Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103028907/sq1144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103028907/sq1144Isup2.hkl |
CCDC reference: 233109
A solution (10 ml) of dimethylformamide containing CuCl2·2H2O (0.5 mmol, 0.085 g) and H4TCB (0.5 mmol, 0.127 g) was added slowly to a solution (10 ml) of dimethylformamide containing 2,2'-bipy (0.5 mmol, 0.078 g). The mixture was stirred for 30 min and left to stand at room temperature for about a month. Light-blue prism-shaped crystals of (I) were obtained.
The all H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of 0.93 Å, with Uiso(H) = 1.2Ueq(parent atom).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Cu2(C10H2O8)(C10H8N2)2] | F(000) = 696 |
Mr = 689.56 | Dx = 1.796 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 532 reflections |
a = 7.2794 (7) Å | θ = 2.4–22.0° |
b = 12.5009 (12) Å | µ = 1.73 mm−1 |
c = 14.4436 (14) Å | T = 273 K |
β = 104.021 (2)° | Prism, blue |
V = 1275.2 (2) Å3 | 0.32 × 0.29 × 0.24 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2263 independent reflections |
Radiation source: fine-focus sealed tube | 2179 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −8→8 |
Tmin = 0.582, Tmax = 0.663 | k = −14→14 |
9055 measured reflections | l = −17→17 |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0367P)2 + 1.7086P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
2263 reflections | Δρmax = 0.48 e Å−3 |
200 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00 |
[Cu2(C10H2O8)(C10H8N2)2] | V = 1275.2 (2) Å3 |
Mr = 689.56 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.2794 (7) Å | µ = 1.73 mm−1 |
b = 12.5009 (12) Å | T = 273 K |
c = 14.4436 (14) Å | 0.32 × 0.29 × 0.24 mm |
β = 104.021 (2)° |
Bruker SMART CCD area-detector diffractometer | 2263 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2179 reflections with I > 2σ(I) |
Tmin = 0.582, Tmax = 0.663 | Rint = 0.024 |
9055 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.48 e Å−3 |
2263 reflections | Δρmin = −0.29 e Å−3 |
200 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 | 0.12671 (5) | 0.51437 (3) | 0.28264 (2) | 0.02411 (15) | |
O1 | −0.4480 (3) | 0.5500 (2) | −0.24253 (15) | 0.0426 (6) | |
O2 | −0.2239 (3) | 0.43644 (19) | −0.17381 (14) | 0.0330 (5) | |
O3 | −0.0839 (3) | 0.44152 (18) | 0.19560 (14) | 0.0324 (5) | |
O4 | −0.1984 (3) | 0.59946 (19) | 0.22122 (15) | 0.0382 (5) | |
N1 | 0.1225 (3) | 0.4282 (2) | 0.39770 (16) | 0.0238 (5) | |
N2 | 0.2687 (3) | 0.6143 (2) | 0.38029 (16) | 0.0242 (5) | |
C1 | 0.0426 (4) | 0.3322 (3) | 0.3988 (2) | 0.0306 (7) | |
H1 | −0.0242 | 0.3022 | 0.3416 | 0.037* | |
C2 | 0.0567 (4) | 0.2764 (3) | 0.4827 (2) | 0.0339 (7) | |
H2 | 0.0002 | 0.2096 | 0.4819 | 0.041* | |
C3 | 0.1547 (4) | 0.3203 (3) | 0.5674 (2) | 0.0325 (7) | |
H3 | 0.1661 | 0.2834 | 0.6244 | 0.039* | |
C4 | 0.2364 (4) | 0.4200 (2) | 0.5671 (2) | 0.0270 (6) | |
H4 | 0.3016 | 0.4517 | 0.6238 | 0.032* | |
C5 | 0.2193 (4) | 0.4722 (2) | 0.4807 (2) | 0.0223 (6) | |
C6 | 0.2981 (4) | 0.5794 (2) | 0.47109 (18) | 0.0214 (6) | |
C7 | 0.3906 (4) | 0.6431 (2) | 0.5471 (2) | 0.0281 (7) | |
H7 | 0.4128 | 0.6180 | 0.6094 | 0.034* | |
C8 | 0.4487 (4) | 0.7443 (3) | 0.5284 (2) | 0.0344 (7) | |
H8 | 0.5097 | 0.7885 | 0.5782 | 0.041* | |
C9 | 0.4154 (5) | 0.7792 (3) | 0.4349 (2) | 0.0363 (7) | |
H9 | 0.4526 | 0.8473 | 0.4211 | 0.044* | |
C10 | 0.3270 (4) | 0.7120 (3) | 0.3631 (2) | 0.0328 (7) | |
H10 | 0.3069 | 0.7351 | 0.3003 | 0.039* | |
C11 | −0.2089 (4) | 0.5153 (2) | 0.17650 (19) | 0.0233 (6) | |
C12 | −0.3650 (4) | 0.5008 (2) | 0.08769 (19) | 0.0189 (6) | |
C13 | −0.3111 (4) | 0.4928 (2) | 0.00192 (19) | 0.0197 (6) | |
H13 | −0.1830 | 0.4877 | 0.0033 | 0.024* | |
C14 | −0.4422 (4) | 0.4924 (2) | −0.08563 (19) | 0.0186 (5) | |
C15 | −0.3708 (4) | 0.4925 (2) | −0.1755 (2) | 0.0221 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0210 (2) | 0.0394 (3) | 0.0107 (2) | 0.00225 (14) | 0.00139 (14) | −0.00150 (13) |
O1 | 0.0477 (14) | 0.0616 (16) | 0.0207 (11) | 0.0184 (12) | 0.0126 (10) | 0.0148 (11) |
O2 | 0.0282 (11) | 0.0565 (14) | 0.0166 (10) | 0.0131 (10) | 0.0098 (8) | 0.0046 (9) |
O3 | 0.0264 (11) | 0.0454 (13) | 0.0196 (10) | 0.0097 (10) | −0.0060 (8) | −0.0056 (9) |
O4 | 0.0401 (13) | 0.0430 (13) | 0.0261 (12) | 0.0014 (11) | −0.0028 (9) | −0.0140 (10) |
N1 | 0.0188 (11) | 0.0359 (14) | 0.0161 (11) | 0.0012 (10) | 0.0028 (9) | −0.0032 (10) |
N2 | 0.0206 (12) | 0.0339 (14) | 0.0177 (12) | 0.0014 (10) | 0.0041 (9) | 0.0012 (10) |
C1 | 0.0275 (15) | 0.0352 (17) | 0.0288 (16) | −0.0013 (13) | 0.0062 (13) | −0.0077 (13) |
C2 | 0.0335 (17) | 0.0290 (16) | 0.0422 (19) | 0.0026 (13) | 0.0151 (14) | 0.0015 (14) |
C3 | 0.0330 (17) | 0.0388 (18) | 0.0274 (16) | 0.0074 (14) | 0.0104 (13) | 0.0065 (13) |
C4 | 0.0253 (15) | 0.0374 (17) | 0.0185 (14) | 0.0058 (13) | 0.0058 (11) | −0.0004 (12) |
C5 | 0.0161 (13) | 0.0329 (16) | 0.0184 (14) | 0.0049 (11) | 0.0053 (11) | −0.0030 (11) |
C6 | 0.0173 (13) | 0.0320 (16) | 0.0152 (13) | 0.0054 (11) | 0.0043 (10) | −0.0017 (11) |
C7 | 0.0253 (15) | 0.0368 (17) | 0.0202 (14) | 0.0023 (12) | 0.0018 (12) | −0.0013 (12) |
C8 | 0.0291 (16) | 0.0392 (18) | 0.0331 (17) | −0.0032 (13) | 0.0042 (13) | −0.0111 (14) |
C9 | 0.0371 (18) | 0.0309 (17) | 0.0421 (19) | −0.0032 (14) | 0.0118 (15) | 0.0004 (14) |
C10 | 0.0340 (17) | 0.0396 (18) | 0.0256 (16) | 0.0012 (14) | 0.0087 (13) | 0.0060 (13) |
C11 | 0.0212 (14) | 0.0376 (17) | 0.0104 (13) | −0.0027 (12) | 0.0024 (11) | −0.0008 (11) |
C12 | 0.0180 (13) | 0.0207 (14) | 0.0159 (13) | −0.0002 (10) | −0.0002 (11) | 0.0013 (10) |
C13 | 0.0168 (13) | 0.0261 (15) | 0.0157 (14) | 0.0006 (11) | 0.0026 (11) | −0.0001 (10) |
C14 | 0.0190 (13) | 0.0224 (14) | 0.0135 (13) | 0.0006 (10) | 0.0023 (10) | 0.0000 (10) |
C15 | 0.0206 (14) | 0.0309 (15) | 0.0144 (14) | −0.0027 (11) | 0.0032 (11) | −0.0020 (11) |
Cu1—O3 | 1.956 (2) | C4—C5 | 1.387 (4) |
Cu1—O2i | 1.972 (2) | C4—H4 | 0.9300 |
Cu1—N2 | 1.978 (2) | C5—C6 | 1.478 (4) |
Cu1—N1 | 1.987 (2) | C6—C7 | 1.391 (4) |
O1—C15 | 1.227 (4) | C7—C8 | 1.381 (5) |
O2—C15 | 1.274 (3) | C7—H7 | 0.9300 |
O2—Cu1i | 1.972 (2) | C8—C9 | 1.384 (5) |
O3—C11 | 1.278 (4) | C8—H8 | 0.9300 |
O4—C11 | 1.228 (4) | C9—C10 | 1.368 (5) |
N1—C1 | 1.336 (4) | C9—H9 | 0.9300 |
N1—C5 | 1.351 (4) | C10—H10 | 0.9300 |
N2—C10 | 1.335 (4) | C11—C12 | 1.504 (4) |
N2—C6 | 1.349 (3) | C12—C13 | 1.391 (4) |
C1—C2 | 1.382 (4) | C12—C14ii | 1.399 (4) |
C1—H1 | 0.9300 | C13—C14 | 1.387 (4) |
C2—C3 | 1.373 (4) | C13—H13 | 0.9300 |
C2—H2 | 0.9300 | C14—C12ii | 1.399 (4) |
C3—C4 | 1.381 (4) | C14—C15 | 1.511 (4) |
C3—H3 | 0.9300 | ||
O3—Cu1—O2i | 90.54 (9) | N2—C6—C5 | 114.3 (2) |
O3—Cu1—N2 | 160.94 (9) | C7—C6—C5 | 124.8 (2) |
O2i—Cu1—N2 | 98.33 (10) | C8—C7—C6 | 118.9 (3) |
O3—Cu1—N1 | 96.71 (9) | C8—C7—H7 | 120.6 |
O2i—Cu1—N1 | 156.50 (9) | C6—C7—H7 | 120.6 |
N2—Cu1—N1 | 81.80 (10) | C7—C8—C9 | 119.4 (3) |
C15—O2—Cu1i | 105.94 (18) | C7—C8—H8 | 120.3 |
C11—O3—Cu1 | 102.07 (18) | C9—C8—H8 | 120.3 |
C1—N1—C5 | 119.4 (3) | C10—C9—C8 | 119.0 (3) |
C1—N1—Cu1 | 126.3 (2) | C10—C9—H9 | 120.5 |
C5—N1—Cu1 | 114.28 (19) | C8—C9—H9 | 120.5 |
C10—N2—C6 | 119.6 (3) | N2—C10—C9 | 122.2 (3) |
C10—N2—Cu1 | 125.5 (2) | N2—C10—H10 | 118.9 |
C6—N2—Cu1 | 114.88 (19) | C9—C10—H10 | 118.9 |
N1—C1—C2 | 121.6 (3) | O4—C11—O3 | 123.7 (3) |
N1—C1—H1 | 119.2 | O4—C11—C12 | 119.3 (3) |
C2—C1—H1 | 119.2 | O3—C11—C12 | 116.7 (2) |
C3—C2—C1 | 119.5 (3) | C13—C12—C14ii | 118.9 (3) |
C3—C2—H2 | 120.3 | C13—C12—C11 | 116.8 (2) |
C1—C2—H2 | 120.3 | C14ii—C12—C11 | 123.9 (3) |
C2—C3—C4 | 119.3 (3) | C14—C13—C12 | 122.1 (3) |
C2—C3—H3 | 120.3 | C14—C13—H13 | 118.9 |
C4—C3—H3 | 120.3 | C12—C13—H13 | 118.9 |
C3—C4—C5 | 118.8 (3) | C13—C14—C12ii | 119.0 (3) |
C3—C4—H4 | 120.6 | C13—C14—C15 | 118.7 (2) |
C5—C4—H4 | 120.6 | C12ii—C14—C15 | 122.2 (2) |
N1—C5—C4 | 121.4 (3) | O1—C15—O2 | 124.0 (3) |
N1—C5—C6 | 114.6 (2) | O1—C15—C14 | 119.4 (2) |
C4—C5—C6 | 123.9 (3) | O2—C15—C14 | 116.4 (2) |
N2—C6—C7 | 120.9 (3) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x−1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C10H2O8)(C10H8N2)2] |
Mr | 689.56 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 7.2794 (7), 12.5009 (12), 14.4436 (14) |
β (°) | 104.021 (2) |
V (Å3) | 1275.2 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.73 |
Crystal size (mm) | 0.32 × 0.29 × 0.24 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.582, 0.663 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9055, 2263, 2179 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.087, 1.16 |
No. of reflections | 2263 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.29 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
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In recent years, the design and construction of metal-organic coordination polymers have been extensively studied, due to the crystallographic diversity of these compounds and their potential applications in catalysis, nonlinear optics and gas adsorption (Chen et al., 2003; Eddaoudi et al., 2001; Shi et al., 2003; Stein et al., 1993). In this field, 1,2,4,5-benzenetetracarboxylic acid (H4TCB) is a good bridging ligand and numerous complexes with TCB4− anions have been prepared. The TCB4− anions usually coordinate to metal ions in a µ2-bridging mode (Hu et al., 2003) and occasionally in a µ4-bridging mode (Shi et al., 2001), while in the title complex, [Cu(2,2'-bpy)(TCB)0.5]n, (I), each TCB4− anion binds four CuII ions in tetramonodentate mode. Moreover, it should be pointed out that new complexes are constantly being obtained via different reaction conditions, such as the use of different solvents, synthesis conditions or H-acceptors. \sch
In (I), each CuII cation has a four-coordinated environment, completed by two carboxyl O atoms belonging to two TCB4− anions and two N atoms from one 2,2'-bipy ligand (Fig. 1). The bond lengths around the CuII centres are 1.956 (2) for Cu1—O3, 1.972 (2) for Cu1—O2i, 1.978 (2) for Cu1—N2 and 1.987 (2) Å for Cu1—N1 [symmetry code: (i) −x, 1 − y, −z]. The N2—Cu1—N1, O3—Cu1—O2i, O3—Cu1—N1 and O2i—Cu1—N2 bond angles are in the range 81.80 (10)–98.33 (10)°, which is significantly different from the ideal value.
From these bond angles and lengths, we can best describe the coordination of the CuII cation as a distorted square-planar geometry. Moreover, the coordination mode of the TCB4− anion is similar to that in [Cu2(TCB)(phen)2]n·(H2O)n (Shi et al., 2001): the four carboxylate groups are all deprotonated and coordinate to four CuII cations in a monodentate fashion, forming an infinite one-dimensional ribbon-like double-chain structure with cavities of approximately 4.5 × 6.1 Å along the a axis (Fig. 1). The Cu1···Cu1i and Cu1i···Cu1ii separation distances are 7.931 and 7.279 Å, respectively [symmetry code: (ii) x − 1, y, z]. Furthermore, there are π–π interactions between the aromatic rings of 2,2'-bipy ligands belonging to two adjacent double chains, with a distance of approximately 3.56 Å, resulting in a two-dimensional network structure (Fig. 2).