The title compound, {[Cu(C10H8N2)(H2O)](C8H4O4)0.5·H2O}n, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The compound consists of nearly linear one-dimensional chains of [Cu(4,4′-bipy)(H2O)]nn+ cations (4,4′-bipy is 4,4′-bipyridyl), surrounded by isophthalate anions and free water molecules. Hydrogen-bonding interactions involving cationic chains, isophthalate anions and free water molecules lead to the formation of a three-dimensional network structure.
Supporting information
CCDC reference: 248127
A mixture of Cu(NO3)2·3H2O (0.241 g, 1 mmol), 4,4'-bipyridine (0.078 g, 0.5 mmol), pyridine-3-carboxylic acid (0.062 g, 0.5 mmol) and isophthalic acid (0.083 g, 0.5 mmol) in water (18 ml) was placed in a 25 ml Teflon-lined stainless steel reactor and heated to 453 K for 76 h. When the reactor was cooled to room temperature over a period of 3 d, orange prismatic single crystals suitable for X-ray diffraction were obtained. ##AUTHOR: Please check changes above.
Water H atoms were located from difference maps and refined with the O—H distances restrained to 0.82 (s.u.?) Å and with Uiso(H) values of 1.5Ueq(O). All other H atoms were positioned geometrically and treated using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)].
Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Crystal data top
[Cu(C10H8N2)(H2O)](C8H4O4)0.5·H2O | F(000) = 1384 |
Mr = 337.82 | Dx = 1.630 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2n2ab | Cell parameters from 2793 reflections |
a = 21.6096 (8) Å | θ = 1.9–25.0° |
b = 7.2160 (2) Å | µ = 1.60 mm−1 |
c = 17.6529 (6) Å | T = 293 K |
V = 2752.70 (16) Å3 | Cubic prism, pale yellow |
Z = 8 | 0.48 × 0.32 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2412 independent reflections |
Radiation source: fine-focus sealed tube | 1585 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −17→25 |
Tmin = 0.434, Tmax = 0.730 | k = −8→8 |
7492 measured reflections | l = −20→11 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.164 | w = 1/[σ2(Fo2) + (0.061P)2 + 7.487P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
2412 reflections | Δρmax = 0.48 e Å−3 |
204 parameters | Δρmin = −0.51 e Å−3 |
4 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0029 (4) |
Crystal data top
[Cu(C10H8N2)(H2O)](C8H4O4)0.5·H2O | V = 2752.70 (16) Å3 |
Mr = 337.82 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 21.6096 (8) Å | µ = 1.60 mm−1 |
b = 7.2160 (2) Å | T = 293 K |
c = 17.6529 (6) Å | 0.48 × 0.32 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2412 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1585 reflections with I > 2σ(I) |
Tmin = 0.434, Tmax = 0.730 | Rint = 0.047 |
7492 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.059 | 4 restraints |
wR(F2) = 0.164 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.48 e Å−3 |
2412 reflections | Δρmin = −0.51 e Å−3 |
204 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.16563 (3) | 0.25725 (10) | 0.05297 (4) | 0.0426 (3) | |
O1W | 0.2284 (3) | 0.4897 (9) | 0.2792 (4) | 0.0954 (18) | |
H1WA | 0.214 (4) | 0.594 (6) | 0.283 (6) | 0.143* | |
H1WB | 0.2645 (18) | 0.454 (14) | 0.281 (6) | 0.143* | |
O2W | 0.1644 (2) | 0.2896 (8) | 0.1766 (3) | 0.0652 (13) | |
H2WB | 0.153 (4) | 0.197 (7) | 0.199 (4) | 0.098* | |
H2WA | 0.188 (3) | 0.344 (10) | 0.205 (4) | 0.098* | |
O3 | 0.1090 (3) | −0.0642 (8) | −0.2277 (3) | 0.0922 (19) | |
O4 | 0.1582 (2) | 0.1949 (11) | −0.1937 (5) | 0.122 (3) | |
N1 | 0.07820 (18) | 0.2481 (6) | 0.0338 (2) | 0.0354 (10) | |
N2 | −0.2471 (2) | 0.2442 (6) | −0.0326 (2) | 0.0395 (10) | |
C1 | 0.0542 (2) | 0.2865 (8) | −0.0354 (3) | 0.0414 (14) | |
H1A | 0.0813 | 0.3141 | −0.0748 | 0.050* | |
C2 | −0.0081 (2) | 0.2864 (7) | −0.0502 (3) | 0.0362 (12) | |
H2C | −0.0224 | 0.3146 | −0.0985 | 0.043* | |
C3 | −0.0503 (2) | 0.2437 (7) | 0.0078 (3) | 0.0293 (10) | |
C4 | −0.0255 (2) | 0.2003 (8) | 0.0784 (3) | 0.0405 (14) | |
H4A | −0.0514 | 0.1685 | 0.1184 | 0.049* | |
C5 | 0.0374 (2) | 0.2049 (8) | 0.0885 (3) | 0.0397 (13) | |
H5A | 0.0528 | 0.1763 | 0.1363 | 0.048* | |
C6 | −0.1186 (2) | 0.2443 (7) | −0.0058 (3) | 0.0338 (11) | |
C7 | −0.1427 (2) | 0.2417 (10) | −0.0780 (3) | 0.059 (2) | |
H7A | −0.1162 | 0.2385 | −0.1195 | 0.071* | |
C8 | −0.2240 (3) | 0.2475 (9) | 0.0381 (3) | 0.0510 (15) | |
H8A | −0.2514 | 0.2514 | 0.0787 | 0.061* | |
C9 | −0.2061 (2) | 0.2437 (10) | −0.0894 (3) | 0.0601 (19) | |
H9A | −0.2208 | 0.2449 | −0.1388 | 0.072* | |
C10 | −0.1612 (2) | 0.2452 (9) | 0.0528 (3) | 0.0503 (16) | |
H10A | −0.1474 | 0.2442 | 0.1027 | 0.060* | |
C11 | 0.0000 | 0.5111 (12) | −0.2500 | 0.047 (2) | |
H11A | 0.0000 | 0.6400 | −0.2500 | 0.057* | |
C12 | 0.0537 (3) | 0.4150 (9) | −0.2345 (3) | 0.0495 (15) | |
H12A | 0.0899 | 0.4800 | −0.2242 | 0.059* | |
C13 | 0.0545 (3) | 0.2218 (8) | −0.2343 (3) | 0.0439 (14) | |
C14 | 0.0000 | 0.1291 (11) | −0.2500 | 0.044 (2) | |
H14A | 0.0000 | 0.0002 | −0.2500 | 0.052* | |
C15 | 0.1127 (3) | 0.1089 (12) | −0.2177 (4) | 0.067 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0186 (4) | 0.0595 (5) | 0.0497 (5) | −0.0011 (3) | 0.0005 (3) | 0.0026 (4) |
O1W | 0.064 (3) | 0.087 (4) | 0.135 (5) | 0.010 (3) | −0.023 (4) | −0.028 (4) |
O2W | 0.058 (3) | 0.094 (4) | 0.044 (2) | −0.020 (3) | −0.001 (2) | −0.002 (2) |
O3 | 0.118 (5) | 0.087 (4) | 0.072 (4) | 0.059 (4) | 0.024 (3) | 0.013 (3) |
O4 | 0.046 (3) | 0.148 (6) | 0.172 (7) | 0.004 (4) | −0.009 (4) | 0.076 (5) |
N1 | 0.022 (2) | 0.046 (2) | 0.037 (2) | −0.003 (2) | 0.0020 (17) | −0.002 (2) |
N2 | 0.0204 (19) | 0.058 (3) | 0.040 (2) | 0.001 (2) | −0.0018 (18) | 0.002 (2) |
C1 | 0.032 (3) | 0.062 (4) | 0.030 (3) | −0.004 (3) | 0.003 (2) | −0.003 (3) |
C2 | 0.025 (3) | 0.057 (3) | 0.026 (2) | −0.003 (2) | 0.001 (2) | −0.001 (2) |
C3 | 0.021 (2) | 0.036 (3) | 0.030 (2) | −0.002 (2) | −0.0011 (19) | −0.004 (2) |
C4 | 0.024 (2) | 0.062 (4) | 0.036 (3) | −0.004 (2) | 0.002 (2) | 0.007 (3) |
C5 | 0.024 (2) | 0.062 (4) | 0.033 (3) | 0.001 (2) | 0.001 (2) | 0.010 (3) |
C6 | 0.024 (2) | 0.044 (3) | 0.033 (2) | 0.000 (2) | 0.002 (2) | −0.001 (3) |
C7 | 0.023 (3) | 0.123 (6) | 0.032 (3) | −0.006 (3) | 0.003 (2) | 0.000 (4) |
C8 | 0.026 (3) | 0.088 (5) | 0.039 (3) | −0.001 (3) | 0.001 (2) | −0.005 (3) |
C9 | 0.031 (3) | 0.119 (6) | 0.031 (3) | −0.006 (4) | −0.005 (2) | 0.005 (4) |
C10 | 0.027 (3) | 0.094 (5) | 0.030 (3) | −0.001 (3) | −0.002 (2) | 0.004 (3) |
C11 | 0.058 (5) | 0.042 (4) | 0.043 (4) | 0.000 | 0.005 (4) | 0.000 |
C12 | 0.047 (4) | 0.066 (4) | 0.035 (3) | −0.022 (3) | 0.008 (3) | −0.001 (3) |
C13 | 0.045 (3) | 0.055 (4) | 0.031 (3) | 0.007 (3) | 0.014 (2) | 0.007 (3) |
C14 | 0.062 (5) | 0.041 (4) | 0.028 (4) | 0.000 | 0.018 (4) | 0.000 |
C15 | 0.050 (4) | 0.099 (6) | 0.051 (4) | 0.009 (4) | 0.024 (3) | 0.028 (4) |
Geometric parameters (Å, º) top
Cu1—N1 | 1.921 (4) | C4—C5 | 1.370 (7) |
Cu1—N2i | 1.920 (4) | C4—H4A | 0.9300 |
Cu1—O2W | 2.195 (5) | C5—H5A | 0.9300 |
O1W—H1WA | 0.81 (5) | C6—C7 | 1.376 (7) |
O1W—H1WB | 0.82 (5) | C6—C10 | 1.386 (7) |
O2W—H2WB | 0.82 (6) | C7—C9 | 1.384 (8) |
O2W—H2WA | 0.82 (7) | C7—H7A | 0.9300 |
O3—C15 | 1.264 (9) | C8—C10 | 1.382 (7) |
O4—C15 | 1.238 (10) | C8—H8A | 0.9300 |
N1—C5 | 1.345 (6) | C9—H9A | 0.9300 |
N1—C1 | 1.355 (6) | C10—H10A | 0.9300 |
N2—C9 | 1.338 (7) | C11—C12 | 1.379 (7) |
N2—C8 | 1.344 (7) | C11—H11A | 0.9300 |
C1—C2 | 1.371 (7) | C12—C13 | 1.394 (8) |
C1—H1A | 0.9300 | C12—H12A | 0.9300 |
C2—C3 | 1.404 (7) | C13—C14 | 1.384 (7) |
C2—H2C | 0.9300 | C13—C15 | 1.525 (9) |
C3—C4 | 1.392 (7) | C14—H14A | 0.9300 |
C3—C6 | 1.497 (6) | | |
| | | |
N1—Cu1—N2i | 158.88 (18) | C7—C6—C10 | 116.2 (5) |
N1—Cu1—O2W | 99.65 (18) | C7—C6—C3 | 121.5 (4) |
N2i—Cu1—O2W | 101.47 (18) | C10—C6—C3 | 122.4 (4) |
H1WA—O1W—H1WB | 130 (10) | C6—C7—C9 | 120.5 (5) |
Cu1—O2W—H2WB | 113 (6) | C6—C7—H7A | 119.7 |
Cu1—O2W—H2WA | 131 (6) | C9—C7—H7A | 119.7 |
H2WB—O2W—H2WA | 107 (9) | N2—C8—C10 | 122.6 (5) |
C5—N1—C1 | 116.3 (4) | N2—C8—H8A | 118.7 |
C5—N1—Cu1 | 121.7 (3) | C10—C8—H8A | 118.7 |
C1—N1—Cu1 | 121.9 (3) | N2—C9—C7 | 123.1 (5) |
C9—N2—C8 | 116.7 (5) | N2—C9—H9A | 118.4 |
C9—N2—Cu1ii | 120.7 (4) | C7—C9—H9A | 118.4 |
C8—N2—Cu1ii | 122.6 (4) | C8—C10—C6 | 120.8 (5) |
N1—C1—C2 | 123.2 (5) | C8—C10—H10A | 119.6 |
N1—C1—H1A | 118.4 | C6—C10—H10A | 119.6 |
C2—C1—H1A | 118.4 | C12iii—C11—C12 | 119.6 (8) |
C1—C2—C3 | 119.9 (5) | C12—C11—H11A | 120.2 |
C1—C2—H2C | 120.0 | C11—C12—C13 | 121.0 (6) |
C3—C2—H2C | 120.0 | C11—C12—H12A | 119.5 |
C4—C3—C2 | 116.9 (4) | C13—C12—H12A | 119.5 |
C4—C3—C6 | 121.6 (4) | C14—C13—C12 | 118.1 (6) |
C2—C3—C6 | 121.5 (4) | C14—C13—C15 | 118.8 (6) |
C5—C4—C3 | 119.5 (5) | C12—C13—C15 | 123.1 (6) |
C5—C4—H4A | 120.2 | C13—C14—C13iii | 122.2 (7) |
C3—C4—H4A | 120.2 | C13—C14—H14A | 118.9 |
N1—C5—C4 | 124.2 (5) | O4—C15—O3 | 126.4 (8) |
N1—C5—H5A | 117.9 | O4—C15—C13 | 116.9 (8) |
C4—C5—H5A | 117.9 | O3—C15—C13 | 116.7 (7) |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, −y+1/2, −z; (iii) −x, y, −z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4iv | 0.81 (5) | 1.99 (4) | 2.777 (9) | 162 (11) |
O1W—H1WB···O4v | 0.82 (5) | 2.04 (4) | 2.829 (8) | 162 (10) |
O2W—H2WB···O3vi | 0.82 (6) | 1.87 (4) | 2.634 (7) | 156 (9) |
O2W—H2WA···O1W | 0.82 (7) | 1.89 (7) | 2.698 (8) | 168 (8) |
Symmetry codes: (iv) x, −y+1, z+1/2; (v) −x+1/2, −y+1/2, z+1/2; (vi) x, −y, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Cu(C10H8N2)(H2O)](C8H4O4)0.5·H2O |
Mr | 337.82 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 293 |
a, b, c (Å) | 21.6096 (8), 7.2160 (2), 17.6529 (6) |
V (Å3) | 2752.70 (16) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.60 |
Crystal size (mm) | 0.48 × 0.32 × 0.20 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.434, 0.730 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7492, 2412, 1585 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.164, 1.11 |
No. of reflections | 2412 |
No. of parameters | 204 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.51 |
Selected geometric parameters (Å, º) topCu1—N1 | 1.921 (4) | Cu1—O2W | 2.195 (5) |
Cu1—N2i | 1.920 (4) | | |
| | | |
N1—Cu1—N2i | 158.88 (18) | N2i—Cu1—O2W | 101.47 (18) |
N1—Cu1—O2W | 99.65 (18) | | |
Symmetry code: (i) x+1/2, −y+1/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4ii | 0.81 (5) | 1.99 (4) | 2.777 (9) | 162 (11) |
O1W—H1WB···O4iii | 0.82 (5) | 2.04 (4) | 2.829 (8) | 162 (10) |
O2W—H2WB···O3iv | 0.82 (6) | 1.87 (4) | 2.634 (7) | 156 (9) |
O2W—H2WA···O1W | 0.82 (7) | 1.89 (7) | 2.698 (8) | 168 (8) |
Symmetry codes: (ii) x, −y+1, z+1/2; (iii) −x+1/2, −y+1/2, z+1/2; (iv) x, −y, z+1/2. |
Recently, much attention has been focused on metal-directed supramolecular complexes becuase of their potential applications as novel magnetic materials, microporous phases and catalysts (Chui et al., 1999; Lo et al., 2000). Usually bi- or multidentate organic ligands containing N or O are used to bind metal centers (Hagrman et al., 1999). For example, 4,4'-bipy is an excellent bridging ligand for coordination chemistry because of its rod-like shape, allowing the ligand to connect metal ions to form an extended array (Park et al., 2001), and is widely used in the construction of transition metal coordination complexes. A large number of one-, two- and three-dimensional infinite metal–4,4'-bipy frameworks have been synthesized by hydrothermal methods (Noro et al., 2000; ##AUTHOR: Should the above reference be 2002 rather than 2000? Wang et al., 1999), and this process has been proved an efficient way to discover new coordination compounds, because it allows the formation of metastable phases. Additionally, 4,4'-bipy and benzenedicarboxylic acid have often been used simultaneously to construct metal-organic frameworks (Tao et al., 2000; Lightfoot et al., 1999; Ma et al., 2003). In this paper, we chose isophthalic acid and 4,4'-bipy as ligands to react with a copper salt, resulting in the isolation of an unexpected novel three-coordinate copper(I) compound, [Cu(4,4'-bipy)(H2O)+.0.5(isophthalate)2−·H2O]n,(I).
As shown in Fig. 1, the crystal structure of (I) reveals a coordinatively unsaturated, approximately T-shaped, copper(I) centre, trigonally coordinated ##AUTHOR: Angles at Cu are closer to a T-shape than a Y-shape. OK ?? by two N atoms from two 4,4'-bipy ligands [Cu—N = 1.920 (4) and 1.921 (4) Å, and N1—Cu1—N2 = 158.88 (18)°],as well as one O atom from a water molecule [Cu—O = 2.195 (5) Å, N1—Cu1—O2W = 99.65 (18) and N2—Cu1—O2W = 101.47 (18)°]. The CuI centre is located in the plane defined by the three donor atoms. The dihedral angle between two pyridine rings of 4,4'-bipy is 15.61°. The CuI centres are linked through 4,4'-bipy ligands to generate a one-dimensional cation chain propagating along the a axis, as shown in Fig. 2. The coordinated water molecules are alternately arranged on opposite sides of the cation chain, with the isophthalate anions interspersed between the chains.
There are extensive hydrogen-bonding interactions involving the isophthalate anions, coordinated water molecules and free water molecules (Table 2). Among them, the distances for O2W—H2WB···O3 and O2W—H2WA···O1W are shorter than those for the other two interactions, implying that the coordinated water molecules may have stronger hydrogen-bonding interactions than free water molecules. As stated above, the structure contains a one-dimensional coordination polymer. However, there is hydrogen bonding through the coordinated water molecule in a second orthogonal direction and through the free water molecule in a third (Table 2), giving overall a three-dimensional framework structure. ##AUTHOR: Please check and approve the additional text above.
The mechanism of hydrothermal reactions involves a shift from kinetic to thermodynamic control, in contrast to conventional solution synthetic systems, and this makes the structures produced more difficult to control. The successful synthesis of the title compound indicates that the copper(II) ion undergoes reduction through an unknown reaction mechanism. According to the known literature (Yaghi & Li, 1995), it is accepted that CuII ions can be reduced to CuI by 4,4'-bipy or pyridine derivatives under hydrothermal conditions. Nevertheless, the further redox mechanism is be studied in the future. ##AUTHOR: please clarify the preceding sentence.
In summary, although the pyridine-3-carboxylic acid starting material is not incorporated into the product, its presence nevertheless proved to be necessary in order to obtain the title compound. When this reagent was omitted, we obtained [Cu2(ipO)(4,4'-bipy)] (ipOH is 2-hydroxyisophthalate), which has been reported previously by Tao et al. (2002) as resulting from a reaction in which no pyridine-3-carboxylic acid was used. These results illustrate the point that the formation of a product can be greatly influenced by the reagants present even if some of them do not appear in the product.