catena-Poly[[tri-aqua-copper(II)]-μ-5-carb-oxy-benzene-1,3-di-carboxyl-ato-κ(2) O (1):O (3)].

In the title complex, [Cu(C9H4O6)(H2O)3] n , the Cu(II) cation exhibits a distorted square-pyramidal coordination geometry involving five O atoms from two monodentate 5-carb-oxy-benzene-1,3-di-carboxyl-ate anions and three water mol-ecules. The 5-carb-oxy-benzene-1,3-di-carboxyl-ate anions bridge Cu(II) cations into zigzag polymeric chains running along the b-axis direction. These chains are further linked by O-H⋯O hydrogen bonds between coordinating water mol-ecules or carboxyl groups and carboxylate groups into a three-dimensional supra-molecular architecture. In the crystal, π-π stacking is observed between parallel benzene rings of adjacent chains, the centroid-centroid distances being 3.584 (3) and 3.684 (3) Å.

Related literature

For background to complexes derived from 1,3,5-benzene­tri­carb­oxy­lic acid and for related structures, see: Lei et al. (2012 ▶); Liu (2012 ▶); Yao & Yuan (2011 ▶).

Experimental

Crystal data

[Cu(C9H4O6)(H2O)3]

M = 325.71

Monoclinic,

a = 6.8551 (14) Å

b = 18.892 (4) Å

c = 10.716 (3) Å

β = 126.87 (2)°

V = 1110.2 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.01 mm−1

T = 293 K

0.24 × 0.21 × 0.21 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.644, T max = 0.677

9530 measured reflections

1957 independent reflections

1744 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.083

S = 1.01

1957 reflections

193 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.47 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813024781/xu5736sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024781/xu5736Isup2.hkl

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

[Cu(C9H4O6)(H2O)3]	F(000) = 660
Mr = 325.71	Dx = 1.949 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10073 reflections
a = 6.8551 (14) Å	θ = 3.2–27.5°
b = 18.892 (4) Å	µ = 2.01 mm−1
c = 10.716 (3) Å	T = 293 K
β = 126.87 (2)°	Block, blue
V = 1110.2 (5) Å3	0.24 × 0.21 × 0.21 mm
Z = 4

Rigaku SCXmini diffractometer	1957 independent reflections
Radiation source: fine-focus sealed tube	1744 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
Tmin = 0.644, Tmax = 0.677	k = −22→22
9530 measured reflections	l = −12→12

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0257P)2 + 3.7798P] where P = (Fo2 + 2Fc2)/3
1957 reflections	(Δ/σ)max = 0.001
193 parameters	Δρmax = 0.42 e Å−3
10 restraints	Δρmin = −0.47 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
Cu1	0.88938 (8)	0.72640 (2)	0.67913 (5)	0.01706 (15)
O1	1.0451 (6)	0.87364 (14)	0.7671 (3)	0.0342 (7)
O2	0.7879 (5)	0.81134 (12)	0.5539 (3)	0.0218 (6)
O3	0.2513 (5)	0.91554 (14)	0.0486 (3)	0.0310 (7)
O4	0.2713 (6)	1.02917 (15)	0.0054 (3)	0.0460 (9)
O5	1.0069 (5)	1.13796 (13)	0.7111 (3)	0.0235 (6)
O6	0.7413 (5)	1.18913 (13)	0.4807 (3)	0.0258 (6)
O2W	1.1364 (6)	0.71108 (15)	0.6410 (4)	0.0398 (8)
O3W	0.6921 (6)	0.75211 (17)	0.7518 (3)	0.0367 (7)
O1W	0.5840 (5)	0.67089 (15)	0.4599 (3)	0.0337 (7)
C2	0.7775 (6)	0.93545 (17)	0.5254 (4)	0.0144 (7)
C1	0.8790 (7)	0.86999 (18)	0.6244 (4)	0.0171 (8)
C9	0.8375 (7)	1.13575 (18)	0.5656 (4)	0.0174 (8)
C7	0.8509 (6)	1.00280 (18)	0.5912 (4)	0.0148 (7)
H7	0.9642	1.0078	0.6986	0.018*
C5	0.5841 (7)	1.05491 (18)	0.3357 (4)	0.0169 (8)
H5	0.5191	1.0949	0.2726	0.020*
C3	0.6077 (6)	0.92832 (18)	0.3648 (4)	0.0160 (8)
H3	0.5587	0.8834	0.3208	0.019*
C4	0.5101 (7)	0.98796 (18)	0.2688 (4)	0.0165 (8)
C8	0.3348 (7)	0.98117 (19)	0.0959 (4)	0.0223 (8)
C6	0.7546 (6)	1.06249 (18)	0.4962 (4)	0.0150 (7)
H1	0.167 (6)	0.915 (2)	−0.0485 (13)	0.023*
H2WA	1.132 (7)	0.7397 (13)	0.579 (4)	0.023*
H3WB	0.715 (6)	0.746 (2)	0.836 (2)	0.023*
H2WB	1.166 (7)	0.6699 (7)	0.628 (4)	0.023*
H1WA	0.439 (3)	0.6782 (16)	0.424 (4)	0.023*
H3WA	0.575 (5)	0.7788 (17)	0.691 (3)	0.023*
H1WB	0.619 (6)	0.6279 (7)	0.475 (4)	0.023*

	U11	U22	U33	U12	U13	U23
Cu1	0.0235 (3)	0.0090 (2)	0.0143 (2)	0.00247 (19)	0.00896 (19)	0.00336 (18)
O1	0.0463 (19)	0.0200 (15)	0.0137 (14)	0.0008 (13)	0.0059 (13)	0.0007 (11)
O2	0.0280 (14)	0.0083 (12)	0.0176 (13)	−0.0011 (11)	0.0074 (12)	0.0014 (10)
O3	0.0441 (18)	0.0208 (14)	0.0097 (13)	−0.0087 (13)	0.0063 (13)	−0.0049 (11)
O4	0.068 (2)	0.0180 (15)	0.0167 (16)	−0.0039 (15)	0.0064 (16)	0.0040 (13)
O5	0.0303 (15)	0.0119 (13)	0.0153 (14)	−0.0014 (11)	0.0068 (12)	−0.0034 (10)
O6	0.0296 (15)	0.0119 (13)	0.0257 (15)	−0.0008 (11)	0.0112 (13)	0.0036 (11)
O2W	0.056 (2)	0.0206 (16)	0.066 (2)	0.0127 (15)	0.0494 (19)	0.0162 (15)
O3W	0.0430 (19)	0.0456 (19)	0.0305 (17)	0.0199 (15)	0.0270 (16)	0.0153 (14)
O1W	0.0320 (17)	0.0236 (15)	0.0294 (16)	−0.0021 (13)	0.0098 (14)	−0.0048 (13)
C2	0.0169 (18)	0.0100 (17)	0.0149 (18)	−0.0020 (14)	0.0088 (15)	−0.0020 (14)
C1	0.023 (2)	0.0138 (18)	0.0140 (19)	0.0014 (15)	0.0103 (17)	0.0002 (14)
C9	0.0220 (19)	0.0128 (18)	0.022 (2)	−0.0017 (15)	0.0152 (17)	−0.0031 (15)
C7	0.0182 (19)	0.0148 (18)	0.0100 (17)	0.0004 (14)	0.0078 (15)	0.0002 (14)
C5	0.025 (2)	0.0094 (17)	0.0167 (19)	0.0022 (15)	0.0124 (16)	0.0014 (14)
C3	0.0208 (19)	0.0088 (17)	0.0180 (19)	−0.0018 (14)	0.0114 (16)	−0.0021 (14)
C4	0.0184 (18)	0.016 (2)	0.0131 (18)	−0.0013 (15)	0.0084 (15)	−0.0009 (14)
C8	0.028 (2)	0.0137 (19)	0.017 (2)	−0.0002 (16)	0.0089 (17)	−0.0029 (16)
C6	0.0161 (18)	0.0126 (17)	0.0148 (18)	−0.0025 (14)	0.0085 (15)	−0.0024 (14)

Cu1—O2	1.934 (2)	O3W—H3WA	0.832 (10)
Cu1—O5i	1.917 (2)	O1W—H1WA	0.836 (10)
Cu1—O1W	2.258 (3)	O1W—H1WB	0.834 (10)
Cu1—O2W	1.987 (3)	C2—C3	1.390 (5)
Cu1—O3W	1.984 (3)	C2—C7	1.394 (5)
O1—C1	1.245 (4)	C2—C1	1.501 (5)
O2—C1	1.273 (4)	C9—C6	1.511 (5)
O3—C8	1.332 (4)	C7—C6	1.392 (5)
O3—H1	0.833 (10)	C7—H7	0.9300
O4—C8	1.202 (5)	C5—C6	1.391 (5)
O5—C9	1.268 (4)	C5—C4	1.391 (5)
O5—Cu1ii	1.917 (2)	C5—H5	0.9300
O6—C9	1.249 (4)	C3—C4	1.396 (5)
O2W—H2WA	0.840 (10)	C3—H3	0.9300
O2W—H2WB	0.838 (10)	C4—C8	1.491 (5)
O3W—H3WB	0.832 (10)
O5i—Cu1—O2	174.44 (11)	O1—C1—O2	122.6 (3)
O5i—Cu1—O3W	93.54 (12)	O1—C1—C2	121.1 (3)
O2—Cu1—O3W	91.33 (12)	O2—C1—C2	116.3 (3)
O5i—Cu1—O2W	87.19 (12)	O6—C9—O5	124.2 (3)
O2—Cu1—O2W	88.53 (12)	O6—C9—C6	120.2 (3)
O3W—Cu1—O2W	169.17 (15)	O5—C9—C6	115.6 (3)
O5i—Cu1—O1W	90.26 (11)	C6—C7—C2	120.0 (3)
O2—Cu1—O1W	86.59 (11)	C6—C7—H7	120.0
O3W—Cu1—O1W	95.58 (13)	C2—C7—H7	120.0
O2W—Cu1—O1W	95.22 (14)	C6—C5—C4	120.5 (3)
C1—O2—Cu1	117.8 (2)	C6—C5—H5	119.8
C8—O3—H1	108 (3)	C4—C5—H5	119.8
C9—O5—Cu1ii	120.8 (2)	C2—C3—C4	120.6 (3)
Cu1—O2W—H2WA	116 (2)	C2—C3—H3	119.7
Cu1—O2W—H2WB	120 (3)	C4—C3—H3	119.7
H2WA—O2W—H2WB	111.3 (17)	C5—C4—C3	119.3 (3)
Cu1—O3W—H3WB	132 (2)	C5—C4—C8	119.4 (3)
Cu1—O3W—H3WA	114 (2)	C3—C4—C8	121.3 (3)
H3WB—O3W—H3WA	113.6 (18)	O4—C8—O3	122.0 (3)
Cu1—O1W—H1WA	120 (3)	O4—C8—C4	124.7 (3)
Cu1—O1W—H1WB	106 (3)	O3—C8—C4	113.3 (3)
H1WA—O1W—H1WB	112.3 (18)	C5—C6—C7	119.9 (3)
C3—C2—C7	119.7 (3)	C5—C6—C9	119.5 (3)
C3—C2—C1	119.0 (3)	C7—C6—C9	120.6 (3)
C7—C2—C1	121.4 (3)
O5i—Cu1—O2—C1	−135.3 (11)	C6—C5—C4—C3	0.4 (5)
O3W—Cu1—O2—C1	73.6 (3)	C6—C5—C4—C8	−177.5 (3)
O2W—Cu1—O2—C1	−95.6 (3)	C2—C3—C4—C5	−0.2 (5)
O1W—Cu1—O2—C1	169.1 (3)	C2—C3—C4—C8	177.8 (3)
Cu1—O2—C1—O1	6.9 (5)	C5—C4—C8—O4	9.3 (6)
Cu1—O2—C1—C2	−174.0 (2)	C3—C4—C8—O4	−168.6 (4)
C3—C2—C1—O1	174.3 (4)	C5—C4—C8—O3	−170.6 (3)
C7—C2—C1—O1	−5.3 (5)	C3—C4—C8—O3	11.5 (5)
C3—C2—C1—O2	−4.8 (5)	C4—C5—C6—C7	−0.5 (5)
C7—C2—C1—O2	175.5 (3)	C4—C5—C6—C9	178.2 (3)
Cu1ii—O5—C9—O6	6.7 (5)	C2—C7—C6—C5	0.3 (5)
Cu1ii—O5—C9—C6	−173.7 (2)	C2—C7—C6—C9	−178.4 (3)
C3—C2—C7—C6	−0.1 (5)	O6—C9—C6—C5	4.9 (5)
C1—C2—C7—C6	179.6 (3)	O5—C9—C6—C5	−174.7 (3)
C7—C2—C3—C4	0.0 (5)	O6—C9—C6—C7	−176.3 (3)
C1—C2—C3—C4	−179.7 (3)	O5—C9—C6—C7	4.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O1iii	0.83 (1)	1.80 (2)	2.570 (4)	153 (4)
O1W—H1WA···O1iv	0.84 (1)	2.37 (2)	3.077 (4)	142 (3)
O1W—H1WB···O4v	0.83 (1)	1.97 (1)	2.801 (4)	171 (4)
O2W—H2WA···O6vi	0.84 (1)	1.91 (2)	2.697 (4)	155 (4)
O2W—H2WB···O3vii	0.84 (1)	2.07 (2)	2.875 (4)	162 (3)
O3W—H3WA···O6viii	0.83 (1)	1.92 (2)	2.717 (4)	161 (4)
O3W—H3WB···O2ix	0.83 (1)	2.33 (2)	3.130 (4)	161 (3)

Table 1

Selected bond lengths (Å)

Cu1—O2	1.934 (2)
Cu1—O5i	1.917 (2)
Cu1—O1W	2.258 (3)
Cu1—O2W	1.987 (3)
Cu1—O3W	1.984 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1⋯O1ii	0.83 (1)	1.80 (2)	2.570 (4)	153 (4)
O1W—H1WA⋯O1iii	0.84 (1)	2.37 (2)	3.077 (4)	142 (3)
O1W—H1WB⋯O4iv	0.83 (1)	1.97 (1)	2.801 (4)	171 (4)
O2W—H2WA⋯O6v	0.84 (1)	1.91 (2)	2.697 (4)	155 (4)
O2W—H2WB⋯O3vi	0.84 (1)	2.07 (2)	2.875 (4)	162 (3)
O3W—H3WA⋯O6vii	0.83 (1)	1.92 (2)	2.717 (4)	161 (4)
O3W—H3WB⋯O2viii	0.83 (1)	2.33 (2)	3.130 (4)	161 (3)

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