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In the title compound, catena-poly­[[[tri­aqua­copper(II)]-μ-acetyl­enedi­carboxyl­ato-κ2O:O′′] hydrate], {[Cu(C4O4)(H2O)3]·H2O}n, the CuII ion is coordinated by two monodentate carboxyl­ate groups in trans positions and three water mol­ecules, thus forming a fivefold coordination polyhedron that can be described as a distorted square pyramid. All atoms are located on general sites. The polyhedra are connected by bifunctional acetyl­ene­di­carboxyl­ate ligands, to form almost linear chains parallel to [001]. Hydro­gen bonds involving the non-coordinated water mol­ecule connect these chains to form a three-dimensional framework.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103003469/jz1547sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103003469/jz1547Isup2.hkl
Contains datablock I

CCDC reference: 211728

Comment top

During our studies of coordination polymers of the acetylenedicarboxylate dianion, C2(COO)22- (Hohn et al., 2002; Ruschewitz & Pantenburg, 2002), blue crystals of the title compound, (I), were obtained, and its crystal structure is presented here.

The structure of (I) comprises fivefold coordination polyhedra at the CuII ions, which are linked by the bifunctional acetylenedicarboxylate ligands to form almost linear chains. The coordination polyhedron around the CuII ion, which can be described as a distorted square pyramid, is formed by two unidentate carboxylate groups in trans positions and three water molecules (Fig. 1). The Cu—O distances range between 1.940 (2) and 2.296 (2) Å (Table 1). As the latter Cu—O distance (Cu1—O6) is about 0.3 Å longer than the second longest Cu—O distance [Cu1—O41i, 1.968 (1) Å] the Cu coordination can alternatively be described as a slightly distorted square planar coordination, with an additional water ligand weakly bonded in an axial position. This coordination of the CuII ion is similar to that found in Cu2(CH3COO)4·2H2O (Cu—O = 1.96–1.99 Å 4×, Cu—OH2 = 2.20 Å; van Niekerk & Schoening, 1953). In contrast to the latter compound, however, where a short Cu—Cu distance (2.64 Å) extends the CuO5 polyhedron to a distorted octahedron, no short Cu—Cu distances are found in (I) [the shortest are Cu1—Cu1iii = 5.246 (12) Å 2×].

The C—O bond distances of the coordinating O atoms are significantly longer [C1—O11 = 1.273 (2) and C4—O41 = 1.270 (3) Å] than the C—O distances of the non-coordinating O atoms [C1—O12 = 1.231 (3) and C4—O42 = 1.233 (2) Å], which is consistent with C—O bond's slightly higher Ueq values and indicates that C—O is more characteristic of a double-bond. The C—C distances in the acetylenedicarboxylate dianion are as expected (Table 1): C1—C2 = 1.472 (3) and C3—C4 = 1.469 (3) Å for C—C single bonds and C2—C3 = 1.191 (3) Å for a C—C triple bond. The dianion is almost linear [C1—C2—C3 178.7 (2) and C2—C3—C4 178.1 (2)°], but in contrast to {Cd[C2(COO)2](H2O)3}·(H2O) (Ruschewitz & Pantenburg, 2002), the carboxylate groups of the anion are not coplanar. The torsion angles are 26.6 (2)° and 25.8 (3)°.

The CuO5 polyhedra are linked by the bifunctional carboxylates to form almost linear chains running parallel to [001] (Fig. 2). A linear polymeric chain structure was also found in {Co[C2(COO)2](H2O)4}.2 H2O (Pantenburg & Ruschewitz, 2002), which is another example of a coordination polymer of acetylenedicarboxylate that crystallizes in a chain structure with CoII coordinated octahedrally by two monodentate carboxylate groups in trans positions and four water molecules. However, in {Cd[C2(COO)2](H2O)3}·(H2O) (Ruschewitz & Pantenburg, 2002), a polymeric zigzag chain is formed.

In all compounds the chains are connected by hydrogen bonds, which include additional water molecules. In (I) the shortest hydrogen bonds [O···O = 2.694 (3)–2.742 (3) Å] connect the polymeric chains to layers parallel to (100). These layers are connected by slightly longer hydrogen bonds [O···O = 2.759 (2)–2.771 (2) Å] to form a three-dimensional network.

Experimental top

CuCl2.2 H2O (0.85 g, 5 mmol) and acetylenedicarboxylic acid (0.57 g, 5 mmol) were dissolved in deionized water (20 ml). After slow evaporation, blue crystals of (I) formed at room temperature. They were filtered off and immediately sealed in a capillary, as the crystals decompose slowly in air by forming a black shock-sensitive solid, which is amorphous to X-rays. This residue is probably Cu2C2 (McCormick et al., 2001). No decomposition of the single-crystal was observed during the X-ray analysis.

Refinement top

H atoms were identified from difference Fourier maps and refined freely.

Compound (I) crystallizes in a monoclinic unit cell with β close to 90°. A symmetry check using PLATON suggests a smaller orthorhombic unit cell with a short c axis (c' = 1/2c). However, inspection of the diffraction data and the refinement results (see Fig. 2) confirms that the larger monoclinic unit cell is correct.

Structure description top

During our studies of coordination polymers of the acetylenedicarboxylate dianion, C2(COO)22- (Hohn et al., 2002; Ruschewitz & Pantenburg, 2002), blue crystals of the title compound, (I), were obtained, and its crystal structure is presented here.

The structure of (I) comprises fivefold coordination polyhedra at the CuII ions, which are linked by the bifunctional acetylenedicarboxylate ligands to form almost linear chains. The coordination polyhedron around the CuII ion, which can be described as a distorted square pyramid, is formed by two unidentate carboxylate groups in trans positions and three water molecules (Fig. 1). The Cu—O distances range between 1.940 (2) and 2.296 (2) Å (Table 1). As the latter Cu—O distance (Cu1—O6) is about 0.3 Å longer than the second longest Cu—O distance [Cu1—O41i, 1.968 (1) Å] the Cu coordination can alternatively be described as a slightly distorted square planar coordination, with an additional water ligand weakly bonded in an axial position. This coordination of the CuII ion is similar to that found in Cu2(CH3COO)4·2H2O (Cu—O = 1.96–1.99 Å 4×, Cu—OH2 = 2.20 Å; van Niekerk & Schoening, 1953). In contrast to the latter compound, however, where a short Cu—Cu distance (2.64 Å) extends the CuO5 polyhedron to a distorted octahedron, no short Cu—Cu distances are found in (I) [the shortest are Cu1—Cu1iii = 5.246 (12) Å 2×].

The C—O bond distances of the coordinating O atoms are significantly longer [C1—O11 = 1.273 (2) and C4—O41 = 1.270 (3) Å] than the C—O distances of the non-coordinating O atoms [C1—O12 = 1.231 (3) and C4—O42 = 1.233 (2) Å], which is consistent with C—O bond's slightly higher Ueq values and indicates that C—O is more characteristic of a double-bond. The C—C distances in the acetylenedicarboxylate dianion are as expected (Table 1): C1—C2 = 1.472 (3) and C3—C4 = 1.469 (3) Å for C—C single bonds and C2—C3 = 1.191 (3) Å for a C—C triple bond. The dianion is almost linear [C1—C2—C3 178.7 (2) and C2—C3—C4 178.1 (2)°], but in contrast to {Cd[C2(COO)2](H2O)3}·(H2O) (Ruschewitz & Pantenburg, 2002), the carboxylate groups of the anion are not coplanar. The torsion angles are 26.6 (2)° and 25.8 (3)°.

The CuO5 polyhedra are linked by the bifunctional carboxylates to form almost linear chains running parallel to [001] (Fig. 2). A linear polymeric chain structure was also found in {Co[C2(COO)2](H2O)4}.2 H2O (Pantenburg & Ruschewitz, 2002), which is another example of a coordination polymer of acetylenedicarboxylate that crystallizes in a chain structure with CoII coordinated octahedrally by two monodentate carboxylate groups in trans positions and four water molecules. However, in {Cd[C2(COO)2](H2O)3}·(H2O) (Ruschewitz & Pantenburg, 2002), a polymeric zigzag chain is formed.

In all compounds the chains are connected by hydrogen bonds, which include additional water molecules. In (I) the shortest hydrogen bonds [O···O = 2.694 (3)–2.742 (3) Å] connect the polymeric chains to layers parallel to (100). These layers are connected by slightly longer hydrogen bonds [O···O = 2.759 (2)–2.771 (2) Å] to form a three-dimensional network.

Computing details top

Data collection: X-AREA V1.15 (Stoe & Cie, 2001); cell refinement: X-AREA V1.15 (Stoe & Cie, 2001); data reduction: X-AREA V1.15 (Stoe & Cie, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND V2.1e (Brandenburg, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-numbering scheme of the asymmetric unit. Displacement ellipsoids are shown at the 50% probability level and H-atom radii are arbitrary.
[Figure 2] Fig. 2. The crystal packing of (I), showing two polymeric chains connected by hydrogen bonds, which involve the non-coordinated H81/O8/H82 water molecule. Three of the four hydrogen bonds around O8 are shown, namely O5···O8, O7···O8 and O42···O8 (see Table 2). H atoms have been omitted for clarity.
catena-poly[[[triaquacopper(II)]-µ-acetylenedicarboxylato-κ2O:O''] hydrate] top
Crystal data top
[Cu(C4O4)(H2O)3]·H2OF(000) = 500
Mr = 247.64Dx = 1.936 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12049 reflections
a = 6.5261 (8) Åθ = 1.9–35.3°
b = 7.0683 (9) ŵ = 2.59 mm1
c = 18.417 (2) ÅT = 293 K
β = 90.418 (10)°Polyhedron, blue
V = 849.54 (18) Å30.2 × 0.1 × 0.1 mm
Z = 4
Data collection top
STOE IPDS II
diffractometer
2468 independent reflections
Radiation source: fine-focus sealed tube1766 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.066
Detector resolution: not measured pixels mm-1θmax = 30.0°, θmin = 3.1°
oscillation scansh = 99
Absorption correction: numerical
The absorption correction (X-RED V1.22; Stoe & Cie, 2001) was performed after optimizing the crystal shape using X-SHAPE V1.06 (Stoe & Cie, 1999).
k = 99
Tmin = 0.296, Tmax = 0.541l = 2525
23355 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029All H-atom parameters refined
wR(F2) = 0.069 w = 1/[σ2(Fo2) + (0.0406P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.93(Δ/σ)max < 0.001
2468 reflectionsΔρmax = 0.38 e Å3
151 parametersΔρmin = 0.42 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0072 (8)
Crystal data top
[Cu(C4O4)(H2O)3]·H2OV = 849.54 (18) Å3
Mr = 247.64Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.5261 (8) ŵ = 2.59 mm1
b = 7.0683 (9) ÅT = 293 K
c = 18.417 (2) Å0.2 × 0.1 × 0.1 mm
β = 90.418 (10)°
Data collection top
STOE IPDS II
diffractometer
2468 independent reflections
Absorption correction: numerical
The absorption correction (X-RED V1.22; Stoe & Cie, 2001) was performed after optimizing the crystal shape using X-SHAPE V1.06 (Stoe & Cie, 1999).
1766 reflections with I > 2σ(I)
Tmin = 0.296, Tmax = 0.541Rint = 0.066
23355 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.069All H-atom parameters refined
S = 0.93Δρmax = 0.38 e Å3
2468 reflectionsΔρmin = 0.42 e Å3
151 parameters
Special details top

Experimental. A suitable single-crystal was carefully selected under a polarizing microscope and mounted in a glass capillary. The scattering intensities were collected on an imaging-plate diffractometer (IPDS II, Stoe & Cie) equipped with a fine-focus sealed-tube X-ray source (Mo Kα, λ = 0.71073 Å) operating at 50 kV and 40 mA. Intensity data for {Cu[C2(COO)2](H2O)3}·(H2O) were collected at 293 K by ω scans in 250 frames (0 < ω < 180°; Ψ = O°, 0 < ω < 180°; Ψ = 45°, 0 < ω < 140°; Ψ = 90°, Δω = 2°, exposure time 2 min) in the 2 Θ range 3.8–70.5°. Structure solution and refinement were carried out using the programs SIR92 (Altomare et al., 1993) and SHELXL97 (Sheldrick, 1997). H atom positions for {Cu[C2(COO)2](H2O)3}·(H2O) were taken from difference Fourier maps at the end of the refinement and refined isotropically without constraints. The last cycles of refinement included atomic positions for all atoms, anisotropic parameters for all non-H atoms and isotropic thermal parameters for all H atoms. The refinement was based on F2 for ALL reflections.

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
Cu10.35202 (3)0.25934 (4)0.15837 (1)0.01935 (9)
C10.1754 (3)0.2286 (3)0.29617 (10)0.0223 (4)
O110.3372 (2)0.2823 (2)0.26402 (8)0.0261 (3)
O120.0193 (3)0.1676 (3)0.26643 (9)0.0329 (4)
C20.1808 (3)0.2440 (4)0.37589 (11)0.0277 (4)
C30.1831 (3)0.2530 (4)0.44047 (11)0.0279 (4)
C40.1792 (3)0.2608 (4)0.52017 (10)0.0251 (4)
O410.3527 (2)0.2503 (3)0.55160 (7)0.0260 (3)
O420.0133 (3)0.2767 (4)0.55115 (9)0.0482 (6)
O50.3597 (3)0.0174 (2)0.16304 (11)0.0293 (4)
H510.451 (6)0.062 (5)0.184 (2)0.046 (10)*
H520.343 (5)0.065 (4)0.128 (2)0.034 (9)*
O60.7021 (3)0.2893 (3)0.16405 (12)0.0412 (5)
H610.771 (7)0.260 (6)0.134 (3)0.075 (14)*
H620.771 (9)0.265 (7)0.205 (3)0.104 (18)*
O70.2909 (3)0.5277 (3)0.15423 (11)0.0337 (4)
H710.194 (6)0.558 (6)0.177 (2)0.065 (12)*
H720.293 (6)0.578 (5)0.117 (2)0.047 (10)*
O80.3159 (3)0.7661 (3)0.04038 (9)0.0316 (4)
H810.207 (7)0.767 (6)0.014 (2)0.071 (13)*
H830.389 (6)0.763 (5)0.018 (2)0.046 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0206 (1)0.0262 (1)0.0113 (1)0.0014 (1)0.0008 (1)0.0003 (1)
C10.0258 (9)0.0281 (10)0.0130 (7)0.0012 (8)0.0013 (7)0.0001 (7)
O110.0292 (7)0.0373 (9)0.0119 (6)0.0071 (6)0.0023 (5)0.0021 (6)
O120.0279 (8)0.0515 (10)0.0193 (8)0.0074 (7)0.0019 (6)0.0030 (7)
C20.0249 (9)0.0419 (11)0.0162 (8)0.0056 (10)0.0019 (7)0.0010 (10)
C30.0220 (8)0.0463 (11)0.0154 (8)0.0001 (10)0.0005 (7)0.0004 (10)
C40.0243 (8)0.0391 (11)0.0118 (7)0.0018 (9)0.0013 (6)0.0010 (9)
O410.0231 (6)0.0427 (8)0.0122 (6)0.0029 (7)0.0007 (5)0.0008 (7)
O420.0248 (8)0.1011 (18)0.0186 (7)0.0044 (10)0.0046 (6)0.0010 (10)
O50.0374 (10)0.0277 (7)0.0226 (9)0.0052 (7)0.0060 (7)0.0018 (7)
O60.0226 (8)0.0723 (15)0.0287 (9)0.0014 (8)0.0003 (7)0.0035 (9)
O70.0450 (11)0.0305 (8)0.0258 (9)0.0101 (7)0.0101 (8)0.0049 (7)
O80.0229 (7)0.0503 (10)0.0216 (7)0.0001 (9)0.0032 (6)0.0004 (8)
Geometric parameters (Å, º) top
Cu1—O71.9396 (18)C4—O421.233 (2)
Cu1—O111.9555 (15)C4—O411.270 (3)
Cu1—O51.9588 (17)O5—H510.78 (4)
Cu1—O41i1.9677 (14)O5—H520.73 (4)
Cu1—O62.2961 (19)O6—H610.75 (5)
C1—O121.231 (3)O6—H620.89 (6)
C1—O111.273 (2)O7—H710.79 (4)
C1—C21.472 (3)O7—H720.77 (4)
C2—C31.191 (3)O8—H810.85 (5)
C3—C41.469 (3)O8—H830.63 (4)
O7—Cu1—O1186.92 (8)O12—C1—C2118.93 (18)
O7—Cu1—O5169.60 (10)O11—C1—C2115.31 (18)
O11—Cu1—O592.34 (7)C3—C2—C1178.6 (3)
O7—Cu1—O41i89.79 (8)C2—C3—C4178.0 (2)
O11—Cu1—O41i176.12 (7)O42—C4—O41125.28 (19)
O5—Cu1—O41i90.52 (8)O42—C4—C3119.17 (19)
O7—Cu1—O696.66 (9)O41—C4—C3115.55 (17)
O11—Cu1—O690.19 (7)H51—O5—H52111 (4)
O5—Cu1—O693.72 (9)H61—O6—H62106 (5)
O41i—Cu1—O692.24 (7)H71—O7—H72112 (4)
O12—C1—O11125.76 (19)H81—O8—H83106 (4)
Symmetry code: (i) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H51···O11ii0.78 (4)2.00 (4)2.771 (2)171 (4)
O5—H52···O8iii0.73 (4)2.02 (4)2.742 (3)170 (3)
O6—H61···O42iv0.75 (5)2.22 (5)2.954 (3)168 (5)
O6—H62···O12v0.89 (6)2.08 (6)2.919 (3)155 (5)
O7—H71···O12vi0.79 (4)1.91 (4)2.694 (3)171 (4)
O7—H72···O80.77 (4)1.95 (4)2.696 (3)164 (4)
O8—H81···O42vi0.85 (5)1.87 (5)2.722 (3)174 (4)
O8—H83···O41vii0.63 (4)2.13 (4)2.759 (2)177 (4)
Symmetry codes: (ii) x+1, y1/2, z+1/2; (iii) x, y1, z; (iv) x+1, y+1/2, z1/2; (v) x+1, y, z; (vi) x, y+1/2, z+1/2; (vii) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu(C4O4)(H2O)3]·H2O
Mr247.64
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)6.5261 (8), 7.0683 (9), 18.417 (2)
β (°) 90.418 (10)
V3)849.54 (18)
Z4
Radiation typeMo Kα
µ (mm1)2.59
Crystal size (mm)0.2 × 0.1 × 0.1
Data collection
DiffractometerSTOE IPDS II
Absorption correctionNumerical
The absorption correction (X-RED V1.22; Stoe & Cie, 2001) was performed after optimizing the crystal shape using X-SHAPE V1.06 (Stoe & Cie, 1999).
Tmin, Tmax0.296, 0.541
No. of measured, independent and
observed [I > 2σ(I)] reflections
23355, 2468, 1766
Rint0.066
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.069, 0.93
No. of reflections2468
No. of parameters151
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.38, 0.42

Computer programs: X-AREA V1.15 (Stoe & Cie, 2001), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), DIAMOND V2.1e (Brandenburg, 2001).

Selected geometric parameters (Å, º) top
Cu1—O71.9396 (18)C1—O111.273 (2)
Cu1—O111.9555 (15)C1—C21.472 (3)
Cu1—O51.9588 (17)C2—C31.191 (3)
Cu1—O41i1.9677 (14)C3—C41.469 (3)
Cu1—O62.2961 (19)C4—O421.233 (2)
C1—O121.231 (3)C4—O411.270 (3)
O7—Cu1—O1186.92 (8)O41i—Cu1—O692.24 (7)
O7—Cu1—O5169.60 (10)O12—C1—O11125.76 (19)
O11—Cu1—O592.34 (7)O12—C1—C2118.93 (18)
O7—Cu1—O41i89.79 (8)O11—C1—C2115.31 (18)
O11—Cu1—O41i176.12 (7)C3—C2—C1178.6 (3)
O5—Cu1—O41i90.52 (8)C2—C3—C4178.0 (2)
O7—Cu1—O696.66 (9)O42—C4—O41125.28 (19)
O11—Cu1—O690.19 (7)O42—C4—C3119.17 (19)
O5—Cu1—O693.72 (9)O41—C4—C3115.55 (17)
Symmetry code: (i) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H51···O11ii0.78 (4)2.00 (4)2.771 (2)171 (4)
O5—H52···O8iii0.73 (4)2.02 (4)2.742 (3)170 (3)
O7—H71···O12iv0.79 (4)1.91 (4)2.694 (3)171 (4)
O7—H72···O80.77 (4)1.95 (4)2.696 (3)164 (4)
O8—H81···O42iv0.85 (5)1.87 (5)2.722 (3)174 (4)
O8—H83···O41v0.63 (4)2.13 (4)2.759 (2)177 (4)
Symmetry codes: (ii) x+1, y1/2, z+1/2; (iii) x, y1, z; (iv) x, y+1/2, z+1/2; (v) x+1, y+1/2, z+1/2.
 

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