy H atoms, C—H = 0.93 Å for aromatic H atoms, and 0.97 Å for methylene H atoms, respectively, and with Uiso(H) = 1.5Ueq(O) for hydroxy, Uiso(H) = 1.2Ueq(C) for aromatic and methylene H atoms.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound, showing ???% probability displacement ellipsoids. H atoms are shown as small spheres of arbitary radii. [Symmetry code; (i) 1 - x, -y, 2 - z.]
[Figure 2] Fig. 2. π···π interactions, O—H···O and N—H···O hydrogen bonds (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry codes: (i) 1/2 + x, 1/2 - y, z + 1/2; (ii) 3/2 - x, y - 1/2, 3/2 - z; (iii) 1/2 + x, 3/2 - y, z + 1/2; (iv) 1 - x, 1 - y, 2 - z; (v) 2 - x, 1 - y, 2 - z; (vi) 3/2 - x, y + 1/2, 3/2 - z; (vii) x - 1/2, 3/2 - y, z - 1/2.]
Piperazindiium bis(3,4,5-trihydroxybenzoate) dihydrate top
Crystal data top
C4H12N22+·2C7H5O5·2H2OF(000) = 488
Mr = 462.41Dx = 1.634 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2556 reflections
a = 8.197 (2) Åθ = 2.7–26.4°
b = 9.449 (2) ŵ = 0.14 mm1
c = 12.655 (2) ÅT = 294 K
β = 106.516 (3)°Block, colorless
V = 939.7 (3) Å30.20 × 0.16 × 0.12 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
1591 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Graphite monochromatorθmax = 26.4°, θmin = 2.7°
Detector resolution: 10.0 pixels mm-1h = 109
ϕ and ω scansk = 1111
5263 measured reflectionsl = 1115
1922 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0541P)2 + 0.3692P]
where P = (Fo2 + 2Fc2)/3
1922 reflections(Δ/σ)max < 0.001
161 parametersΔρmax = 0.23 e Å3
4 restraintsΔρmin = 0.42 e Å3
Crystal data top
C4H12N22+·2C7H5O5·2H2OV = 939.7 (3) Å3
Mr = 462.41Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.197 (2) ŵ = 0.14 mm1
b = 9.449 (2) ÅT = 294 K
c = 12.655 (2) Å0.20 × 0.16 × 0.12 mm
β = 106.516 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1591 reflections with I > 2σ(I)
5263 measured reflectionsRint = 0.028
1922 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0394 restraints
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.23 e Å3
1922 reflectionsΔρmin = 0.42 e Å3
161 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.58286 (17)0.49827 (12)0.69747 (9)0.0276 (3)
O20.53936 (15)0.33368 (12)0.81110 (9)0.0270 (3)
O30.83718 (16)0.49981 (12)1.19238 (9)0.0279 (3)
H30.77190.43331.18960.042*
O41.02059 (15)0.72094 (12)1.17301 (9)0.0277 (3)
H41.07440.78761.15830.042*
O51.02560 (14)0.82015 (12)0.96955 (9)0.0249 (3)
H51.01600.84170.90530.037*
O60.2251 (2)0.26564 (15)0.68561 (10)0.0325 (3)
H6A0.325 (4)0.295 (3)0.717 (2)0.067 (9)*
H6B0.161 (3)0.282 (3)0.724 (2)0.064 (8)*
N0.58220 (17)0.12224 (14)0.97017 (12)0.0215 (3)
H1A0.651 (2)0.151 (2)1.0349 (18)0.030 (5)*
H1B0.592 (3)0.186 (2)0.9169 (19)0.042 (6)*
C10.6055 (2)0.44903 (16)0.79314 (12)0.0196 (3)
C20.71553 (19)0.52807 (16)0.89041 (12)0.0179 (3)
C30.7195 (2)0.48134 (16)0.99537 (12)0.0194 (3)
H3A0.64950.40711.00330.023*
C40.8266 (2)0.54420 (16)1.08790 (12)0.0187 (3)
C50.92582 (19)0.65932 (16)1.07747 (12)0.0185 (3)
C60.92217 (19)0.70748 (16)0.97240 (13)0.0179 (3)
C70.81769 (19)0.64194 (16)0.87896 (12)0.0186 (3)
H70.81600.67390.80920.022*
C80.6298 (2)0.02284 (17)0.94383 (14)0.0257 (4)
H8A0.74930.02480.94670.031*
H8B0.56380.04840.86980.031*
C90.4030 (2)0.12800 (18)0.97492 (15)0.0268 (4)
H9A0.32710.10840.90230.032*
H9B0.37840.22260.99590.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0437 (7)0.0207 (6)0.0155 (6)0.0033 (5)0.0037 (5)0.0001 (4)
O20.0343 (7)0.0218 (6)0.0215 (6)0.0079 (5)0.0024 (5)0.0016 (5)
O30.0448 (8)0.0233 (6)0.0148 (6)0.0069 (5)0.0072 (5)0.0005 (4)
O40.0376 (7)0.0228 (6)0.0180 (6)0.0087 (5)0.0002 (5)0.0020 (5)
O50.0268 (6)0.0243 (6)0.0210 (6)0.0077 (5)0.0026 (5)0.0036 (5)
O60.0358 (8)0.0343 (7)0.0252 (7)0.0079 (6)0.0050 (6)0.0087 (5)
N0.0236 (7)0.0196 (7)0.0214 (7)0.0013 (5)0.0067 (6)0.0028 (6)
C10.0221 (8)0.0173 (7)0.0191 (7)0.0017 (6)0.0053 (6)0.0001 (6)
C20.0183 (7)0.0171 (7)0.0174 (7)0.0020 (6)0.0034 (6)0.0011 (6)
C30.0231 (8)0.0155 (7)0.0197 (8)0.0005 (6)0.0065 (6)0.0007 (6)
C40.0240 (8)0.0171 (7)0.0150 (7)0.0043 (6)0.0057 (6)0.0012 (6)
C50.0198 (7)0.0165 (7)0.0167 (7)0.0032 (6)0.0011 (6)0.0028 (6)
C60.0158 (7)0.0153 (7)0.0224 (8)0.0022 (6)0.0052 (6)0.0014 (6)
C70.0206 (7)0.0200 (8)0.0154 (7)0.0029 (6)0.0056 (6)0.0025 (6)
C80.0250 (8)0.0244 (8)0.0311 (9)0.0010 (7)0.0135 (7)0.0023 (7)
C90.0234 (8)0.0217 (8)0.0351 (9)0.0074 (7)0.0082 (7)0.0051 (7)
Geometric parameters (Å, º) top
O1—C11.261 (2)C2—C31.391 (2)
O2—C11.266 (2)C2—C71.396 (2)
O3—C41.366 (2)C3—C41.382 (2)
O3—H30.8200C3—H3A0.9300
O4—C51.368 (2)C4—C51.387 (2)
O4—H40.8200C5—C61.398 (2)
O5—C61.368 (2)C6—C71.393 (2)
O5—H50.8200C7—H70.9300
O6—H6A0.85 (3)C8—C9i1.508 (2)
O6—H6B0.83 (3)C8—H8A0.9700
N—C91.488 (2)C8—H8B0.9700
N—C81.489 (2)C9—C8i1.508 (2)
N—H1A0.89 (2)C9—H9A0.9700
N—H1B0.92 (2)C9—H9B0.9700
C1—C21.502 (2)
C4—O3—H3109.5O4—C5—C4116.8 (1)
C5—O4—H4109.5O4—C5—C6123.8 (1)
C6—O5—H5109.5C4—C5—C6119.4 (1)
H6A—O6—H6B111 (3)O5—C6—C7124.1 (1)
C9—N—C8111.6 (1)O5—C6—C5115.6 (1)
C9—N—H1A109 (1)C7—C6—C5120.3 (1)
C8—N—H1A110 (1)C6—C7—C2119.8 (1)
C9—N—H1B107 (1)C6—C7—H7120.1
C8—N—H1B111 (1)C2—C7—H7120.1
H1A—N—H1B108 (2)N—C8—C9i110.17 (13)
O1—C1—O2122.4 (1)N—C8—H8A109.6
O1—C1—C2119.6 (1)C9i—C8—H8A109.6
O2—C1—C2118.0 (1)N—C8—H8B109.6
C3—C2—C7119.6 (1)C9i—C8—H8B109.6
C3—C2—C1118.1 (1)H8A—C8—H8B108.1
C7—C2—C1122.5 (1)N—C9—C8i111.90 (13)
C4—C3—C2120.6 (2)N—C9—H9A109.2
C4—C3—H3A119.7C8i—C9—H9A109.2
C2—C3—H3A119.7N—C9—H9B109.2
O3—C4—C3122.6 (1)C8i—C9—H9B109.2
O3—C4—C5117.1 (1)H9A—C9—H9B107.9
C3—C4—C5120.3 (1)
O1—C1—C2—C3171.50 (14)C3—C4—C5—C62.8 (2)
O2—C1—C2—C38.9 (2)O4—C5—C6—O52.1 (2)
O1—C1—C2—C711.1 (2)C4—C5—C6—O5179.08 (13)
O2—C1—C2—C7168.51 (14)O4—C5—C6—C7177.75 (14)
C7—C2—C3—C41.7 (2)C4—C5—C6—C71.1 (2)
C1—C2—C3—C4175.86 (14)O5—C6—C7—C2179.52 (13)
C2—C3—C4—O3178.62 (14)C5—C6—C7—C20.3 (2)
C2—C3—C4—C53.1 (2)C3—C2—C7—C60.0 (2)
O3—C4—C5—O42.3 (2)C1—C2—C7—C6177.44 (14)
C3—C4—C5—O4176.13 (14)C9—N—C8—C9i55.1 (2)
O3—C4—C5—C6178.85 (13)C8—N—C9—C8i56.0 (2)
Symmetry code: (i) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O6ii0.821.922.664 (2)151
O4—H4···O1iii0.822.082.703 (2)133
O5—H5···O1iv0.821.982.650 (2)138
O6—H6A···O20.85 (3)1.85 (3)2.691 (2)167 (3)
O6—H6B···O3v0.83 (3)2.31 (3)2.829 (2)121 (2)
O6—H6B···O4v0.83 (3)2.23 (3)3.054 (2)169 (3)
N—H1B···O20.92 (2)1.90 (2)2.787 (2)161 (2)
N—H1A···O6ii0.89 (2)1.99 (2)2.848 (2)160.0 (17)
Symmetry codes: (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y+3/2, z+1/2; (iv) x+3/2, y+1/2, z+3/2; (v) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC4H12N22+·2C7H5O5·2H2O
Mr462.41
Crystal system, space groupMonoclinic, P21/n
Temperature (K)294
a, b, c (Å)8.197 (2), 9.449 (2), 12.655 (2)
β (°) 106.516 (3)
V3)939.7 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.20 × 0.16 × 0.12
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5263, 1922, 1591
Rint0.028
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.107, 1.10
No. of reflections1922
No. of parameters161
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.42

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O6i0.821.922.664 (2)151.2
O4—H4···O1ii0.822.082.703 (2)132.6
O5—H5···O1iii0.821.982.650 (2)137.8
O6—H6A···O20.85 (3)1.85 (3)2.691 (2)167 (3)
O6—H6B···O3iv0.83 (3)2.31 (3)2.829 (2)121 (2)
O6—H6B···O4iv0.83 (3)2.23 (3)3.054 (2)169 (3)
N—H1B···O20.92 (2)1.90 (2)2.787 (2)161 (2)
N—H1A···O6i0.89 (2)1.99 (2)2.848 (2)160.0 (17)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1/2, y+3/2, z+1/2; (iii) x+3/2, y+1/2, z+3/2; (iv) x+1, y+1, z+2.
 

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