catena-Poly[[[bis­(2-pyridine­carboxyl­ato-κ²N,O)copper(II)]-μ-benzene-1,2,4,5-tetracarboxylic acid] dihydrate]

In the title compound, {[Cu(C₆H₄NO₂)₂(C₁₀H₆O₈)]·2H₂O}_n, the Cu^II atom lies on an inversion centre in a distorted octa­hedral coordination environment. Two 2-carboxyl­atopyridine ligands chelate to each copper centre through their N and carboxyl­ate O atoms. The axial coordination positions are occupied by carboxyl­ate O atoms from different fully protonated 1,2,4,5-benzene­tetra­carboxylic acid mol­ecules. These also bridge adjacent copper centres to form infinite one-dimensional chains. Hydrogen bonds formed by the ligand O atoms and water mol­ecules link the individual chains.

Key indicators

• Single-crystal X-ray study
• T = 153 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.027
• wR factor = 0.072
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          5
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.41
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            N1  -CU1 -N1  -C5     13.00  0.00   7.556   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          4
            N1  -CU1 -N1  -C1      5.00  0.00   7.556   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          9
            O1  -CU1 -O1  -C6     13.00  0.00   7.556   1.555   1.555   1.555

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C22 H18 Cu1 N2 O14
            Atom count from _chemical_formula_moiety:H4 O2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: RAPID AUTO (Rigaku, 2001); cell refinement: RAPID AUTO; data reduction: RAPID AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXL97.

(I)

Crystal data

[Cu(C10H6O8)(C6H4NO2)2]·2H2O	F(000) = 1220
Mr = 597.92	Dx = 1.704 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.5546 (6) Å	Cell parameters from 2670 reflections
b = 11.5095 (4) Å	θ = 2.3–27.5°
c = 13.9115 (6) Å	µ = 1.02 mm^−1
β = 90.487 (2)°	T = 153 K
V = 2330.32 (16) Å^3	Block, blue
Z = 4	0.45 × 0.26 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer	2670 independent reflections
Radiation source: fine-focus sealed tube	2083 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.3°
ω scans	h = 0→18
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = 0→14
Tmin = 0.749, Tmax = 0.846	l = −18→17
2670 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: difference Fourier map
wR(F^2) = 0.072	All H-atom parameters refined
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0434P)^2] where P = (Fo^2 + 2Fc^2)/3
2670 reflections	(Δ/σ)max = 0.001
214 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.2500	0.2500	0.5000	0.02885 (10)
N1	0.38114 (9)	0.28862 (12)	0.49034 (9)	0.0255 (3)
O1	0.24538 (8)	0.31140 (11)	0.36821 (8)	0.0316 (3)
O2	0.33305 (8)	0.39563 (12)	0.25818 (8)	0.0380 (3)
O3	0.23959 (8)	0.44551 (11)	0.57931 (8)	0.0344 (3)
O4	0.18872 (9)	0.61054 (12)	0.64210 (10)	0.0415 (3)
H4A	0.2380 (17)	0.610 (2)	0.6754 (16)	0.067 (8)*
O5	0.12605 (10)	0.59630 (18)	0.28900 (9)	0.0710 (5)
O6	0.22089 (10)	0.61049 (15)	0.41248 (10)	0.0478 (4)
H6A	0.2527 (19)	0.629 (2)	0.370 (2)	0.076 (9)*
C1	0.40153 (11)	0.34157 (16)	0.40714 (11)	0.0286 (4)
C2	0.48814 (13)	0.3815 (2)	0.38824 (14)	0.0448 (5)
H2	0.4995 (15)	0.4195 (19)	0.3323 (15)	0.052 (6)*
C3	0.55649 (14)	0.3655 (2)	0.45715 (15)	0.0492 (6)
H3	0.6130 (18)	0.391 (2)	0.4451 (16)	0.066 (7)*
C4	0.53578 (13)	0.31102 (18)	0.54120 (13)	0.0399 (5)
H4	0.5775 (14)	0.3024 (18)	0.5897 (14)	0.044 (6)*
C5	0.44737 (12)	0.27373 (16)	0.55611 (12)	0.0311 (4)
H5	0.4297 (13)	0.2373 (14)	0.6079 (14)	0.028 (5)*
C6	0.32148 (11)	0.35129 (15)	0.33817 (11)	0.0286 (4)
C7	0.08886 (11)	0.51270 (14)	0.53782 (11)	0.0257 (3)
C8	0.07126 (11)	0.53943 (15)	0.44159 (11)	0.0272 (4)
C9	−0.01711 (11)	0.52590 (15)	0.40518 (12)	0.0290 (4)
H9	−0.0264 (13)	0.5411 (15)	0.3401 (13)	0.035 (5)*
C10	0.18161 (11)	0.51963 (15)	0.58646 (11)	0.0263 (3)
C11	0.14177 (12)	0.58414 (17)	0.37275 (12)	0.0342 (4)
O7	0.33615 (10)	0.35078 (16)	0.76704 (10)	0.0419 (3)
H7B	0.3333 (18)	0.416 (2)	0.7376 (19)	0.077 (9)*
H7A	0.319 (2)	0.296 (3)	0.729 (2)	0.090 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01979 (15)	0.04419 (19)	0.02249 (14)	−0.00174 (13)	−0.00453 (10)	0.00631 (13)
N1	0.0228 (7)	0.0312 (7)	0.0223 (6)	0.0028 (6)	−0.0035 (5)	−0.0006 (6)
O1	0.0230 (6)	0.0457 (7)	0.0260 (6)	−0.0029 (5)	−0.0063 (5)	0.0054 (5)
O2	0.0304 (7)	0.0564 (8)	0.0272 (6)	−0.0006 (6)	−0.0041 (5)	0.0122 (6)
O3	0.0252 (6)	0.0408 (7)	0.0372 (6)	0.0069 (5)	−0.0065 (5)	−0.0086 (6)
O4	0.0354 (7)	0.0433 (8)	0.0453 (7)	0.0080 (6)	−0.0196 (6)	−0.0180 (6)
O5	0.0414 (8)	0.1460 (16)	0.0256 (7)	−0.0260 (10)	−0.0061 (6)	0.0110 (9)
O6	0.0343 (7)	0.0779 (11)	0.0311 (7)	−0.0214 (7)	−0.0066 (6)	0.0112 (7)
C1	0.0245 (8)	0.0384 (10)	0.0228 (7)	0.0012 (7)	−0.0031 (6)	0.0008 (7)
C2	0.0302 (10)	0.0718 (15)	0.0325 (9)	−0.0098 (10)	−0.0013 (8)	0.0100 (10)
C3	0.0231 (9)	0.0806 (17)	0.0439 (11)	−0.0113 (10)	−0.0041 (8)	0.0026 (11)
C4	0.0276 (9)	0.0561 (13)	0.0357 (10)	0.0029 (9)	−0.0125 (8)	−0.0047 (9)
C5	0.0283 (9)	0.0406 (11)	0.0244 (8)	0.0038 (7)	−0.0058 (7)	0.0005 (8)
C6	0.0265 (8)	0.0361 (9)	0.0232 (7)	0.0024 (7)	−0.0047 (6)	0.0014 (7)
C7	0.0229 (8)	0.0292 (8)	0.0249 (7)	0.0023 (7)	−0.0064 (6)	−0.0040 (7)
C8	0.0252 (8)	0.0328 (9)	0.0237 (7)	0.0017 (7)	−0.0028 (6)	−0.0036 (7)
C9	0.0277 (9)	0.0377 (10)	0.0215 (7)	0.0008 (7)	−0.0063 (6)	−0.0009 (7)
C10	0.0247 (8)	0.0335 (9)	0.0206 (7)	−0.0007 (7)	−0.0041 (6)	−0.0010 (7)
C11	0.0281 (9)	0.0474 (11)	0.0269 (8)	−0.0037 (8)	−0.0029 (7)	−0.0001 (8)
O7	0.0416 (8)	0.0482 (9)	0.0359 (7)	0.0047 (7)	−0.0039 (6)	−0.0034 (7)

Geometric parameters (Å, º)

Cu1—N1	1.9654 (14)	C2—H2	0.91 (2)
Cu1—N1^i	1.9654 (14)	C3—C4	1.363 (3)
Cu1—O1	1.9655 (11)	C3—H3	0.89 (3)
Cu1—O1^i	1.9655 (11)	C4—C5	1.374 (3)
N1—C5	1.3346 (19)	C4—H4	0.91 (2)
N1—C1	1.344 (2)	C5—H5	0.874 (19)
O1—C6	1.273 (2)	C7—C9^ii	1.389 (2)
O2—C6	1.2370 (19)	C7—C8	1.395 (2)
O3—C10	1.2046 (19)	C7—C10	1.507 (2)
O4—C10	1.305 (2)	C8—C9	1.387 (2)
O4—H4A	0.85 (2)	C8—C11	1.501 (2)
O5—C11	1.194 (2)	C9—C7^ii	1.389 (2)
O6—C11	1.309 (2)	C9—H9	0.931 (18)
O6—H6A	0.79 (3)	O7—H7B	0.86 (3)
C1—C2	1.369 (2)	O7—H7A	0.85 (3)
C1—C6	1.507 (2)	Cu1—O3	2.5113 (12)
C2—C3	1.388 (3)
N1—Cu1—N1^i	180.0	C5—C4—H4	118.3 (13)
N1—Cu1—O1	83.14 (5)	N1—C5—C4	121.90 (17)
N1^i—Cu1—O1	96.86 (5)	N1—C5—H5	114.3 (13)
N1—Cu1—O1^i	96.86 (5)	C4—C5—H5	123.8 (13)
N1^i—Cu1—O1^i	83.14 (5)	O2—C6—O1	124.72 (15)
O1—Cu1—O1^i	180.0	O2—C6—C1	119.53 (15)
C5—N1—C1	119.03 (15)	O1—C6—C1	115.75 (13)
C5—N1—Cu1	128.34 (12)	C9^ii—C7—C8	119.03 (14)
C1—N1—Cu1	112.54 (10)	C9^ii—C7—C10	115.81 (14)
C6—O1—Cu1	114.39 (9)	C8—C7—C10	125.14 (15)
C10—O4—H4A	112.0 (17)	C9—C8—C7	119.19 (15)
C11—O6—H6A	105.2 (19)	C9—C8—C11	116.26 (14)
N1—C1—C2	121.89 (15)	C7—C8—C11	124.54 (15)
N1—C1—C6	114.00 (14)	C8—C9—C7^ii	121.77 (15)
C2—C1—C6	124.11 (15)	C8—C9—H9	117.5 (12)
C1—C2—C3	118.56 (18)	C7^ii—C9—H9	120.7 (12)
C1—C2—H2	120.1 (14)	O3—C10—O4	124.38 (15)
C3—C2—H2	121.4 (14)	O3—C10—C7	123.43 (15)
C4—C3—C2	119.44 (19)	O4—C10—C7	112.02 (14)
C4—C3—H3	121.8 (15)	O5—C11—O6	123.07 (17)
C2—C3—H3	118.8 (15)	O5—C11—C8	122.46 (16)
C3—C4—C5	119.17 (17)	O6—C11—C8	114.45 (14)
C3—C4—H4	122.4 (13)	H7B—O7—H7A	110 (3)
N1^i—Cu1—N1—C5	128 (48)	Cu1—O1—C6—O2	−178.68 (14)
O1—Cu1—N1—C5	−179.53 (16)	Cu1—O1—C6—C1	1.60 (19)
O1^i—Cu1—N1—C5	0.47 (16)	N1—C1—C6—O2	−177.97 (15)
N1^i—Cu1—N1—C1	−49 (44)	C2—C1—C6—O2	1.5 (3)
O1—Cu1—N1—C1	3.96 (11)	N1—C1—C6—O1	1.8 (2)
O1^i—Cu1—N1—C1	−176.04 (11)	C2—C1—C6—O1	−178.75 (18)
N1—Cu1—O1—C6	−3.06 (12)	C9^ii—C7—C8—C9	−0.5 (3)
N1^i—Cu1—O1—C6	176.94 (12)	C10—C7—C8—C9	178.07 (16)
O1^i—Cu1—O1—C6	132 (100)	C9^ii—C7—C8—C11	178.70 (16)
C5—N1—C1—C2	−0.5 (3)	C10—C7—C8—C11	−2.7 (3)
Cu1—N1—C1—C2	176.34 (16)	C7—C8—C9—C7^ii	0.5 (3)
C5—N1—C1—C6	178.98 (15)	C11—C8—C9—C7^ii	−178.75 (16)
Cu1—N1—C1—C6	−4.15 (18)	C9^ii—C7—C10—O3	98.5 (2)
N1—C1—C2—C3	0.6 (3)	C8—C7—C10—O3	−80.1 (2)
C6—C1—C2—C3	−178.88 (19)	C9^ii—C7—C10—O4	−76.90 (19)
C1—C2—C3—C4	−0.1 (3)	C8—C7—C10—O4	104.47 (19)
C2—C3—C4—C5	−0.4 (3)	C9—C8—C11—O5	−7.5 (3)
C1—N1—C5—C4	0.0 (3)	C7—C8—C11—O5	173.2 (2)
Cu1—N1—C5—C4	−176.30 (14)	C9—C8—C11—O6	171.29 (17)
C3—C4—C5—N1	0.4 (3)	C7—C8—C11—O6	−8.0 (3)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O1^i	0.85 (3)	2.06 (3)	2.8973 (19)	168 (3)
O7—H7B···O2^iii	0.86 (3)	2.19 (3)	2.922 (2)	144 (2)
O7—H7B···O3	0.86 (3)	2.60 (3)	3.1498 (18)	123 (2)
O4—H4A···O2^iii	0.85 (2)	1.79 (2)	2.6397 (17)	173 (2)
O6—H6A···O7^iv	0.79 (3)	1.90 (3)	2.677 (2)	171 (3)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (iii) x, −y+1, z+1/2; (iv) x, −y+1, z−1/2.