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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2893.
Published online 2010 October 23. doi:  10.1107/S1600536810042182
PMCID: PMC3009286

Ethyl­enediammonium bis­(3,4-dihy­droxy­benzoate) monohydrate

Abstract

In the title compound, C2H10N2 2+·2C7H5O4 ·H2O, 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 weak π–π stacking inter­actions with centroid–centroid distances between symmetry-related benzene rings ranging from 3.5249 (13) to 3.7566 (14) Å.

Related literature

For protocatechuic acid (3,4-dihydroxybenzoic acid) and its pharmacological activity, see: An et al. (2006 [triangle]); Guan et al. (2006 [triangle]); Lin et al. (2009 [triangle]); Tseng et al. (1998 [triangle]); Yip et al. (2006 [triangle]). For related structures, see: Mazurek et al. (2007 [triangle]); Xu et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2893-scheme1.jpg

Experimental

Crystal data

  • C2H10N2 2+·2C7H5O4 ·H2O
  • M r = 386.36
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2893-efi1.jpg
  • a = 6.8489 (8) Å
  • b = 10.7999 (12) Å
  • c = 12.0137 (13) Å
  • α = 75.866 (1)°
  • β = 81.387 (2)°
  • γ = 83.599 (1)°
  • V = 849.40 (16) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 296 K
  • 0.30 × 0.28 × 0.25 mm

Data collection

  • Bruker APEXII area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.963, T max = 0.969
  • 4432 measured reflections
  • 3011 independent reflections
  • 2215 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.112
  • S = 1.02
  • 3011 reflections
  • 256 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810042182/su2221sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042182/su2221Isup2.hkl

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

Acknowledgments

The author acknowledges South China Normal University for supporting this work.

supplementary crystallographic information

Comment

Protocatechuic acid (3,4-dihydroxybenzoic acid) is one of the main secondary metabolites in the plant kingdom (Guan et al., 2006). Significantly, it has been found that protocatechuic acid and its derivatives possess diverse pharmacological activities such as, antioxidant, antiapoptosis, anticarcinogen, anticoagulatory and antiinflammatory (An et al., 2006; Lin et al., 2009; Tseng et al., 1998; Yip et al., 2006). Herein, we report on the molecular and crystal structure of the title compound.

In the asymmetric unit of the title compound, illustrated in Fig. 1, there are two half protonated ethylenediammonium cations located about inversion centers, two singly deprotonated 3,4-dihydroxybenzoate anions, and one water molecule of crystallization. The bond distances and angles in the title compound are normal (Mazurek et al., 2007; Xu et al., 2008).

In the crystal the cations and anions are self-assembled by various intermolecular O—H···O and N—H···O hydrogen bonds (Table 1 and Fig. 2) to form a supramolecular network. The crystal structure is further stabilized by weak π-π stacking interactions (Fig. 2) occurring between adjacent benzene rings, with centroid-to-centroid distances of 3.5249 (13) Å [Cg1···Cg1i; Cg1 = centroid of ring (C1-C6); symmetry code (i) = 1-x, 2-y, 1-z], 3.7165 (13) Å [Cg1···Cg1ii; Cg1 = centroid of ring (C1-C6); symmetry code (ii) = -x, 2-y, 1-z] and 3.7566 (14) [Cg2···Cg2iii; Cg2 = centroid of ring (C8-C13); symmetry code (iii) = 2-x, 1-y, -z] .

Experimental

A solution of ethylenediamine (1 mmol in 0.2 ml water) was added dropwise to a solution of protocatechuic acid (2 mmol) in acetonitrile (15 ml), and the mixture was stirred for 30 min at RT. After several days colourless block-like crystals, suitable for X-ray diffraction analysis, were obtained by slow evaporation of the solution.

Refinement

The water molecule H-atoms were located in difference Fourier maps and were refined distance restraints of O—H = 0.86 Å and Uiso(H) = 1.5Ueq(O). All other H atoms were positioned geometrically and refined as riding: N—H = 0.89 Å, O—H = 0.82 Å, and C—H = 0.93 and 0.97 Å for CH and CH2 H-atoms, respectively, with Uiso(H) = k × Ueq(parent N, O or C-atom), with k = 1.2 for CH and CH2 H-atoms, and k = 1.5 for the NH3+ and OH H-atoms.

Figures

Fig. 1.
The molecular structure of the title compound showing the atomic-numbering scheme and displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (A) 1 - x, -y, -z; (B) -x, 1 - y, 1 - z.
Fig. 2.
The crystal packing of the title compound showing the intermolecular hydrogen bonding interactions as broken lines (see Table 1 for details).

Crystal data

C2H10N22+·2C7H5O4·H2OZ = 2
Mr = 386.36F(000) = 408
Triclinic, P1Dx = 1.511 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.8489 (8) ÅCell parameters from 1194 reflections
b = 10.7999 (12) Åθ = 2.9–24.2°
c = 12.0137 (13) ŵ = 0.13 mm1
α = 75.866 (1)°T = 296 K
β = 81.387 (2)°Block, colourless
γ = 83.599 (1)°0.30 × 0.28 × 0.25 mm
V = 849.40 (16) Å3

Data collection

Bruker APEXII area-detector diffractometer3011 independent reflections
Radiation source: fine-focus sealed tube2215 reflections with I > 2σ(I)
graphiteRint = 0.018
[var phi] and ω scanθmax = 25.2°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −8→8
Tmin = 0.963, Tmax = 0.969k = −11→12
4432 measured reflectionsl = −7→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0467P)2 + 0.4204P] where P = (Fo2 + 2Fc2)/3
3011 reflections(Δ/σ)max < 0.001
256 parametersΔρmax = 0.38 e Å3
3 restraintsΔρmin = −0.22 e Å3

Special details

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)

xyzUiso*/Ueq
C10.2895 (3)0.8335 (2)0.5353 (2)0.0292 (6)
H10.30310.74890.57690.035*
C20.2487 (3)0.9308 (2)0.5934 (2)0.0301 (6)
H20.23220.91100.67380.036*
C30.2320 (3)1.0577 (2)0.5330 (2)0.0262 (5)
C40.2557 (3)1.0857 (2)0.4127 (2)0.0261 (5)
C50.2916 (3)0.9881 (2)0.3553 (2)0.0268 (5)
H50.30371.00760.27480.032*
C60.3103 (3)0.8606 (2)0.4157 (2)0.0258 (5)
C70.3510 (3)0.7571 (2)0.3514 (2)0.0280 (5)
C80.7469 (3)0.3983 (2)0.1577 (2)0.0295 (6)
H80.65710.33860.16100.035*
C90.6777 (3)0.5199 (2)0.1690 (2)0.0297 (6)
C100.8130 (3)0.6106 (2)0.1619 (2)0.0269 (5)
C111.0130 (3)0.5753 (2)0.1497 (2)0.0291 (6)
H111.10300.63440.14810.035*
C121.0809 (3)0.4523 (2)0.1397 (2)0.0286 (5)
H121.21630.42920.13180.034*
C130.9487 (3)0.3636 (2)0.1413 (2)0.0258 (5)
C141.0255 (3)0.2336 (2)0.12291 (19)0.0247 (5)
C150.5818 (4)0.0203 (2)0.0254 (2)0.0299 (6)
H15A0.5688−0.01560.10820.036*
H15B0.7091−0.0117−0.00850.036*
C160.0738 (4)0.4632 (3)0.5389 (2)0.0377 (6)
H16A0.10910.51730.58530.045*
H16B0.01450.38960.59100.045*
N10.2550 (3)0.41936 (18)0.46971 (18)0.0344 (5)
H1B0.22490.36270.43350.052*
H1C0.34520.38300.51640.052*
H1D0.30360.48620.41780.052*
N20.5721 (3)0.16219 (18)0.00223 (18)0.0323 (5)
H2B0.58030.1949−0.07370.048*
H2C0.67230.18570.02980.048*
H2D0.45790.19100.03670.048*
O10.1944 (3)1.15782 (15)0.58542 (14)0.0342 (4)
H1A0.15751.13110.65450.051*
O20.2417 (3)1.21302 (14)0.35551 (14)0.0358 (4)
H2A0.23851.21870.28650.054*
O30.3090 (2)0.77974 (16)0.24853 (15)0.0343 (4)
O40.4239 (3)0.64879 (15)0.40190 (15)0.0359 (4)
O50.4788 (3)0.55228 (19)0.1832 (2)0.0518 (6)
H5A0.45670.61280.21450.078*
O60.7346 (2)0.73121 (15)0.16717 (17)0.0385 (5)
H60.82450.77750.16140.058*
O71.2060 (2)0.19869 (15)0.13369 (14)0.0319 (4)
O80.9088 (2)0.16349 (15)0.09982 (15)0.0344 (4)
O1W−0.0308 (3)0.90641 (16)0.18631 (16)0.0340 (4)
H1W0.084 (4)0.885 (3)0.208 (2)0.051*
H2W−0.040 (4)0.990 (2)0.159 (2)0.051*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0341 (14)0.0220 (12)0.0300 (14)−0.0018 (10)−0.0076 (11)−0.0010 (10)
C20.0336 (14)0.0305 (14)0.0256 (13)−0.0035 (10)−0.0042 (11)−0.0043 (11)
C30.0246 (12)0.0263 (13)0.0301 (14)−0.0003 (10)−0.0049 (10)−0.0109 (11)
C40.0278 (13)0.0202 (12)0.0304 (14)−0.0019 (9)−0.0088 (10)−0.0031 (10)
C50.0301 (13)0.0284 (13)0.0229 (13)−0.0034 (10)−0.0069 (10)−0.0055 (10)
C60.0233 (12)0.0222 (12)0.0319 (14)−0.0018 (9)−0.0053 (10)−0.0050 (10)
C70.0216 (12)0.0260 (13)0.0369 (15)−0.0029 (10)−0.0032 (11)−0.0079 (11)
C80.0287 (13)0.0263 (13)0.0367 (15)−0.0064 (10)−0.0054 (11)−0.0107 (11)
C90.0228 (12)0.0336 (14)0.0361 (15)−0.0005 (10)−0.0051 (11)−0.0146 (11)
C100.0319 (13)0.0220 (12)0.0286 (13)−0.0009 (10)−0.0073 (10)−0.0080 (10)
C110.0310 (13)0.0260 (13)0.0319 (14)−0.0080 (10)−0.0073 (11)−0.0055 (11)
C120.0259 (13)0.0261 (13)0.0334 (14)0.0002 (10)−0.0084 (11)−0.0041 (11)
C130.0271 (12)0.0258 (12)0.0250 (13)−0.0001 (10)−0.0062 (10)−0.0057 (10)
C140.0304 (13)0.0235 (12)0.0191 (12)−0.0016 (10)−0.0052 (10)−0.0016 (10)
C150.0289 (13)0.0294 (13)0.0317 (14)0.0011 (10)−0.0066 (10)−0.0071 (11)
C160.0424 (15)0.0335 (14)0.0356 (15)0.0022 (12)−0.0085 (12)−0.0051 (12)
N10.0377 (12)0.0235 (11)0.0413 (13)−0.0021 (9)−0.0100 (10)−0.0031 (9)
N20.0302 (11)0.0325 (12)0.0365 (12)−0.0019 (9)−0.0078 (9)−0.0105 (10)
O10.0466 (11)0.0267 (9)0.0298 (10)−0.0037 (8)−0.0008 (8)−0.0098 (7)
O20.0575 (12)0.0204 (9)0.0296 (10)−0.0020 (8)−0.0139 (9)−0.0018 (7)
O30.0369 (10)0.0352 (10)0.0339 (10)0.0056 (8)−0.0091 (8)−0.0151 (8)
O40.0416 (10)0.0203 (9)0.0457 (11)0.0010 (7)−0.0107 (9)−0.0057 (8)
O50.0277 (10)0.0471 (13)0.0925 (17)−0.0009 (8)−0.0053 (10)−0.0408 (11)
O60.0314 (10)0.0264 (9)0.0618 (13)−0.0010 (7)−0.0062 (9)−0.0183 (9)
O70.0299 (9)0.0305 (9)0.0351 (10)0.0051 (7)−0.0080 (8)−0.0082 (8)
O80.0386 (10)0.0249 (9)0.0445 (11)−0.0009 (7)−0.0168 (8)−0.0112 (8)
O1W0.0348 (10)0.0251 (9)0.0438 (11)−0.0016 (8)−0.0115 (8)−0.0074 (8)

Geometric parameters (Å, °)

C1—C21.379 (3)C12—H120.9300
C1—C61.383 (3)C13—C141.500 (3)
C1—H10.9300C14—O81.262 (3)
C2—C31.386 (3)C14—O71.268 (3)
C2—H20.9300C15—N21.485 (3)
C3—O11.362 (3)C15—C15i1.506 (5)
C3—C41.391 (3)C15—H15A0.9700
C4—C51.376 (3)C15—H15B0.9700
C4—O21.379 (3)C16—N11.486 (3)
C5—C61.393 (3)C16—C16ii1.507 (5)
C5—H50.9300C16—H16A0.9700
C6—C71.487 (3)C16—H16B0.9700
C7—O41.265 (3)N1—H1B0.8900
C7—O31.270 (3)N1—H1C0.8900
C8—C91.377 (3)N1—H1D0.8900
C8—C131.389 (3)N2—H2B0.8900
C8—H80.9300N2—H2C0.8900
C9—O51.364 (3)N2—H2D0.8900
C9—C101.401 (3)O1—H1A0.8200
C10—O61.365 (3)O2—H2A0.8200
C10—C111.376 (3)O5—H5A0.8200
C11—C121.385 (3)O6—H60.8200
C11—H110.9300O1W—H1W0.85 (2)
C12—C131.384 (3)O1W—H2W0.88 (2)
C2—C1—C6120.6 (2)C12—C13—C8119.0 (2)
C2—C1—H1119.7C12—C13—C14119.6 (2)
C6—C1—H1119.7C8—C13—C14121.4 (2)
C1—C2—C3120.7 (2)O8—C14—O7123.1 (2)
C1—C2—H2119.7O8—C14—C13119.3 (2)
C3—C2—H2119.7O7—C14—C13117.6 (2)
O1—C3—C2123.4 (2)N2—C15—C15i109.9 (2)
O1—C3—C4117.6 (2)N2—C15—H15A109.7
C2—C3—C4119.0 (2)C15i—C15—H15A109.7
C5—C4—O2122.5 (2)N2—C15—H15B109.7
C5—C4—C3120.1 (2)C15i—C15—H15B109.7
O2—C4—C3117.4 (2)H15A—C15—H15B108.2
C4—C5—C6121.0 (2)N1—C16—C16ii110.7 (3)
C4—C5—H5119.5N1—C16—H16A109.5
C6—C5—H5119.5C16ii—C16—H16A109.5
C1—C6—C5118.6 (2)N1—C16—H16B109.5
C1—C6—C7121.5 (2)C16ii—C16—H16B109.5
C5—C6—C7119.9 (2)H16A—C16—H16B108.1
O4—C7—O3122.3 (2)C16—N1—H1B109.5
O4—C7—C6118.7 (2)C16—N1—H1C109.5
O3—C7—C6119.1 (2)H1B—N1—H1C109.5
C9—C8—C13121.0 (2)C16—N1—H1D109.5
C9—C8—H8119.5H1B—N1—H1D109.5
C13—C8—H8119.5H1C—N1—H1D109.5
O5—C9—C8119.9 (2)C15—N2—H2B109.5
O5—C9—C10120.6 (2)C15—N2—H2C109.5
C8—C9—C10119.5 (2)H2B—N2—H2C109.5
O6—C10—C11123.9 (2)C15—N2—H2D109.5
O6—C10—C9116.5 (2)H2B—N2—H2D109.5
C11—C10—C9119.6 (2)H2C—N2—H2D109.5
C10—C11—C12120.3 (2)C3—O1—H1A109.5
C10—C11—H11119.8C4—O2—H2A109.5
C12—C11—H11119.8C9—O5—H5A109.5
C13—C12—C11120.5 (2)C10—O6—H6109.5
C13—C12—H12119.8H1W—O1W—H2W108 (2)
C11—C12—H12119.8

Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···O2iii0.892.042.904 (3)163
N1—H1C···O4iv0.891.942.803 (3)163
N1—H1D···O40.891.982.741 (3)143
N2—H2B···O3v0.892.092.931 (3)158
N2—H2B···O6v0.892.543.079 (3)120
N2—H2C···O80.891.902.742 (2)157
N2—H2D···O7vi0.891.942.799 (3)163
O1—H1A···O1Wvii0.821.942.753 (3)169
O2—H2A···O7viii0.821.952.755 (2)168
O5—H5A···O30.822.072.834 (2)156
O5—H5A···O40.822.353.014 (3)139
O6—H6···O1Wix0.821.902.686 (2)160
O1W—H1W···O30.85 (2)1.86 (2)2.676 (2)159 (3)
O1W—H2W···O8viii0.88 (2)1.85 (2)2.725 (2)173 (3)

Symmetry codes: (iii) x, y−1, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+1, −z; (vi) x−1, y, z; (vii) −x, −y+2, −z+1; (viii) x−1, y+1, z; (ix) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2221).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography