In the title compound, [Cu(C
10H
4O
8)(C
12H
8N
2)]
n, the Cu
II cation has a four-coordination environment completed by two N atoms from one 1,10-phenanthroline (phen) ligand and two O atoms belonging to two dihydrogen benzene-1,2,4,5-tetracarboxylate anions (H
2TCB
2-). There is a twofold axis passing through the Cu
II cation and the centre of the phen ligand. The [Cu(phen)]
2+ moieties are bridged by H
2TCB
2- anions to form an infinite one-dimensional coordination polymer with a zigzag chain structure along the
c axis. A double-chain structure is formed by hydrogen bonds between adjacent zigzag chains. Furthermore, there are
-
stacking interactions between the phen ligands, with an average distance of 3.64 Å, resulting in a two-dimensional network structure.
Supporting information
CCDC reference: 226101
The title compound was synthesized by a hydrothermal method from a mixture of 1,2,4,5-benzenetetracarboxylic acid (1 mmol, 0.25 g), CuSO4·5H2O (1 mmol, 0.25 g), 1,10-phenanthroline (3 mmol, 0.54 g) and water (20 ml) in a 30 ml Teflon-lined stainless steel reactor. The solution was heated to 433 K for 3 d. After slow cooling of the reaction system to room temperature, blue prism crystals of (I) were collected and washed with distilled water.
The O—H distances were refined subject to O—H = 0.85 (1) Å. The other H atoms were positioned geometrically and allowed to ride on their parent atoms at C—H distances of 0.93 Å with Uiso(H) = 1.2Ueq(C).
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.
catena-Poly[(µ-dihydrogen-1,2,4,5-benzenetetracarboxylato-1:2
κ2O1:
O3) (1,10-phenanthroline-
κ2N,
N')copper(II)]
top
Crystal data top
[Cu(C10H4O8)(C12H8N2)] | F(000) = 1004 |
Mr = 495.88 | Dx = 1.797 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 596 reflections |
a = 10.718 (5) Å | θ = 2.6–21.4° |
b = 14.292 (7) Å | µ = 1.25 mm−1 |
c = 12.192 (6) Å | T = 298 K |
β = 101.119 (7)° | Prism, blue |
V = 1832.5 (16) Å3 | 0.37 × 0.18 × 0.12 mm |
Z = 4 | |
Data collection top
Make Model CCD area-detector diffractometer | 2129 independent reflections |
Radiation source: fine-focus sealed tube | 1567 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ϕ and ω scans | θmax = 27.9°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −14→11 |
Tmin = 0.763, Tmax = 0.860 | k = −16→18 |
5730 measured reflections | l = −16→15 |
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)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0491P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
2129 reflections | Δρmax = 0.49 e Å−3 |
155 parameters | Δρmin = −0.39 e Å−3 |
1 restraint | Extinction correction: SHELXL97 in SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.67 (3) |
Crystal data top
[Cu(C10H4O8)(C12H8N2)] | V = 1832.5 (16) Å3 |
Mr = 495.88 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.718 (5) Å | µ = 1.25 mm−1 |
b = 14.292 (7) Å | T = 298 K |
c = 12.192 (6) Å | 0.37 × 0.18 × 0.12 mm |
β = 101.119 (7)° | |
Data collection top
Make Model CCD area-detector diffractometer | 2129 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1567 reflections with I > 2σ(I) |
Tmin = 0.763, Tmax = 0.860 | Rint = 0.036 |
5730 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.49 e Å−3 |
2129 reflections | Δρmin = −0.39 e Å−3 |
155 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 1.0000 | 0.45912 (3) | 0.2500 | 0.02602 (18) | |
N1 | 1.0429 (2) | 0.35303 (15) | 0.35841 (18) | 0.0240 (5) | |
O1 | 0.92329 (19) | 0.55613 (13) | 0.14804 (16) | 0.0288 (5) | |
O2 | 0.72008 (19) | 0.51031 (14) | 0.09839 (16) | 0.0302 (5) | |
O3 | 0.8091 (2) | 0.88635 (15) | 0.25518 (17) | 0.0405 (6) | |
O4 | 0.6893 (2) | 0.97471 (13) | 0.12813 (16) | 0.0342 (5) | |
C1 | 0.8090 (3) | 0.56568 (18) | 0.0991 (2) | 0.0226 (6) | |
C2 | 0.7801 (2) | 0.65964 (18) | 0.0428 (2) | 0.0203 (6) | |
C3 | 0.7846 (3) | 0.73627 (19) | 0.1128 (2) | 0.0241 (6) | |
H2 | 0.8085 | 0.7272 | 0.1895 | 0.029* | |
C4 | 0.7548 (2) | 0.82625 (18) | 0.0730 (2) | 0.0204 (6) | |
C5 | 0.7493 (3) | 0.90419 (19) | 0.1529 (2) | 0.0228 (6) | |
C6 | 1.0772 (3) | 0.3562 (2) | 0.4686 (2) | 0.0321 (7) | |
H3 | 1.0912 | 0.4140 | 0.5039 | 0.039* | |
C7 | 1.0930 (3) | 0.2748 (2) | 0.5333 (3) | 0.0415 (8) | |
H4 | 1.1157 | 0.2791 | 0.6107 | 0.050* | |
C8 | 1.0755 (3) | 0.1901 (2) | 0.4839 (3) | 0.0435 (9) | |
H5 | 1.0876 | 0.1361 | 0.5272 | 0.052* | |
C9 | 1.0391 (3) | 0.1834 (2) | 0.3678 (3) | 0.0315 (7) | |
C10 | 1.0215 (3) | 0.26828 (19) | 0.3092 (2) | 0.0242 (6) | |
C11 | 1.0181 (3) | 0.0985 (2) | 0.3056 (3) | 0.0398 (8) | |
H6 | 1.0299 | 0.0417 | 0.3433 | 0.048* | |
H1 | 0.796 (4) | 0.9337 (18) | 0.294 (3) | 0.072 (14)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0340 (3) | 0.0154 (3) | 0.0253 (3) | 0.000 | −0.0026 (2) | 0.000 |
N1 | 0.0296 (13) | 0.0174 (12) | 0.0238 (12) | 0.0008 (10) | 0.0017 (10) | 0.0005 (10) |
O1 | 0.0328 (12) | 0.0210 (11) | 0.0289 (11) | 0.0027 (8) | −0.0032 (9) | 0.0056 (8) |
O2 | 0.0389 (12) | 0.0213 (11) | 0.0285 (11) | −0.0059 (9) | 0.0015 (9) | 0.0061 (9) |
O3 | 0.0689 (17) | 0.0268 (13) | 0.0203 (11) | 0.0173 (11) | −0.0052 (10) | −0.0068 (9) |
O4 | 0.0512 (14) | 0.0213 (11) | 0.0265 (11) | 0.0141 (9) | −0.0016 (10) | −0.0023 (8) |
C1 | 0.0383 (17) | 0.0154 (13) | 0.0140 (13) | 0.0046 (12) | 0.0048 (11) | −0.0006 (10) |
C2 | 0.0240 (15) | 0.0155 (13) | 0.0214 (14) | 0.0015 (11) | 0.0043 (11) | 0.0016 (11) |
C3 | 0.0341 (16) | 0.0212 (14) | 0.0158 (13) | 0.0033 (12) | 0.0019 (11) | 0.0018 (11) |
C4 | 0.0253 (15) | 0.0147 (13) | 0.0210 (14) | 0.0019 (11) | 0.0042 (11) | −0.0001 (10) |
C5 | 0.0305 (16) | 0.0186 (14) | 0.0193 (14) | −0.0025 (11) | 0.0047 (11) | 0.0004 (11) |
C6 | 0.0361 (18) | 0.0331 (17) | 0.0257 (16) | 0.0002 (14) | 0.0026 (13) | −0.0009 (13) |
C7 | 0.049 (2) | 0.047 (2) | 0.0255 (17) | 0.0023 (16) | 0.0007 (15) | 0.0086 (15) |
C8 | 0.049 (2) | 0.038 (2) | 0.042 (2) | 0.0050 (16) | 0.0031 (16) | 0.0199 (16) |
C9 | 0.0313 (17) | 0.0209 (15) | 0.0432 (19) | 0.0042 (12) | 0.0095 (14) | 0.0082 (13) |
C10 | 0.0252 (15) | 0.0190 (15) | 0.0284 (15) | 0.0006 (11) | 0.0052 (12) | 0.0010 (11) |
C11 | 0.043 (2) | 0.0162 (15) | 0.062 (2) | 0.0027 (13) | 0.0147 (18) | 0.0072 (14) |
Geometric parameters (Å, º) top
Cu1—O1i | 1.9363 (19) | C3—H2 | 0.9300 |
Cu1—O1 | 1.9363 (19) | C4—C2ii | 1.403 (4) |
Cu1—N1i | 2.006 (2) | C4—C5 | 1.489 (4) |
Cu1—N1 | 2.006 (2) | C6—C7 | 1.397 (4) |
N1—C6 | 1.324 (3) | C6—H3 | 0.9300 |
N1—C10 | 1.352 (3) | C7—C8 | 1.349 (5) |
O1—C1 | 1.262 (3) | C7—H4 | 0.9300 |
O2—C1 | 1.238 (3) | C8—C9 | 1.398 (4) |
O3—C5 | 1.313 (3) | C8—H5 | 0.9300 |
O3—H1 | 0.85 (3) | C9—C10 | 1.402 (4) |
O4—C5 | 1.202 (3) | C9—C11 | 1.426 (4) |
C1—C2 | 1.513 (4) | C10—C10i | 1.427 (5) |
C2—C3 | 1.383 (4) | C11—C11i | 1.336 (6) |
C2—C4ii | 1.403 (4) | C11—H6 | 0.9300 |
C3—C4 | 1.390 (4) | | |
| | | |
O1i—Cu1—O1 | 88.55 (12) | C3—C4—C5 | 119.9 (2) |
O1i—Cu1—N1i | 168.32 (9) | O4—C5—O3 | 122.8 (3) |
O1—Cu1—N1i | 95.93 (9) | O4—C5—C4 | 123.4 (2) |
O1i—Cu1—N1 | 95.93 (9) | O3—C5—C4 | 113.7 (2) |
O1—Cu1—N1 | 168.32 (9) | N1—C6—C7 | 121.7 (3) |
N1i—Cu1—N1 | 81.78 (13) | N1—C6—H3 | 119.2 |
C6—N1—C10 | 118.1 (2) | C7—C6—H3 | 119.2 |
C6—N1—Cu1 | 128.8 (2) | C8—C7—C6 | 120.3 (3) |
C10—N1—Cu1 | 112.77 (18) | C8—C7—H4 | 119.9 |
C1—O1—Cu1 | 129.37 (18) | C6—C7—H4 | 119.9 |
C5—O3—H1 | 106 (3) | C7—C8—C9 | 120.1 (3) |
O2—C1—O1 | 127.6 (2) | C7—C8—H5 | 120.0 |
O2—C1—C2 | 118.3 (2) | C9—C8—H5 | 120.0 |
O1—C1—C2 | 113.9 (2) | C10—C9—C11 | 118.3 (3) |
C3—C2—C4ii | 118.5 (2) | C10—C9—C8 | 116.2 (3) |
C3—C2—C1 | 116.3 (2) | C11—C9—C8 | 125.6 (3) |
C4ii—C2—C1 | 125.1 (2) | C9—C10—N1 | 123.7 (3) |
C2—C3—C4 | 122.6 (3) | C9—C10—C10i | 120.04 (17) |
C2—C3—H2 | 118.7 | N1—C10—C10i | 116.30 (15) |
C4—C3—H2 | 118.7 | C11i—C11—C9 | 121.65 (18) |
C2ii—C4—C3 | 118.9 (2) | C11i—C11—H6 | 119.2 |
C2ii—C4—C5 | 121.0 (2) | C9—C11—H6 | 119.2 |
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) −x+3/2, −y+3/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O2iii | 0.85 (3) | 1.74 (3) | 2.577 (3) | 165 (4) |
Symmetry code: (iii) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Cu(C10H4O8)(C12H8N2)] |
Mr | 495.88 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.718 (5), 14.292 (7), 12.192 (6) |
β (°) | 101.119 (7) |
V (Å3) | 1832.5 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.37 × 0.18 × 0.12 |
|
Data collection |
Diffractometer | Make Model CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.763, 0.860 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5730, 2129, 1567 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.657 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.100, 0.96 |
No. of reflections | 2129 |
No. of parameters | 155 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.49, −0.39 |
Selected geometric parameters (Å, º) topCu1—O1 | 1.9363 (19) | Cu1—N1 | 2.006 (2) |
| | | |
O1i—Cu1—O1 | 88.55 (12) | O1—Cu1—N1 | 168.32 (9) |
O1—Cu1—N1i | 95.93 (9) | N1i—Cu1—N1 | 81.78 (13) |
Symmetry code: (i) −x+2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O2ii | 0.85 (3) | 1.74 (3) | 2.577 (3) | 165 (4) |
Symmetry code: (ii) −x+3/2, y+1/2, −z+1/2. |
In recent years, intense research activity has been directed toward the assembly of coordination polymers, due to their potential application in gas adsorption, catalysis and optoelectronic devices (Fujita et al., 1994; Sato et al., 1996). The key step in the design of coordination polymers is to select suitable multidentate bridging ligands and spacers. Accordingly, 1,2,4,5-benzetetracarboxylic acid (H4TCB) has a very versatile coordination behaviour, since it can form bridges between metallic centres, generating varied and sometimes surprising molecular architectures. Therefore, numerous complexes with the H4TCB ligand have been extensively studied (Cheng et al., 2001; Chu et al., 2001; Wang et al., 2000), while the construction of complexes from H4TCB, 1,10-phenanthroline (phen) and CuII building blocks is still limited (Shi et al., 2001; Zou et al., 1998). To the best of our knowledge, only a one-dimensional double-chain polymer, [Cu2(TCB)(phen)2]n.nH2O has been reported to date (Shi et al., 2001). Here, we report the hydrothermal synthesis and structure of the title one-dimensional zigzag chain polymer, [Cu(phen)(H2TCB)]n, (I). It is entirely possible to prepare [Cu2(TCB)(phen)2]and [Cu(phen)(H2TCB)] separately. The compositions of the complexes can be controlled by using different molar ratios of the reactants and different H-atom receptors, such as phen alone, phen and NaOH, etc. \sch
In (I), the CuII cation is coordinated by two N atoms from one phen ligand and two O atoms from two H2TCB2−anions (Fig. 1 and Table 1). There is a twofold axis passing through the CuII cation and the centre of the phen ligand. An infinite one-dimensional coordination polymer with a zigzag chain structure is formed by the CuII cations, the µ2-bridging H2TCB2− anions and the terminal phen ligands.
The Cu—O bond lengths are 1.9363 (19) Å, which is within the normal range for Cu—Ocarboxylate distances (1.927–2.010 Å; Zou et al., 1998), while the Cu—N distance of 2.006 (2) Å is longer than that in [Cu2(TCB)(phen)2]n.nH2O [1.984 (4) Å]. The bond angles around the CuII cation are characteristic of a distorted square-planar geometry.
An O3—H1···O2(3/2 − x, 1/2 + y, 1/2 − z) hydrogen bond (Table 2) is formed between neighbouring one-dimensional zigzag chains. This leads to a one-dimensional double-chain structure and the two chains interweave with each other to produce grid voids (Fig. 2). Furthermore, there are π–π stacking interactions between the aromatic rings of the phen ligands and the H2TCB2− anions of two neighbouring chains, with an average distance of 3.64 Å, which is different from the interactions between phen ligands observed in [Cu2(TCB)(phen)2]n.nH2O, resulting in a two-dimensional network structure.