Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053020/lx2020sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053020/lx2020Isup2.hkl |
CCDC reference: 672792
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (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
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).
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.
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.
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).
C4H12N22+·2C7H5O5−·2H2O | F(000) = 488 |
Mr = 462.41 | Dx = 1.634 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2556 reflections |
a = 8.197 (2) Å | θ = 2.7–26.4° |
b = 9.449 (2) Å | µ = 0.14 mm−1 |
c = 12.655 (2) Å | T = 294 K |
β = 106.516 (3)° | Block, colorless |
V = 939.7 (3) Å3 | 0.20 × 0.16 × 0.12 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1591 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 26.4°, θmin = 2.7° |
Detector resolution: 10.0 pixels mm-1 | h = −10→9 |
ϕ and ω scans | k = −11→11 |
5263 measured reflections | l = −11→15 |
1922 independent reflections |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H 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 parameters | Δρmax = 0.23 e Å−3 |
4 restraints | Δρmin = −0.42 e Å−3 |
C4H12N22+·2C7H5O5−·2H2O | V = 939.7 (3) Å3 |
Mr = 462.41 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.197 (2) Å | µ = 0.14 mm−1 |
b = 9.449 (2) Å | T = 294 K |
c = 12.655 (2) Å | 0.20 × 0.16 × 0.12 mm |
β = 106.516 (3)° |
Bruker SMART CCD area-detector diffractometer | 1591 reflections with I > 2σ(I) |
5263 measured reflections | Rint = 0.028 |
1922 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 4 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.23 e Å−3 |
1922 reflections | Δρmin = −0.42 e Å−3 |
161 parameters |
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 | ||
O1 | 0.58286 (17) | 0.49827 (12) | 0.69747 (9) | 0.0276 (3) | |
O2 | 0.53936 (15) | 0.33368 (12) | 0.81110 (9) | 0.0270 (3) | |
O3 | 0.83718 (16) | 0.49981 (12) | 1.19238 (9) | 0.0279 (3) | |
H3 | 0.7719 | 0.4333 | 1.1896 | 0.042* | |
O4 | 1.02059 (15) | 0.72094 (12) | 1.17301 (9) | 0.0277 (3) | |
H4 | 1.0744 | 0.7876 | 1.1583 | 0.042* | |
O5 | 1.02560 (14) | 0.82015 (12) | 0.96955 (9) | 0.0249 (3) | |
H5 | 1.0160 | 0.8417 | 0.9053 | 0.037* | |
O6 | 0.2251 (2) | 0.26564 (15) | 0.68561 (10) | 0.0325 (3) | |
H6A | 0.325 (4) | 0.295 (3) | 0.717 (2) | 0.067 (9)* | |
H6B | 0.161 (3) | 0.282 (3) | 0.724 (2) | 0.064 (8)* | |
N | 0.58220 (17) | 0.12224 (14) | 0.97017 (12) | 0.0215 (3) | |
H1A | 0.651 (2) | 0.151 (2) | 1.0349 (18) | 0.030 (5)* | |
H1B | 0.592 (3) | 0.186 (2) | 0.9169 (19) | 0.042 (6)* | |
C1 | 0.6055 (2) | 0.44903 (16) | 0.79314 (12) | 0.0196 (3) | |
C2 | 0.71553 (19) | 0.52807 (16) | 0.89041 (12) | 0.0179 (3) | |
C3 | 0.7195 (2) | 0.48134 (16) | 0.99537 (12) | 0.0194 (3) | |
H3A | 0.6495 | 0.4071 | 1.0033 | 0.023* | |
C4 | 0.8266 (2) | 0.54420 (16) | 1.08790 (12) | 0.0187 (3) | |
C5 | 0.92582 (19) | 0.65932 (16) | 1.07747 (12) | 0.0185 (3) | |
C6 | 0.92217 (19) | 0.70748 (16) | 0.97240 (13) | 0.0179 (3) | |
C7 | 0.81769 (19) | 0.64194 (16) | 0.87896 (12) | 0.0186 (3) | |
H7 | 0.8160 | 0.6739 | 0.8092 | 0.022* | |
C8 | 0.6298 (2) | −0.02284 (17) | 0.94383 (14) | 0.0257 (4) | |
H8A | 0.7493 | −0.0248 | 0.9467 | 0.031* | |
H8B | 0.5638 | −0.0484 | 0.8698 | 0.031* | |
C9 | 0.4030 (2) | 0.12800 (18) | 0.97492 (15) | 0.0268 (4) | |
H9A | 0.3271 | 0.1084 | 0.9023 | 0.032* | |
H9B | 0.3784 | 0.2226 | 0.9959 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0437 (7) | 0.0207 (6) | 0.0155 (6) | −0.0033 (5) | 0.0037 (5) | 0.0001 (4) |
O2 | 0.0343 (7) | 0.0218 (6) | 0.0215 (6) | −0.0079 (5) | 0.0024 (5) | 0.0016 (5) |
O3 | 0.0448 (8) | 0.0233 (6) | 0.0148 (6) | −0.0069 (5) | 0.0072 (5) | 0.0005 (4) |
O4 | 0.0376 (7) | 0.0228 (6) | 0.0180 (6) | −0.0087 (5) | 0.0002 (5) | −0.0020 (5) |
O5 | 0.0268 (6) | 0.0243 (6) | 0.0210 (6) | −0.0077 (5) | 0.0026 (5) | 0.0036 (5) |
O6 | 0.0358 (8) | 0.0343 (7) | 0.0252 (7) | 0.0079 (6) | 0.0050 (6) | −0.0087 (5) |
N | 0.0236 (7) | 0.0196 (7) | 0.0214 (7) | −0.0013 (5) | 0.0067 (6) | 0.0028 (6) |
C1 | 0.0221 (8) | 0.0173 (7) | 0.0191 (7) | 0.0017 (6) | 0.0053 (6) | 0.0001 (6) |
C2 | 0.0183 (7) | 0.0171 (7) | 0.0174 (7) | 0.0020 (6) | 0.0034 (6) | −0.0011 (6) |
C3 | 0.0231 (8) | 0.0155 (7) | 0.0197 (8) | −0.0005 (6) | 0.0065 (6) | 0.0007 (6) |
C4 | 0.0240 (8) | 0.0171 (7) | 0.0150 (7) | 0.0043 (6) | 0.0057 (6) | 0.0012 (6) |
C5 | 0.0198 (7) | 0.0165 (7) | 0.0167 (7) | 0.0032 (6) | 0.0011 (6) | −0.0028 (6) |
C6 | 0.0158 (7) | 0.0153 (7) | 0.0224 (8) | 0.0022 (6) | 0.0052 (6) | 0.0014 (6) |
C7 | 0.0206 (7) | 0.0200 (8) | 0.0154 (7) | 0.0029 (6) | 0.0056 (6) | 0.0025 (6) |
C8 | 0.0250 (8) | 0.0244 (8) | 0.0311 (9) | 0.0010 (7) | 0.0135 (7) | −0.0023 (7) |
C9 | 0.0234 (8) | 0.0217 (8) | 0.0351 (9) | 0.0074 (7) | 0.0082 (7) | 0.0051 (7) |
O1—C1 | 1.261 (2) | C2—C3 | 1.391 (2) |
O2—C1 | 1.266 (2) | C2—C7 | 1.396 (2) |
O3—C4 | 1.366 (2) | C3—C4 | 1.382 (2) |
O3—H3 | 0.8200 | C3—H3A | 0.9300 |
O4—C5 | 1.368 (2) | C4—C5 | 1.387 (2) |
O4—H4 | 0.8200 | C5—C6 | 1.398 (2) |
O5—C6 | 1.368 (2) | C6—C7 | 1.393 (2) |
O5—H5 | 0.8200 | C7—H7 | 0.9300 |
O6—H6A | 0.85 (3) | C8—C9i | 1.508 (2) |
O6—H6B | 0.83 (3) | C8—H8A | 0.9700 |
N—C9 | 1.488 (2) | C8—H8B | 0.9700 |
N—C8 | 1.489 (2) | C9—C8i | 1.508 (2) |
N—H1A | 0.89 (2) | C9—H9A | 0.9700 |
N—H1B | 0.92 (2) | C9—H9B | 0.9700 |
C1—C2 | 1.502 (2) | ||
C4—O3—H3 | 109.5 | O4—C5—C4 | 116.8 (1) |
C5—O4—H4 | 109.5 | O4—C5—C6 | 123.8 (1) |
C6—O5—H5 | 109.5 | C4—C5—C6 | 119.4 (1) |
H6A—O6—H6B | 111 (3) | O5—C6—C7 | 124.1 (1) |
C9—N—C8 | 111.6 (1) | O5—C6—C5 | 115.6 (1) |
C9—N—H1A | 109 (1) | C7—C6—C5 | 120.3 (1) |
C8—N—H1A | 110 (1) | C6—C7—C2 | 119.8 (1) |
C9—N—H1B | 107 (1) | C6—C7—H7 | 120.1 |
C8—N—H1B | 111 (1) | C2—C7—H7 | 120.1 |
H1A—N—H1B | 108 (2) | N—C8—C9i | 110.17 (13) |
O1—C1—O2 | 122.4 (1) | N—C8—H8A | 109.6 |
O1—C1—C2 | 119.6 (1) | C9i—C8—H8A | 109.6 |
O2—C1—C2 | 118.0 (1) | N—C8—H8B | 109.6 |
C3—C2—C7 | 119.6 (1) | C9i—C8—H8B | 109.6 |
C3—C2—C1 | 118.1 (1) | H8A—C8—H8B | 108.1 |
C7—C2—C1 | 122.5 (1) | N—C9—C8i | 111.90 (13) |
C4—C3—C2 | 120.6 (2) | N—C9—H9A | 109.2 |
C4—C3—H3A | 119.7 | C8i—C9—H9A | 109.2 |
C2—C3—H3A | 119.7 | N—C9—H9B | 109.2 |
O3—C4—C3 | 122.6 (1) | C8i—C9—H9B | 109.2 |
O3—C4—C5 | 117.1 (1) | H9A—C9—H9B | 107.9 |
C3—C4—C5 | 120.3 (1) | ||
O1—C1—C2—C3 | 171.50 (14) | C3—C4—C5—C6 | −2.8 (2) |
O2—C1—C2—C3 | −8.9 (2) | O4—C5—C6—O5 | 2.1 (2) |
O1—C1—C2—C7 | −11.1 (2) | C4—C5—C6—O5 | −179.08 (13) |
O2—C1—C2—C7 | 168.51 (14) | O4—C5—C6—C7 | −177.75 (14) |
C7—C2—C3—C4 | −1.7 (2) | C4—C5—C6—C7 | 1.1 (2) |
C1—C2—C3—C4 | 175.86 (14) | O5—C6—C7—C2 | −179.52 (13) |
C2—C3—C4—O3 | −178.62 (14) | C5—C6—C7—C2 | 0.3 (2) |
C2—C3—C4—C5 | 3.1 (2) | C3—C2—C7—C6 | 0.0 (2) |
O3—C4—C5—O4 | −2.3 (2) | C1—C2—C7—C6 | −177.44 (14) |
C3—C4—C5—O4 | 176.13 (14) | C9—N—C8—C9i | −55.1 (2) |
O3—C4—C5—C6 | 178.85 (13) | C8—N—C9—C8i | 56.0 (2) |
Symmetry code: (i) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O6ii | 0.82 | 1.92 | 2.664 (2) | 151 |
O4—H4···O1iii | 0.82 | 2.08 | 2.703 (2) | 133 |
O5—H5···O1iv | 0.82 | 1.98 | 2.650 (2) | 138 |
O6—H6A···O2 | 0.85 (3) | 1.85 (3) | 2.691 (2) | 167 (3) |
O6—H6B···O3v | 0.83 (3) | 2.31 (3) | 2.829 (2) | 121 (2) |
O6—H6B···O4v | 0.83 (3) | 2.23 (3) | 3.054 (2) | 169 (3) |
N—H1B···O2 | 0.92 (2) | 1.90 (2) | 2.787 (2) | 161 (2) |
N—H1A···O6ii | 0.89 (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 formula | C4H12N22+·2C7H5O5−·2H2O |
Mr | 462.41 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 8.197 (2), 9.449 (2), 12.655 (2) |
β (°) | 106.516 (3) |
V (Å3) | 939.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.20 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5263, 1922, 1591 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.107, 1.10 |
No. of reflections | 1922 |
No. of parameters | 161 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.42 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O6i | 0.82 | 1.92 | 2.664 (2) | 151.2 |
O4—H4···O1ii | 0.82 | 2.08 | 2.703 (2) | 132.6 |
O5—H5···O1iii | 0.82 | 1.98 | 2.650 (2) | 137.8 |
O6—H6A···O2 | 0.85 (3) | 1.85 (3) | 2.691 (2) | 167 (3) |
O6—H6B···O3iv | 0.83 (3) | 2.31 (3) | 2.829 (2) | 121 (2) |
O6—H6B···O4iv | 0.83 (3) | 2.23 (3) | 3.054 (2) | 169 (3) |
N—H1B···O2 | 0.92 (2) | 1.90 (2) | 2.787 (2) | 161 (2) |
N—H1A···O6i | 0.89 (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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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 π—π 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).