Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109011299/bm3078sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109011299/bm3078Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109011299/bm3078IIsup3.hkl |
CCDC references: 735104; 735105
##AUTHOR: Some re-wording here - please check.
All the reactants and solvents (see below) were obtained commercially. For (I), an aqueous solution (4 ml) of Cu(NO3)2.2.5H2O (0.058 g, 0.25 mmol) was added dropwise with stirring to a solution containing 2,3-benzenofurandicarboxylic acid (0.052 g, 0.25 mmol) and NaOH (0.02 g, 0.5 mmol) in 1:1 DMF/H2O (10 ml). The color of the solution changed from (##AUTHOR: from which colour?) to bluish-green. To this solution, 4,4'-bipyridine (0.078 g, 0.5 mmol) dissolved in DMF (5 ml) was added dropwise with stirring. The reaction mixture was then stirred further for 1 h, filtered, and the filtrate left undisturbed to allow slow evaporation. After a few days, green crystals were deposited, filtered, washed with DMF and air-dried. IR (KBr, cm-1): (A) 1598s (νas of OCO-),1380m (νs of OCO-); (B) 1491m, 1402m, 1323s, ring stretching of the coordinated 4,4'-bipyridyl ligand. (C) 1308, 1298, 1270, 1224 and 1205, a series of bands associated with C—O and C—N stretching in the two ligands. For (II), CuCl2.2(H2O) (0.043 g, 0.25 mmol) was initially mixed with NaOH (0.02 g, 0.5 mmol) in water (10 ml), to yield Cu(OH)2. The Cu(OH)2 (0.25 mmol), 2,3-benzofurandicarboxylic acid (0.052 g, 0.25 mmol) and 1,2-bis(4-pyridyl)ethane (0.092 g, 0.5 mmol) were then dissolved in ammonia (25% v/v, 3 ml). Slow evaporation from the resulting solution at ambient temperature yielded blue single crystals of the final product. IR (KBr, cm-1): 3383 (broad band of water O—H stretching modes), 1635s and 1609m (νas OCO), 1556s and 1487m (νs OCO).
The H atoms bound to C atoms were located in calculated positions, and were constrained to ride on their parent atoms with C—H distances of 0.95 and 0.99 Å and with Uiso(H) = 1.2 Ueq(C). H atoms bound to O atoms in (II) were either located in difference Fourier maps, or positioned to optimize intermolecular hydrogen bonding. All the O—H bond lengths were first restrained to 0.90 (2) Å, but then kept fixed in final least-squares cycles with Uiso(H) = 1.2 Ueq(O).
For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-III (Burnett & Johnson, 1996); Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Cu(CHO2)2(C10H8N2)] | Dx = 1.839 Mg m−3 |
Mr = 309.76 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P41212 | Cell parameters from 1314 reflections |
Hall symbol: P 4abw 2nw | θ = 1.4–27.9° |
a = 7.8505 (1) Å | µ = 1.96 mm−1 |
c = 18.1513 (5) Å | T = 110 K |
V = 1118.67 (4) Å3 | Prism, blue |
Z = 4 | 0.30 × 0.20 × 0.15 mm |
F(000) = 628 |
Nonius KappaCCD diffractometer | 1331 independent reflections |
Radiation source: fine-focus sealed tube | 1248 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 12.8 pixels mm-1 | θmax = 27.9°, θmin = 2.8° |
1 deg. ϕ scans | h = −10→10 |
Absorption correction: multi-scan (Blessing, 1995) | k = −9→9 |
Tmin = 0.590, Tmax = 0.757 | l = −18→23 |
6143 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.059P)2 + 0.855P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.096 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 1.04 e Å−3 |
1331 reflections | Δρmin = −0.65 e Å−3 |
89 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0073 (17) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.04 (3) |
[Cu(CHO2)2(C10H8N2)] | Z = 4 |
Mr = 309.76 | Mo Kα radiation |
Tetragonal, P41212 | µ = 1.96 mm−1 |
a = 7.8505 (1) Å | T = 110 K |
c = 18.1513 (5) Å | 0.30 × 0.20 × 0.15 mm |
V = 1118.67 (4) Å3 |
Nonius KappaCCD diffractometer | 1331 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1248 reflections with I > 2σ(I) |
Tmin = 0.590, Tmax = 0.757 | Rint = 0.046 |
6143 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.096 | Δρmax = 1.04 e Å−3 |
S = 1.05 | Δρmin = −0.65 e Å−3 |
1331 reflections | Absolute structure: Flack (1983) |
89 parameters | Absolute structure parameter: −0.04 (3) |
0 restraints |
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 | 1.26627 (4) | 0.26627 (4) | 0.0000 | 0.01512 (18) | |
O2 | 1.1303 (3) | 0.3879 (3) | 0.07594 (13) | 0.0205 (5) | |
C3 | 1.1710 (4) | 0.5157 (4) | 0.11449 (17) | 0.0206 (7) | |
H3 | 1.2827 | 0.5597 | 0.1079 | 0.025* | |
O4 | 1.0792 (3) | 0.5887 (3) | 0.15995 (13) | 0.0221 (5) | |
N5 | 1.0870 | 0.0870 | 0.0000 | 0.0162 (7) | |
C6 | 0.9193 (4) | 0.1239 (4) | 0.00905 (19) | 0.0196 (6) | |
H6 | 0.8889 | 0.2399 | 0.0162 | 0.023* | |
C7 | 0.7894 (4) | 0.0044 (4) | 0.00865 (17) | 0.0188 (6) | |
H7 | 0.6738 | 0.0380 | 0.0141 | 0.023* | |
C8 | 0.8331 (4) | −0.1669 (4) | 0.0000 | 0.0159 (8) | |
C9 | 0.6992 (4) | −0.3008 (4) | 0.0000 | 0.0144 (8) | |
C10 | 0.5533 (4) | −0.2852 (4) | −0.04349 (17) | 0.0182 (6) | |
H10 | 0.5372 | −0.1873 | −0.0734 | 0.022* | |
C11 | 0.4330 (4) | −0.4128 (4) | −0.04267 (17) | 0.0181 (6) | |
H11 | 0.3358 | −0.4021 | −0.0735 | 0.022* | |
N12 | 0.4478 (3) | −0.5522 (3) | 0.0000 | 0.0160 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0131 (2) | 0.0131 (2) | 0.0192 (3) | −0.00253 (19) | 0.00209 (13) | −0.00209 (13) |
O2 | 0.0164 (11) | 0.0168 (11) | 0.0284 (12) | −0.0036 (9) | 0.0021 (9) | −0.0061 (9) |
C3 | 0.0162 (15) | 0.0201 (16) | 0.0255 (16) | −0.0016 (13) | 0.0018 (12) | −0.0034 (13) |
O4 | 0.0203 (11) | 0.0210 (11) | 0.0248 (11) | 0.0025 (10) | 0.0013 (9) | −0.0043 (9) |
N5 | 0.0141 (10) | 0.0141 (10) | 0.0204 (17) | −0.0018 (13) | −0.0004 (12) | 0.0004 (12) |
C6 | 0.0126 (13) | 0.0151 (14) | 0.0310 (17) | 0.0027 (11) | −0.0007 (12) | −0.0037 (12) |
C7 | 0.0139 (13) | 0.0169 (13) | 0.0255 (16) | 0.0007 (12) | −0.0012 (13) | −0.0008 (13) |
C8 | 0.0164 (12) | 0.0164 (12) | 0.0149 (18) | −0.0035 (15) | −0.0028 (12) | 0.0028 (12) |
C9 | 0.0138 (12) | 0.0138 (12) | 0.0155 (18) | 0.0039 (14) | 0.0032 (11) | −0.0032 (11) |
C10 | 0.0182 (14) | 0.0151 (14) | 0.0213 (15) | 0.0003 (12) | 0.0000 (11) | 0.0003 (12) |
C11 | 0.0138 (14) | 0.0166 (14) | 0.0240 (15) | −0.0004 (11) | −0.0010 (12) | 0.0019 (12) |
N12 | 0.0145 (10) | 0.0145 (10) | 0.0190 (17) | 0.0006 (13) | 0.0041 (11) | −0.0041 (11) |
Cu1—O2 | 1.988 (2) | C6—H6 | 0.9500 |
Cu1—O4i | 2.468 (3) | C7—C8 | 1.397 (3) |
Cu1—N5 | 1.9903 (5) | C7—H7 | 0.9500 |
Cu1—N12ii | 2.015 (3) | C8—C9 | 1.487 (6) |
O2—C3 | 1.264 (4) | C9—C10 | 1.396 (4) |
C3—O4 | 1.237 (4) | C10—C11 | 1.377 (4) |
C3—H3 | 0.9500 | C10—H10 | 0.9500 |
N5—C6 | 1.358 (3) | C11—N12 | 1.346 (3) |
C6—C7 | 1.386 (4) | C11—H11 | 0.9500 |
O2—Cu1—O2iii | 175.39 (13) | C8—C7—H7 | 120.9 |
O2—Cu1—N5 | 87.70 (6) | C6—C7—H7 | 120.9 |
O2—Cu1—N12ii | 92.30 (6) | C7—C8—C7iii | 119.1 (4) |
N5—Cu1—N12ii | 180.0 | C7—C8—C9 | 120.46 (19) |
C3—O2—Cu1 | 129.0 (2) | C10—C9—C10iii | 117.6 (4) |
O4—C3—O2 | 126.1 (3) | C10—C9—C8 | 121.2 (2) |
O4—C3—H3 | 117.0 | C11—C10—C9 | 119.5 (3) |
O2—C3—H3 | 117.0 | C11—C10—H10 | 120.3 |
C6iii—N5—C6 | 115.4 (2) | C9—C10—H10 | 120.3 |
C6—N5—Cu1 | 122.32 (12) | N12—C11—C10 | 122.6 (3) |
N5—C6—C7 | 124.6 (2) | N12—C11—H11 | 118.7 |
N5—C6—H6 | 117.7 | C10—C11—H11 | 118.7 |
C7—C6—H6 | 117.7 | C11—N12—C11iii | 118.1 (4) |
C8—C7—C6 | 118.1 (3) | C11—N12—Cu1iv | 120.96 (19) |
Symmetry codes: (i) −x+5/2, y−1/2, −z+1/4; (ii) x+1, y+1, z; (iii) y+1, x−1, −z; (iv) x−1, y−1, z. |
[Cu(C10H4O5)(C12H12N2)(H2O)2]·2H2O | F(000) = 1084 |
Mr = 523.97 | Dx = 1.552 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5078 reflections |
a = 13.3333 (3) Å | θ = 1.4–27.9° |
b = 15.1250 (3) Å | µ = 1.03 mm−1 |
c = 11.9108 (2) Å | T = 110 K |
β = 110.9824 (7)° | Prism, blue |
V = 2242.73 (8) Å3 | 0.40 × 0.25 × 0.20 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 5329 independent reflections |
Radiation source: fine-focus sealed tube | 3899 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 12.8 pixels mm-1 | θmax = 27.9°, θmin = 2.3° |
1 deg. ϕ and ω scans | h = −17→16 |
Absorption correction: multi-scan (Blessing, 1995) | k = −19→0 |
Tmin = 0.683, Tmax = 0.820 | l = 0→15 |
18429 measured reflections |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0858P)2] where P = (Fo2 + 2Fc2)/3 |
5329 reflections | (Δ/σ)max = 0.001 |
307 parameters | Δρmax = 0.80 e Å−3 |
0 restraints | Δρmin = −0.83 e Å−3 |
[Cu(C10H4O5)(C12H12N2)(H2O)2]·2H2O | V = 2242.73 (8) Å3 |
Mr = 523.97 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.3333 (3) Å | µ = 1.03 mm−1 |
b = 15.1250 (3) Å | T = 110 K |
c = 11.9108 (2) Å | 0.40 × 0.25 × 0.20 mm |
β = 110.9824 (7)° |
Nonius KappaCCD diffractometer | 5329 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3899 reflections with I > 2σ(I) |
Tmin = 0.683, Tmax = 0.820 | Rint = 0.052 |
18429 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.80 e Å−3 |
5329 reflections | Δρmin = −0.83 e Å−3 |
307 parameters |
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 | 0.36126 (3) | 0.23473 (2) | 0.60351 (3) | 0.01696 (13) | |
O2 | 0.29595 (15) | 0.18012 (13) | 0.44165 (16) | 0.0194 (4) | |
O3 | 0.27857 (16) | 0.06147 (13) | 0.54377 (16) | 0.0231 (4) | |
C4 | 0.1799 (2) | 0.06463 (18) | 0.3353 (2) | 0.0176 (6) | |
C5 | 0.0670 (2) | 0.05405 (18) | 0.3131 (2) | 0.0184 (6) | |
C6 | 0.0000 (2) | 0.06911 (19) | 0.3789 (2) | 0.0218 (6) | |
H6 | 0.0280 | 0.0926 | 0.4580 | 0.026* | |
C7 | −0.1079 (2) | 0.04877 (19) | 0.3254 (2) | 0.0231 (6) | |
H7 | −0.1540 | 0.0561 | 0.3698 | 0.028* | |
C8 | −0.1505 (2) | 0.01747 (19) | 0.2066 (2) | 0.0228 (6) | |
H8 | −0.2255 | 0.0065 | 0.1712 | 0.027* | |
C9 | −0.0858 (2) | 0.00217 (19) | 0.1393 (2) | 0.0215 (6) | |
H9 | −0.1142 | −0.0183 | 0.0586 | 0.026* | |
C10 | 0.0228 (2) | 0.01875 (18) | 0.1977 (2) | 0.0198 (6) | |
O11 | 0.10146 (15) | 0.00451 (13) | 0.14996 (16) | 0.0205 (4) | |
C12 | 0.1970 (2) | 0.03324 (18) | 0.2371 (2) | 0.0189 (6) | |
C13 | 0.2982 (2) | 0.02230 (19) | 0.2113 (2) | 0.0205 (6) | |
C14 | 0.2593 (2) | 0.10290 (19) | 0.4488 (2) | 0.0194 (6) | |
O15 | 0.29016 (16) | −0.00579 (14) | 0.10919 (17) | 0.0248 (5) | |
O16 | 0.38236 (15) | 0.04371 (13) | 0.29652 (16) | 0.0226 (4) | |
N17 | 0.51119 (19) | 0.21458 (16) | 0.6054 (2) | 0.0197 (5) | |
C18 | 0.5884 (2) | 0.2757 (2) | 0.6587 (3) | 0.0279 (7) | |
H18 | 0.5696 | 0.3266 | 0.6936 | 0.033* | |
C19 | 0.6914 (3) | 0.2668 (2) | 0.6640 (3) | 0.0338 (8) | |
H19 | 0.7427 | 0.3112 | 0.7023 | 0.041* | |
C20 | 0.7228 (2) | 0.1935 (2) | 0.6138 (3) | 0.0282 (7) | |
C21 | 0.6431 (2) | 0.13121 (19) | 0.5585 (2) | 0.0224 (6) | |
H21 | 0.6598 | 0.0803 | 0.5218 | 0.027* | |
C22 | 0.5402 (2) | 0.14334 (19) | 0.5570 (2) | 0.0199 (6) | |
H22 | 0.4876 | 0.0995 | 0.5202 | 0.024* | |
C23 | 0.8368 (3) | 0.1811 (2) | 0.6220 (4) | 0.0411 (9) | |
H23A | 0.8822 | 0.1693 | 0.7067 | 0.049* | |
H23B | 0.8407 | 0.1287 | 0.5739 | 0.049* | |
C24 | 0.8807 (3) | 0.2594 (3) | 0.5783 (4) | 0.0418 (9) | |
H24A | 0.8726 | 0.3119 | 0.6240 | 0.050* | |
H24B | 0.8358 | 0.2694 | 0.4929 | 0.050* | |
C25 | 0.9958 (2) | 0.2542 (2) | 0.5877 (3) | 0.0239 (6) | |
C26 | 1.0714 (2) | 0.2018 (2) | 0.6728 (3) | 0.0250 (6) | |
H26 | 1.0506 | 0.1670 | 0.7271 | 0.030* | |
C27 | 1.1762 (2) | 0.2004 (2) | 0.6782 (2) | 0.0221 (6) | |
H27 | 1.2267 | 0.1652 | 0.7383 | 0.027* | |
N28 | 1.21064 (19) | 0.24653 (15) | 0.6023 (2) | 0.0185 (5) | |
C29 | 1.1378 (2) | 0.2970 (2) | 0.5196 (2) | 0.0215 (6) | |
H29 | 1.1604 | 0.3303 | 0.4653 | 0.026* | |
C30 | 1.0319 (2) | 0.3026 (2) | 0.5102 (3) | 0.0230 (6) | |
H30 | 0.9835 | 0.3396 | 0.4508 | 0.028* | |
O31 | 0.41935 (19) | 0.26374 (16) | 0.7807 (2) | 0.0345 (5) | |
H31A | 0.4592 | 0.2181 | 0.8218 | 0.041* | |
H31B | 0.4496 | 0.3179 | 0.7914 | 0.041* | |
O32 | 0.36172 (16) | 0.36795 (14) | 0.51047 (17) | 0.0257 (5) | |
H32A | 0.3386 | 0.4165 | 0.5376 | 0.031* | |
H32B | 0.4196 | 0.3803 | 0.4913 | 0.031* | |
O33 | 0.42844 (18) | −0.02449 (15) | 0.73691 (18) | 0.0319 (5) | |
H33A | 0.3819 | 0.0054 | 0.6748 | 0.038* | |
H33B | 0.4859 | −0.0254 | 0.7141 | 0.038* | |
O34 | 0.52177 (19) | 0.09979 (16) | 0.91024 (19) | 0.0351 (5) | |
H34A | 0.5921 | 0.0861 | 0.9356 | 0.042* | |
H34B | 0.4814 | 0.0521 | 0.8778 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01330 (19) | 0.0211 (2) | 0.01723 (19) | −0.00048 (13) | 0.00634 (13) | −0.00199 (12) |
O2 | 0.0160 (10) | 0.0238 (11) | 0.0191 (9) | −0.0044 (8) | 0.0073 (7) | −0.0025 (8) |
O3 | 0.0231 (11) | 0.0244 (11) | 0.0183 (9) | 0.0014 (8) | 0.0030 (8) | 0.0014 (8) |
C4 | 0.0167 (14) | 0.0159 (14) | 0.0189 (13) | −0.0011 (11) | 0.0047 (10) | 0.0016 (10) |
C5 | 0.0190 (14) | 0.0157 (13) | 0.0200 (13) | −0.0014 (11) | 0.0062 (10) | 0.0007 (10) |
C6 | 0.0236 (15) | 0.0231 (15) | 0.0181 (13) | −0.0001 (12) | 0.0067 (11) | −0.0020 (11) |
C7 | 0.0214 (15) | 0.0244 (16) | 0.0257 (14) | 0.0011 (12) | 0.0110 (11) | 0.0006 (11) |
C8 | 0.0163 (14) | 0.0213 (15) | 0.0286 (15) | −0.0046 (11) | 0.0056 (11) | 0.0006 (12) |
C9 | 0.0220 (15) | 0.0181 (14) | 0.0218 (13) | −0.0023 (11) | 0.0045 (11) | −0.0010 (11) |
C10 | 0.0216 (15) | 0.0171 (14) | 0.0212 (13) | 0.0012 (11) | 0.0084 (11) | 0.0018 (11) |
O11 | 0.0162 (10) | 0.0261 (11) | 0.0186 (9) | −0.0027 (8) | 0.0056 (7) | −0.0025 (8) |
C12 | 0.0169 (14) | 0.0206 (14) | 0.0172 (12) | −0.0021 (11) | 0.0036 (10) | −0.0007 (11) |
C13 | 0.0213 (15) | 0.0201 (14) | 0.0201 (13) | 0.0013 (11) | 0.0075 (11) | 0.0015 (11) |
C14 | 0.0132 (13) | 0.0244 (15) | 0.0211 (13) | 0.0019 (11) | 0.0068 (10) | −0.0026 (11) |
O15 | 0.0240 (11) | 0.0303 (12) | 0.0222 (10) | −0.0014 (9) | 0.0107 (8) | −0.0035 (8) |
O16 | 0.0174 (10) | 0.0268 (11) | 0.0233 (10) | −0.0021 (8) | 0.0069 (8) | −0.0030 (8) |
N17 | 0.0148 (11) | 0.0249 (13) | 0.0195 (11) | 0.0001 (9) | 0.0062 (9) | −0.0012 (9) |
C18 | 0.0210 (16) | 0.0278 (17) | 0.0350 (17) | −0.0050 (12) | 0.0100 (13) | −0.0109 (13) |
C19 | 0.0186 (16) | 0.0313 (18) | 0.051 (2) | −0.0078 (13) | 0.0118 (14) | −0.0115 (15) |
C20 | 0.0203 (15) | 0.0222 (16) | 0.0447 (18) | −0.0013 (12) | 0.0147 (13) | −0.0013 (13) |
C21 | 0.0224 (15) | 0.0205 (15) | 0.0261 (14) | 0.0031 (12) | 0.0107 (11) | −0.0010 (11) |
C22 | 0.0197 (14) | 0.0205 (14) | 0.0209 (13) | 0.0003 (11) | 0.0092 (11) | 0.0001 (11) |
C23 | 0.0197 (17) | 0.0322 (19) | 0.076 (3) | 0.0008 (14) | 0.0233 (17) | −0.0015 (17) |
C24 | 0.0233 (17) | 0.044 (2) | 0.067 (3) | 0.0089 (15) | 0.0262 (17) | 0.0222 (18) |
C25 | 0.0173 (15) | 0.0241 (16) | 0.0335 (16) | 0.0029 (11) | 0.0131 (12) | 0.0007 (12) |
C26 | 0.0239 (16) | 0.0273 (16) | 0.0289 (15) | 0.0011 (13) | 0.0156 (12) | 0.0044 (12) |
C27 | 0.0201 (15) | 0.0243 (15) | 0.0237 (13) | 0.0030 (12) | 0.0101 (11) | 0.0019 (11) |
N28 | 0.0155 (11) | 0.0234 (13) | 0.0174 (11) | 0.0004 (9) | 0.0068 (9) | −0.0008 (9) |
C29 | 0.0189 (14) | 0.0225 (15) | 0.0231 (14) | −0.0014 (12) | 0.0074 (11) | 0.0013 (11) |
C30 | 0.0170 (14) | 0.0244 (15) | 0.0271 (14) | 0.0030 (12) | 0.0071 (11) | 0.0043 (12) |
O31 | 0.0324 (13) | 0.0358 (13) | 0.0330 (12) | 0.0011 (10) | 0.0088 (10) | −0.0011 (10) |
O32 | 0.0255 (11) | 0.0227 (11) | 0.0326 (11) | 0.0002 (9) | 0.0151 (9) | 0.0014 (9) |
O33 | 0.0274 (12) | 0.0399 (13) | 0.0303 (11) | 0.0084 (10) | 0.0126 (9) | 0.0119 (10) |
O34 | 0.0343 (13) | 0.0359 (13) | 0.0377 (12) | 0.0081 (10) | 0.0160 (10) | 0.0017 (10) |
Cu1—O2 | 1.9887 (18) | C20—C21 | 1.396 (4) |
Cu1—O31 | 2.019 (2) | C20—C23 | 1.499 (4) |
Cu1—O32 | 2.301 (2) | C21—C22 | 1.378 (4) |
Cu1—N17 | 2.014 (2) | C21—H21 | 0.9500 |
Cu1—N28i | 2.011 (2) | C22—H22 | 0.9500 |
O2—C14 | 1.281 (3) | C23—C24 | 1.495 (5) |
O3—C14 | 1.236 (3) | C23—H23A | 0.9900 |
C4—C12 | 1.355 (4) | C23—H23B | 0.9900 |
C4—C5 | 1.440 (4) | C24—C25 | 1.501 (5) |
C4—C14 | 1.503 (4) | C24—H24A | 0.9900 |
C5—C10 | 1.393 (4) | C24—H24B | 0.9900 |
C5—C6 | 1.402 (4) | C25—C30 | 1.391 (4) |
C6—C7 | 1.383 (4) | C25—C26 | 1.393 (4) |
C6—H6 | 0.9500 | C26—C27 | 1.376 (4) |
C7—C8 | 1.405 (4) | C26—H26 | 0.9500 |
C7—H7 | 0.9500 | C27—N28 | 1.346 (4) |
C8—C9 | 1.391 (4) | C27—H27 | 0.9500 |
C8—H8 | 0.9500 | N28—C29 | 1.346 (4) |
C9—C10 | 1.387 (4) | N28—Cu1ii | 2.011 (2) |
C9—H9 | 0.9500 | C29—C30 | 1.379 (4) |
C10—O11 | 1.377 (3) | C29—H29 | 0.9500 |
O11—C12 | 1.393 (3) | C30—H30 | 0.9500 |
C12—C13 | 1.498 (4) | O31—H31A | 0.9010 |
C13—O15 | 1.256 (3) | O31—H31B | 0.9012 |
C13—O16 | 1.256 (3) | O32—H32A | 0.8995 |
N17—C22 | 1.342 (4) | O32—H32B | 0.8994 |
N17—C18 | 1.360 (4) | O33—H33A | 0.8994 |
C18—C19 | 1.359 (5) | O33—H33B | 0.8994 |
C18—H18 | 0.9500 | O34—H34A | 0.8998 |
C19—C20 | 1.394 (5) | O34—H34B | 0.8996 |
C19—H19 | 0.9500 | ||
O2—Cu1—O31 | 167.04 (9) | C18—C19—H19 | 119.6 |
O2—Cu1—O32 | 88.43 (7) | C20—C19—H19 | 119.6 |
O2—Cu1—N17 | 92.08 (9) | C19—C20—C21 | 116.4 (3) |
O2—Cu1—N28i | 86.58 (9) | C19—C20—C23 | 121.6 (3) |
O31—Cu1—O32 | 104.30 (9) | C21—C20—C23 | 121.9 (3) |
O31—Cu1—N17 | 90.78 (10) | C22—C21—C20 | 120.2 (3) |
O31—Cu1—N28i | 89.79 (10) | C22—C21—H21 | 119.9 |
O32—Cu1—N17 | 87.94 (9) | C20—C21—H21 | 119.9 |
O32—Cu1—N28i | 95.38 (8) | N17—C22—C21 | 122.7 (3) |
N17—Cu1—N28i | 176.38 (10) | N17—C22—H22 | 118.7 |
C14—O2—Cu1 | 111.04 (16) | C21—C22—H22 | 118.7 |
C12—C4—C5 | 106.9 (2) | C24—C23—C20 | 113.1 (3) |
C12—C4—C14 | 129.0 (2) | C24—C23—H23A | 109.0 |
C5—C4—C14 | 124.1 (2) | C20—C23—H23A | 109.0 |
C10—C5—C6 | 119.0 (3) | C24—C23—H23B | 109.0 |
C10—C5—C4 | 105.6 (2) | C20—C23—H23B | 109.0 |
C6—C5—C4 | 135.4 (3) | H23A—C23—H23B | 107.8 |
C7—C6—C5 | 118.2 (3) | C23—C24—C25 | 116.8 (3) |
C7—C6—H6 | 120.9 | C23—C24—H24A | 108.1 |
C5—C6—H6 | 120.9 | C25—C24—H24A | 108.1 |
C6—C7—C8 | 121.2 (3) | C23—C24—H24B | 108.1 |
C6—C7—H7 | 119.4 | C25—C24—H24B | 108.1 |
C8—C7—H7 | 119.4 | H24A—C24—H24B | 107.3 |
C9—C8—C7 | 121.7 (3) | C30—C25—C26 | 116.8 (3) |
C9—C8—H8 | 119.1 | C30—C25—C24 | 120.7 (3) |
C7—C8—H8 | 119.1 | C26—C25—C24 | 122.6 (3) |
C10—C9—C8 | 115.7 (3) | C27—C26—C25 | 120.1 (3) |
C10—C9—H9 | 122.2 | C27—C26—H26 | 120.0 |
C8—C9—H9 | 122.2 | C25—C26—H26 | 120.0 |
O11—C10—C9 | 125.3 (3) | N28—C27—C26 | 123.0 (3) |
O11—C10—C5 | 110.6 (2) | N28—C27—H27 | 118.5 |
C9—C10—C5 | 124.1 (3) | C26—C27—H27 | 118.5 |
C10—O11—C12 | 105.8 (2) | C27—N28—C29 | 117.1 (2) |
C4—C12—O11 | 111.2 (2) | C27—N28—Cu1ii | 121.92 (19) |
C4—C12—C13 | 131.2 (2) | C29—N28—Cu1ii | 120.85 (19) |
O11—C12—C13 | 117.6 (2) | N28—C29—C30 | 123.0 (3) |
O15—C13—O16 | 127.7 (3) | N28—C29—H29 | 118.5 |
O15—C13—C12 | 117.7 (2) | C30—C29—H29 | 118.5 |
O16—C13—C12 | 114.5 (2) | C29—C30—C25 | 120.1 (3) |
O3—C14—O2 | 124.3 (2) | C29—C30—H30 | 120.0 |
O3—C14—C4 | 118.5 (3) | C25—C30—H30 | 120.0 |
O2—C14—C4 | 117.0 (2) | Cu1—O31—H31A | 109.4 |
C22—N17—C18 | 117.4 (2) | Cu1—O31—H31B | 109.2 |
C22—N17—Cu1 | 123.62 (19) | H31A—O31—H31B | 118.1 |
C18—N17—Cu1 | 119.0 (2) | Cu1—O32—H32A | 118.8 |
C19—C18—N17 | 122.5 (3) | Cu1—O32—H32B | 117.0 |
C19—C18—H18 | 118.7 | H32A—O32—H32B | 110.9 |
N17—C18—H18 | 118.7 | H33A—O33—H33B | 99.9 |
C18—C19—C20 | 120.8 (3) | H34A—O34—H34B | 110.5 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O31—H31B···O16iii | 0.90 | 2.29 | 2.971 (3) | 133 |
O31—H31A···O34 | 0.90 | 2.09 | 2.981 (3) | 168 |
O32—H32A···O15iii | 0.90 | 1.83 | 2.728 (3) | 172 |
O32—H32B···O34iv | 0.90 | 1.95 | 2.836 (3) | 166 |
O33—H33A···O3 | 0.90 | 1.87 | 2.772 (3) | 176 |
O33—H33B···O16v | 0.90 | 1.83 | 2.707 (3) | 165 |
O34—H34A···O15v | 0.90 | 2.20 | 2.963 (3) | 143 |
O34—H34B···O33 | 0.90 | 1.95 | 2.739 (3) | 145 |
Symmetry codes: (iii) x, −y+1/2, z+1/2; (iv) x, −y+1/2, z−1/2; (v) −x+1, −y, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu(CHO2)2(C10H8N2)] | [Cu(C10H4O5)(C12H12N2)(H2O)2]·2H2O |
Mr | 309.76 | 523.97 |
Crystal system, space group | Tetragonal, P41212 | Monoclinic, P21/c |
Temperature (K) | 110 | 110 |
a, b, c (Å) | 7.8505 (1), 7.8505 (1), 18.1513 (5) | 13.3333 (3), 15.1250 (3), 11.9108 (2) |
α, β, γ (°) | 90, 90, 90 | 90, 110.9824 (7), 90 |
V (Å3) | 1118.67 (4) | 2242.73 (8) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.96 | 1.03 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 | 0.40 × 0.25 × 0.20 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.590, 0.757 | 0.683, 0.820 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6143, 1331, 1248 | 18429, 5329, 3899 |
Rint | 0.046 | 0.052 |
(sin θ/λ)max (Å−1) | 0.657 | 0.658 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.096, 1.05 | 0.050, 0.141, 1.05 |
No. of reflections | 1331 | 5329 |
No. of parameters | 89 | 307 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.04, −0.65 | 0.80, −0.83 |
Absolute structure | Flack (1983) | ? |
Absolute structure parameter | −0.04 (3) | ? |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-III (Burnett & Johnson, 1996); Mercury (Macrae et al., 2006).
Cu1—O2 | 1.988 (2) | Cu1—N5 | 1.9903 (5) |
Cu1—O4i | 2.468 (3) | Cu1—N12ii | 2.015 (3) |
O2—Cu1—O2iii | 175.39 (13) | O2—Cu1—N12ii | 92.30 (6) |
O2—Cu1—N5 | 87.70 (6) |
Symmetry codes: (i) −x+5/2, y−1/2, −z+1/4; (ii) x+1, y+1, z; (iii) y+1, x−1, −z. |
Cu1—O2 | 1.9887 (18) | Cu1—N17 | 2.014 (2) |
Cu1—O31 | 2.019 (2) | Cu1—N28i | 2.011 (2) |
Cu1—O32 | 2.301 (2) | ||
O2—Cu1—O31 | 167.04 (9) | O31—Cu1—N17 | 90.78 (10) |
O2—Cu1—O32 | 88.43 (7) | O31—Cu1—N28i | 89.79 (10) |
O2—Cu1—N17 | 92.08 (9) | O32—Cu1—N17 | 87.94 (9) |
O2—Cu1—N28i | 86.58 (9) | O32—Cu1—N28i | 95.38 (8) |
O31—Cu1—O32 | 104.30 (9) | N17—Cu1—N28i | 176.38 (10) |
Symmetry code: (i) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O31—H31B···O16ii | 0.90 | 2.29 | 2.971 (3) | 133 |
O31—H31A···O34 | 0.90 | 2.09 | 2.981 (3) | 168 |
O32—H32A···O15ii | 0.90 | 1.83 | 2.728 (3) | 172 |
O32—H32B···O34iii | 0.90 | 1.95 | 2.836 (3) | 166 |
O33—H33A···O3 | 0.90 | 1.87 | 2.772 (3) | 176 |
O33—H33B···O16iv | 0.90 | 1.83 | 2.707 (3) | 165 |
O34—H34A···O15iv | 0.90 | 2.20 | 2.963 (3) | 143 |
O34—H34B···O33 | 0.90 | 1.95 | 2.739 (3) | 145 |
Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x+1, −y, −z+1. |
This study is part of our exploratory search for multidentate polycarboxylic acid ligands that can be utilized, in combination with metal ions, in the construction of framework solids (Goldberg, 2005). In earlier reports we investigated the supramolecular reactivity of a novel, previously unexplored ligand, 1-benzofuran-2,3-dicarboxylic acid (BFDC) (Koner & Goldberg, 2009a,b). It was shown that in reactions of BFDC with various metal ions, carried out under mild conditions, this ligand converts readily into a monoanionic species (BFDC-) by deprotonation of one carboxylic group. The H atom in the second carboxylic group is then involved in an intramolecular hydrogen bond to the carboxylate function. BFDC- was found to act as a good coordinating ligand, as well as a singly charged noncoordinated counter-anion to 2+ and 3+ transition metal cations (Koner & Goldberg, 2009a,b). It has also been shown that in more forcing (strongly basic) reaction environments it is possible to doubly deprotonate this ligand to a dianion, BFDC2-, which can then function as a bridging ligand in the construction of extended coordination networks with an oxophilic metal ion such as LaIII (Koner & Goldberg, 2009c). In subsequent investigations we have examined the reactivity of BFDC2- towards CuII ions in the presence of dipyridyl ligands. As no coordination polymers have been obtained thus far by direct reaction between the benzofurandicarboxylic acid and copper ion moieties, we introduced (in addition to the BFDC) different bipyridine reagents into the reaction mixtures, anticipating that the latter might provide additional connectivity features and assist in the formation of polymeric aggregates (see Experimental). Here we report the structural features of two compounds synthesized in the above context: catena-poly[[diformatocopper(II)]-µ-4,4'-bipyridyl], (I), and catena-poly[[[diaqua(1-benzofuran-2,3-dicarboxylato)copper(II)]-µ-1, 2-di-4-pyridylethane] dihydrate], (II).
Displacement ellipsoid plots of the structures of (I) and (II) are depicted in Figs. 1 and 2, respectively. Disappointingly, in neither case was the BFDC2- ligand involved in the formation of the polymer. It has not been incorporated into (I) at all, while in (II) it plays the role of a counter-ion coordinated to only one metal site. Instead, the two structures contain linear coordination polymers composed of alternating CuII ions and the respective bipyridyl ligands. Structure (I) resulted from the reaction of copper nitrate with 4,4'-bipyridine, BFDC and sodium hydroxide in a DMF (N,N-dimethylformamide)–water solvent environment. It turned out that in these experimental conditions, the DMF was hydrolysed to dimethylamine with the release of the formate (HCO2-) anion (Burrows et al., 2005; Muniappan et al., 2007), and the latter was incorporated into the crystal structure along with the copper ions. The FT IR (Fourier transform infrared?) spectrum of the solid product (see Experimental) was difficult to analyse due to partial overlap between absorption bands of the 4,4'-bipyridyl ligand (Litvinov et al., 2005; Popov et al., 1961) and the formate anion (Ito & Bernstein, 1956). It revealed typical signals for symmetric and asymmetric vibrations of the COO- group and [for?] to ring vibrations of the coordinated 4,4'-bipyridyl ligand, as well as C—O and C—N stretch vibrations in the 1200–1300 cm-1 region which could not be assigned to a specific group. The [Cu(CHO2)2–(4,4'-bipyridyl)]n linear coordination polymer which formed is shown in Fig. 3. The polymer is located on a twofold rotation axis at (x, x, 0), with the metal ion and the N···N axis of the bipyridyl ligand positioned on it. The two formate anions are directed sideways. The polymers are aligned side by side in layers parallel to the ab plane of the tetragonal crystal (Fig. 3). The layers are centered at the z = 0, 1/4, 1/2 and 3/4 levels of the unit cell. Polymeric arrays located at z = 0 and 1/2 propagate along the [110] axis, while those at the z = 1/4 and 3/4 levels extend along the [110] axis (Fig. 4). Coordination of the pyridyl ligands and the two formate anions to the CuII ions define a square-based planar geometry [##AUTHOR: this metal centre is octahedral, not square planar - please re-word] with the corresponding Cu—N and Cu—O bond distances being around 2.0 Å (Table 1). A distorted octahedral environment around the metal ions is completed by two mutually trans axial Cu—O4 [2.468 (3) Å] bonds from adjacent polymeric arrays (Fig. 4). Thus, the O2 donor of every formate anion binds to the copper ion of a given polymeric chain, while the O4 donor is more weakly coordinated to a neighboring array. This corresponds to a strong Jahn–Teller effect, associated with a considerable axial distortion of the octahedral environment around the copper ions. The resulting intercoordinated structure thus represents a single-framework coordination polymer, with an unexpected connectivity scheme. There are no apparent voids in this architecture. The [(µ2-4,4'-bipyridyl-N,N')copper]n and [(µ2-formato-O,O')copper]n coordination polymers are abundant in the literature; a search of the Cambridge Structural Database (CSD; Allen, 2002; version 5.30, November 2008) revealed 438 and 57 hits, respectively, for these motifs. However, the simultaneous inter-coordination of copper ions via the two ligands into polymeric architectures has not been observed before.
The use of copper chloride instead of the copper nitrate in the second experiment with the 1,2-bis(4'-bipyridyl)ethane is associated with the replacement of the CHO2- anions by BFDC2-. The polymeric arrangement of the constituent species in (II) is illustrated in Fig. 5. The copper(II) ion in this compound occupies a general position and is five coordinate with a square-based pyramidal geometry. The two mutually trans N-pyridyl donors, the monocoordinated carboxylate donor, and the O31 water molecule define the base of the pyramid, with Cu—O and Cu—N bonds of around 2.0 Å (Table 2). The O32 molecule of water coordinated at the apical site is more distant, as expected (Table 2). [##AUTHOR: it would be normal here to specify how far, and in what direction, the metal atom lies out of the basal plane.] The polymeric arrays propagate along the a axis (##AUTHOR: is "a-axis" correct?) of the crystal and are aligned parallel to the ab plane. The side-coordinated bulky BFDC2- ligands impart an irregular shape to the polymeric arrays, apparently preventing close packing next to one another and inducing the incorporation of noncoordinated molecules of water as crystallization solvent in order to fill the interchain space. The latter are involved in hydrogen bonds with the surrounding polymers, interacting with the free carboxylate site of BFDC2- and the Cu-bound water ligands (Table 3). The resulting structure thus combines coordination polymerization and hydrogen bonding between the constituent moieties (Fig. 6). Coordination polymers involving copper ions and the 1,2-bis(4-pyridyl)ethane ligand are also known, although to a much lesser extent than those with 4,4'-bipyridine; the CSD (Allen, 2002) lists a few tens of structures with the former versus hundreds with the latter (see above). However, in most of the reported examples the polymeric arrays are not in a fully extended form due to the flexibility of this ligand about the central CH2—CH2 bond (e.g. Power et al., 1998; Carlucci et al., 2000; Noro et al., 2006). Coordination complexes and polymers of copper with the divalent BFDC2- ligand as counter-ion have not been reported before.
With a single exceptional example (Koner & Goldberg, 2009c), it is tentatively evident from our studies that the benzofurandicarboxylic acid has a low capacity to act as a bridging ligand and induce the formation of coordination polymers with transition metal ions. Copper(II) ions reveal a preference for N-donor over O-donor ligands, and thus more readily form coordination polymers with the bipyridyl moieties. The trans-disposition of the N sites in the bipyridine ligand, as opposed to the cis-disposition of the carboxylic functions in BFDC, may also favor coordination polymerization with the former. With CuII, both BFDC1- (Koner & Goldberg, 2009a) and BFDC2- (this study) play the role of coordinating counter-ions only. A somewhat more favorable situation has been experienced with LaIII ions, which are characterized by a considerably higher affinity for oxo ligands, as is reflected in a recent report of a two-dimensional coordination network composed of La2(BFDC2-)3 building blocks (Koner & Goldberg, 2009c).