Triethyl-ammonium 3,4-dihy-droxy-benzoate monohydrate.

In the structure of the title compound, C(6)H(16)N(+)·C(7)H(5)O(4) (-)·H(2)O, O-H⋯O and N-H⋯O hydrogen bonds link the components into a three-dimensional array. The 3,4-dihy-droxy-benzoate anion is approximately planar, with a maximum deviation of 0.083 (2) Å.

Related literature

For protocatechuic acid (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 ▶).

Experimental

Crystal data

C6H16N+·C7H5O4 −·H2O

M = 273.32

Orthorhombic,

a = 10.7163 (16) Å

b = 11.5973 (17) Å

c = 11.7690 (17) Å

V = 1462.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.30 × 0.28 × 0.28 mm

Data collection

Bruker APEXII area-detector diffractometer

7531 measured reflections

1519 independent reflections

1211 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.093

S = 1.04

1519 reflections

186 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.14 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810046441/zl2325sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046441/zl2325Isup2.hkl

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

C6H16N+·C7H5O4−·H2O	F(000) = 592
Mr = 273.32	Dx = 1.241 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1465 reflections
a = 10.7163 (16) Å	θ = 2.5–21.3°
b = 11.5973 (17) Å	µ = 0.10 mm−1
c = 11.7690 (17) Å	T = 296 K
V = 1462.7 (4) Å3	Block, colourless
Z = 4	0.30 × 0.28 × 0.28 mm

Bruker APEXII area-detector diffractometer	1211 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
graphite	θmax = 25.2°, θmin = 2.5°
φ and ω scans	h = −12→6
7531 measured reflections	k = −13→13
1519 independent reflections	l = −14→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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0404P)2 + 0.2897P] where P = (Fo2 + 2Fc2)/3
1519 reflections	(Δ/σ)max < 0.001
186 parameters	Δρmax = 0.20 e Å−3
3 restraints	Δρmin = −0.14 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	0.9308 (3)	0.5565 (2)	0.8260 (2)	0.0342 (6)
H1	0.9565	0.5065	0.7688	0.041*
C6	0.9902 (3)	0.6627 (2)	0.8383 (2)	0.0325 (6)
C3	0.7962 (3)	0.5995 (2)	0.9826 (2)	0.0368 (7)
C2	0.8350 (3)	0.5241 (2)	0.8967 (2)	0.0344 (6)
C5	0.9503 (3)	0.7362 (2)	0.9238 (2)	0.0414 (7)
H5	0.9891	0.8073	0.9334	0.050*
C4	0.8538 (3)	0.7050 (2)	0.9948 (2)	0.0422 (7)
H4	0.8273	0.7555	1.0513	0.051*
C7	1.0953 (3)	0.6967 (2)	0.7614 (2)	0.0359 (7)
O1	1.1524 (2)	0.79093 (17)	0.78093 (16)	0.0458 (5)
O2	1.12389 (19)	0.6316 (2)	0.68029 (18)	0.0531 (6)
O4	0.7734 (2)	0.42081 (17)	0.89033 (19)	0.0537 (6)
H4A	0.8011	0.3831	0.8370	0.081*
O3	0.7002 (2)	0.56347 (19)	1.05036 (17)	0.0491 (6)
H3	0.6853	0.6129	1.0983	0.074*
N1	0.3697 (2)	0.6142 (2)	0.6203 (2)	0.0417 (6)
C10	0.4121 (3)	0.6946 (3)	0.5286 (3)	0.0608 (9)
H10A	0.4949	0.6720	0.5039	0.073*
H10B	0.4178	0.7720	0.5595	0.073*
C12	0.3732 (4)	0.4905 (3)	0.5826 (3)	0.0574 (9)
H12A	0.3205	0.4817	0.5162	0.069*
H12B	0.4578	0.4710	0.5608	0.069*
C11	0.3266 (4)	0.6960 (4)	0.4277 (3)	0.0885 (14)
H11A	0.3283	0.6220	0.3912	0.133*
H11B	0.3536	0.7541	0.3751	0.133*
H11C	0.2431	0.7128	0.4523	0.133*
C13	0.3304 (5)	0.4082 (3)	0.6726 (4)	0.0840 (13)
H13A	0.3883	0.4094	0.7348	0.126*
H13B	0.3264	0.3318	0.6415	0.126*
H13C	0.2493	0.4307	0.6990	0.126*
C8	0.4404 (3)	0.6357 (3)	0.7284 (3)	0.0577 (9)
H8A	0.4001	0.5934	0.7894	0.069*
H8B	0.4349	0.7171	0.7466	0.069*
C9	0.5759 (3)	0.6018 (4)	0.7247 (4)	0.0822 (13)
H9A	0.5825	0.5197	0.7161	0.123*
H9B	0.6159	0.6249	0.7941	0.123*
H9C	0.6157	0.6392	0.6616	0.123*
H14	0.288 (2)	0.633 (4)	0.637 (4)	0.123*
O1W	0.0402 (3)	0.5325 (3)	0.4727 (2)	0.0719 (8)
H1W	−0.035 (2)	0.514 (4)	0.482 (4)	0.108*
H2W	0.066 (4)	0.568 (3)	0.533 (3)	0.108*

	U11	U22	U33	U12	U13	U23
C1	0.0341 (15)	0.0357 (15)	0.0328 (14)	0.0014 (13)	0.0032 (13)	−0.0061 (12)
C6	0.0319 (15)	0.0328 (15)	0.0329 (14)	0.0021 (12)	−0.0029 (12)	0.0010 (12)
C3	0.0340 (16)	0.0435 (17)	0.0327 (15)	0.0026 (14)	0.0009 (13)	−0.0001 (13)
C2	0.0343 (16)	0.0341 (14)	0.0347 (14)	−0.0005 (12)	−0.0006 (13)	−0.0044 (13)
C5	0.0458 (19)	0.0339 (15)	0.0446 (16)	−0.0034 (14)	−0.0005 (15)	−0.0077 (14)
C4	0.0415 (17)	0.0403 (18)	0.0448 (17)	0.0033 (15)	0.0063 (15)	−0.0131 (14)
C7	0.0336 (16)	0.0405 (17)	0.0335 (15)	−0.0009 (14)	−0.0043 (12)	−0.0001 (13)
O1	0.0550 (13)	0.0438 (12)	0.0387 (11)	−0.0165 (11)	0.0005 (10)	0.0018 (9)
O2	0.0471 (14)	0.0624 (14)	0.0497 (12)	−0.0131 (11)	0.0134 (11)	−0.0191 (11)
O4	0.0581 (15)	0.0441 (13)	0.0590 (15)	−0.0146 (11)	0.0204 (12)	−0.0139 (11)
O3	0.0463 (14)	0.0550 (13)	0.0459 (12)	−0.0037 (11)	0.0149 (10)	−0.0132 (10)
N1	0.0393 (15)	0.0445 (14)	0.0413 (14)	−0.0017 (12)	0.0058 (12)	−0.0020 (11)
C10	0.055 (2)	0.061 (2)	0.067 (2)	−0.0040 (19)	0.0120 (18)	0.0178 (18)
C12	0.065 (2)	0.0475 (19)	0.060 (2)	0.0024 (17)	0.0031 (19)	−0.0145 (17)
C11	0.081 (3)	0.117 (4)	0.068 (3)	0.002 (3)	−0.003 (2)	0.039 (3)
C13	0.098 (3)	0.055 (2)	0.099 (3)	−0.013 (2)	−0.013 (3)	0.013 (2)
C8	0.060 (2)	0.060 (2)	0.0527 (19)	−0.0054 (19)	−0.0044 (18)	−0.0096 (17)
C9	0.055 (2)	0.099 (3)	0.094 (3)	−0.003 (2)	−0.018 (2)	0.003 (3)
O1W	0.0682 (19)	0.0815 (19)	0.0658 (16)	−0.0147 (16)	0.0034 (15)	−0.0133 (14)

C1—C2	1.374 (4)	C10—C11	1.500 (5)
C1—C6	1.395 (4)	C10—H10A	0.9700
C1—H1	0.9300	C10—H10B	0.9700
C6—C5	1.387 (4)	C12—C13	1.497 (5)
C6—C7	1.498 (4)	C12—H12A	0.9700
C3—O3	1.368 (3)	C12—H12B	0.9700
C3—C4	1.378 (4)	C11—H11A	0.9600
C3—C2	1.400 (4)	C11—H11B	0.9600
C2—O4	1.370 (3)	C11—H11C	0.9600
C5—C4	1.379 (4)	C13—H13A	0.9600
C5—H5	0.9300	C13—H13B	0.9600
C4—H4	0.9300	C13—H13C	0.9600
C7—O2	1.255 (3)	C8—C9	1.505 (5)
C7—O1	1.273 (3)	C8—H8A	0.9700
O4—H4A	0.8200	C8—H8B	0.9700
O3—H3	0.8200	C9—H9A	0.9600
N1—C10	1.497 (4)	C9—H9B	0.9600
N1—C12	1.501 (4)	C9—H9C	0.9600
N1—C8	1.502 (4)	O1W—H1W	0.841 (19)
N1—H14	0.92 (2)	O1W—H2W	0.87 (4)
C2—C1—C6	121.3 (3)	C11—C10—H10B	109.0
C2—C1—H1	119.3	H10A—C10—H10B	107.8
C6—C1—H1	119.3	C13—C12—N1	113.1 (3)
C5—C6—C1	118.6 (3)	C13—C12—H12A	108.9
C5—C6—C7	120.6 (2)	N1—C12—H12A	108.9
C1—C6—C7	120.9 (2)	C13—C12—H12B	108.9
O3—C3—C4	123.2 (3)	N1—C12—H12B	108.9
O3—C3—C2	117.0 (3)	H12A—C12—H12B	107.8
C4—C3—C2	119.8 (3)	C10—C11—H11A	109.5
O4—C2—C1	124.5 (2)	C10—C11—H11B	109.5
O4—C2—C3	116.3 (2)	H11A—C11—H11B	109.5
C1—C2—C3	119.3 (3)	C10—C11—H11C	109.5
C4—C5—C6	120.7 (3)	H11A—C11—H11C	109.5
C4—C5—H5	119.7	H11B—C11—H11C	109.5
C6—C5—H5	119.7	C12—C13—H13A	109.5
C3—C4—C5	120.4 (3)	C12—C13—H13B	109.5
C3—C4—H4	119.8	H13A—C13—H13B	109.5
C5—C4—H4	119.8	C12—C13—H13C	109.5
O2—C7—O1	122.5 (3)	H13A—C13—H13C	109.5
O2—C7—C6	119.0 (2)	H13B—C13—H13C	109.5
O1—C7—C6	118.6 (2)	N1—C8—C9	114.8 (3)
C2—O4—H4A	109.5	N1—C8—H8A	108.6
C3—O3—H3	109.5	C9—C8—H8A	108.6
C10—N1—C12	112.0 (2)	N1—C8—H8B	108.6
C10—N1—C8	110.7 (3)	C9—C8—H8B	108.6
C12—N1—C8	113.3 (3)	H8A—C8—H8B	107.6
C10—N1—H14	107 (3)	C8—C9—H9A	109.5
C12—N1—H14	108 (3)	C8—C9—H9B	109.5
C8—N1—H14	105 (3)	H9A—C9—H9B	109.5
N1—C10—C11	113.0 (3)	C8—C9—H9C	109.5
N1—C10—H10A	109.0	H9A—C9—H9C	109.5
C11—C10—H10A	109.0	H9B—C9—H9C	109.5
N1—C10—H10B	109.0	H1W—O1W—H2W	108 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O2i	0.87 (4)	1.98 (2)	2.845 (3)	173 (4)
O1W—H1W···O3ii	0.84 (2)	2.14 (2)	2.951 (3)	162 (4)
N1—H14···O2i	0.92 (2)	1.83 (2)	2.734 (3)	166 (5)
O3—H3···O1iii	0.82	1.84	2.656 (3)	173
O4—H4A···O1iv	0.82	1.82	2.639 (3)	174

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯O2i	0.87 (4)	1.98 (2)	2.845 (3)	173 (4)
O1W—H1W⋯O3ii	0.84 (2)	2.14 (2)	2.951 (3)	162 (4)
N1—H14⋯O2i	0.92 (2)	1.83 (2)	2.734 (3)	166 (5)
O3—H3⋯O1iii	0.82	1.84	2.656 (3)	173
O4—H4A⋯O1iv	0.82	1.82	2.639 (3)	174

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