supplementary materials
Aqua(2,2'-bipyridine-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N,N')(pyridine-2,6-dicarboxylate N-oxide-2O1,O2)copper(II) trihydrate
In the title complex, [Cu(C7H3NO5)(C10H8N2)(H2O)]·3H2O, the CuII atom has a slightly distorted square-pyramidal coordination geometry, with a basal plane formed by two N atoms of the 2,2'-bipyridine ligand and two O atoms of the pyridine-2,6-dicarboxylate N-oxide. The apical position is occupied by a water molecule. The crystal structure contains O-H
O intermolecular hydrogen bonds.
Pydco(0.050 g, 8 mmol), Cu(CH3COO)2 (0.180 g, 12 mmol) and 2,2-pyridine
(0.230 g, 15 mmol) were added in a mixed solvent of dry ethanol and
acetonitrile. The mixture was heated for 5 h under reflux. During the process
stirring and influx were required. The resultant was then filtered to give a
pure solution which was infiltrated by diethyl ether freely in a closed
vessel. After a week, single crystals of (I), suitable for X-Ray diffraction,
were obtained.
H atoms on water molecules were located in a difference Fourier map and fixed in
the refinement with Uiso(H) = 1.5Ueq(O). The other H atoms
were positioned geometrically and refined as riding atoms, with C—H =
0.93Å and Uiso(H) = 1.2Ueq(C). The highest residual
electron density was found 2.22Å from atom H2.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); 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, 1998); software used to prepare material for publication: SHELXTL.
Aqua[(pyridine-2,6-dicarboxylato-N-oxide-
κ2O1,
O2)
(2,2'-bipyridine-
κ2N,
N')]copper(II) trihydrate
top
Crystal data top
| [Cu(C7H3NO5)(C10H8N2)(H2O)]·3H2O | Z = 2 |
| Mr = 472.89 | F(000) = 486 |
| Triclinic, P1 | Dx = 1.563 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.8293 (2) Å | Cell parameters from 3133 reflections |
| b = 11.8827 (4) Å | θ = 1.6–26.0° |
| c = 12.5673 (4) Å | µ = 1.14 mm−1 |
| α = 86.136 (2)° | T = 297 K |
| β = 81.584 (2)° | Block, blue |
| γ = 86.151 (2)° | 0.20 × 0.18 × 0.10 mm |
| V = 1004.87 (6) Å3 | |
Data collection top
Bruker SMART APEX area-detector
diffractometer | 3953 independent reflections |
| Radiation source: fine-focus sealed tube | 3133 reflections with I > 2σ(I) |
| graphite | Rint = 0.031 |
| φ and ω scans | θmax = 26.0°, θmin = 1.6° |
Absorption correction: multi-scan
SADABS (Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.804, Tmax = 0.894 | k = −14→14 |
| 13440 measured reflections | l = −15→15 |
Refinement top
| 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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.140 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0811P)2 + 0.7343P]
where P = (Fo2 + 2Fc2)/3 |
| 3953 reflections | (Δ/σ)max < 0.001 |
| 271 parameters | Δρmax = 1.14 e Å−3 |
| 12 restraints | Δρmin = −0.45 e Å−3 |
Crystal data top
| [Cu(C7H3NO5)(C10H8N2)(H2O)]·3H2O | γ = 86.151 (2)° |
| Mr = 472.89 | V = 1004.87 (6) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.8293 (2) Å | Mo Kα radiation |
| b = 11.8827 (4) Å | µ = 1.14 mm−1 |
| c = 12.5673 (4) Å | T = 297 K |
| α = 86.136 (2)° | 0.20 × 0.18 × 0.10 mm |
| β = 81.584 (2)° | |
Data collection top
Bruker SMART APEX area-detector
diffractometer | 3953 independent reflections |
Absorption correction: multi-scan
SADABS (Sheldrick, 1996) | 3133 reflections with I > 2σ(I) |
| Tmin = 0.804, Tmax = 0.894 | Rint = 0.031 |
| 13440 measured reflections | θmax = 26.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.140 | Δρmax = 1.14 e Å−3 |
| S = 1.03 | Δρmin = −0.45 e Å−3 |
| 3953 reflections | Absolute structure: ? |
| 271 parameters | Flack parameter: ? |
| 12 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| Cu1 | 0.73423 (8) | 0.66865 (4) | 0.54386 (4) | 0.0387 (2) | |
| N1 | 0.8064 (5) | 0.5462 (3) | 0.7427 (3) | 0.0340 (8) | |
| N2 | 0.7508 (6) | 0.8345 (3) | 0.5462 (3) | 0.0434 (9) | |
| N3 | 0.7073 (5) | 0.7095 (3) | 0.3898 (3) | 0.0399 (8) | |
| C1 | 0.7578 (8) | 0.8909 (4) | 0.6340 (5) | 0.0544 (13) | |
| H1 | 0.7615 | 0.8507 | 0.6998 | 0.065* | |
| C2 | 0.7598 (8) | 1.0069 (4) | 0.6297 (6) | 0.0673 (17) | |
| H2 | 0.7645 | 1.0449 | 0.6916 | 0.081* | |
| C3 | 0.7546 (8) | 1.0655 (4) | 0.5315 (6) | 0.0687 (18) | |
| H3 | 0.7577 | 1.1438 | 0.5264 | 0.082* | |
| C4 | 0.7450 (8) | 1.0084 (4) | 0.4411 (5) | 0.0613 (15) | |
| H4 | 0.7398 | 1.0476 | 0.3748 | 0.074* | |
| C5 | 0.7430 (7) | 0.8909 (4) | 0.4501 (4) | 0.0464 (11) | |
| C6 | 0.7264 (7) | 0.8198 (4) | 0.3611 (4) | 0.0455 (11) | |
| C7 | 0.7262 (9) | 0.8595 (5) | 0.2544 (5) | 0.0705 (17) | |
| H7 | 0.7398 | 0.9357 | 0.2347 | 0.085* | |
| C8 | 0.7053 (10) | 0.7840 (6) | 0.1777 (5) | 0.0756 (18) | |
| H8 | 0.7048 | 0.8091 | 0.1060 | 0.091* | |
| C9 | 0.6854 (8) | 0.6722 (5) | 0.2089 (4) | 0.0621 (14) | |
| H9 | 0.6705 | 0.6206 | 0.1587 | 0.074* | |
| C10 | 0.6875 (7) | 0.6371 (4) | 0.3152 (4) | 0.0483 (11) | |
| H10 | 0.6749 | 0.5611 | 0.3360 | 0.058* | |
| C11 | 0.7941 (7) | 0.5565 (4) | 0.8504 (3) | 0.0403 (10) | |
| C12 | 0.7898 (8) | 0.4624 (4) | 0.9192 (4) | 0.0544 (13) | |
| H12 | 0.7823 | 0.4699 | 0.9929 | 0.065* | |
| C13 | 0.7967 (9) | 0.3565 (4) | 0.8801 (4) | 0.0591 (14) | |
| H13 | 0.7951 | 0.2922 | 0.9266 | 0.071* | |
| C14 | 0.8059 (7) | 0.3481 (4) | 0.7708 (4) | 0.0473 (11) | |
| H14 | 0.8098 | 0.2770 | 0.7435 | 0.057* | |
| C15 | 0.8096 (6) | 0.4430 (3) | 0.7008 (3) | 0.0353 (9) | |
| C16 | 0.7824 (8) | 0.6755 (4) | 0.8890 (3) | 0.0460 (11) | |
| C17 | 0.8104 (7) | 0.4285 (3) | 0.5819 (3) | 0.0376 (9) | |
| O1 | 0.4036 (5) | 0.6858 (3) | 0.6071 (3) | 0.0617 (10) | |
| H1A | 0.3575 | 0.6869 | 0.6737 | 0.093* | |
| H1B | 0.3193 | 0.6594 | 0.5732 | 0.093* | |
| O2 | 0.6125 (6) | 0.7199 (3) | 0.9079 (3) | 0.0702 (11) | |
| O3 | 0.9396 (6) | 0.7143 (3) | 0.9032 (3) | 0.0634 (10) | |
| O4 | 0.7598 (5) | 0.5109 (2) | 0.5205 (2) | 0.0484 (8) | |
| O5 | 0.8520 (5) | 0.3325 (2) | 0.5520 (3) | 0.0514 (8) | |
| O6 | 0.8213 (5) | 0.6428 (2) | 0.6828 (2) | 0.0472 (8) | |
| O7 | 0.6884 (6) | 0.3775 (3) | 0.1792 (3) | 0.0639 (10) | |
| H7A | 0.8030 | 0.3448 | 0.1597 | 0.096* | |
| H7B | 0.6013 | 0.3375 | 0.1596 | 0.096* | |
| O8 | 0.5451 (13) | 0.0649 (6) | 0.0755 (9) | 0.199 (4) | |
| H8A | 0.4633 | 0.1262 | 0.0799 | 0.299* | |
| H8B | 0.6187 | 0.0809 | 0.1323 | 0.299* | |
| O9 | 0.9391 (12) | 0.0685 (6) | 0.0931 (9) | 0.193 (4) | |
| H9B | 0.9337 | 0.0859 | 0.0239 | 0.290* | |
| H9A | 0.9730 | 0.1342 | 0.1132 | 0.290* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cu1 | 0.0540 (4) | 0.0304 (3) | 0.0327 (3) | −0.0019 (2) | −0.0102 (2) | 0.00015 (19) |
| N1 | 0.037 (2) | 0.0344 (17) | 0.0310 (18) | −0.0007 (14) | −0.0097 (14) | 0.0005 (13) |
| N2 | 0.043 (2) | 0.0346 (18) | 0.052 (2) | −0.0025 (16) | −0.0064 (17) | −0.0023 (16) |
| N3 | 0.037 (2) | 0.043 (2) | 0.039 (2) | 0.0019 (15) | −0.0065 (16) | 0.0039 (15) |
| C1 | 0.058 (3) | 0.039 (2) | 0.066 (3) | −0.003 (2) | −0.006 (3) | −0.011 (2) |
| C2 | 0.056 (3) | 0.046 (3) | 0.104 (5) | −0.001 (2) | −0.012 (3) | −0.028 (3) |
| C3 | 0.049 (3) | 0.033 (2) | 0.123 (6) | −0.002 (2) | −0.012 (3) | 0.001 (3) |
| C4 | 0.042 (3) | 0.042 (3) | 0.097 (5) | −0.001 (2) | −0.011 (3) | 0.018 (3) |
| C5 | 0.034 (3) | 0.040 (2) | 0.063 (3) | −0.0007 (19) | −0.005 (2) | 0.007 (2) |
| C6 | 0.039 (3) | 0.047 (3) | 0.047 (3) | 0.0040 (19) | −0.004 (2) | 0.011 (2) |
| C7 | 0.073 (4) | 0.066 (4) | 0.065 (4) | 0.003 (3) | −0.002 (3) | 0.028 (3) |
| C8 | 0.084 (5) | 0.100 (5) | 0.038 (3) | 0.007 (4) | −0.008 (3) | 0.013 (3) |
| C9 | 0.059 (4) | 0.088 (4) | 0.040 (3) | 0.000 (3) | −0.013 (2) | −0.003 (3) |
| C10 | 0.047 (3) | 0.060 (3) | 0.039 (3) | 0.001 (2) | −0.012 (2) | −0.003 (2) |
| C11 | 0.039 (3) | 0.048 (2) | 0.034 (2) | 0.0001 (19) | −0.0069 (18) | −0.0038 (18) |
| C12 | 0.068 (4) | 0.062 (3) | 0.034 (2) | −0.002 (3) | −0.011 (2) | 0.005 (2) |
| C13 | 0.075 (4) | 0.054 (3) | 0.047 (3) | −0.003 (3) | −0.014 (3) | 0.016 (2) |
| C14 | 0.054 (3) | 0.039 (2) | 0.048 (3) | −0.002 (2) | −0.008 (2) | 0.0042 (19) |
| C15 | 0.035 (2) | 0.035 (2) | 0.036 (2) | 0.0003 (17) | −0.0075 (17) | 0.0010 (16) |
| C16 | 0.054 (3) | 0.055 (3) | 0.030 (2) | 0.001 (2) | −0.011 (2) | −0.0052 (19) |
| C17 | 0.040 (2) | 0.034 (2) | 0.040 (2) | −0.0056 (17) | −0.0072 (19) | −0.0037 (17) |
| O1 | 0.057 (2) | 0.091 (3) | 0.0394 (19) | −0.022 (2) | −0.0063 (16) | −0.0050 (17) |
| O2 | 0.059 (3) | 0.072 (2) | 0.084 (3) | 0.011 (2) | −0.017 (2) | −0.032 (2) |
| O3 | 0.060 (2) | 0.067 (2) | 0.069 (2) | −0.0102 (19) | −0.0181 (19) | −0.0174 (19) |
| O4 | 0.077 (2) | 0.0356 (16) | 0.0361 (17) | 0.0006 (15) | −0.0208 (16) | −0.0035 (13) |
| O5 | 0.076 (2) | 0.0313 (16) | 0.0492 (19) | 0.0016 (15) | −0.0160 (17) | −0.0059 (13) |
| O6 | 0.076 (2) | 0.0322 (15) | 0.0362 (17) | −0.0070 (15) | −0.0180 (15) | 0.0010 (12) |
| O7 | 0.060 (2) | 0.082 (3) | 0.049 (2) | −0.006 (2) | −0.0057 (17) | −0.0002 (18) |
| O8 | 0.183 (8) | 0.102 (5) | 0.341 (13) | 0.055 (5) | −0.136 (8) | −0.074 (6) |
| O9 | 0.153 (7) | 0.092 (5) | 0.327 (13) | −0.040 (5) | 0.007 (7) | −0.019 (6) |
Geometric parameters (Å, °) top
| Cu1—O4 | 1.910 (3) | C8—H8 | 0.9300 |
| Cu1—O6 | 1.925 (3) | C9—C10 | 1.374 (7) |
| Cu1—N2 | 1.984 (4) | C9—H9 | 0.9300 |
| Cu1—N3 | 1.996 (4) | C10—H10 | 0.9300 |
| Cu1—O1 | 2.282 (4) | C11—C12 | 1.366 (6) |
| N1—O6 | 1.331 (4) | C11—C16 | 1.518 (6) |
| N1—C11 | 1.357 (5) | C12—C13 | 1.376 (7) |
| N1—C15 | 1.365 (5) | C12—H12 | 0.9300 |
| N2—C1 | 1.336 (6) | C13—C14 | 1.376 (7) |
| N2—C5 | 1.348 (6) | C13—H13 | 0.9300 |
| N3—C10 | 1.340 (6) | C14—C15 | 1.382 (6) |
| N3—C6 | 1.345 (6) | C14—H14 | 0.9300 |
| C1—C2 | 1.376 (7) | C15—C17 | 1.515 (6) |
| C1—H1 | 0.9300 | C16—O3 | 1.237 (6) |
| C2—C3 | 1.380 (9) | C16—O2 | 1.239 (6) |
| C2—H2 | 0.9300 | C17—O5 | 1.227 (5) |
| C3—C4 | 1.373 (9) | C17—O4 | 1.266 (5) |
| C3—H3 | 0.9300 | O1—H1A | 0.85 |
| C4—C5 | 1.394 (7) | O1—H1B | 0.85 |
| C4—H4 | 0.9300 | O7—H7A | 0.86 |
| C5—C6 | 1.468 (7) | O7—H7B | 0.86 |
| C6—C7 | 1.391 (7) | O8—H8A | 0.89 |
| C7—C8 | 1.389 (9) | O8—H8B | 0.97 |
| C7—H7 | 0.9300 | O9—H9B | 0.89 |
| C8—C9 | 1.370 (9) | O9—H9A | 0.89 |
| | | |
| O4—Cu1—O6 | 91.68 (12) | C6—C7—H7 | 120.4 |
| O4—Cu1—N2 | 169.20 (16) | C9—C8—C7 | 119.1 (5) |
| O6—Cu1—N2 | 92.21 (14) | C9—C8—H8 | 120.4 |
| O4—Cu1—N3 | 92.26 (14) | C7—C8—H8 | 120.4 |
| O6—Cu1—N3 | 166.45 (15) | C8—C9—C10 | 119.4 (6) |
| N2—Cu1—N3 | 81.76 (15) | C8—C9—H9 | 120.3 |
| O4—Cu1—O1 | 99.39 (15) | C10—C9—H9 | 120.3 |
| O6—Cu1—O1 | 96.04 (14) | N3—C10—C9 | 121.8 (5) |
| N2—Cu1—O1 | 90.21 (15) | N3—C10—H10 | 119.1 |
| N3—Cu1—O1 | 96.10 (14) | C9—C10—H10 | 119.1 |
| O6—N1—C11 | 115.0 (3) | N1—C11—C12 | 120.1 (4) |
| O6—N1—C15 | 123.6 (3) | N1—C11—C16 | 117.1 (4) |
| C11—N1—C15 | 121.4 (4) | C12—C11—C16 | 122.8 (4) |
| C1—N2—C5 | 120.2 (4) | C11—C12—C13 | 120.4 (5) |
| C1—N2—Cu1 | 125.4 (3) | C11—C12—H12 | 119.8 |
| C5—N2—Cu1 | 114.2 (3) | C13—C12—H12 | 119.8 |
| C10—N3—C6 | 119.9 (4) | C12—C13—C14 | 118.5 (4) |
| C10—N3—Cu1 | 126.0 (3) | C12—C13—H13 | 120.7 |
| C6—N3—Cu1 | 113.9 (3) | C14—C13—H13 | 120.7 |
| N2—C1—C2 | 121.9 (5) | C13—C14—C15 | 121.4 (5) |
| N2—C1—H1 | 119.0 | C13—C14—H14 | 119.3 |
| C2—C1—H1 | 119.0 | C15—C14—H14 | 119.3 |
| C1—C2—C3 | 118.4 (6) | N1—C15—C14 | 118.2 (4) |
| C1—C2—H2 | 120.8 | N1—C15—C17 | 122.9 (3) |
| C3—C2—H2 | 120.8 | C14—C15—C17 | 118.9 (4) |
| C4—C3—C2 | 120.2 (5) | O3—C16—O2 | 127.6 (5) |
| C4—C3—H3 | 119.9 | O3—C16—C11 | 117.2 (4) |
| C2—C3—H3 | 119.9 | O2—C16—C11 | 115.0 (4) |
| C3—C4—C5 | 119.0 (5) | O5—C17—O4 | 123.5 (4) |
| C3—C4—H4 | 120.5 | O5—C17—C15 | 115.9 (4) |
| C5—C4—H4 | 120.5 | O4—C17—C15 | 120.5 (4) |
| N2—C5—C4 | 120.3 (5) | Cu1—O1—H1A | 123.5 |
| N2—C5—C6 | 115.0 (4) | Cu1—O1—H1B | 120.5 |
| C4—C5—C6 | 124.7 (5) | H1A—O1—H1B | 109.6 |
| N3—C6—C7 | 120.5 (5) | C17—O4—Cu1 | 129.6 (3) |
| N3—C6—C5 | 114.9 (4) | N1—O6—Cu1 | 124.5 (2) |
| C7—C6—C5 | 124.6 (5) | H7A—O7—H7B | 107.6 |
| C8—C7—C6 | 119.3 (5) | H8A—O8—H8B | 96.9 |
| C8—C7—H7 | 120.4 | H9B—O9—H9A | 100.1 |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···O7i | 0.85 | 1.94 | 2.733 (5) | 154 |
| O1—H1B···O5i | 0.85 | 2.09 | 2.867 (5) | 152 |
| O1—H1B···O4i | 0.85 | 2.53 | 3.265 (5) | 144 |
| O7—H7A···O3ii | 0.86 | 1.93 | 2.780 (6) | 171 |
| O7—H7B···O2i | 0.86 | 1.97 | 2.813 (5) | 166 |
| O8—H8A···O2i | 0.89 | 1.88 | 2.716 (8) | 157 |
| O8—H8B···O9 | 0.97 | 2.17 | 2.735 (12) | 116 |
| O9—H9A···O3ii | 0.89 | 1.92 | 2.768 (7) | 158 |
| O9—H9B···O9iii | 0.89 | 2.46 | 2.930 (19) | 113 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y, −z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···O7i | 0.85 | 1.94 | 2.733 (5) | 154 |
| O1—H1B···O5i | 0.85 | 2.09 | 2.867 (5) | 152 |
| O1—H1B···O4i | 0.85 | 2.53 | 3.265 (5) | 144 |
| O7—H7A···O3ii | 0.86 | 1.93 | 2.780 (6) | 171 |
| O7—H7B···O2i | 0.86 | 1.97 | 2.813 (5) | 166 |
| O8—H8A···O2i | 0.89 | 1.88 | 2.716 (8) | 157 |
| O8—H8B···O9 | 0.97 | 2.17 | 2.735 (12) | 116 |
| O9—H9A···O3ii | 0.89 | 1.92 | 2.768 (7) | 158 |
| O9—H9B···O9iii | 0.89 | 2.46 | 2.930 (19) | 113 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y, −z. |
Bruker (1998). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Moulton, B. & Zaworotko, M. J. (2001). J. Chem. Rev. 101, 1629–1658.
Paul, D. B. (1984). Aust. J. Chem. 37, 87–93.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Wen, L.-L., Dang, D.-B., Duan, C.-Y., Li, Y.-Z., Tian, Z.-F. & Meng, Q.-J. (2005). Inorg. Chem. 44, 7161–7170.
![[Figure 1]](./hy2059fig1thm.gif)
Many of the efforts have so far devoted to the study of transition-metal-based coordination polymers because of their potential applications as functional solid materials in ion exchange, catalysis, and optical electronic and magnetic devices (Moulton & Zaworotko, 2001; Wen et al., 2005). Pyridine-2,6-dicarboxylic acid N-oxide (pydco) shows limited steric hindrance and weak stacking interactions and can offer possibilities to form coordination polymers through a bridge formed by a carboxylate and N-oxide, which is a better electron donor than the ring N atom of pydco (Paul, 1984; Wen et al., 2005)
The Cu1 atom in the title complex, (I), has a distorted square-pyramidal coordination geometry (Fig.1). The basal plane formed by two N atoms from the 2,2'-pyridine ligand and two O atoms from the pydco ligand. The apical position is occupied by a water molecule. A long distance [2.905 (3) Å] between Cu1 and O5(2 - x, 1 - y, 1 - z) at the other apical position indicates a very weak interaction. In the crystal strucrure, the intermolecular hydrogen bonds between the lattice water molecules and the coordination water molecule, and between the lattice water molecules and carboxylate O atoms form a sheet structure (Table 1). The sheets are linked by π···π interactions, forming a three dimensional supramolecular structure.