Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047976/hb2560sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047976/hb2560Isup2.hkl |
CCDC reference: 667123
A mixture of CuCl2.2H2O (0.5 mmol), 1,3-H2BDC (0.5 mmol), L (0.5 mmol), and H2O (500 mmol) was adjusted to pH = 5.8 by addition of aqueous NaOH solution, and heated at 458 K for 2 days. After the mixture was slowly cooled to room temperature, blue crystals of (I) were yielded (29% yield).
All H atoms on C atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
In the presence of secondary ligands, such as 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen), bidentate organic carboxylic acid ligands can construct polymeric structures (Qi et al., 2003). Two coordination positions of metal ions can be occupied by the N atoms from the secondary ligand. The rest of the coordination positions are available for the carboxylate ligands, leading to the formation of a chain structure. We have now selected 1,3-benzenedicarboxylic acid (1,3-H2BDC) as a bridging ligand and 1-ethyl-1H-imidazole (L) as a secondary ligand, generating the title coordination polymer, [Cu(1,3-BDC)(L)2], (I), (Table 1) which is reported here.
In compound (I), the CuII atom (site symmetry 1) is four-coordinated by two carboxylate O atoms from two different 1,3-BDC ligands, and two N atoms from two L ligands in a square-planar coordination environment (Fig. 1). The Cu—O and Cu—N distances are within their normal ranges (Table 1). A very long Cu1—O2 contact of 2.652 (2)Å would lead to a very distorted CuN2O4 octahedron. The complete 1,3-BDC dianion is generated by crystallographic 2-fold symmetry. As shown in Fig. 2, each 1,4-BDC acts as a bis-modentate ligand that binds two CuII atoms, generating a unique chain. Interestingly, the L ligands are attached on both sides of the chains.
For related literature, see: see: Qi et al. (2003).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Cu(C8H4O4)(C5H8N2)2] | F(000) = 868 |
Mr = 419.92 | Dx = 1.468 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 7827 reflections |
a = 15.817 (3) Å | θ = 3.0–27.5° |
b = 7.2249 (14) Å | µ = 1.18 mm−1 |
c = 17.509 (4) Å | T = 293 K |
β = 108.29 (3)° | Block, blue |
V = 1899.9 (7) Å3 | 0.33 × 0.21 × 0.19 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 2178 independent reflections |
Radiation source: rotating anode | 1801 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −18→20 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −9→9 |
Tmin = 0.671, Tmax = 0.798 | l = −22→22 |
9040 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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0642P)2 + 0.6587P] where P = (Fo2 + 2Fc2)/3 |
2178 reflections | (Δ/σ)max = 0.001 |
125 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
[Cu(C8H4O4)(C5H8N2)2] | V = 1899.9 (7) Å3 |
Mr = 419.92 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.817 (3) Å | µ = 1.18 mm−1 |
b = 7.2249 (14) Å | T = 293 K |
c = 17.509 (4) Å | 0.33 × 0.21 × 0.19 mm |
β = 108.29 (3)° |
Rigaku R-AXIS RAPID diffractometer | 2178 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1801 reflections with I > 2σ(I) |
Tmin = 0.671, Tmax = 0.798 | Rint = 0.033 |
9040 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.29 e Å−3 |
2178 reflections | Δρmin = −0.38 e Å−3 |
125 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 | ||
C1 | 1.14471 (14) | −0.2801 (3) | 0.55401 (13) | 0.0411 (5) | |
H1 | 1.1061 | −0.3779 | 0.5332 | 0.049* | |
C2 | 1.2802 (2) | −0.4741 (4) | 0.6142 (2) | 0.0550 (7) | |
H2A | 1.3402 | −0.4590 | 0.6118 | 0.066* | |
H2B | 1.2508 | −0.5680 | 0.5753 | 0.066* | |
C3 | 1.26507 (16) | −0.1258 (4) | 0.61419 (16) | 0.0538 (6) | |
H3 | 1.3238 | −0.0954 | 0.6420 | 0.065* | |
C4 | 1.19657 (18) | −0.0070 (4) | 0.58733 (19) | 0.0528 (7) | |
H4 | 1.2000 | 0.1208 | 0.5937 | 0.063* | |
C5 | 1.02334 (13) | 0.2495 (3) | 0.61465 (13) | 0.0382 (5) | |
C6 | 1.01289 (13) | 0.3540 (3) | 0.68534 (13) | 0.0364 (5) | |
C7 | 1.0000 | 0.2586 (4) | 0.7500 | 0.0328 (6) | |
H7 | 1.0000 | 0.1299 | 0.7500 | 0.039* | |
C8 | 1.01330 (17) | 0.5460 (4) | 0.68607 (19) | 0.0514 (7) | |
H8 | 1.0225 | 0.6109 | 0.6435 | 0.062* | |
C9 | 1.0000 | 0.6412 (5) | 0.7500 | 0.0596 (10) | |
H9 | 1.0000 | 0.7699 | 0.7500 | 0.072* | |
C10 | 1.2842 (2) | −0.5379 (5) | 0.6975 (2) | 0.0709 (9) | |
H10A | 1.3160 | −0.6528 | 0.7095 | 0.106* | |
H10B | 1.2248 | −0.5549 | 0.6998 | 0.106* | |
H10C | 1.3142 | −0.4463 | 0.7363 | 0.106* | |
N1 | 1.12108 (11) | −0.1053 (3) | 0.54914 (11) | 0.0399 (4) | |
N2 | 1.23206 (12) | −0.2991 (3) | 0.59294 (12) | 0.0432 (5) | |
O1 | 0.99755 (10) | 0.0808 (2) | 0.60769 (9) | 0.0419 (4) | |
O2 | 1.05357 (11) | 0.3279 (3) | 0.56545 (10) | 0.0507 (4) | |
Cu1 | 1.0000 | 0.0000 | 0.5000 | 0.03463 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0336 (10) | 0.0512 (14) | 0.0385 (11) | −0.0042 (9) | 0.0114 (9) | 0.0039 (10) |
C2 | 0.0433 (14) | 0.0570 (17) | 0.0656 (18) | 0.0091 (11) | 0.0181 (13) | 0.0106 (12) |
C3 | 0.0326 (11) | 0.0609 (16) | 0.0605 (15) | −0.0072 (11) | 0.0041 (11) | −0.0050 (13) |
C4 | 0.0374 (14) | 0.0526 (16) | 0.0620 (17) | −0.0073 (10) | 0.0064 (13) | −0.0069 (12) |
C5 | 0.0279 (9) | 0.0486 (13) | 0.0346 (10) | 0.0005 (8) | 0.0049 (9) | 0.0071 (9) |
C6 | 0.0232 (9) | 0.0399 (12) | 0.0430 (11) | −0.0007 (8) | 0.0057 (8) | 0.0031 (9) |
C7 | 0.0241 (12) | 0.0329 (15) | 0.0368 (14) | 0.000 | 0.0027 (11) | 0.000 |
C8 | 0.0448 (13) | 0.0417 (13) | 0.0746 (19) | 0.0004 (10) | 0.0287 (13) | 0.0125 (12) |
C9 | 0.060 (2) | 0.0329 (19) | 0.097 (3) | 0.000 | 0.040 (2) | 0.000 |
C10 | 0.0600 (19) | 0.078 (2) | 0.067 (2) | 0.0048 (15) | 0.0088 (16) | 0.0277 (16) |
N1 | 0.0298 (8) | 0.0495 (12) | 0.0382 (9) | −0.0041 (8) | 0.0075 (7) | 0.0015 (8) |
N2 | 0.0311 (9) | 0.0544 (12) | 0.0437 (10) | 0.0017 (8) | 0.0108 (8) | 0.0065 (9) |
O1 | 0.0425 (8) | 0.0473 (10) | 0.0361 (8) | −0.0061 (7) | 0.0127 (7) | −0.0019 (7) |
O2 | 0.0496 (9) | 0.0599 (12) | 0.0455 (9) | −0.0032 (8) | 0.0189 (8) | 0.0111 (8) |
Cu1 | 0.0287 (2) | 0.0414 (2) | 0.0322 (2) | −0.00322 (13) | 0.00727 (16) | 0.00134 (14) |
Cu1—N1 | 1.9881 (18) | C4—H4 | 0.9300 |
Cu1—O1 | 1.9858 (16) | C5—O2 | 1.245 (3) |
Cu1—O1i | 1.9858 (16) | C5—O1 | 1.280 (3) |
Cu1—N1i | 1.9881 (18) | C5—C6 | 1.502 (3) |
C1—N1 | 1.313 (3) | C6—C8 | 1.387 (3) |
C1—N2 | 1.342 (3) | C6—C7 | 1.394 (3) |
C1—H1 | 0.9300 | C7—C6ii | 1.394 (3) |
C2—N2 | 1.462 (3) | C7—H7 | 0.9300 |
C2—C10 | 1.513 (4) | C8—C9 | 1.385 (4) |
C2—H2A | 0.9700 | C8—H8 | 0.9300 |
C2—H2B | 0.9700 | C9—C8ii | 1.385 (4) |
C3—C4 | 1.346 (4) | C9—H9 | 0.9300 |
C3—N2 | 1.362 (3) | C10—H10A | 0.9600 |
C3—H3 | 0.9300 | C10—H10B | 0.9600 |
C4—N1 | 1.370 (3) | C10—H10C | 0.9600 |
O1i—Cu1—O1 | 180.0 | C8—C6—C5 | 120.6 (2) |
O1i—Cu1—N1i | 90.26 (8) | C7—C6—C5 | 120.2 (2) |
O1—Cu1—N1i | 89.74 (8) | C6ii—C7—C6 | 120.8 (3) |
O1i—Cu1—N1 | 89.74 (8) | C6ii—C7—H7 | 119.6 |
O1—Cu1—N1 | 90.26 (8) | C6—C7—H7 | 119.6 |
N1i—Cu1—N1 | 180.0 | C9—C8—C6 | 120.2 (3) |
N1—C1—N2 | 111.0 (2) | C9—C8—H8 | 119.9 |
N1—C1—H1 | 124.5 | C6—C8—H8 | 119.9 |
N2—C1—H1 | 124.5 | C8—C9—C8ii | 120.5 (4) |
N2—C2—C10 | 111.7 (3) | C8—C9—H9 | 119.8 |
N2—C2—H2A | 109.3 | C8ii—C9—H9 | 119.8 |
C10—C2—H2A | 109.3 | C2—C10—H10A | 109.5 |
N2—C2—H2B | 109.3 | C2—C10—H10B | 109.5 |
C10—C2—H2B | 109.3 | H10A—C10—H10B | 109.5 |
H2A—C2—H2B | 107.9 | C2—C10—H10C | 109.5 |
C4—C3—N2 | 107.0 (2) | H10A—C10—H10C | 109.5 |
C4—C3—H3 | 126.5 | H10B—C10—H10C | 109.5 |
N2—C3—H3 | 126.5 | C1—N1—C4 | 106.3 (2) |
C3—C4—N1 | 108.8 (2) | C1—N1—Cu1 | 127.75 (15) |
C3—C4—H4 | 125.6 | C4—N1—Cu1 | 125.94 (18) |
N1—C4—H4 | 125.6 | C1—N2—C3 | 106.9 (2) |
O2—C5—O1 | 123.2 (2) | C1—N2—C2 | 126.0 (2) |
O2—C5—C6 | 120.5 (2) | C3—N2—C2 | 126.9 (2) |
O1—C5—C6 | 116.28 (18) | C5—O1—Cu1 | 105.65 (14) |
C8—C6—C7 | 119.2 (2) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C8H4O4)(C5H8N2)2] |
Mr | 419.92 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 15.817 (3), 7.2249 (14), 17.509 (4) |
β (°) | 108.29 (3) |
V (Å3) | 1899.9 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.18 |
Crystal size (mm) | 0.33 × 0.21 × 0.19 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.671, 0.798 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9040, 2178, 1801 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.112, 1.15 |
No. of reflections | 2178 |
No. of parameters | 125 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.38 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).
In the presence of secondary ligands, such as 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen), bidentate organic carboxylic acid ligands can construct polymeric structures (Qi et al., 2003). Two coordination positions of metal ions can be occupied by the N atoms from the secondary ligand. The rest of the coordination positions are available for the carboxylate ligands, leading to the formation of a chain structure. We have now selected 1,3-benzenedicarboxylic acid (1,3-H2BDC) as a bridging ligand and 1-ethyl-1H-imidazole (L) as a secondary ligand, generating the title coordination polymer, [Cu(1,3-BDC)(L)2], (I), (Table 1) which is reported here.
In compound (I), the CuII atom (site symmetry 1) is four-coordinated by two carboxylate O atoms from two different 1,3-BDC ligands, and two N atoms from two L ligands in a square-planar coordination environment (Fig. 1). The Cu—O and Cu—N distances are within their normal ranges (Table 1). A very long Cu1—O2 contact of 2.652 (2)Å would lead to a very distorted CuN2O4 octahedron. The complete 1,3-BDC dianion is generated by crystallographic 2-fold symmetry. As shown in Fig. 2, each 1,4-BDC acts as a bis-modentate ligand that binds two CuII atoms, generating a unique chain. Interestingly, the L ligands are attached on both sides of the chains.