Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104001027/tr1072sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104001027/tr1072Isup2.hkl |
CCDC reference: 235310
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.
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.
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).
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. | |
Fig. 2. : One tetrameric moiety. |
[Cu4(C7H3NO4)4(C7H5NO4)4(H2O)2] | Z = 1 |
Mr = 1619.09 | F(000) = 816 |
Triclinic, P1 | Dx = 1.890 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1350 (2) Å | Cell parameters from 3414 reflections |
b = 11.8614 (1) Å | θ = 1.2–27.0° |
c = 17.0675 (3) Å | µ = 1.59 mm−1 |
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 |
Bruker SMART 1K CCD diffractometer | 6126 independent reflections |
Radiation source: fine-focus sealed tube | 3728 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 27.0°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −9→9 |
Tmin = 0.785, Tmax = 0.911 | k = −15→11 |
8996 measured reflections | l = −21→21 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-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 parameters | Δρmax = 0.53 e Å−3 |
2 restraints | Δρmin = −1.00 e Å−3 |
[Cu4(C7H3NO4)4(C7H5NO4)4(H2O)2] | γ = 95.229 (1)° |
Mr = 1619.09 | V = 1422.36 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.1350 (2) Å | Mo Kα radiation |
b = 11.8614 (1) Å | µ = 1.59 mm−1 |
c = 17.0675 (3) Å | T = 296 K |
α = 96.480 (1)° | 0.16 × 0.10 × 0.06 mm |
β = 94.971 (1)° |
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 = 0.911 | Rint = 0.034 |
8996 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 2 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.53 e Å−3 |
6126 reflections | Δρmin = −1.00 e Å−3 |
471 parameters |
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 |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.47689 (8) | 0.29266 (4) | 0.14473 (3) | 0.02788 (17) | |
Cu2 | −0.20124 (8) | 0.08634 (4) | 0.38766 (3) | 0.03103 (18) | |
N1A | 0.3499 (5) | 0.1374 (3) | 0.1431 (2) | 0.0257 (8) | |
C1B | 0.2971 (6) | 0.1005 (4) | 0.2101 (3) | 0.0280 (10) | |
H1B | 0.3276 | 0.1477 | 0.2577 | 0.034* | |
C1C | 0.1982 (6) | −0.0060 (4) | 0.2109 (3) | 0.0249 (10) | |
C1D | 0.1538 (6) | −0.0745 (4) | 0.1396 (3) | 0.0280 (10) | |
H1D | 0.0856 | −0.1455 | 0.1382 | 0.034* | |
C1E | 0.2097 (6) | −0.0383 (4) | 0.0704 (3) | 0.0264 (10) | |
C1F | 0.3052 (6) | 0.0687 (4) | 0.0740 (3) | 0.0281 (10) | |
H1F | 0.3401 | 0.0946 | 0.0274 | 0.034* | |
C1G | 0.1554 (7) | −0.1142 (4) | −0.0052 (3) | 0.0303 (11) | |
C1H | 0.1381 (6) | −0.0405 (4) | 0.2874 (3) | 0.0277 (10) | |
O1I | 0.2288 (5) | −0.0743 (3) | −0.06623 (18) | 0.0377 (8) | |
H1I | 0.2066 | −0.1221 | −0.1053 | 0.057* | |
O1J | 0.0569 (5) | −0.2036 (3) | −0.00920 (19) | 0.0405 (9) | |
O1K | 0.1398 (5) | 0.0262 (3) | 0.34677 (19) | 0.0409 (9) | |
O1L | 0.0832 (5) | −0.1502 (3) | 0.28148 (19) | 0.0393 (9) | |
H1L | 0.0406 | −0.1652 | 0.3226 | 0.059* | |
O1W | 0.2056 (5) | 0.3731 (3) | 0.1264 (2) | 0.0446 (9) | |
H1W | 0.123 (7) | 0.329 (4) | 0.091 (3) | 0.08 (2)* | |
H2W | 0.249 (8) | 0.429 (4) | 0.102 (3) | 0.080* | |
N2A | 0.6478 (5) | 0.4269 (3) | 0.1530 (2) | 0.0245 (8) | |
C2B | 0.7051 (6) | 0.4804 (3) | 0.2247 (2) | 0.0243 (10) | |
C2C | 0.8368 (7) | 0.5751 (4) | 0.2348 (3) | 0.0325 (11) | |
H2C | 0.8787 | 0.6131 | 0.2848 | 0.039* | |
C2D | 0.9039 (7) | 0.6110 (4) | 0.1661 (3) | 0.0355 (12) | |
H2D | 0.9920 | 0.6748 | 0.1704 | 0.043* | |
C2E | 0.8425 (7) | 0.5540 (4) | 0.0920 (3) | 0.0327 (11) | |
H2E | 0.8880 | 0.5781 | 0.0465 | 0.039* | |
C2F | 0.7107 (6) | 0.4597 (3) | 0.0876 (3) | 0.0233 (10) | |
C2G | 0.6293 (6) | 0.3793 (4) | 0.0154 (3) | 0.0278 (10) | |
C2H | 0.6144 (6) | 0.4219 (4) | 0.2882 (3) | 0.0269 (10) | |
O2I | 0.6682 (5) | 0.4020 (3) | −0.05112 (18) | 0.0396 (9) | |
O2J | 0.5264 (5) | 0.2922 (3) | 0.02922 (18) | 0.0347 (8) | |
O2K | 0.6526 (5) | 0.4613 (3) | 0.35901 (18) | 0.0344 (8) | |
O2L | 0.5065 (4) | 0.3314 (2) | 0.26316 (18) | 0.0320 (8) | |
N3A | −0.3356 (5) | −0.0648 (3) | 0.3843 (2) | 0.0269 (9) | |
C3B | −0.3730 (6) | −0.1056 (4) | 0.4521 (2) | 0.0266 (10) | |
H3E | −0.3319 | −0.0608 | 0.4999 | 0.032* | |
C3C | −0.4700 (6) | −0.2111 (4) | 0.4538 (3) | 0.0253 (10) | |
C3D | −0.5270 (6) | −0.2773 (4) | 0.3818 (3) | 0.0291 (11) | |
H3D | −0.5878 | −0.3503 | 0.3810 | 0.035* | |
C3E | −0.4939 (6) | −0.2353 (4) | 0.3112 (3) | 0.0267 (10) | |
C3F | −0.3981 (6) | −0.1286 (4) | 0.3150 (3) | 0.0268 (10) | |
H3F | −0.3756 | −0.0993 | 0.2680 | 0.032* | |
C3G | −0.5699 (6) | −0.3071 (4) | 0.2349 (3) | 0.0272 (10) | |
C3H | −0.5153 (6) | −0.2492 (4) | 0.5308 (3) | 0.0277 (10) | |
O3I | −0.5329 (6) | −0.2594 (3) | 0.17212 (18) | 0.0433 (9) | |
H3I | −0.5662 | −0.3049 | 0.1324 | 0.065* | |
O3J | −0.6577 (5) | −0.3988 (3) | 0.23503 (19) | 0.0397 (8) | |
O3K | −0.4979 (5) | 0.1845 (3) | 0.40894 (18) | 0.0384 (8) | |
O3L | −0.5742 (5) | −0.3579 (3) | 0.52396 (18) | 0.0376 (8) | |
H3L | −0.5774 | −0.3784 | 0.5682 | 0.056* | |
N4A | −0.0590 (5) | 0.2298 (3) | 0.3932 (2) | 0.0242 (8) | |
C4B | 0.0145 (6) | 0.2828 (4) | 0.4640 (3) | 0.0243 (10) | |
C4C | 0.1263 (7) | 0.3832 (4) | 0.4695 (3) | 0.0302 (11) | |
H4C | 0.1764 | 0.4218 | 0.5183 | 0.036* | |
C4D | 0.1627 (7) | 0.4262 (4) | 0.3983 (3) | 0.0387 (13) | |
H4D | 0.2402 | 0.4940 | 0.4001 | 0.046* | |
C4E | 0.0861 (7) | 0.3700 (4) | 0.3260 (3) | 0.0316 (11) | |
H4E | 0.1108 | 0.3988 | 0.2791 | 0.038* | |
C4F | −0.0275 (6) | 0.2705 (4) | 0.3253 (2) | 0.0253 (10) | |
C4G | −0.1311 (7) | 0.1921 (4) | 0.2550 (3) | 0.0281 (10) | |
C4H | −0.0421 (6) | 0.2135 (3) | 0.5298 (3) | 0.0245 (10) | |
O4L | −0.1375 (5) | 0.1185 (3) | 0.50492 (18) | 0.0363 (8) | |
O4K | 0.0097 (5) | 0.2508 (3) | 0.59891 (17) | 0.0352 (8) | |
O4J | −0.2199 (5) | 0.1016 (2) | 0.27177 (17) | 0.0343 (8) | |
O4I | −0.1226 (5) | 0.2211 (3) | 0.18808 (18) | 0.0391 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0383 (4) | 0.0236 (3) | 0.0189 (3) | −0.0113 (2) | 0.0043 (2) | 0.0006 (2) |
Cu2 | 0.0493 (4) | 0.0232 (3) | 0.0168 (3) | −0.0136 (3) | 0.0025 (3) | 0.0007 (2) |
N1A | 0.031 (2) | 0.025 (2) | 0.019 (2) | −0.0075 (16) | 0.0021 (16) | −0.0004 (15) |
C1B | 0.034 (3) | 0.026 (2) | 0.023 (3) | −0.004 (2) | 0.001 (2) | 0.0022 (19) |
C1C | 0.030 (3) | 0.024 (2) | 0.019 (2) | −0.0040 (19) | 0.0013 (19) | 0.0028 (18) |
C1D | 0.033 (3) | 0.022 (2) | 0.028 (3) | −0.002 (2) | 0.001 (2) | 0.0046 (19) |
C1E | 0.032 (3) | 0.024 (2) | 0.021 (2) | −0.0046 (19) | 0.000 (2) | 0.0025 (19) |
C1F | 0.035 (3) | 0.026 (2) | 0.023 (2) | 0.000 (2) | 0.007 (2) | 0.0042 (19) |
C1G | 0.034 (3) | 0.032 (3) | 0.024 (3) | −0.002 (2) | 0.000 (2) | 0.003 (2) |
C1H | 0.027 (3) | 0.025 (2) | 0.030 (3) | −0.0063 (19) | 0.004 (2) | 0.004 (2) |
O1I | 0.057 (2) | 0.0338 (19) | 0.0180 (17) | −0.0136 (16) | 0.0043 (16) | −0.0013 (14) |
O1J | 0.054 (2) | 0.0351 (19) | 0.0260 (19) | −0.0186 (17) | 0.0050 (16) | −0.0045 (15) |
O1K | 0.063 (2) | 0.0347 (19) | 0.0226 (19) | −0.0065 (17) | 0.0101 (17) | −0.0008 (15) |
O1L | 0.065 (2) | 0.0284 (18) | 0.0228 (18) | −0.0118 (16) | 0.0119 (17) | 0.0024 (14) |
O1W | 0.045 (2) | 0.031 (2) | 0.055 (3) | −0.0058 (17) | 0.004 (2) | 0.0058 (18) |
N2A | 0.029 (2) | 0.026 (2) | 0.0173 (19) | −0.0034 (16) | 0.0029 (16) | 0.0033 (15) |
C2B | 0.035 (3) | 0.022 (2) | 0.015 (2) | −0.0050 (19) | 0.0015 (19) | 0.0032 (17) |
C2C | 0.043 (3) | 0.028 (3) | 0.025 (3) | −0.004 (2) | −0.001 (2) | 0.003 (2) |
C2D | 0.041 (3) | 0.032 (3) | 0.030 (3) | −0.020 (2) | 0.002 (2) | 0.005 (2) |
C2E | 0.038 (3) | 0.035 (3) | 0.024 (3) | −0.009 (2) | 0.007 (2) | 0.006 (2) |
C2F | 0.025 (2) | 0.020 (2) | 0.023 (2) | −0.0037 (18) | 0.0032 (19) | 0.0006 (18) |
C2G | 0.034 (3) | 0.028 (2) | 0.019 (2) | −0.004 (2) | 0.001 (2) | −0.0001 (19) |
C2H | 0.032 (3) | 0.028 (2) | 0.021 (2) | −0.001 (2) | 0.005 (2) | 0.0064 (19) |
O2I | 0.059 (2) | 0.040 (2) | 0.0159 (17) | −0.0162 (17) | 0.0032 (16) | 0.0014 (14) |
O2J | 0.047 (2) | 0.0299 (18) | 0.0227 (18) | −0.0138 (15) | 0.0026 (15) | −0.0007 (14) |
O2K | 0.052 (2) | 0.0300 (17) | 0.0170 (17) | −0.0119 (15) | 0.0034 (15) | −0.0010 (13) |
O2L | 0.044 (2) | 0.0271 (17) | 0.0215 (17) | −0.0134 (14) | 0.0070 (15) | 0.0012 (13) |
N3A | 0.036 (2) | 0.024 (2) | 0.021 (2) | −0.0013 (16) | 0.0069 (17) | 0.0025 (16) |
C3B | 0.033 (3) | 0.027 (2) | 0.017 (2) | −0.004 (2) | 0.0021 (19) | −0.0043 (18) |
C3C | 0.027 (3) | 0.027 (2) | 0.021 (2) | −0.0011 (19) | 0.0034 (19) | 0.0043 (19) |
C3D | 0.039 (3) | 0.020 (2) | 0.026 (3) | −0.007 (2) | 0.003 (2) | 0.0038 (19) |
C3E | 0.030 (3) | 0.028 (2) | 0.022 (2) | −0.0015 (19) | 0.004 (2) | 0.0034 (19) |
C3F | 0.034 (3) | 0.026 (2) | 0.019 (2) | −0.007 (2) | 0.003 (2) | 0.0040 (19) |
C3G | 0.033 (3) | 0.026 (2) | 0.022 (2) | 0.000 (2) | 0.001 (2) | 0.0000 (19) |
C3H | 0.034 (3) | 0.028 (2) | 0.019 (2) | −0.006 (2) | 0.001 (2) | 0.004 (2) |
O3I | 0.074 (3) | 0.037 (2) | 0.0152 (17) | −0.0112 (18) | 0.0042 (18) | −0.0005 (14) |
O3J | 0.055 (2) | 0.0271 (18) | 0.033 (2) | −0.0153 (16) | 0.0024 (16) | 0.0013 (15) |
O3K | 0.058 (2) | 0.0360 (19) | 0.0186 (18) | −0.0086 (17) | 0.0046 (16) | 0.0003 (15) |
O3L | 0.056 (2) | 0.0303 (18) | 0.0250 (18) | −0.0128 (16) | 0.0060 (17) | 0.0080 (14) |
N4A | 0.035 (2) | 0.0208 (19) | 0.0151 (19) | −0.0048 (16) | 0.0021 (16) | 0.0001 (15) |
C4B | 0.026 (2) | 0.025 (2) | 0.021 (2) | 0.0005 (19) | 0.0033 (19) | 0.0005 (18) |
C4C | 0.038 (3) | 0.025 (2) | 0.023 (2) | −0.010 (2) | 0.000 (2) | −0.0037 (19) |
C4D | 0.045 (3) | 0.033 (3) | 0.035 (3) | −0.017 (2) | 0.008 (2) | 0.005 (2) |
C4E | 0.037 (3) | 0.034 (3) | 0.025 (3) | −0.005 (2) | 0.008 (2) | 0.012 (2) |
C4F | 0.032 (3) | 0.028 (2) | 0.017 (2) | 0.0003 (19) | 0.0035 (19) | 0.0049 (18) |
C4G | 0.035 (3) | 0.027 (2) | 0.020 (2) | −0.003 (2) | 0.002 (2) | −0.0008 (19) |
C4H | 0.030 (3) | 0.022 (2) | 0.020 (2) | −0.0031 (19) | 0.0015 (19) | 0.0009 (18) |
O4L | 0.055 (2) | 0.0285 (18) | 0.0219 (18) | −0.0154 (16) | 0.0015 (15) | 0.0052 (14) |
O4K | 0.050 (2) | 0.0358 (18) | 0.0151 (17) | −0.0139 (15) | −0.0029 (15) | 0.0005 (14) |
O4J | 0.053 (2) | 0.0293 (18) | 0.0168 (17) | −0.0096 (16) | 0.0013 (15) | −0.0017 (13) |
O4I | 0.067 (2) | 0.0308 (18) | 0.0172 (17) | −0.0086 (16) | 0.0065 (16) | 0.0018 (14) |
Cu1—N1A | 1.973 (3) | C2E—H2E | 0.9300 |
Cu1—N2A | 1.899 (3) | C2F—C2G | 1.508 (6) |
Cu1—O2J | 2.032 (3) | C2G—O2I | 1.245 (5) |
Cu1—O2L | 2.010 (3) | C2G—O2J | 1.268 (5) |
Cu1—O1W | 2.249 (4) | C2H—O2K | 1.243 (5) |
Cu2—N3A | 1.946 (4) | C2H—O2L | 1.272 (5) |
Cu2—N4A | 1.889 (3) | N3A—C3B | 1.343 (5) |
Cu2—O1K | 2.724 (4) | N3A—C3F | 1.347 (5) |
Cu2—O3K | 2.541 (4) | C3B—C3C | 1.378 (6) |
Cu2—O4J | 2.001 (3) | C3B—H3E | 0.9300 |
Cu2—O4L | 1.999 (3) | C3C—C3D | 1.389 (6) |
N1A—C1B | 1.342 (5) | C3C—C3H | 1.489 (6) |
N1A—C1F | 1.351 (5) | C3D—C3E | 1.387 (6) |
C1B—C1C | 1.392 (6) | C3D—H3D | 0.9300 |
C1B—H1B | 0.9300 | C3E—C3F | 1.374 (6) |
C1C—C1D | 1.379 (6) | C3E—C3G | 1.502 (6) |
C1C—C1H | 1.498 (6) | C3F—H3F | 0.9300 |
C1D—C1E | 1.380 (6) | C3G—O3J | 1.206 (5) |
C1D—H1D | 0.9300 | C3G—O3I | 1.302 (5) |
C1E—C1F | 1.378 (6) | C3H—O3Ki | 1.203 (5) |
C1E—C1G | 1.487 (6) | C3H—O3L | 1.308 (5) |
C1F—H1F | 0.9300 | O3I—H3I | 0.8200 |
C1G—O1J | 1.209 (5) | O3K—C3Hi | 1.203 (5) |
C1G—O1I | 1.321 (5) | O3L—H3L | 0.8200 |
C1H—O1K | 1.211 (5) | N4A—C4F | 1.332 (5) |
C1H—O1L | 1.314 (5) | N4A—C4B | 1.338 (5) |
O1I—H1I | 0.8200 | C4B—C4C | 1.361 (6) |
O1L—H1L | 0.8200 | C4B—C4H | 1.525 (6) |
O1W—H1W | 0.89 (2) | C4C—C4D | 1.404 (6) |
O1W—H2W | 0.87 (2) | C4C—H4C | 0.9300 |
N2A—C2F | 1.324 (5) | C4D—C4E | 1.377 (7) |
N2A—C2B | 1.325 (5) | C4D—H4D | 0.9300 |
C2B—C2C | 1.382 (6) | C4E—C4F | 1.368 (6) |
C2B—C2H | 1.511 (6) | C4E—H4E | 0.9300 |
C2C—C2D | 1.400 (6) | C4F—C4G | 1.523 (6) |
C2C—H2C | 0.9300 | C4G—O4I | 1.235 (5) |
C2D—C2E | 1.380 (6) | C4G—O4J | 1.270 (5) |
C2D—H2D | 0.9300 | C4H—O4K | 1.225 (5) |
C2E—C2F | 1.385 (6) | C4H—O4L | 1.272 (5) |
N2A—Cu1—N1A | 167.35 (15) | C2D—C2E—C2F | 117.7 (4) |
N2A—Cu1—O2L | 80.85 (13) | C2D—C2E—H2E | 121.2 |
N1A—Cu1—O2L | 96.38 (13) | C2F—C2E—H2E | 121.2 |
N2A—Cu1—O2J | 80.30 (13) | N2A—C2F—C2E | 120.1 (4) |
N1A—Cu1—O2J | 100.91 (13) | N2A—C2F—C2G | 111.4 (4) |
O2L—Cu1—O2J | 160.47 (13) | C2E—C2F—C2G | 128.3 (4) |
N2A—Cu1—O1W | 98.23 (14) | O2I—C2G—O2J | 125.8 (4) |
N1A—Cu1—O1W | 94.30 (14) | O2I—C2G—C2F | 118.9 (4) |
O2L—Cu1—O1W | 95.06 (14) | O2J—C2G—C2F | 115.3 (4) |
O2J—Cu1—O1W | 92.65 (14) | O2K—C2H—O2L | 125.1 (4) |
N4A—Cu2—N3A | 176.90 (15) | O2K—C2H—C2B | 119.8 (4) |
N4A—Cu2—O4L | 80.47 (13) | O2L—C2H—C2B | 115.0 (4) |
N3A—Cu2—O4L | 98.14 (13) | C2G—O2J—Cu1 | 114.0 (3) |
N4A—Cu2—O4J | 81.73 (13) | C2H—O2L—Cu1 | 114.4 (3) |
N3A—Cu2—O4J | 99.65 (14) | C3B—N3A—C3F | 118.7 (4) |
O4L—Cu2—O4J | 162.20 (12) | C3B—N3A—Cu2 | 119.8 (3) |
N4A—Cu2—O3K | 90.12 (13) | C3F—N3A—Cu2 | 121.5 (3) |
N3A—Cu2—O3K | 92.57 (13) | N3A—C3B—C3C | 122.7 (4) |
O4L—Cu2—O3K | 86.53 (12) | N3A—C3B—H3E | 118.7 |
O4J—Cu2—O3K | 93.18 (12) | C3C—C3B—H3E | 118.7 |
N4A—Cu2—O1K | 78.09 (13) | C3B—C3C—C3D | 117.7 (4) |
N3A—Cu2—O1K | 99.43 (13) | C3B—C3C—C3H | 120.1 (4) |
O4L—Cu2—O1K | 98.66 (12) | C3D—C3C—C3H | 122.2 (4) |
O4J—Cu2—O1K | 77.91 (12) | C3E—C3D—C3C | 120.4 (4) |
O3K—Cu2—O1K | 166.05 (10) | C3E—C3D—H3D | 119.8 |
C1B—N1A—C1F | 118.8 (4) | C3C—C3D—H3D | 119.8 |
C1B—N1A—Cu1 | 120.4 (3) | C3F—C3E—C3D | 118.0 (4) |
C1F—N1A—Cu1 | 120.7 (3) | C3F—C3E—C3G | 123.7 (4) |
N1A—C1B—C1C | 122.2 (4) | C3D—C3E—C3G | 118.3 (4) |
N1A—C1B—H1B | 118.9 | N3A—C3F—C3E | 122.5 (4) |
C1C—C1B—H1B | 118.9 | N3A—C3F—H3F | 118.7 |
C1D—C1C—C1B | 117.9 (4) | C3E—C3F—H3F | 118.7 |
C1D—C1C—C1H | 122.5 (4) | O3J—C3G—O3I | 125.6 (4) |
C1B—C1C—C1H | 119.5 (4) | O3J—C3G—C3E | 120.9 (4) |
C1C—C1D—C1E | 120.4 (4) | O3I—C3G—C3E | 113.5 (4) |
C1C—C1D—H1D | 119.8 | O3Ki—C3H—O3L | 125.4 (4) |
C1E—C1D—H1D | 119.8 | O3Ki—C3H—C3C | 122.3 (4) |
C1F—C1E—C1D | 118.4 (4) | O3L—C3H—C3C | 112.3 (4) |
C1F—C1E—C1G | 123.0 (4) | C3G—O3I—H3I | 109.5 |
C1D—C1E—C1G | 118.5 (4) | C3Hi—O3K—Cu2 | 113.6 (3) |
N1A—C1F—C1E | 122.2 (4) | C3H—O3L—H3L | 109.5 |
N1A—C1F—H1F | 118.9 | C4F—N4A—C4B | 122.9 (4) |
C1E—C1F—H1F | 118.9 | C4F—N4A—Cu2 | 117.9 (3) |
O1J—C1G—O1I | 124.3 (4) | C4B—N4A—Cu2 | 119.1 (3) |
O1J—C1G—C1E | 122.9 (4) | N4A—C4B—C4C | 120.4 (4) |
O1I—C1G—C1E | 112.8 (4) | N4A—C4B—C4H | 110.5 (4) |
O1K—C1H—O1L | 125.1 (4) | C4C—C4B—C4H | 129.1 (4) |
O1K—C1H—C1C | 123.2 (4) | C4B—C4C—C4D | 117.2 (4) |
O1L—C1H—C1C | 111.8 (4) | C4B—C4C—H4C | 121.4 |
C1G—O1I—H1I | 109.5 | C4D—C4C—H4C | 121.4 |
C1H—O1K—Cu2 | 116.7 (3) | C4E—C4D—C4C | 121.4 (4) |
C1H—O1L—H1L | 109.5 | C4E—C4D—H4D | 119.3 |
Cu1—O1W—H1W | 111 (4) | C4C—C4D—H4D | 119.3 |
Cu1—O1W—H2W | 98 (4) | C4F—C4E—C4D | 118.0 (4) |
H1W—O1W—H2W | 106 (6) | C4F—C4E—H4E | 121.0 |
C2F—N2A—C2B | 123.1 (4) | C4D—C4E—H4E | 121.0 |
C2F—N2A—Cu1 | 118.7 (3) | N4A—C4F—C4E | 120.1 (4) |
C2B—N2A—Cu1 | 118.1 (3) | N4A—C4F—C4G | 110.8 (4) |
N2A—C2B—C2C | 120.8 (4) | C4E—C4F—C4G | 129.2 (4) |
N2A—C2B—C2H | 111.5 (4) | O4I—C4G—O4J | 126.0 (4) |
C2C—C2B—C2H | 127.7 (4) | O4I—C4G—C4F | 118.4 (4) |
C2B—C2C—C2D | 116.7 (4) | O4J—C4G—C4F | 115.6 (4) |
C2B—C2C—H2C | 121.6 | O4K—C4H—O4L | 126.7 (4) |
C2D—C2C—H2C | 121.6 | O4K—C4H—C4B | 119.3 (4) |
C2E—C2D—C2C | 121.5 (4) | O4L—C4H—C4B | 113.9 (4) |
C2E—C2D—H2D | 119.2 | C4H—O4L—Cu2 | 115.9 (3) |
C2C—C2D—H2D | 119.2 | C4G—O4J—Cu2 | 113.9 (3) |
N2A—Cu1—N1A—C1B | 83.6 (8) | O4L—Cu2—N3A—C3B | 7.0 (4) |
O2L—Cu1—N1A—C1B | 7.0 (4) | O4J—Cu2—N3A—C3B | −173.5 (3) |
O2J—Cu1—N1A—C1B | 177.9 (3) | O3K—Cu2—N3A—C3B | −79.8 (3) |
O1W—Cu1—N1A—C1B | −88.5 (3) | O1K—Cu2—N3A—C3B | 107.3 (3) |
N2A—Cu1—N1A—C1F | −100.1 (7) | O4L—Cu2—N3A—C3F | −175.2 (3) |
O2L—Cu1—N1A—C1F | −176.6 (3) | O4J—Cu2—N3A—C3F | 4.2 (4) |
O2J—Cu1—N1A—C1F | −5.8 (4) | O3K—Cu2—N3A—C3F | 97.9 (4) |
O1W—Cu1—N1A—C1F | 87.8 (4) | O1K—Cu2—N3A—C3F | −75.0 (4) |
C1F—N1A—C1B—C1C | 0.1 (7) | C3F—N3A—C3B—C3C | 1.2 (7) |
Cu1—N1A—C1B—C1C | 176.5 (3) | Cu2—N3A—C3B—C3C | 179.0 (3) |
N1A—C1B—C1C—C1D | −0.3 (7) | N3A—C3B—C3C—C3D | 1.1 (7) |
N1A—C1B—C1C—C1H | −178.0 (4) | N3A—C3B—C3C—C3H | −177.0 (4) |
C1B—C1C—C1D—C1E | 1.3 (7) | C3B—C3C—C3D—C3E | −2.8 (7) |
C1H—C1C—C1D—C1E | 179.0 (4) | C3H—C3C—C3D—C3E | 175.3 (4) |
C1C—C1D—C1E—C1F | −2.0 (7) | C3C—C3D—C3E—C3F | 2.1 (7) |
C1C—C1D—C1E—C1G | −178.9 (4) | C3C—C3D—C3E—C3G | −175.9 (4) |
C1B—N1A—C1F—C1E | −0.9 (7) | C3B—N3A—C3F—C3E | −2.0 (7) |
Cu1—N1A—C1F—C1E | −177.3 (3) | Cu2—N3A—C3F—C3E | −179.7 (3) |
C1D—C1E—C1F—N1A | 1.9 (7) | C3D—C3E—C3F—N3A | 0.3 (7) |
C1G—C1E—C1F—N1A | 178.6 (4) | C3G—C3E—C3F—N3A | 178.3 (4) |
C1F—C1E—C1G—O1J | −173.1 (5) | C3F—C3E—C3G—O3J | −177.9 (4) |
C1D—C1E—C1G—O1J | 3.7 (7) | C3D—C3E—C3G—O3J | 0.1 (7) |
C1F—C1E—C1G—O1I | 8.0 (7) | C3F—C3E—C3G—O3I | 1.3 (7) |
C1D—C1E—C1G—O1I | −175.3 (4) | C3D—C3E—C3G—O3I | 179.3 (4) |
C1D—C1C—C1H—O1K | −163.8 (5) | C3B—C3C—C3H—O3Ki | 13.9 (7) |
C1B—C1C—C1H—O1K | 13.8 (7) | C3D—C3C—C3H—O3Ki | −164.1 (5) |
C1D—C1C—C1H—O1L | 15.8 (6) | C3B—C3C—C3H—O3L | −167.7 (4) |
C1B—C1C—C1H—O1L | −166.6 (4) | C3D—C3C—C3H—O3L | 14.2 (6) |
O1L—C1H—O1K—Cu2 | −73.8 (5) | N4A—Cu2—O3K—C3Hi | −57.5 (3) |
C1C—C1H—O1K—Cu2 | 105.7 (4) | N3A—Cu2—O3K—C3Hi | 120.9 (3) |
N4A—Cu2—O1K—C1H | −130.5 (3) | O4L—Cu2—O3K—C3Hi | 22.9 (3) |
N3A—Cu2—O1K—C1H | 51.4 (3) | O4J—Cu2—O3K—C3Hi | −139.2 (3) |
O4L—Cu2—O1K—C1H | 151.2 (3) | O1K—Cu2—O3K—C3Hi | −89.5 (5) |
O4J—Cu2—O1K—C1H | −46.6 (3) | O4L—Cu2—N4A—C4F | 176.8 (3) |
O3K—Cu2—O1K—C1H | −97.7 (5) | O4J—Cu2—N4A—C4F | −3.5 (3) |
N1A—Cu1—N2A—C2F | 98.9 (7) | O3K—Cu2—N4A—C4F | −96.7 (3) |
O2L—Cu1—N2A—C2F | 177.2 (3) | O1K—Cu2—N4A—C4F | 75.8 (3) |
O2J—Cu1—N2A—C2F | 2.3 (3) | O4L—Cu2—N4A—C4B | 0.6 (3) |
O1W—Cu1—N2A—C2F | −89.0 (3) | O4J—Cu2—N4A—C4B | −179.7 (4) |
N1A—Cu1—N2A—C2B | −78.0 (8) | O3K—Cu2—N4A—C4B | 87.1 (3) |
O2L—Cu1—N2A—C2B | 0.2 (3) | O1K—Cu2—N4A—C4B | −100.4 (3) |
O2J—Cu1—N2A—C2B | −174.6 (4) | C4F—N4A—C4B—C4C | 0.4 (7) |
O1W—Cu1—N2A—C2B | 94.1 (3) | Cu2—N4A—C4B—C4C | 176.4 (3) |
C2F—N2A—C2B—C2C | −0.1 (7) | C4F—N4A—C4B—C4H | −178.2 (4) |
Cu1—N2A—C2B—C2C | 176.7 (3) | Cu2—N4A—C4B—C4H | −2.2 (5) |
C2F—N2A—C2B—C2H | −178.2 (4) | N4A—C4B—C4C—C4D | −1.2 (7) |
Cu1—N2A—C2B—C2H | −1.4 (5) | C4H—C4B—C4C—C4D | 177.1 (4) |
N2A—C2B—C2C—C2D | 0.4 (7) | C4B—C4C—C4D—C4E | 1.0 (7) |
C2H—C2B—C2C—C2D | 178.1 (4) | C4C—C4D—C4E—C4F | 0.0 (8) |
C2B—C2C—C2D—C2E | −0.5 (7) | C4B—N4A—C4F—C4E | 0.7 (7) |
C2C—C2D—C2E—C2F | 0.3 (7) | Cu2—N4A—C4F—C4E | −175.3 (3) |
C2B—N2A—C2F—C2E | −0.1 (7) | C4B—N4A—C4F—C4G | −179.5 (4) |
Cu1—N2A—C2F—C2E | −176.8 (3) | Cu2—N4A—C4F—C4G | 4.4 (5) |
C2B—N2A—C2F—C2G | 176.8 (4) | C4D—C4E—C4F—N4A | −0.9 (7) |
Cu1—N2A—C2F—C2G | 0.0 (5) | C4D—C4E—C4F—C4G | 179.4 (5) |
C2D—C2E—C2F—N2A | 0.0 (7) | N4A—C4F—C4G—O4I | 176.7 (4) |
C2D—C2E—C2F—C2G | −176.3 (4) | C4E—C4F—C4G—O4I | −3.5 (8) |
N2A—C2F—C2G—O2I | 176.5 (4) | N4A—C4F—C4G—O4J | −3.0 (6) |
C2E—C2F—C2G—O2I | −6.9 (7) | C4E—C4F—C4G—O4J | 176.7 (5) |
N2A—C2F—C2G—O2J | −4.1 (6) | N4A—C4B—C4H—O4K | −178.4 (4) |
C2E—C2F—C2G—O2J | 172.5 (4) | C4C—C4B—C4H—O4K | 3.1 (7) |
N2A—C2B—C2H—O2K | −179.9 (4) | N4A—C4B—C4H—O4L | 3.4 (6) |
C2C—C2B—C2H—O2K | 2.3 (7) | C4C—C4B—C4H—O4L | −175.1 (5) |
N2A—C2B—C2H—O2L | 2.4 (6) | O4K—C4H—O4L—Cu2 | 179.0 (4) |
C2C—C2B—C2H—O2L | −175.5 (4) | C4B—C4H—O4L—Cu2 | −3.0 (5) |
O2I—C2G—O2J—Cu1 | −174.8 (4) | N4A—Cu2—O4L—C4H | 1.5 (3) |
C2F—C2G—O2J—Cu1 | 5.9 (5) | N3A—Cu2—O4L—C4H | 178.7 (3) |
N2A—Cu1—O2J—C2G | −4.7 (3) | O4J—Cu2—O4L—C4H | 0.4 (7) |
N1A—Cu1—O2J—C2G | −171.9 (3) | O3K—Cu2—O4L—C4H | −89.2 (3) |
O2L—Cu1—O2J—C2G | −20.0 (6) | O1K—Cu2—O4L—C4H | 77.8 (3) |
O1W—Cu1—O2J—C2G | 93.2 (3) | O4I—C4G—O4J—Cu2 | −179.4 (4) |
O2K—C2H—O2L—Cu1 | −179.8 (4) | C4F—C4G—O4J—Cu2 | 0.3 (5) |
C2B—C2H—O2L—Cu1 | −2.2 (5) | N4A—Cu2—O4J—C4G | 1.6 (3) |
N2A—Cu1—O2L—C2H | 1.2 (3) | N3A—Cu2—O4J—C4G | −175.6 (3) |
N1A—Cu1—O2L—C2H | 168.7 (3) | O4L—Cu2—O4J—C4G | 2.7 (6) |
O2J—Cu1—O2L—C2H | 16.5 (6) | O3K—Cu2—O4J—C4G | 91.2 (3) |
O1W—Cu1—O2L—C2H | −96.4 (3) | O1K—Cu2—O4J—C4G | −77.9 (3) |
Symmetry code: (i) −x−1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1I—H1I···O4Iii | 0.82 | 1.76 | 2.569 (4) | 171 |
O1L—H1L···O4Kiii | 0.82 | 1.81 | 2.583 (4) | 157 |
O1W—H1W···O1Jii | 0.89 (2) | 2.17 (2) | 3.051 (5) | 172 (6) |
O1W—H2W···O2Iiv | 0.87 (2) | 2.32 (2) | 3.180 (5) | 170 (6) |
O3I—H3I···O2Iii | 0.82 | 1.76 | 2.574 (4) | 172 |
O3L—H3L···O2Kiii | 0.82 | 1.76 | 2.536 (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] |
Mr | 1619.09 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 1422.36 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.16 × 0.10 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.785, 0.911 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8996, 6126, 3728 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.138, 0.99 |
No. of reflections | 6126 |
No. of parameters | 471 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
Cu1—N1A | 1.973 (3) | Cu2—N4A | 1.889 (3) |
Cu1—N2A | 1.899 (3) | Cu2—O1K | 2.724 (4) |
Cu1—O2J | 2.032 (3) | Cu2—O3K | 2.541 (4) |
Cu1—O2L | 2.010 (3) | Cu2—O4J | 2.001 (3) |
Cu1—O1W | 2.249 (4) | Cu2—O4L | 1.999 (3) |
Cu2—N3A | 1.946 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1I—H1I···O4Ii | 0.82 | 1.76 | 2.569 (4) | 171 |
O1L—H1L···O4Kii | 0.82 | 1.81 | 2.583 (4) | 157 |
O1W—H1W···O1Ji | 0.89 (2) | 2.17 (2) | 3.051 (5) | 172 (6) |
O1W—H2W···O2Iiii | 0.87 (2) | 2.32 (2) | 3.180 (5) | 170 (6) |
O3I—H3I···O2Ii | 0.82 | 1.76 | 2.574 (4) | 172 |
O3L—H3L···O2Kii | 0.82 | 1.76 | 2.536 (4) | 157 |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z. |
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.