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In the title compound, [Cu(C10H4O8)(C12H8N2)]n, the CuII 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 (H2TCB2-). There is a twofold axis passing through the CuII cation and the centre of the phen ligand. The [Cu(phen)]2+ moieties are bridged by H2TCB2- 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 [pi]-[pi] stacking inter­actions between the phen ligands, with an average distance of 3.64 Å, resulting in a two-dimensional network structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103021097/ob1146sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103021097/ob1146Isup2.hkl
Contains datablock I

CCDC reference: 226101

Comment top

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 ππ 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.

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The coordination environment of the CuII cation in (I) with the atom-numbering scheme, showing displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. The double-chain structure with grid voids in (I).
catena-Poly[(µ-dihydrogen-1,2,4,5-benzenetetracarboxylato-1:2κ2O1:O3) (1,10-phenanthroline-κ2N,N')copper(II)] top
Crystal data top
[Cu(C10H4O8)(C12H8N2)]F(000) = 1004
Mr = 495.88Dx = 1.797 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 596 reflections
a = 10.718 (5) Åθ = 2.6–21.4°
b = 14.292 (7) ŵ = 1.25 mm1
c = 12.192 (6) ÅT = 298 K
β = 101.119 (7)°Prism, blue
V = 1832.5 (16) Å30.37 × 0.18 × 0.12 mm
Z = 4
Data collection top
Make Model CCD area-detector
diffractometer
2129 independent reflections
Radiation source: fine-focus sealed tube1567 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ϕ and ω scansθmax = 27.9°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1411
Tmin = 0.763, Tmax = 0.860k = 1618
5730 measured reflectionsl = 1615
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H 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 reflectionsΔρmax = 0.49 e Å3
155 parametersΔρmin = 0.39 e Å3
1 restraintExtinction correction: SHELXL97 in SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.67 (3)
Crystal data top
[Cu(C10H4O8)(C12H8N2)]V = 1832.5 (16) Å3
Mr = 495.88Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.718 (5) ŵ = 1.25 mm1
b = 14.292 (7) ÅT = 298 K
c = 12.192 (6) Å0.37 × 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 = 0.860Rint = 0.036
5730 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0411 restraint
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.49 e Å3
2129 reflectionsΔρmin = 0.39 e Å3
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
xyzUiso*/Ueq
Cu11.00000.45912 (3)0.25000.02602 (18)
N11.0429 (2)0.35303 (15)0.35841 (18)0.0240 (5)
O10.92329 (19)0.55613 (13)0.14804 (16)0.0288 (5)
O20.72008 (19)0.51031 (14)0.09839 (16)0.0302 (5)
O30.8091 (2)0.88635 (15)0.25518 (17)0.0405 (6)
O40.6893 (2)0.97471 (13)0.12813 (16)0.0342 (5)
C10.8090 (3)0.56568 (18)0.0991 (2)0.0226 (6)
C20.7801 (2)0.65964 (18)0.0428 (2)0.0203 (6)
C30.7846 (3)0.73627 (19)0.1128 (2)0.0241 (6)
H20.80850.72720.18950.029*
C40.7548 (2)0.82625 (18)0.0730 (2)0.0204 (6)
C50.7493 (3)0.90419 (19)0.1529 (2)0.0228 (6)
C61.0772 (3)0.3562 (2)0.4686 (2)0.0321 (7)
H31.09120.41400.50390.039*
C71.0930 (3)0.2748 (2)0.5333 (3)0.0415 (8)
H41.11570.27910.61070.050*
C81.0755 (3)0.1901 (2)0.4839 (3)0.0435 (9)
H51.08760.13610.52720.052*
C91.0391 (3)0.1834 (2)0.3678 (3)0.0315 (7)
C101.0215 (3)0.26828 (19)0.3092 (2)0.0242 (6)
C111.0181 (3)0.0985 (2)0.3056 (3)0.0398 (8)
H61.02990.04170.34330.048*
H10.796 (4)0.9337 (18)0.294 (3)0.072 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0340 (3)0.0154 (3)0.0253 (3)0.0000.0026 (2)0.000
N10.0296 (13)0.0174 (12)0.0238 (12)0.0008 (10)0.0017 (10)0.0005 (10)
O10.0328 (12)0.0210 (11)0.0289 (11)0.0027 (8)0.0032 (9)0.0056 (8)
O20.0389 (12)0.0213 (11)0.0285 (11)0.0059 (9)0.0015 (9)0.0061 (9)
O30.0689 (17)0.0268 (13)0.0203 (11)0.0173 (11)0.0052 (10)0.0068 (9)
O40.0512 (14)0.0213 (11)0.0265 (11)0.0141 (9)0.0016 (10)0.0023 (8)
C10.0383 (17)0.0154 (13)0.0140 (13)0.0046 (12)0.0048 (11)0.0006 (10)
C20.0240 (15)0.0155 (13)0.0214 (14)0.0015 (11)0.0043 (11)0.0016 (11)
C30.0341 (16)0.0212 (14)0.0158 (13)0.0033 (12)0.0019 (11)0.0018 (11)
C40.0253 (15)0.0147 (13)0.0210 (14)0.0019 (11)0.0042 (11)0.0001 (10)
C50.0305 (16)0.0186 (14)0.0193 (14)0.0025 (11)0.0047 (11)0.0004 (11)
C60.0361 (18)0.0331 (17)0.0257 (16)0.0002 (14)0.0026 (13)0.0009 (13)
C70.049 (2)0.047 (2)0.0255 (17)0.0023 (16)0.0007 (15)0.0086 (15)
C80.049 (2)0.038 (2)0.042 (2)0.0050 (16)0.0031 (16)0.0199 (16)
C90.0313 (17)0.0209 (15)0.0432 (19)0.0042 (12)0.0095 (14)0.0082 (13)
C100.0252 (15)0.0190 (15)0.0284 (15)0.0006 (11)0.0052 (12)0.0010 (11)
C110.043 (2)0.0162 (15)0.062 (2)0.0027 (13)0.0147 (18)0.0072 (14)
Geometric parameters (Å, º) top
Cu1—O1i1.9363 (19)C3—H20.9300
Cu1—O11.9363 (19)C4—C2ii1.403 (4)
Cu1—N1i2.006 (2)C4—C51.489 (4)
Cu1—N12.006 (2)C6—C71.397 (4)
N1—C61.324 (3)C6—H30.9300
N1—C101.352 (3)C7—C81.349 (5)
O1—C11.262 (3)C7—H40.9300
O2—C11.238 (3)C8—C91.398 (4)
O3—C51.313 (3)C8—H50.9300
O3—H10.85 (3)C9—C101.402 (4)
O4—C51.202 (3)C9—C111.426 (4)
C1—C21.513 (4)C10—C10i1.427 (5)
C2—C31.383 (4)C11—C11i1.336 (6)
C2—C4ii1.403 (4)C11—H60.9300
C3—C41.390 (4)
O1i—Cu1—O188.55 (12)C3—C4—C5119.9 (2)
O1i—Cu1—N1i168.32 (9)O4—C5—O3122.8 (3)
O1—Cu1—N1i95.93 (9)O4—C5—C4123.4 (2)
O1i—Cu1—N195.93 (9)O3—C5—C4113.7 (2)
O1—Cu1—N1168.32 (9)N1—C6—C7121.7 (3)
N1i—Cu1—N181.78 (13)N1—C6—H3119.2
C6—N1—C10118.1 (2)C7—C6—H3119.2
C6—N1—Cu1128.8 (2)C8—C7—C6120.3 (3)
C10—N1—Cu1112.77 (18)C8—C7—H4119.9
C1—O1—Cu1129.37 (18)C6—C7—H4119.9
C5—O3—H1106 (3)C7—C8—C9120.1 (3)
O2—C1—O1127.6 (2)C7—C8—H5120.0
O2—C1—C2118.3 (2)C9—C8—H5120.0
O1—C1—C2113.9 (2)C10—C9—C11118.3 (3)
C3—C2—C4ii118.5 (2)C10—C9—C8116.2 (3)
C3—C2—C1116.3 (2)C11—C9—C8125.6 (3)
C4ii—C2—C1125.1 (2)C9—C10—N1123.7 (3)
C2—C3—C4122.6 (3)C9—C10—C10i120.04 (17)
C2—C3—H2118.7N1—C10—C10i116.30 (15)
C4—C3—H2118.7C11i—C11—C9121.65 (18)
C2ii—C4—C3118.9 (2)C11i—C11—H6119.2
C2ii—C4—C5121.0 (2)C9—C11—H6119.2
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···AD—HH···AD···AD—H···A
O3—H1···O2iii0.85 (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)]
Mr495.88
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)10.718 (5), 14.292 (7), 12.192 (6)
β (°) 101.119 (7)
V3)1832.5 (16)
Z4
Radiation typeMo Kα
µ (mm1)1.25
Crystal size (mm)0.37 × 0.18 × 0.12
Data collection
DiffractometerMake Model CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.763, 0.860
No. of measured, independent and
observed [I > 2σ(I)] reflections
5730, 2129, 1567
Rint0.036
(sin θ/λ)max1)0.657
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.100, 0.96
No. of reflections2129
No. of parameters155
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.49, 0.39

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.

Selected geometric parameters (Å, º) top
Cu1—O11.9363 (19)Cu1—N12.006 (2)
O1i—Cu1—O188.55 (12)O1—Cu1—N1168.32 (9)
O1—Cu1—N1i95.93 (9)N1i—Cu1—N181.78 (13)
Symmetry code: (i) x+2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H1···O2ii0.85 (3)1.74 (3)2.577 (3)165 (4)
Symmetry code: (ii) x+3/2, y+1/2, z+1/2.
 

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