Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010703781X/av3097sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010703781X/av3097Isup2.hkl |
CCDC reference: 661789
For related literature, see: Addison et al. (1984); Bai et al. (2006); Iskander et al. (2000); Kim et al. (2001); Kitagawa et al. (2004); Müller-Dethlefs & Hobza (2000); Paital et al. (2007); Paschke et al. (2003); Shyu et al. (1996); Steel (2005); Takaoka et al. (2005).
For the synthesis of 4-(salicylideneamino)benzoic acid (H2L), a solution of salicylaldehyde (0.9780 g, 8 mmol) in CH3OH (10 ml) was added to a solution of 4-aminobenzoic acid (1.096 g, 8 mmol) in CH3OH (50 ml) with stirring, and a large amount of yellow precipitate was formed immediately. The slurry mixture was further vigorously stirred for 4 h and filtered. The yellow powder product was recrystallized in CH3CH2OH (80 ml) for purification. For the synthesis of the title complex, a solution of Cu(ClO4)2·6H2O (0.0373 g, 0.1 mmol) in DMF (5 ml) was added to a solution of H2L (0.0482 g, 0.2 mmol) and Et3N (0.0552 ml, 0.4 mmol) in DMF (5 ml) with stirring. The resulting precipitate was filtered off and then dissolved in pyridine (2 ml). Ethyl ether was diffused into the pyridine solution. Two weeks later, crystals were selected for X-ray diffraction.
Anisotropic displacement parameters were applied to all non-hydrogen atoms, except for solvent molecules. All H atoms were positioned geometrically with C—H distances of 0.93 or 0.96 Å and refined using a riding model.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
[Cu(C14H9NO3)(C5H5N)]·C3H7NO | V = 1051.7 (3) Å3 |
Mr = 454.96 | Z = 2 |
Triclinic, P1 | F(000) = 470 |
Hall symbol: -P 1 | Dx = 1.437 Mg m−3 |
a = 8.9547 (13) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.6215 (15) Å | θ = 2.5–28.3° |
c = 11.3899 (16) Å | µ = 1.07 mm−1 |
α = 80.393 (5)° | T = 298 K |
β = 86.408 (3)° | Prism, black |
γ = 80.138 (2)° | 0.23 × 0.20 × 0.16 mm |
Bruker SMART CCD area-detector diffractometer | 4757 independent reflections |
Radiation source: fine-focus sealed tube | 3900 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
ω scans | θmax = 28.3°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→11 |
Tmin = 0.752, Tmax = 0.842 | k = −13→14 |
7282 measured reflections | l = −14→15 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.1101P)2] where P = (Fo2 + 2Fc2)/3 |
4757 reflections | (Δ/σ)max < 0.001 |
246 parameters | Δρmax = 1.07 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
[Cu(C14H9NO3)(C5H5N)]·C3H7NO | γ = 80.138 (2)° |
Mr = 454.96 | V = 1051.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9547 (13) Å | Mo Kα radiation |
b = 10.6215 (15) Å | µ = 1.07 mm−1 |
c = 11.3899 (16) Å | T = 298 K |
α = 80.393 (5)° | 0.23 × 0.20 × 0.16 mm |
β = 86.408 (3)° |
Bruker SMART CCD area-detector diffractometer | 4757 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 3900 reflections with I > 2σ(I) |
Tmin = 0.752, Tmax = 0.842 | Rint = 0.093 |
7282 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.07 e Å−3 |
4757 reflections | Δρmin = −0.64 e Å−3 |
246 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 | 0.44343 (4) | −0.07274 (4) | 0.39760 (3) | 0.02736 (18) | |
O1 | 0.3492 (3) | −0.0224 (2) | 0.54311 (19) | 0.0312 (5) | |
O2 | 0.6357 (3) | 0.2253 (3) | −0.2139 (2) | 0.0481 (7) | |
O3 | 0.4509 (3) | 0.1227 (2) | −0.2554 (2) | 0.0337 (5) | |
O4 | −0.1534 (10) | 0.3646 (9) | 0.1886 (7) | 0.185 (3)* | |
N1 | 0.5252 (3) | −0.2498 (3) | 0.4904 (2) | 0.0326 (6) | |
N2 | 0.3216 (3) | 0.0842 (3) | 0.3017 (2) | 0.0286 (6) | |
N3 | −0.1575 (6) | 0.4098 (6) | −0.0063 (5) | 0.0835 (14)* | |
C1 | 0.4470 (5) | −0.3025 (4) | 0.5862 (3) | 0.0417 (9) | |
H1 | 0.3554 | −0.2563 | 0.6097 | 0.050* | |
C2 | 0.4982 (6) | −0.4213 (4) | 0.6493 (4) | 0.0585 (13) | |
H2 | 0.4411 | −0.4556 | 0.7141 | 0.070* | |
C3 | 0.6347 (7) | −0.4902 (4) | 0.6169 (4) | 0.0629 (14) | |
H3 | 0.6718 | −0.5706 | 0.6602 | 0.075* | |
C4 | 0.7147 (6) | −0.4386 (4) | 0.5201 (4) | 0.0613 (13) | |
H4 | 0.8067 | −0.4837 | 0.4958 | 0.074* | |
C5 | 0.6567 (5) | −0.3180 (4) | 0.4589 (3) | 0.0399 (8) | |
H5 | 0.7116 | −0.2831 | 0.3930 | 0.048* | |
C6 | 0.2127 (4) | 0.0440 (3) | 0.5565 (3) | 0.0283 (7) | |
C7 | 0.1424 (4) | 0.0393 (4) | 0.6711 (3) | 0.0360 (8) | |
H7 | 0.1922 | −0.0119 | 0.7361 | 0.043* | |
C8 | 0.0004 (4) | 0.1100 (4) | 0.6879 (3) | 0.0410 (9) | |
H8 | −0.0434 | 0.1052 | 0.7644 | 0.049* | |
C9 | −0.0780 (4) | 0.1868 (4) | 0.5956 (4) | 0.0445 (9) | |
H9 | −0.1743 | 0.2322 | 0.6086 | 0.053* | |
C10 | −0.0110 (4) | 0.1953 (4) | 0.4828 (3) | 0.0385 (8) | |
H10 | −0.0620 | 0.2492 | 0.4199 | 0.046* | |
C11 | 0.1329 (4) | 0.1242 (3) | 0.4608 (3) | 0.0299 (7) | |
C12 | 0.1946 (4) | 0.1429 (3) | 0.3404 (3) | 0.0325 (7) | |
H12 | 0.1371 | 0.2032 | 0.2851 | 0.039* | |
C13 | 0.3612 (4) | 0.1199 (3) | 0.1776 (3) | 0.0280 (7) | |
C14 | 0.4978 (4) | 0.1656 (3) | 0.1470 (3) | 0.0321 (7) | |
H14 | 0.5584 | 0.1783 | 0.2060 | 0.039* | |
C15 | 0.5421 (4) | 0.1916 (3) | 0.0288 (3) | 0.0349 (8) | |
H15 | 0.6314 | 0.2249 | 0.0082 | 0.042* | |
C16 | 0.4554 (4) | 0.1690 (3) | −0.0602 (3) | 0.0262 (6) | |
C17 | 0.3184 (4) | 0.1262 (3) | −0.0285 (3) | 0.0304 (7) | |
H17 | 0.2578 | 0.1129 | −0.0872 | 0.037* | |
C18 | 0.2712 (4) | 0.1032 (3) | 0.0902 (3) | 0.0316 (7) | |
H18 | 0.1782 | 0.0762 | 0.1106 | 0.038* | |
C19 | 0.5200 (4) | 0.1763 (3) | −0.1867 (3) | 0.0305 (7) | |
C20 | −0.0747 (14) | 0.3537 (14) | −0.1090 (10) | 0.207 (6)* | |
H20A | −0.1114 | 0.4045 | −0.1825 | 0.310* | |
H20B | −0.0917 | 0.2663 | −0.1053 | 0.310* | |
H20C | 0.0319 | 0.3544 | −0.1051 | 0.310* | |
C21 | −0.2667 (13) | 0.5097 (11) | −0.0481 (8) | 0.165 (4)* | |
H21A | −0.3199 | 0.5456 | 0.0177 | 0.248* | |
H21B | −0.3367 | 0.4790 | −0.0926 | 0.248* | |
H21C | −0.2208 | 0.5752 | −0.0988 | 0.248* | |
C22 | −0.1006 (17) | 0.3341 (15) | 0.1051 (13) | 0.201 (6)* | |
H22 | −0.0234 | 0.2633 | 0.1062 | 0.241* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0310 (3) | 0.0299 (3) | 0.0180 (2) | 0.00142 (17) | 0.00179 (15) | −0.00217 (16) |
O1 | 0.0297 (12) | 0.0403 (13) | 0.0204 (11) | 0.0010 (10) | 0.0016 (9) | −0.0037 (10) |
O2 | 0.0538 (18) | 0.0603 (18) | 0.0320 (14) | −0.0221 (14) | 0.0136 (12) | −0.0048 (12) |
O3 | 0.0374 (13) | 0.0377 (13) | 0.0223 (11) | 0.0036 (10) | 0.0027 (9) | −0.0060 (10) |
N1 | 0.0432 (17) | 0.0289 (14) | 0.0250 (14) | −0.0035 (12) | −0.0048 (12) | −0.0031 (11) |
N2 | 0.0322 (14) | 0.0318 (14) | 0.0188 (12) | 0.0002 (11) | 0.0024 (10) | −0.0026 (10) |
C1 | 0.055 (2) | 0.039 (2) | 0.0312 (19) | −0.0096 (17) | −0.0007 (16) | −0.0034 (15) |
C2 | 0.097 (4) | 0.045 (2) | 0.033 (2) | −0.021 (3) | −0.011 (2) | 0.0077 (18) |
C3 | 0.096 (4) | 0.033 (2) | 0.054 (3) | 0.002 (2) | −0.027 (3) | 0.0055 (19) |
C4 | 0.065 (3) | 0.040 (2) | 0.075 (3) | 0.013 (2) | −0.020 (3) | −0.012 (2) |
C5 | 0.045 (2) | 0.0327 (19) | 0.039 (2) | −0.0009 (16) | −0.0060 (16) | −0.0024 (15) |
C6 | 0.0316 (17) | 0.0295 (16) | 0.0239 (15) | −0.0058 (13) | 0.0055 (12) | −0.0065 (12) |
C7 | 0.042 (2) | 0.042 (2) | 0.0257 (17) | −0.0108 (16) | 0.0069 (14) | −0.0077 (15) |
C8 | 0.045 (2) | 0.052 (2) | 0.0286 (18) | −0.0147 (18) | 0.0157 (15) | −0.0133 (16) |
C9 | 0.0331 (19) | 0.045 (2) | 0.054 (2) | 0.0005 (16) | 0.0113 (17) | −0.0166 (18) |
C10 | 0.0333 (18) | 0.041 (2) | 0.0376 (19) | 0.0032 (15) | 0.0020 (15) | −0.0079 (16) |
C11 | 0.0284 (16) | 0.0342 (17) | 0.0274 (16) | −0.0047 (13) | 0.0036 (13) | −0.0077 (13) |
C12 | 0.0330 (17) | 0.0340 (18) | 0.0287 (17) | −0.0013 (14) | −0.0028 (13) | −0.0035 (14) |
C13 | 0.0333 (17) | 0.0258 (15) | 0.0193 (15) | 0.0048 (13) | 0.0008 (12) | 0.0018 (12) |
C14 | 0.0367 (18) | 0.0377 (18) | 0.0230 (16) | −0.0066 (14) | −0.0019 (13) | −0.0069 (13) |
C15 | 0.0373 (19) | 0.0343 (18) | 0.0335 (18) | −0.0090 (15) | 0.0060 (14) | −0.0061 (14) |
C16 | 0.0328 (16) | 0.0217 (14) | 0.0205 (15) | 0.0021 (12) | 0.0024 (12) | −0.0011 (11) |
C17 | 0.0324 (17) | 0.0359 (18) | 0.0206 (15) | 0.0012 (14) | −0.0037 (12) | −0.0038 (13) |
C18 | 0.0269 (16) | 0.0388 (18) | 0.0269 (17) | −0.0038 (13) | 0.0010 (12) | −0.0013 (13) |
C19 | 0.0395 (18) | 0.0251 (16) | 0.0214 (15) | 0.0045 (13) | 0.0028 (13) | 0.0011 (12) |
Cu1—O1 | 1.927 (2) | C7—C8 | 1.381 (5) |
Cu1—O1i | 2.440 (2) | C7—H7 | 0.9300 |
Cu1—O3ii | 1.930 (2) | C8—C9 | 1.369 (6) |
Cu1—N2 | 2.020 (3) | C8—H8 | 0.9300 |
Cu1—N1 | 2.038 (3) | C9—C10 | 1.378 (5) |
O1—C6 | 1.316 (4) | C9—H9 | 0.9300 |
O1—Cu1i | 2.440 (2) | C10—C11 | 1.408 (5) |
O2—C19 | 1.238 (4) | C10—H10 | 0.9300 |
O3—C19 | 1.284 (4) | C11—C12 | 1.442 (4) |
O3—Cu1ii | 1.930 (2) | C12—H12 | 0.9300 |
O4—C22 | 1.107 (14) | C13—C18 | 1.372 (4) |
N1—C5 | 1.335 (5) | C13—C14 | 1.395 (5) |
N1—C1 | 1.352 (4) | C14—C15 | 1.376 (4) |
N2—C12 | 1.289 (4) | C14—H14 | 0.9300 |
N2—C13 | 1.439 (4) | C15—C16 | 1.390 (5) |
N3—C21 | 1.358 (11) | C15—H15 | 0.9300 |
N3—C22 | 1.455 (13) | C16—C17 | 1.387 (5) |
N3—C20 | 1.498 (12) | C16—C19 | 1.513 (4) |
C1—C2 | 1.364 (6) | C17—C18 | 1.385 (4) |
C1—H1 | 0.9300 | C17—H17 | 0.9300 |
C2—C3 | 1.376 (7) | C18—H18 | 0.9300 |
C2—H2 | 0.9300 | C20—H20A | 0.9600 |
C3—C4 | 1.365 (7) | C20—H20B | 0.9600 |
C3—H3 | 0.9300 | C20—H20C | 0.9600 |
C4—C5 | 1.384 (6) | C21—H21A | 0.9599 |
C4—H4 | 0.9300 | C21—H21B | 0.9599 |
C5—H5 | 0.9300 | C21—H21C | 0.9601 |
C6—C7 | 1.411 (4) | C22—H22 | 0.9300 |
C6—C11 | 1.415 (5) | ||
O1—Cu1—O3ii | 176.68 (9) | C8—C9—H9 | 120.7 |
O1—Cu1—N2 | 90.46 (10) | C10—C9—H9 | 120.7 |
O3ii—Cu1—N2 | 91.26 (10) | C9—C10—C11 | 121.5 (3) |
O1—Cu1—N1 | 89.10 (11) | C9—C10—H10 | 119.3 |
O3ii—Cu1—N1 | 89.86 (11) | C11—C10—H10 | 119.3 |
N2—Cu1—N1 | 167.16 (12) | C10—C11—C6 | 119.6 (3) |
O1—Cu1—O1i | 82.50 (9) | C10—C11—C12 | 117.1 (3) |
O3ii—Cu1—O1i | 94.38 (10) | C6—C11—C12 | 123.2 (3) |
N2—Cu1—O1i | 100.60 (10) | N2—C12—C11 | 126.5 (3) |
N1—Cu1—O1i | 92.06 (10) | N2—C12—H12 | 116.8 |
C6—O1—Cu1 | 126.9 (2) | C11—C12—H12 | 116.8 |
C6—O1—Cu1i | 115.3 (2) | C18—C13—C14 | 120.0 (3) |
Cu1—O1—Cu1i | 97.50 (9) | C18—C13—N2 | 121.1 (3) |
C19—O3—Cu1ii | 118.6 (2) | C14—C13—N2 | 118.8 (3) |
C5—N1—C1 | 117.7 (3) | C15—C14—C13 | 119.4 (3) |
C5—N1—Cu1 | 121.5 (2) | C15—C14—H14 | 120.3 |
C1—N1—Cu1 | 120.8 (3) | C13—C14—H14 | 120.3 |
C12—N2—C13 | 116.7 (3) | C14—C15—C16 | 121.0 (3) |
C12—N2—Cu1 | 122.9 (2) | C14—C15—H15 | 119.5 |
C13—N2—Cu1 | 119.5 (2) | C16—C15—H15 | 119.5 |
C21—N3—C22 | 140.8 (9) | C17—C16—C15 | 118.8 (3) |
C21—N3—C20 | 109.4 (7) | C17—C16—C19 | 121.2 (3) |
C22—N3—C20 | 109.6 (9) | C15—C16—C19 | 119.5 (3) |
N1—C1—C2 | 122.1 (4) | C18—C17—C16 | 120.4 (3) |
N1—C1—H1 | 118.9 | C18—C17—H17 | 119.8 |
C2—C1—H1 | 118.9 | C16—C17—H17 | 119.8 |
C1—C2—C3 | 119.7 (4) | C13—C18—C17 | 120.2 (3) |
C1—C2—H2 | 120.1 | C13—C18—H18 | 119.9 |
C3—C2—H2 | 120.1 | C17—C18—H18 | 119.9 |
C4—C3—C2 | 118.9 (4) | O2—C19—O3 | 125.7 (3) |
C4—C3—H3 | 120.6 | O2—C19—C16 | 119.3 (3) |
C2—C3—H3 | 120.6 | O3—C19—C16 | 114.8 (3) |
C3—C4—C5 | 118.9 (4) | N3—C20—H20A | 109.5 |
C3—C4—H4 | 120.6 | N3—C20—H20B | 109.5 |
C5—C4—H4 | 120.6 | H20A—C20—H20B | 109.5 |
N1—C5—C4 | 122.7 (4) | N3—C20—H20C | 109.5 |
N1—C5—H5 | 118.6 | H20A—C20—H20C | 109.5 |
C4—C5—H5 | 118.6 | H20B—C20—H20C | 109.5 |
O1—C6—C7 | 119.5 (3) | N3—C21—H21A | 109.5 |
O1—C6—C11 | 123.0 (3) | N3—C21—H21B | 109.5 |
C7—C6—C11 | 117.5 (3) | H21A—C21—H21B | 109.5 |
C8—C7—C6 | 120.6 (3) | N3—C21—H21C | 109.5 |
C8—C7—H7 | 119.7 | H21A—C21—H21C | 109.5 |
C6—C7—H7 | 119.7 | H21B—C21—H21C | 109.5 |
C9—C8—C7 | 122.1 (3) | O4—C22—N3 | 117.1 (14) |
C9—C8—H8 | 118.9 | O4—C22—H22 | 121.5 |
C7—C8—H8 | 118.9 | N3—C22—H22 | 121.5 |
C8—C9—C10 | 118.6 (3) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C14H9NO3)(C5H5N)]·C3H7NO |
Mr | 454.96 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.9547 (13), 10.6215 (15), 11.3899 (16) |
α, β, γ (°) | 80.393 (5), 86.408 (3), 80.138 (2) |
V (Å3) | 1051.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.07 |
Crystal size (mm) | 0.23 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.752, 0.842 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7282, 4757, 3900 |
Rint | 0.093 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.184, 1.09 |
No. of reflections | 4757 |
No. of parameters | 246 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.07, −0.64 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Cu1—O1 | 1.927 (2) | Cu1—N2 | 2.020 (3) |
Cu1—O1i | 2.440 (2) | Cu1—N1 | 2.038 (3) |
Cu1—O3ii | 1.930 (2) | ||
O1—Cu1—O3ii | 176.68 (9) | O1—Cu1—O1i | 82.50 (9) |
O1—Cu1—N2 | 90.46 (10) | O3ii—Cu1—O1i | 94.38 (10) |
O3ii—Cu1—N2 | 91.26 (10) | N2—Cu1—O1i | 100.60 (10) |
O1—Cu1—N1 | 89.10 (11) | N1—Cu1—O1i | 92.06 (10) |
O3ii—Cu1—N1 | 89.86 (11) | Cu1—O1—Cu1i | 97.50 (9) |
N2—Cu1—N1 | 167.16 (12) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z. |
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The design and construction of metal-organic frameworks is of great interest owing to their potential as new functional materials, as well as their fascinating variety of topologies (Kitagawa et al., 2004; Steel, 2005; Takaoka et al., 2005). By rational choice of organic ligand and transition metal ion, one aims to modify the structure and the physical properties of complex architectures. Recently, use of a second building block has been demonstrated to be fruitful in constructing and analyzing structures of complex architecture (Kim et al., 2001). Schiff bases are excellent as ligands and are employed for preparing complexes with special functions such as biological activities, catalysis or magnetism. A salen-type Schiff base is one of the most appealing candidates for the formation of dimeric dinuclear complexes through the bridging phenol O atoms (Bai et al., 2006; Iskander et al., 2000). Numerous dimeric copper complexes with these ligands exhibit antiferromagnetic exchange (Bai et al., 2006; Shyu et al., 1996). Considering that these dimers as `magnetic brick' building blocks introduced into the framework would exhibit unusual magnetic behavior, we focused our preparative efforts on exploiting these `magnetic bricks' to create new architectures. In this paper, the bridging ligand 4-(salicylideneamino)benzoic acid (H2L) (see scheme), which was derived from the condensation of salicylaldehyde and 4-aminobenzoic acid, was exploited to bridge the bricks of a dimeric dicopper complex into polymeric {[CuL(py)]2}n, (I), through a self-assembly process.
Single-crystal structural analysis reveals that the title compound, crystallized in the triclinic P1 group, is composed of dimeric [CuL(py)]2 building units which are interlinked through the formation of Cu—Ocarboxylate into a one-dimensional polymer along the crystallographic c axis. The asymmetric unit of complex (I) consists of half of the dimer along with one solvent dimethylformamide (DMF) molecule (Fig. 1). The dimeric unit is centrosymmetric, with the Cu2O2 plane bridged by two phenol O atoms. The Cu···Cu separation is 3.300 (5) Å and the Cu1—O1—Cu1i angle is 97.50 (9)° in the Cu2O2 plane [symmetry code: (i) 1 - x, -y, 1 - z]. This dimerization via the bridging phenol O atoms has previously been noted in the generation of simple binuclear complexes.
In the dimeric unit, each copper(II) center is in a square-pyramidal geometric environment, with the basal plane consisting of a chelating phenol O atom and an imine N atom from one ligand, a carboxylate O atom from a neighboring dimer and a pyridyl N atom, and the apical site occupied by a bridging phenol O atom from another ligand in the dimer. The coordination polyhedron around each copper center is best described as (4 + 1) distorted square pyramidal, with the value of tetragonality parameter τ equal to 0.158 [τ = (b - α)/60, where α and β are the N1—Cu1—N2 and O1—Cu1—O3ii angles, respectively (Addison et al., 1984); symmetry code as in Table 1]. The Cu—O bond lengths (average 1.928 Å) are shorter than the Cu—N bonds (average 2.029 Å) in the basal plane. The chelating Cu—O length of 1.927 (2) Å is shorter than the bridging length of 2.440 (2) Å, as is the situation in [Cu(LBPh3)]2 [LBPh3 is N-(salicylidene)-N'- (1-triphenylborylimidazol-2-ylmethylene)-1,3-propanediamine; Shyu et al., 1996]. However, the Cu···Cu separation in the Cu2O2 plane is longer than that [3.085 (4) Å] in [Cu(LBPh3)]2, possibly because of the steric hindrance of pyridyl rings and phenyl rings around the Cu2O2 plane. The pyridyl ring is almost perpendicular to the plane of Cu2O2 with a dihedral angle of 91.6°. In further comparison to the most closely related phenol-O-bridging dinuclear copper compounds, it was found that the bridging bond lengths of Cu—Ophenol are similar to the chelating ones if the chelating and bridged phenol O atoms are in the same equatorial plane (Paschke et al., 2003). The long bridging bond length and the long separation of Cu···Cu in the Cu2O2 plane reveal that the dimerization of the title compound is a little loose. In the polymer, there is one subunit of binuclear macrocycle Cu2L2, which is stabilized by π–π stacking interactions between the rings of the benzoate groups, with a centroid–centroid distance of 3.677 Å, an interplanar distance of 3.154 Å and the shift between the centroid of 1.890 Å. The Cu···Cu distance in this macrocycle is 8.953 Å, an intermediate between those observed for other CuII2 complexes containing similar aromatic spacers (Paital et al., 2007). Adjacent macrocycles are linked by two bridging phenol O atoms. Therefore, this polymer can also be described as being composed of binuclear macrocycles interlinked through the formation of bridging Cu—Ophenol bonds (Fig. 2), based on the long bridging Cu—Ophenol distances.
It is worth noting that unusual supramolecular interactions in the solid state, including C—H···O hydrogen bonds and π–π stacking, generate a unique supramolecular architecture. The interchain contacts of C3—H3···O2iii [C3···O2iii = 3.300 (5) Å, H3···O2iii = 2.45 Å and C3—H3···O2iii = 152°; symmetry code: (iii) x, y - 1, z + 1] together with π–π stacking interactions between pyridyl rings (the centroid-centroid distance is 3.718 Å, the interplanar distance 2.738 Å, and the shift between the centroids 2.517 Å) drive polymers to arrange along the crystallographic b axis, while the polymers also extend along the a axis through the interchain π–π stacking interactions between aromatic rings of salicylaldimine groups (the centroid–centroid distance is 3.638 Å, the interplanar distance 2.742 Å and the shift between the centroids 2.391 Å) (Müller-Dethlefs & Hobza, 2000). These weak interactions are responsible for an extensive three-dimensional structure in which the resulting channels are filled by solvent DMF molecules (Fig. 3).