Ethyl-enediammonium bis-(3,4-dihy-droxy-benzoate) monohydrate.

In the title compound, C(2)H(10)N(2) (2+)·2C(7)H(5)O(4) (-)·H(2)O, the cation lies on a centre of symmetry. The crystal structure is stabilized by various inter-molecular O-H⋯O and N-H⋯O hydrogen bonds, and by weak π-π stacking inter-actions with centroid-centroid distances between symmetry-related benzene rings ranging from 3.5249 (13) to 3.7566 (14) Å.

Related literature

For protocatechuic acid (n class="Chemical">3,4-dihydroxybenzoic acid) and its pharmacological activity, see: An et al. (2006 ▶); Guan et al. (2006 ▶); Lin et al. (2009 ▶); Tseng et al. (1998 ▶); Yip et al. (2006 ▶). For related structures, see: Mazurek et al. (2007 ▶); Xu et al. (2008 ▶).

Experimental

Crystal data

C2H10N2 2+·2C7H5O4 −·n class="Chemical">H2O

M = 386.36

Triclinic,

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

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

C2H10N22+·2C7H5O4−·H2O	Z = 2
Mr = 386.36	F(000) = 408
Triclinic, P1	Dx = 1.511 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8489 (8) Å	Cell parameters from 1194 reflections
b = 10.7999 (12) Å	θ = 2.9–24.2°
c = 12.0137 (13) Å	µ = 0.13 mm−1
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

Bruker APEXII area-detector diffractometer	3011 independent reflections
Radiation source: fine-focus sealed tube	2215 reflections with I > 2σ(I)
graphite	Rint = 0.018
φ and ω scan	θmax = 25.2°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.963, Tmax = 0.969	k = −11→12
4432 measured reflections	l = −7→14

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0467P)2 + 0.4204P] where P = (Fo2 + 2Fc2)/3
3011 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 0.38 e Å−3
3 restraints	Δρmin = −0.22 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	0.2895 (3)	0.8335 (2)	0.5353 (2)	0.0292 (6)
H1	0.3031	0.7489	0.5769	0.035*
C2	0.2487 (3)	0.9308 (2)	0.5934 (2)	0.0301 (6)
H2	0.2322	0.9110	0.6738	0.036*
C3	0.2320 (3)	1.0577 (2)	0.5330 (2)	0.0262 (5)
C4	0.2557 (3)	1.0857 (2)	0.4127 (2)	0.0261 (5)
C5	0.2916 (3)	0.9881 (2)	0.3553 (2)	0.0268 (5)
H5	0.3037	1.0076	0.2748	0.032*
C6	0.3103 (3)	0.8606 (2)	0.4157 (2)	0.0258 (5)
C7	0.3510 (3)	0.7571 (2)	0.3514 (2)	0.0280 (5)
C8	0.7469 (3)	0.3983 (2)	0.1577 (2)	0.0295 (6)
H8	0.6571	0.3386	0.1610	0.035*
C9	0.6777 (3)	0.5199 (2)	0.1690 (2)	0.0297 (6)
C10	0.8130 (3)	0.6106 (2)	0.1619 (2)	0.0269 (5)
C11	1.0130 (3)	0.5753 (2)	0.1497 (2)	0.0291 (6)
H11	1.1030	0.6344	0.1481	0.035*
C12	1.0809 (3)	0.4523 (2)	0.1397 (2)	0.0286 (5)
H12	1.2163	0.4292	0.1318	0.034*
C13	0.9487 (3)	0.3636 (2)	0.1413 (2)	0.0258 (5)
C14	1.0255 (3)	0.2336 (2)	0.12291 (19)	0.0247 (5)
C15	0.5818 (4)	0.0203 (2)	0.0254 (2)	0.0299 (6)
H15A	0.5688	−0.0156	0.1082	0.036*
H15B	0.7091	−0.0117	−0.0085	0.036*
C16	0.0738 (4)	0.4632 (3)	0.5389 (2)	0.0377 (6)
H16A	0.1091	0.5173	0.5853	0.045*
H16B	0.0145	0.3896	0.5910	0.045*
N1	0.2550 (3)	0.41936 (18)	0.46971 (18)	0.0344 (5)
H1B	0.2249	0.3627	0.4335	0.052*
H1C	0.3452	0.3830	0.5164	0.052*
H1D	0.3036	0.4862	0.4178	0.052*
N2	0.5721 (3)	0.16219 (18)	0.00223 (18)	0.0323 (5)
H2B	0.5803	0.1949	−0.0737	0.048*
H2C	0.6723	0.1857	0.0298	0.048*
H2D	0.4579	0.1910	0.0367	0.048*
O1	0.1944 (3)	1.15782 (15)	0.58542 (14)	0.0342 (4)
H1A	0.1575	1.1311	0.6545	0.051*
O2	0.2417 (3)	1.21302 (14)	0.35551 (14)	0.0358 (4)
H2A	0.2385	1.2187	0.2865	0.054*
O3	0.3090 (2)	0.77974 (16)	0.24853 (15)	0.0343 (4)
O4	0.4239 (3)	0.64879 (15)	0.40190 (15)	0.0359 (4)
O5	0.4788 (3)	0.55228 (19)	0.1832 (2)	0.0518 (6)
H5A	0.4567	0.6128	0.2145	0.078*
O6	0.7346 (2)	0.73121 (15)	0.16717 (17)	0.0385 (5)
H6	0.8245	0.7775	0.1614	0.058*
O7	1.2060 (2)	0.19869 (15)	0.13369 (14)	0.0319 (4)
O8	0.9088 (2)	0.16349 (15)	0.09982 (15)	0.0344 (4)
O1W	−0.0308 (3)	0.90641 (16)	0.18631 (16)	0.0340 (4)
H1W	0.084 (4)	0.885 (3)	0.208 (2)	0.051*
H2W	−0.040 (4)	0.990 (2)	0.159 (2)	0.051*

	U11	U22	U33	U12	U13	U23
C1	0.0341 (14)	0.0220 (12)	0.0300 (14)	−0.0018 (10)	−0.0076 (11)	−0.0010 (10)
C2	0.0336 (14)	0.0305 (14)	0.0256 (13)	−0.0035 (10)	−0.0042 (11)	−0.0043 (11)
C3	0.0246 (12)	0.0263 (13)	0.0301 (14)	−0.0003 (10)	−0.0049 (10)	−0.0109 (11)
C4	0.0278 (13)	0.0202 (12)	0.0304 (14)	−0.0019 (9)	−0.0088 (10)	−0.0031 (10)
C5	0.0301 (13)	0.0284 (13)	0.0229 (13)	−0.0034 (10)	−0.0069 (10)	−0.0055 (10)
C6	0.0233 (12)	0.0222 (12)	0.0319 (14)	−0.0018 (9)	−0.0053 (10)	−0.0050 (10)
C7	0.0216 (12)	0.0260 (13)	0.0369 (15)	−0.0029 (10)	−0.0032 (11)	−0.0079 (11)
C8	0.0287 (13)	0.0263 (13)	0.0367 (15)	−0.0064 (10)	−0.0054 (11)	−0.0107 (11)
C9	0.0228 (12)	0.0336 (14)	0.0361 (15)	−0.0005 (10)	−0.0051 (11)	−0.0146 (11)
C10	0.0319 (13)	0.0220 (12)	0.0286 (13)	−0.0009 (10)	−0.0073 (10)	−0.0080 (10)
C11	0.0310 (13)	0.0260 (13)	0.0319 (14)	−0.0080 (10)	−0.0073 (11)	−0.0055 (11)
C12	0.0259 (13)	0.0261 (13)	0.0334 (14)	0.0002 (10)	−0.0084 (11)	−0.0041 (11)
C13	0.0271 (12)	0.0258 (12)	0.0250 (13)	−0.0001 (10)	−0.0062 (10)	−0.0057 (10)
C14	0.0304 (13)	0.0235 (12)	0.0191 (12)	−0.0016 (10)	−0.0052 (10)	−0.0016 (10)
C15	0.0289 (13)	0.0294 (13)	0.0317 (14)	0.0011 (10)	−0.0066 (10)	−0.0071 (11)
C16	0.0424 (15)	0.0335 (14)	0.0356 (15)	0.0022 (12)	−0.0085 (12)	−0.0051 (12)
N1	0.0377 (12)	0.0235 (11)	0.0413 (13)	−0.0021 (9)	−0.0100 (10)	−0.0031 (9)
N2	0.0302 (11)	0.0325 (12)	0.0365 (12)	−0.0019 (9)	−0.0078 (9)	−0.0105 (10)
O1	0.0466 (11)	0.0267 (9)	0.0298 (10)	−0.0037 (8)	−0.0008 (8)	−0.0098 (7)
O2	0.0575 (12)	0.0204 (9)	0.0296 (10)	−0.0020 (8)	−0.0139 (9)	−0.0018 (7)
O3	0.0369 (10)	0.0352 (10)	0.0339 (10)	0.0056 (8)	−0.0091 (8)	−0.0151 (8)
O4	0.0416 (10)	0.0203 (9)	0.0457 (11)	0.0010 (7)	−0.0107 (9)	−0.0057 (8)
O5	0.0277 (10)	0.0471 (13)	0.0925 (17)	−0.0009 (8)	−0.0053 (10)	−0.0408 (11)
O6	0.0314 (10)	0.0264 (9)	0.0618 (13)	−0.0010 (7)	−0.0062 (9)	−0.0183 (9)
O7	0.0299 (9)	0.0305 (9)	0.0351 (10)	0.0051 (7)	−0.0080 (8)	−0.0082 (8)
O8	0.0386 (10)	0.0249 (9)	0.0445 (11)	−0.0009 (7)	−0.0168 (8)	−0.0112 (8)
O1W	0.0348 (10)	0.0251 (9)	0.0438 (11)	−0.0016 (8)	−0.0115 (8)	−0.0074 (8)

C1—C2	1.379 (3)	C12—H12	0.9300
C1—C6	1.383 (3)	C13—C14	1.500 (3)
C1—H1	0.9300	C14—O8	1.262 (3)
C2—C3	1.386 (3)	C14—O7	1.268 (3)
C2—H2	0.9300	C15—N2	1.485 (3)
C3—O1	1.362 (3)	C15—C15i	1.506 (5)
C3—C4	1.391 (3)	C15—H15A	0.9700
C4—C5	1.376 (3)	C15—H15B	0.9700
C4—O2	1.379 (3)	C16—N1	1.486 (3)
C5—C6	1.393 (3)	C16—C16ii	1.507 (5)
C5—H5	0.9300	C16—H16A	0.9700
C6—C7	1.487 (3)	C16—H16B	0.9700
C7—O4	1.265 (3)	N1—H1B	0.8900
C7—O3	1.270 (3)	N1—H1C	0.8900
C8—C9	1.377 (3)	N1—H1D	0.8900
C8—C13	1.389 (3)	N2—H2B	0.8900
C8—H8	0.9300	N2—H2C	0.8900
C9—O5	1.364 (3)	N2—H2D	0.8900
C9—C10	1.401 (3)	O1—H1A	0.8200
C10—O6	1.365 (3)	O2—H2A	0.8200
C10—C11	1.376 (3)	O5—H5A	0.8200
C11—C12	1.385 (3)	O6—H6	0.8200
C11—H11	0.9300	O1W—H1W	0.85 (2)
C12—C13	1.384 (3)	O1W—H2W	0.88 (2)
C2—C1—C6	120.6 (2)	C12—C13—C8	119.0 (2)
C2—C1—H1	119.7	C12—C13—C14	119.6 (2)
C6—C1—H1	119.7	C8—C13—C14	121.4 (2)
C1—C2—C3	120.7 (2)	O8—C14—O7	123.1 (2)
C1—C2—H2	119.7	O8—C14—C13	119.3 (2)
C3—C2—H2	119.7	O7—C14—C13	117.6 (2)
O1—C3—C2	123.4 (2)	N2—C15—C15i	109.9 (2)
O1—C3—C4	117.6 (2)	N2—C15—H15A	109.7
C2—C3—C4	119.0 (2)	C15i—C15—H15A	109.7
C5—C4—O2	122.5 (2)	N2—C15—H15B	109.7
C5—C4—C3	120.1 (2)	C15i—C15—H15B	109.7
O2—C4—C3	117.4 (2)	H15A—C15—H15B	108.2
C4—C5—C6	121.0 (2)	N1—C16—C16ii	110.7 (3)
C4—C5—H5	119.5	N1—C16—H16A	109.5
C6—C5—H5	119.5	C16ii—C16—H16A	109.5
C1—C6—C5	118.6 (2)	N1—C16—H16B	109.5
C1—C6—C7	121.5 (2)	C16ii—C16—H16B	109.5
C5—C6—C7	119.9 (2)	H16A—C16—H16B	108.1
O4—C7—O3	122.3 (2)	C16—N1—H1B	109.5
O4—C7—C6	118.7 (2)	C16—N1—H1C	109.5
O3—C7—C6	119.1 (2)	H1B—N1—H1C	109.5
C9—C8—C13	121.0 (2)	C16—N1—H1D	109.5
C9—C8—H8	119.5	H1B—N1—H1D	109.5
C13—C8—H8	119.5	H1C—N1—H1D	109.5
O5—C9—C8	119.9 (2)	C15—N2—H2B	109.5
O5—C9—C10	120.6 (2)	C15—N2—H2C	109.5
C8—C9—C10	119.5 (2)	H2B—N2—H2C	109.5
O6—C10—C11	123.9 (2)	C15—N2—H2D	109.5
O6—C10—C9	116.5 (2)	H2B—N2—H2D	109.5
C11—C10—C9	119.6 (2)	H2C—N2—H2D	109.5
C10—C11—C12	120.3 (2)	C3—O1—H1A	109.5
C10—C11—H11	119.8	C4—O2—H2A	109.5
C12—C11—H11	119.8	C9—O5—H5A	109.5
C13—C12—C11	120.5 (2)	C10—O6—H6	109.5
C13—C12—H12	119.8	H1W—O1W—H2W	108 (2)
C11—C12—H12	119.8

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2iii	0.89	2.04	2.904 (3)	163
N1—H1C···O4iv	0.89	1.94	2.803 (3)	163
N1—H1D···O4	0.89	1.98	2.741 (3)	143
N2—H2B···O3v	0.89	2.09	2.931 (3)	158
N2—H2B···O6v	0.89	2.54	3.079 (3)	120
N2—H2C···O8	0.89	1.90	2.742 (2)	157
N2—H2D···O7vi	0.89	1.94	2.799 (3)	163
O1—H1A···O1Wvii	0.82	1.94	2.753 (3)	169
O2—H2A···O7viii	0.82	1.95	2.755 (2)	168
O5—H5A···O3	0.82	2.07	2.834 (2)	156
O5—H5A···O4	0.82	2.35	3.014 (3)	139
O6—H6···O1Wix	0.82	1.90	2.686 (2)	160
O1W—H1W···O3	0.85 (2)	1.86 (2)	2.676 (2)	159 (3)
O1W—H2W···O8viii	0.88 (2)	1.85 (2)	2.725 (2)	173 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2i	0.89	2.04	2.904 (3)	163
N1—H1C⋯O4ii	0.89	1.94	2.803 (3)	163
N1—H1D⋯O4	0.89	1.98	2.741 (3)	143
N2—H2B⋯O3iii	0.89	2.09	2.931 (3)	158
N2—H2B⋯O6iii	0.89	2.54	3.079 (3)	120
N2—H2C⋯O8	0.89	1.90	2.742 (2)	157
N2—H2D⋯O7iv	0.89	1.94	2.799 (3)	163
O1—H1A⋯O1Wv	0.82	1.94	2.753 (3)	169
O2—H2A⋯O7vi	0.82	1.95	2.755 (2)	168
O5—H5A⋯O3	0.82	2.07	2.834 (2)	156
O5—H5A⋯O4	0.82	2.35	3.014 (3)	139
O6—H6⋯O1Wvii	0.82	1.90	2.686 (2)	160
O1W—H1W⋯O3	0.85 (2)	1.86 (2)	2.676 (2)	159 (3)
O1W—H2W⋯O8vi	0.88 (2)	1.85 (2)	2.725 (2)	173 (3)

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