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Crystals of the title tetramer, [Cu4(C7H3NO4)4(C7H5NO4)4(H2O)2], were synthesized hydro­thermally at 433 K. The triclinic structure consists of tetrameric molecular species, which interact via strong hydrogen bonds. The CuII ions are distributed equally between one square-pyramidal site and one octahedral site distorted by the Jahn-Teller effect. This coordination complex exhibits the peculiarity of having CuII ions linked to both the 2,6- and the 3,5-isomers of pyridine­di­carboxyl­ic acid.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104001027/tr1072sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104001027/tr1072Isup2.hkl
Contains datablock I

CCDC reference: 235310

Comment top

Hybrid microporous compounds exhibit structures built up from inorganic moieties connected by organic linkers. The anchorage of the organic molecules on the inorganic moieties is ensured by complexing functions as carboxylates, phosphonates or hetero-atoms involved in the coordination sphere of the metal ions (Férey, 2001 and references therein). Being able to act as ligands via both their carboxylate functions and the N atom of the aromatic ring, different isomers of pyridine dicarboxylic acid have been widely used in this field (Suga & Okabe, 1996; Sileo et al., 1996, 1997; Min et al., 2001a). They principally give rise to coordination complexes with low-dimensional structures. The chelation of the metal ion by one N atom and one O atom is often observed for isomers where one carboxylate function is located on the 2- or 6-positions of the pyridine ring. In order to modulate the connectivity of the metal ion with the pyridine dicarboxylic acids, we have tried to associate two different isomers into the same structure; 2,6-pyridinedicarboxylic (or dipicolinic acid) acid gives rise to the chelation, whereas 3,5-pyridinedicarboxylic (or dinicotinic acid) acid favours the polymerization processes (Min et al., 2001b).

The structure of Cu2(Cu(H2O))2(NC5H3(COO)2)4(NC5H3(COOH)2)4, (I), contains two cationic sites occupied by Cu2+ ions. Atom Cu1 (Fig. 1 and Table 1) is fivefold coordinated in a distorted square pyramid. It is doubly chelated by one dipicolinate anion, sharing one N atom and two O atoms provided by the two α-located carboxylate functions; the two remaining apices are filled by an N ligand from the dinicotinic acid, completing the basal plane of the pyramid, and one terminal water molecule, perpendicularly disposed. Atom Cu2 is sixfold coordinated, creating an elongated octahedron. In the equatorial plane, it is doubly chelated by the dipicolinate anion and the N atom of the dinicotinic acid moelcule. Axially, it forms two long bonds with O atoms of the carboxylate functions of two 3,5-pyridinedicarboxylic acid complexes. As a consequence, the complex moieties built around atom Cu2 give rise to a polycondensation process, whereas the complex around atom Cu1 terminates a similar mechanism. Indeed, each Cu2 complex is linked to a similar entity, forming a dimeric central core on to which two Cu1 complexes are grafted (Fig. 2).

Inside this tetrameric unit, all the 3,5-pyridinedicarboxylic acid molecules are fully protonated and all the dipicolinate moieties are fully deprotonated. The stability of the structure is ensured via a network of intermolecular hydrogen bonds involving the OH groups of the carboxylate functions and the water molecules (Table 2). Although the nuclearity and the resulting complexity of the tetrameric unit is high, no intramolecular hydrogen bonding is observed. The title compound shows that the connection of the multidentate ligand dipicolinate to the metal ion is strongly anisotropic. The double chelation requires that all the donor–acceptor bonds are on the same side of the coordination sphere of the cation, meaning that the opposite side remains open. This structural observation allows us to project the synthesis of new dipicolinate compounds incorporating other kinds of ligands utilizing the available part of the coordination sphere.

Experimental top

Compound (I) was prepared from a mixture of copper dichloride dihydrate, 2,6-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid and deionized water in a 1:0.25:0.25:250 molar ratio. This mixture was sealed in to a teflon-lined autoclave from Parr and then heated for 48 h at 433 K under autogeneous pressure. The pH measured before and after heating remained equal to 1 throughout the synthesis. After cooling at room temperature, the solid was separated from the liquid phase by filtration, washed with water and dried in air. The pure compound was obtained in the form of small blue platelets. Thermogravimetric experiments performed under an O2 flow show a small initial weight loss at 523 K corresponding to the dehydration (measured 2.3%, calculated 2.22%) followed by the combustion of the organic linkers at 593 K (measured 78.8%, calculated 79.9% for CuO residue). The calcined residue is amorphous.

Refinement top

The H atoms of the pyridine rings and the carboxylic functions were positioned geometrically, whereas those of the water molecules were found from difference Fourier syntheses and then restrained to give two similar O—H bonds close to 0.85 Å.

Computing details top

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1996); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. : The two elementary complexes, showing the different neighbourhoods of (a) atom Cu1 and (b) atom Cu2. h atoms are shown a circles of arbitrary radii.
[Figure 2] Fig. 2. : One tetrameric moiety.
(I) top
Crystal data top
[Cu4(C7H3NO4)4(C7H5NO4)4(H2O)2]Z = 1
Mr = 1619.09F(000) = 816
Triclinic, P1Dx = 1.890 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1350 (2) ÅCell parameters from 3414 reflections
b = 11.8614 (1) Åθ = 1.2–27.0°
c = 17.0675 (3) ŵ = 1.59 mm1
α = 96.480 (1)°T = 296 K
β = 94.971 (1)°Parallelepiped, blue
γ = 95.229 (1)°0.16 × 0.10 × 0.06 mm
V = 1422.36 (5) Å3
Data collection top
Bruker SMART 1K CCD
diffractometer
6126 independent reflections
Radiation source: fine-focus sealed tube3728 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 27.0°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
h = 99
Tmin = 0.785, Tmax = 0.911k = 1511
8996 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0645P)2]
where P = (Fo2 + 2Fc2)/3
6126 reflections(Δ/σ)max < 0.001
471 parametersΔρmax = 0.53 e Å3
2 restraintsΔρmin = 1.00 e Å3
Crystal data top
[Cu4(C7H3NO4)4(C7H5NO4)4(H2O)2]γ = 95.229 (1)°
Mr = 1619.09V = 1422.36 (5) Å3
Triclinic, P1Z = 1
a = 7.1350 (2) ÅMo Kα radiation
b = 11.8614 (1) ŵ = 1.59 mm1
c = 17.0675 (3) ÅT = 296 K
α = 96.480 (1)°0.16 × 0.10 × 0.06 mm
β = 94.971 (1)°
Data collection top
Bruker SMART 1K CCD
diffractometer
6126 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
3728 reflections with I > 2σ(I)
Tmin = 0.785, Tmax = 0.911Rint = 0.034
8996 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0492 restraints
wR(F2) = 0.138H-atom parameters constrained
S = 0.99Δρmax = 0.53 e Å3
6126 reflectionsΔρmin = 1.00 e Å3
471 parameters
Special details top

Experimental. Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

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.

Highest peak 0.53 at 0.8639 0.0970 0.4437 Deepest hole −1.00 at 0.8565 0.0660 0.3508

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.47689 (8)0.29266 (4)0.14473 (3)0.02788 (17)
Cu20.20124 (8)0.08634 (4)0.38766 (3)0.03103 (18)
N1A0.3499 (5)0.1374 (3)0.1431 (2)0.0257 (8)
C1B0.2971 (6)0.1005 (4)0.2101 (3)0.0280 (10)
H1B0.32760.14770.25770.034*
C1C0.1982 (6)0.0060 (4)0.2109 (3)0.0249 (10)
C1D0.1538 (6)0.0745 (4)0.1396 (3)0.0280 (10)
H1D0.08560.14550.13820.034*
C1E0.2097 (6)0.0383 (4)0.0704 (3)0.0264 (10)
C1F0.3052 (6)0.0687 (4)0.0740 (3)0.0281 (10)
H1F0.34010.09460.02740.034*
C1G0.1554 (7)0.1142 (4)0.0052 (3)0.0303 (11)
C1H0.1381 (6)0.0405 (4)0.2874 (3)0.0277 (10)
O1I0.2288 (5)0.0743 (3)0.06623 (18)0.0377 (8)
H1I0.20660.12210.10530.057*
O1J0.0569 (5)0.2036 (3)0.00920 (19)0.0405 (9)
O1K0.1398 (5)0.0262 (3)0.34677 (19)0.0409 (9)
O1L0.0832 (5)0.1502 (3)0.28148 (19)0.0393 (9)
H1L0.04060.16520.32260.059*
O1W0.2056 (5)0.3731 (3)0.1264 (2)0.0446 (9)
H1W0.123 (7)0.329 (4)0.091 (3)0.08 (2)*
H2W0.249 (8)0.429 (4)0.102 (3)0.080*
N2A0.6478 (5)0.4269 (3)0.1530 (2)0.0245 (8)
C2B0.7051 (6)0.4804 (3)0.2247 (2)0.0243 (10)
C2C0.8368 (7)0.5751 (4)0.2348 (3)0.0325 (11)
H2C0.87870.61310.28480.039*
C2D0.9039 (7)0.6110 (4)0.1661 (3)0.0355 (12)
H2D0.99200.67480.17040.043*
C2E0.8425 (7)0.5540 (4)0.0920 (3)0.0327 (11)
H2E0.88800.57810.04650.039*
C2F0.7107 (6)0.4597 (3)0.0876 (3)0.0233 (10)
C2G0.6293 (6)0.3793 (4)0.0154 (3)0.0278 (10)
C2H0.6144 (6)0.4219 (4)0.2882 (3)0.0269 (10)
O2I0.6682 (5)0.4020 (3)0.05112 (18)0.0396 (9)
O2J0.5264 (5)0.2922 (3)0.02922 (18)0.0347 (8)
O2K0.6526 (5)0.4613 (3)0.35901 (18)0.0344 (8)
O2L0.5065 (4)0.3314 (2)0.26316 (18)0.0320 (8)
N3A0.3356 (5)0.0648 (3)0.3843 (2)0.0269 (9)
C3B0.3730 (6)0.1056 (4)0.4521 (2)0.0266 (10)
H3E0.33190.06080.49990.032*
C3C0.4700 (6)0.2111 (4)0.4538 (3)0.0253 (10)
C3D0.5270 (6)0.2773 (4)0.3818 (3)0.0291 (11)
H3D0.58780.35030.38100.035*
C3E0.4939 (6)0.2353 (4)0.3112 (3)0.0267 (10)
C3F0.3981 (6)0.1286 (4)0.3150 (3)0.0268 (10)
H3F0.37560.09930.26800.032*
C3G0.5699 (6)0.3071 (4)0.2349 (3)0.0272 (10)
C3H0.5153 (6)0.2492 (4)0.5308 (3)0.0277 (10)
O3I0.5329 (6)0.2594 (3)0.17212 (18)0.0433 (9)
H3I0.56620.30490.13240.065*
O3J0.6577 (5)0.3988 (3)0.23503 (19)0.0397 (8)
O3K0.4979 (5)0.1845 (3)0.40894 (18)0.0384 (8)
O3L0.5742 (5)0.3579 (3)0.52396 (18)0.0376 (8)
H3L0.57740.37840.56820.056*
N4A0.0590 (5)0.2298 (3)0.3932 (2)0.0242 (8)
C4B0.0145 (6)0.2828 (4)0.4640 (3)0.0243 (10)
C4C0.1263 (7)0.3832 (4)0.4695 (3)0.0302 (11)
H4C0.17640.42180.51830.036*
C4D0.1627 (7)0.4262 (4)0.3983 (3)0.0387 (13)
H4D0.24020.49400.40010.046*
C4E0.0861 (7)0.3700 (4)0.3260 (3)0.0316 (11)
H4E0.11080.39880.27910.038*
C4F0.0275 (6)0.2705 (4)0.3253 (2)0.0253 (10)
C4G0.1311 (7)0.1921 (4)0.2550 (3)0.0281 (10)
C4H0.0421 (6)0.2135 (3)0.5298 (3)0.0245 (10)
O4L0.1375 (5)0.1185 (3)0.50492 (18)0.0363 (8)
O4K0.0097 (5)0.2508 (3)0.59891 (17)0.0352 (8)
O4J0.2199 (5)0.1016 (2)0.27177 (17)0.0343 (8)
O4I0.1226 (5)0.2211 (3)0.18808 (18)0.0391 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0383 (4)0.0236 (3)0.0189 (3)0.0113 (2)0.0043 (2)0.0006 (2)
Cu20.0493 (4)0.0232 (3)0.0168 (3)0.0136 (3)0.0025 (3)0.0007 (2)
N1A0.031 (2)0.025 (2)0.019 (2)0.0075 (16)0.0021 (16)0.0004 (15)
C1B0.034 (3)0.026 (2)0.023 (3)0.004 (2)0.001 (2)0.0022 (19)
C1C0.030 (3)0.024 (2)0.019 (2)0.0040 (19)0.0013 (19)0.0028 (18)
C1D0.033 (3)0.022 (2)0.028 (3)0.002 (2)0.001 (2)0.0046 (19)
C1E0.032 (3)0.024 (2)0.021 (2)0.0046 (19)0.000 (2)0.0025 (19)
C1F0.035 (3)0.026 (2)0.023 (2)0.000 (2)0.007 (2)0.0042 (19)
C1G0.034 (3)0.032 (3)0.024 (3)0.002 (2)0.000 (2)0.003 (2)
C1H0.027 (3)0.025 (2)0.030 (3)0.0063 (19)0.004 (2)0.004 (2)
O1I0.057 (2)0.0338 (19)0.0180 (17)0.0136 (16)0.0043 (16)0.0013 (14)
O1J0.054 (2)0.0351 (19)0.0260 (19)0.0186 (17)0.0050 (16)0.0045 (15)
O1K0.063 (2)0.0347 (19)0.0226 (19)0.0065 (17)0.0101 (17)0.0008 (15)
O1L0.065 (2)0.0284 (18)0.0228 (18)0.0118 (16)0.0119 (17)0.0024 (14)
O1W0.045 (2)0.031 (2)0.055 (3)0.0058 (17)0.004 (2)0.0058 (18)
N2A0.029 (2)0.026 (2)0.0173 (19)0.0034 (16)0.0029 (16)0.0033 (15)
C2B0.035 (3)0.022 (2)0.015 (2)0.0050 (19)0.0015 (19)0.0032 (17)
C2C0.043 (3)0.028 (3)0.025 (3)0.004 (2)0.001 (2)0.003 (2)
C2D0.041 (3)0.032 (3)0.030 (3)0.020 (2)0.002 (2)0.005 (2)
C2E0.038 (3)0.035 (3)0.024 (3)0.009 (2)0.007 (2)0.006 (2)
C2F0.025 (2)0.020 (2)0.023 (2)0.0037 (18)0.0032 (19)0.0006 (18)
C2G0.034 (3)0.028 (2)0.019 (2)0.004 (2)0.001 (2)0.0001 (19)
C2H0.032 (3)0.028 (2)0.021 (2)0.001 (2)0.005 (2)0.0064 (19)
O2I0.059 (2)0.040 (2)0.0159 (17)0.0162 (17)0.0032 (16)0.0014 (14)
O2J0.047 (2)0.0299 (18)0.0227 (18)0.0138 (15)0.0026 (15)0.0007 (14)
O2K0.052 (2)0.0300 (17)0.0170 (17)0.0119 (15)0.0034 (15)0.0010 (13)
O2L0.044 (2)0.0271 (17)0.0215 (17)0.0134 (14)0.0070 (15)0.0012 (13)
N3A0.036 (2)0.024 (2)0.021 (2)0.0013 (16)0.0069 (17)0.0025 (16)
C3B0.033 (3)0.027 (2)0.017 (2)0.004 (2)0.0021 (19)0.0043 (18)
C3C0.027 (3)0.027 (2)0.021 (2)0.0011 (19)0.0034 (19)0.0043 (19)
C3D0.039 (3)0.020 (2)0.026 (3)0.007 (2)0.003 (2)0.0038 (19)
C3E0.030 (3)0.028 (2)0.022 (2)0.0015 (19)0.004 (2)0.0034 (19)
C3F0.034 (3)0.026 (2)0.019 (2)0.007 (2)0.003 (2)0.0040 (19)
C3G0.033 (3)0.026 (2)0.022 (2)0.000 (2)0.001 (2)0.0000 (19)
C3H0.034 (3)0.028 (2)0.019 (2)0.006 (2)0.001 (2)0.004 (2)
O3I0.074 (3)0.037 (2)0.0152 (17)0.0112 (18)0.0042 (18)0.0005 (14)
O3J0.055 (2)0.0271 (18)0.033 (2)0.0153 (16)0.0024 (16)0.0013 (15)
O3K0.058 (2)0.0360 (19)0.0186 (18)0.0086 (17)0.0046 (16)0.0003 (15)
O3L0.056 (2)0.0303 (18)0.0250 (18)0.0128 (16)0.0060 (17)0.0080 (14)
N4A0.035 (2)0.0208 (19)0.0151 (19)0.0048 (16)0.0021 (16)0.0001 (15)
C4B0.026 (2)0.025 (2)0.021 (2)0.0005 (19)0.0033 (19)0.0005 (18)
C4C0.038 (3)0.025 (2)0.023 (2)0.010 (2)0.000 (2)0.0037 (19)
C4D0.045 (3)0.033 (3)0.035 (3)0.017 (2)0.008 (2)0.005 (2)
C4E0.037 (3)0.034 (3)0.025 (3)0.005 (2)0.008 (2)0.012 (2)
C4F0.032 (3)0.028 (2)0.017 (2)0.0003 (19)0.0035 (19)0.0049 (18)
C4G0.035 (3)0.027 (2)0.020 (2)0.003 (2)0.002 (2)0.0008 (19)
C4H0.030 (3)0.022 (2)0.020 (2)0.0031 (19)0.0015 (19)0.0009 (18)
O4L0.055 (2)0.0285 (18)0.0219 (18)0.0154 (16)0.0015 (15)0.0052 (14)
O4K0.050 (2)0.0358 (18)0.0151 (17)0.0139 (15)0.0029 (15)0.0005 (14)
O4J0.053 (2)0.0293 (18)0.0168 (17)0.0096 (16)0.0013 (15)0.0017 (13)
O4I0.067 (2)0.0308 (18)0.0172 (17)0.0086 (16)0.0065 (16)0.0018 (14)
Geometric parameters (Å, º) top
Cu1—N1A1.973 (3)C2E—H2E0.9300
Cu1—N2A1.899 (3)C2F—C2G1.508 (6)
Cu1—O2J2.032 (3)C2G—O2I1.245 (5)
Cu1—O2L2.010 (3)C2G—O2J1.268 (5)
Cu1—O1W2.249 (4)C2H—O2K1.243 (5)
Cu2—N3A1.946 (4)C2H—O2L1.272 (5)
Cu2—N4A1.889 (3)N3A—C3B1.343 (5)
Cu2—O1K2.724 (4)N3A—C3F1.347 (5)
Cu2—O3K2.541 (4)C3B—C3C1.378 (6)
Cu2—O4J2.001 (3)C3B—H3E0.9300
Cu2—O4L1.999 (3)C3C—C3D1.389 (6)
N1A—C1B1.342 (5)C3C—C3H1.489 (6)
N1A—C1F1.351 (5)C3D—C3E1.387 (6)
C1B—C1C1.392 (6)C3D—H3D0.9300
C1B—H1B0.9300C3E—C3F1.374 (6)
C1C—C1D1.379 (6)C3E—C3G1.502 (6)
C1C—C1H1.498 (6)C3F—H3F0.9300
C1D—C1E1.380 (6)C3G—O3J1.206 (5)
C1D—H1D0.9300C3G—O3I1.302 (5)
C1E—C1F1.378 (6)C3H—O3Ki1.203 (5)
C1E—C1G1.487 (6)C3H—O3L1.308 (5)
C1F—H1F0.9300O3I—H3I0.8200
C1G—O1J1.209 (5)O3K—C3Hi1.203 (5)
C1G—O1I1.321 (5)O3L—H3L0.8200
C1H—O1K1.211 (5)N4A—C4F1.332 (5)
C1H—O1L1.314 (5)N4A—C4B1.338 (5)
O1I—H1I0.8200C4B—C4C1.361 (6)
O1L—H1L0.8200C4B—C4H1.525 (6)
O1W—H1W0.89 (2)C4C—C4D1.404 (6)
O1W—H2W0.87 (2)C4C—H4C0.9300
N2A—C2F1.324 (5)C4D—C4E1.377 (7)
N2A—C2B1.325 (5)C4D—H4D0.9300
C2B—C2C1.382 (6)C4E—C4F1.368 (6)
C2B—C2H1.511 (6)C4E—H4E0.9300
C2C—C2D1.400 (6)C4F—C4G1.523 (6)
C2C—H2C0.9300C4G—O4I1.235 (5)
C2D—C2E1.380 (6)C4G—O4J1.270 (5)
C2D—H2D0.9300C4H—O4K1.225 (5)
C2E—C2F1.385 (6)C4H—O4L1.272 (5)
N2A—Cu1—N1A167.35 (15)C2D—C2E—C2F117.7 (4)
N2A—Cu1—O2L80.85 (13)C2D—C2E—H2E121.2
N1A—Cu1—O2L96.38 (13)C2F—C2E—H2E121.2
N2A—Cu1—O2J80.30 (13)N2A—C2F—C2E120.1 (4)
N1A—Cu1—O2J100.91 (13)N2A—C2F—C2G111.4 (4)
O2L—Cu1—O2J160.47 (13)C2E—C2F—C2G128.3 (4)
N2A—Cu1—O1W98.23 (14)O2I—C2G—O2J125.8 (4)
N1A—Cu1—O1W94.30 (14)O2I—C2G—C2F118.9 (4)
O2L—Cu1—O1W95.06 (14)O2J—C2G—C2F115.3 (4)
O2J—Cu1—O1W92.65 (14)O2K—C2H—O2L125.1 (4)
N4A—Cu2—N3A176.90 (15)O2K—C2H—C2B119.8 (4)
N4A—Cu2—O4L80.47 (13)O2L—C2H—C2B115.0 (4)
N3A—Cu2—O4L98.14 (13)C2G—O2J—Cu1114.0 (3)
N4A—Cu2—O4J81.73 (13)C2H—O2L—Cu1114.4 (3)
N3A—Cu2—O4J99.65 (14)C3B—N3A—C3F118.7 (4)
O4L—Cu2—O4J162.20 (12)C3B—N3A—Cu2119.8 (3)
N4A—Cu2—O3K90.12 (13)C3F—N3A—Cu2121.5 (3)
N3A—Cu2—O3K92.57 (13)N3A—C3B—C3C122.7 (4)
O4L—Cu2—O3K86.53 (12)N3A—C3B—H3E118.7
O4J—Cu2—O3K93.18 (12)C3C—C3B—H3E118.7
N4A—Cu2—O1K78.09 (13)C3B—C3C—C3D117.7 (4)
N3A—Cu2—O1K99.43 (13)C3B—C3C—C3H120.1 (4)
O4L—Cu2—O1K98.66 (12)C3D—C3C—C3H122.2 (4)
O4J—Cu2—O1K77.91 (12)C3E—C3D—C3C120.4 (4)
O3K—Cu2—O1K166.05 (10)C3E—C3D—H3D119.8
C1B—N1A—C1F118.8 (4)C3C—C3D—H3D119.8
C1B—N1A—Cu1120.4 (3)C3F—C3E—C3D118.0 (4)
C1F—N1A—Cu1120.7 (3)C3F—C3E—C3G123.7 (4)
N1A—C1B—C1C122.2 (4)C3D—C3E—C3G118.3 (4)
N1A—C1B—H1B118.9N3A—C3F—C3E122.5 (4)
C1C—C1B—H1B118.9N3A—C3F—H3F118.7
C1D—C1C—C1B117.9 (4)C3E—C3F—H3F118.7
C1D—C1C—C1H122.5 (4)O3J—C3G—O3I125.6 (4)
C1B—C1C—C1H119.5 (4)O3J—C3G—C3E120.9 (4)
C1C—C1D—C1E120.4 (4)O3I—C3G—C3E113.5 (4)
C1C—C1D—H1D119.8O3Ki—C3H—O3L125.4 (4)
C1E—C1D—H1D119.8O3Ki—C3H—C3C122.3 (4)
C1F—C1E—C1D118.4 (4)O3L—C3H—C3C112.3 (4)
C1F—C1E—C1G123.0 (4)C3G—O3I—H3I109.5
C1D—C1E—C1G118.5 (4)C3Hi—O3K—Cu2113.6 (3)
N1A—C1F—C1E122.2 (4)C3H—O3L—H3L109.5
N1A—C1F—H1F118.9C4F—N4A—C4B122.9 (4)
C1E—C1F—H1F118.9C4F—N4A—Cu2117.9 (3)
O1J—C1G—O1I124.3 (4)C4B—N4A—Cu2119.1 (3)
O1J—C1G—C1E122.9 (4)N4A—C4B—C4C120.4 (4)
O1I—C1G—C1E112.8 (4)N4A—C4B—C4H110.5 (4)
O1K—C1H—O1L125.1 (4)C4C—C4B—C4H129.1 (4)
O1K—C1H—C1C123.2 (4)C4B—C4C—C4D117.2 (4)
O1L—C1H—C1C111.8 (4)C4B—C4C—H4C121.4
C1G—O1I—H1I109.5C4D—C4C—H4C121.4
C1H—O1K—Cu2116.7 (3)C4E—C4D—C4C121.4 (4)
C1H—O1L—H1L109.5C4E—C4D—H4D119.3
Cu1—O1W—H1W111 (4)C4C—C4D—H4D119.3
Cu1—O1W—H2W98 (4)C4F—C4E—C4D118.0 (4)
H1W—O1W—H2W106 (6)C4F—C4E—H4E121.0
C2F—N2A—C2B123.1 (4)C4D—C4E—H4E121.0
C2F—N2A—Cu1118.7 (3)N4A—C4F—C4E120.1 (4)
C2B—N2A—Cu1118.1 (3)N4A—C4F—C4G110.8 (4)
N2A—C2B—C2C120.8 (4)C4E—C4F—C4G129.2 (4)
N2A—C2B—C2H111.5 (4)O4I—C4G—O4J126.0 (4)
C2C—C2B—C2H127.7 (4)O4I—C4G—C4F118.4 (4)
C2B—C2C—C2D116.7 (4)O4J—C4G—C4F115.6 (4)
C2B—C2C—H2C121.6O4K—C4H—O4L126.7 (4)
C2D—C2C—H2C121.6O4K—C4H—C4B119.3 (4)
C2E—C2D—C2C121.5 (4)O4L—C4H—C4B113.9 (4)
C2E—C2D—H2D119.2C4H—O4L—Cu2115.9 (3)
C2C—C2D—H2D119.2C4G—O4J—Cu2113.9 (3)
N2A—Cu1—N1A—C1B83.6 (8)O4L—Cu2—N3A—C3B7.0 (4)
O2L—Cu1—N1A—C1B7.0 (4)O4J—Cu2—N3A—C3B173.5 (3)
O2J—Cu1—N1A—C1B177.9 (3)O3K—Cu2—N3A—C3B79.8 (3)
O1W—Cu1—N1A—C1B88.5 (3)O1K—Cu2—N3A—C3B107.3 (3)
N2A—Cu1—N1A—C1F100.1 (7)O4L—Cu2—N3A—C3F175.2 (3)
O2L—Cu1—N1A—C1F176.6 (3)O4J—Cu2—N3A—C3F4.2 (4)
O2J—Cu1—N1A—C1F5.8 (4)O3K—Cu2—N3A—C3F97.9 (4)
O1W—Cu1—N1A—C1F87.8 (4)O1K—Cu2—N3A—C3F75.0 (4)
C1F—N1A—C1B—C1C0.1 (7)C3F—N3A—C3B—C3C1.2 (7)
Cu1—N1A—C1B—C1C176.5 (3)Cu2—N3A—C3B—C3C179.0 (3)
N1A—C1B—C1C—C1D0.3 (7)N3A—C3B—C3C—C3D1.1 (7)
N1A—C1B—C1C—C1H178.0 (4)N3A—C3B—C3C—C3H177.0 (4)
C1B—C1C—C1D—C1E1.3 (7)C3B—C3C—C3D—C3E2.8 (7)
C1H—C1C—C1D—C1E179.0 (4)C3H—C3C—C3D—C3E175.3 (4)
C1C—C1D—C1E—C1F2.0 (7)C3C—C3D—C3E—C3F2.1 (7)
C1C—C1D—C1E—C1G178.9 (4)C3C—C3D—C3E—C3G175.9 (4)
C1B—N1A—C1F—C1E0.9 (7)C3B—N3A—C3F—C3E2.0 (7)
Cu1—N1A—C1F—C1E177.3 (3)Cu2—N3A—C3F—C3E179.7 (3)
C1D—C1E—C1F—N1A1.9 (7)C3D—C3E—C3F—N3A0.3 (7)
C1G—C1E—C1F—N1A178.6 (4)C3G—C3E—C3F—N3A178.3 (4)
C1F—C1E—C1G—O1J173.1 (5)C3F—C3E—C3G—O3J177.9 (4)
C1D—C1E—C1G—O1J3.7 (7)C3D—C3E—C3G—O3J0.1 (7)
C1F—C1E—C1G—O1I8.0 (7)C3F—C3E—C3G—O3I1.3 (7)
C1D—C1E—C1G—O1I175.3 (4)C3D—C3E—C3G—O3I179.3 (4)
C1D—C1C—C1H—O1K163.8 (5)C3B—C3C—C3H—O3Ki13.9 (7)
C1B—C1C—C1H—O1K13.8 (7)C3D—C3C—C3H—O3Ki164.1 (5)
C1D—C1C—C1H—O1L15.8 (6)C3B—C3C—C3H—O3L167.7 (4)
C1B—C1C—C1H—O1L166.6 (4)C3D—C3C—C3H—O3L14.2 (6)
O1L—C1H—O1K—Cu273.8 (5)N4A—Cu2—O3K—C3Hi57.5 (3)
C1C—C1H—O1K—Cu2105.7 (4)N3A—Cu2—O3K—C3Hi120.9 (3)
N4A—Cu2—O1K—C1H130.5 (3)O4L—Cu2—O3K—C3Hi22.9 (3)
N3A—Cu2—O1K—C1H51.4 (3)O4J—Cu2—O3K—C3Hi139.2 (3)
O4L—Cu2—O1K—C1H151.2 (3)O1K—Cu2—O3K—C3Hi89.5 (5)
O4J—Cu2—O1K—C1H46.6 (3)O4L—Cu2—N4A—C4F176.8 (3)
O3K—Cu2—O1K—C1H97.7 (5)O4J—Cu2—N4A—C4F3.5 (3)
N1A—Cu1—N2A—C2F98.9 (7)O3K—Cu2—N4A—C4F96.7 (3)
O2L—Cu1—N2A—C2F177.2 (3)O1K—Cu2—N4A—C4F75.8 (3)
O2J—Cu1—N2A—C2F2.3 (3)O4L—Cu2—N4A—C4B0.6 (3)
O1W—Cu1—N2A—C2F89.0 (3)O4J—Cu2—N4A—C4B179.7 (4)
N1A—Cu1—N2A—C2B78.0 (8)O3K—Cu2—N4A—C4B87.1 (3)
O2L—Cu1—N2A—C2B0.2 (3)O1K—Cu2—N4A—C4B100.4 (3)
O2J—Cu1—N2A—C2B174.6 (4)C4F—N4A—C4B—C4C0.4 (7)
O1W—Cu1—N2A—C2B94.1 (3)Cu2—N4A—C4B—C4C176.4 (3)
C2F—N2A—C2B—C2C0.1 (7)C4F—N4A—C4B—C4H178.2 (4)
Cu1—N2A—C2B—C2C176.7 (3)Cu2—N4A—C4B—C4H2.2 (5)
C2F—N2A—C2B—C2H178.2 (4)N4A—C4B—C4C—C4D1.2 (7)
Cu1—N2A—C2B—C2H1.4 (5)C4H—C4B—C4C—C4D177.1 (4)
N2A—C2B—C2C—C2D0.4 (7)C4B—C4C—C4D—C4E1.0 (7)
C2H—C2B—C2C—C2D178.1 (4)C4C—C4D—C4E—C4F0.0 (8)
C2B—C2C—C2D—C2E0.5 (7)C4B—N4A—C4F—C4E0.7 (7)
C2C—C2D—C2E—C2F0.3 (7)Cu2—N4A—C4F—C4E175.3 (3)
C2B—N2A—C2F—C2E0.1 (7)C4B—N4A—C4F—C4G179.5 (4)
Cu1—N2A—C2F—C2E176.8 (3)Cu2—N4A—C4F—C4G4.4 (5)
C2B—N2A—C2F—C2G176.8 (4)C4D—C4E—C4F—N4A0.9 (7)
Cu1—N2A—C2F—C2G0.0 (5)C4D—C4E—C4F—C4G179.4 (5)
C2D—C2E—C2F—N2A0.0 (7)N4A—C4F—C4G—O4I176.7 (4)
C2D—C2E—C2F—C2G176.3 (4)C4E—C4F—C4G—O4I3.5 (8)
N2A—C2F—C2G—O2I176.5 (4)N4A—C4F—C4G—O4J3.0 (6)
C2E—C2F—C2G—O2I6.9 (7)C4E—C4F—C4G—O4J176.7 (5)
N2A—C2F—C2G—O2J4.1 (6)N4A—C4B—C4H—O4K178.4 (4)
C2E—C2F—C2G—O2J172.5 (4)C4C—C4B—C4H—O4K3.1 (7)
N2A—C2B—C2H—O2K179.9 (4)N4A—C4B—C4H—O4L3.4 (6)
C2C—C2B—C2H—O2K2.3 (7)C4C—C4B—C4H—O4L175.1 (5)
N2A—C2B—C2H—O2L2.4 (6)O4K—C4H—O4L—Cu2179.0 (4)
C2C—C2B—C2H—O2L175.5 (4)C4B—C4H—O4L—Cu23.0 (5)
O2I—C2G—O2J—Cu1174.8 (4)N4A—Cu2—O4L—C4H1.5 (3)
C2F—C2G—O2J—Cu15.9 (5)N3A—Cu2—O4L—C4H178.7 (3)
N2A—Cu1—O2J—C2G4.7 (3)O4J—Cu2—O4L—C4H0.4 (7)
N1A—Cu1—O2J—C2G171.9 (3)O3K—Cu2—O4L—C4H89.2 (3)
O2L—Cu1—O2J—C2G20.0 (6)O1K—Cu2—O4L—C4H77.8 (3)
O1W—Cu1—O2J—C2G93.2 (3)O4I—C4G—O4J—Cu2179.4 (4)
O2K—C2H—O2L—Cu1179.8 (4)C4F—C4G—O4J—Cu20.3 (5)
C2B—C2H—O2L—Cu12.2 (5)N4A—Cu2—O4J—C4G1.6 (3)
N2A—Cu1—O2L—C2H1.2 (3)N3A—Cu2—O4J—C4G175.6 (3)
N1A—Cu1—O2L—C2H168.7 (3)O4L—Cu2—O4J—C4G2.7 (6)
O2J—Cu1—O2L—C2H16.5 (6)O3K—Cu2—O4J—C4G91.2 (3)
O1W—Cu1—O2L—C2H96.4 (3)O1K—Cu2—O4J—C4G77.9 (3)
Symmetry code: (i) x1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1I—H1I···O4Iii0.821.762.569 (4)171
O1L—H1L···O4Kiii0.821.812.583 (4)157
O1W—H1W···O1Jii0.89 (2)2.17 (2)3.051 (5)172 (6)
O1W—H2W···O2Iiv0.87 (2)2.32 (2)3.180 (5)170 (6)
O3I—H3I···O2Iii0.821.762.574 (4)172
O3L—H3L···O2Kiii0.821.762.536 (4)157
Symmetry codes: (ii) x, y, z; (iii) x, y, z+1; (iv) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu4(C7H3NO4)4(C7H5NO4)4(H2O)2]
Mr1619.09
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)7.1350 (2), 11.8614 (1), 17.0675 (3)
α, β, γ (°)96.480 (1), 94.971 (1), 95.229 (1)
V3)1422.36 (5)
Z1
Radiation typeMo Kα
µ (mm1)1.59
Crystal size (mm)0.16 × 0.10 × 0.06
Data collection
DiffractometerBruker SMART 1K CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1997)
Tmin, Tmax0.785, 0.911
No. of measured, independent and
observed [I > 2σ(I)] reflections
8996, 6126, 3728
Rint0.034
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.138, 0.99
No. of reflections6126
No. of parameters471
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.53, 1.00

Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1996), SHELXTL and PLATON (Spek, 2003).

Selected bond lengths (Å) top
Cu1—N1A1.973 (3)Cu2—N4A1.889 (3)
Cu1—N2A1.899 (3)Cu2—O1K2.724 (4)
Cu1—O2J2.032 (3)Cu2—O3K2.541 (4)
Cu1—O2L2.010 (3)Cu2—O4J2.001 (3)
Cu1—O1W2.249 (4)Cu2—O4L1.999 (3)
Cu2—N3A1.946 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1I—H1I···O4Ii0.821.762.569 (4)171
O1L—H1L···O4Kii0.821.812.583 (4)157
O1W—H1W···O1Ji0.89 (2)2.17 (2)3.051 (5)172 (6)
O1W—H2W···O2Iiii0.87 (2)2.32 (2)3.180 (5)170 (6)
O3I—H3I···O2Ii0.821.762.574 (4)172
O3L—H3L···O2Kii0.821.762.536 (4)157
Symmetry codes: (i) x, y, z; (ii) x, y, z+1; (iii) x+1, y+1, z.
 

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