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The coordination mode of the dimethyl­malonate ligand in the two title CuII complexes, {[Cu(C5H3O4)(H2O)]·H2O}n, (I), and [Cu(C5H3O4)(H2O)]n, (II), is the same, with chelated six-membered, bis-monodentate and bridging bonding modes. However, the coordination environment of the CuII atoms, the connectivity of their metal-organic frameworks and their hydrogen-bonding inter­actions are different. Complex (I) has a perfect square-pyramidal CuII environment with the aqua ligand in the apical position, and only one type of square grid consisting of CuII atoms linked via carboxyl­ate bridges to three dimethyl­malonate ligands, with weak hydrogen-bond inter­actions within and between its two-dimensional layers. Complex (II) has a coordination geometry that is closer to square pyramidal than trigonal bipyramidal for its CuII atoms with the aqua ligand now in the basal plane. Its two-dimensional layer structure comprises two alternating grids, which involve two and four different dimethyl­malonate anions, respectively. There are strong hydrogen bonds only within its layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011004761X/sk3385sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011004761X/sk3385Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011004761X/sk3385IIsup3.hkl
Contains datablock II

CCDC references: 810001; 810002

Comment top

In complexes of copper with malonic acid, the malonate dianion and protonated malonate have proved to have a great versatility. Structural complexity is associated with the simultaneous adoption of chelating bidentate and different carboxylate-bridging coordination modes (Pasan et al., 2007; Rodriguez-Martin et al. 2002; Delgado et al. 2004; Gil de Muro et al., 2004). For dimethylmalonate, however, in spite of this wealth of possibilities, no binary complexes with the CuII cation have been reported to date. Two related structural studies have been published, one containing the methylmalonate dianion (Pasan et al., 2007) and the other involving our previously reported heterobimetallic complex, poly[diaquabis(µ3-2,2-dimethylpropanedioato)calcium(II)copper(II)] (Guo & Wang, 2010). In the course of an attempt to obtain such a heterobimetallic complex we also obtained the two title complexes, (I) and (II). Interestingly, both these complexes have the same coordination mode, but the connectivity of their metal–organic frameworks is different and there are different hydrogen-bond interactions. A comparison with the previously reported methylmalonate CuII complexes (Pasan et al., 2007) reveals that the presence of two methyl groups, due to geometric constraints that would contribute to the overall stability of the resulting complexes, induces different coordination geometries of the metal. We report the crystal structures of (I) and (II) here.

Apart from the solvent water molecule in (I), both asymmetric units comprise one CuII atom, one complete dimethylmalonate dianion and one coordinated water molecule (Figs. 1a and 1b). In (I), the CuII atom exhibits a perfect square-pyramidal environment (τ = 0.023; Addison et al., 1984), with atoms O1, O3, O2i and O4ii (see Fig. 1a for symmetry codes) of two non-equivalent dimethylmalonate dianions in a planar arrangement and a mean Cu—O(eq) bond distance of 1.964 (7) Å, comparable with that reported for poly[(µ3-methylmalonato-O,O',O'',O''')-aqua-copper(II)] (Pasan et al., 2007). The apical position is occupied by a water molecule [Cu1—O5 = 2.306 (7) Å]. The CuII atom is shifted by 0.034 (3) Å towards the apical position. In the case of (II), the CuII atom has a geometry that is closer to square pyramidal than trigonal bipyramidal (τ = 0.381), with atoms O1, O3, O2i and O5 (see Fig. 1b for symmetry codes) in a planar arrangement and a mean Cu—O(eq) bond distance of 1.949 (2) Å. The apical position is occupied by atom O4ii [Cu1—O4ii = 2.251 (2) Å]. The Cu atom deviates by 0.2132 (5) Å from its least-squares plane towards the apical atom O4ii. The Cu—O(eq) bond lengths are somewhat longer than those reported for the square-planar CuII atom in poly[diaquabis(µ3-2,2-dimethylpropanedioato)calcium(II)copper(II)] (Guo & Wang, 2010). There are no additional Cu—O contacts in (I) and (II) out to 3 Å.

The coordination behaviour of the dimethylmalonate ligands in (I) and (II) is the same, with chelated six-membered, bis-monodentate and bridging bonding modes, but the connectivity in their structures is different (Figs. 2a and 2b). In both complexes, there is one methyl group directed towards the open space opposite the apical Cu1—O bond. For (I), the coordinated water molecule, O5, is opposite this methyl group, while in the case of (II), it is the O4 atom from a different dimethylmalonate ligand which lies on the opposite side of the Cu1 atom from the methyl group. In (I), the basal plane of four O atoms (defined by O1/O3/O2i/O4ii) makes a dihedral angle of 81.8 (3)° with the corresponding plane in the next CuII square pyramid in the network (Fig. 2a). This value is very close to that observed in the 1,1-cyclobutanedicarboxylate CuII complex [82.2 (8)°; Pasan et al., 2006] but it is somewhat smaller than that found in poly[(µ3-methylmalonato-O,O',O'',O''')-aqua-copper(II)] [84.44 (9)°; Pasan et al., 2007].

In the case of (II), if its configuration is visualized as being a considerably distorted trigonal bipyramid, with atoms O1, O4ii and O5 in the equatorial plane, the CuII atom deviates by 0.0078 (4) Å from the least-squares plane and the equatorial planes of its CuII atoms also have an almost perfect arrangement, the value of the dihedral angle between the basal planes of adjacent CuII atoms being 75.35 (13)°. This is larger than the value found in the isotypic complex (τ = 0.58) poly[aqua-µ3-2,2-dimethylmalonato-zinc(II)] [68.70 (8)°; Guo & Zhao, 2006].

The O—C—O angles for the four carboxylate groups of (I) and (II) are close to 120° (Tables 1 and 3). The values of the C—O bond distances in these carboxylate groups indicate that the mesomeric effect for the carboxylate groups of (II) is larger than that of the carboxylate groups of (I). In the structures of (I) and (II), each dimethylmalonate dianion binds to three CuII atoms, and each group of four CuII atoms are linked together via carboxylate bridges, forming a 16-membered ring, but there is only one such connectivity in (I), while there are two in (II). An alternative description, perhaps more revealing from the viewpoint of crystal engineering, is as follows. The structure of (I) consists of one type of square grid of CuII atoms linked in the ab plane via three different dimethylmalonate anions (Fig. 2a), and the intralayer Cu···Cuiii and Cu···Cuiv (see Table 1 for symmetry codes) separations through the carboxylate bridges are 4.8583 (18) and 4.8847 (18) Å, respectively, while the structure of (II) comprises two different grids in the direction of the bc plane, one involving two different dimethylmalonate anions and the other containing four. The intralayer Cu···Cuiii and Cu···Cuiv (see Table 3 for symmetry codes) separations through the carboxylate bridges are 5.052 (1) and 5.310 (1) Å, respectively.

Within the two-dimensional layer of (I), atom O2 of the dimethylmalonate dianion, acting as hydrogen-bond acceptor, is involved in a weak intermolecular hydrogen-bonding interaction with atom H5D of the coordinated water molecule (Table 2, Fig. 2a). Between the two-dimensional layers, solvent water molecule O6 is responsible for the formation of a six-membered hydrogen-bonded ring of graph set R12(6) (Bernstein et al., 1995) (Fig. 3a). Furthermore, the hydrogen bonds formed by water molecule O5 are also engaged in forming 12-membered hydrogen-bonded rings of graph set R45(12) along the b direction. In contrast, within the two-dimensional layer of (II), there are two strong intermolecular hydrogen-bonding interactions (Brown, 1976) between atoms O1, O4 and water molecule O5 (Table 4). These hydrogen bonds play an important role in the propagation of the two-dimensional layer structure, due to their formation of different hydrogen-bonded rings with graph sets R(6), R12(10) and R22(8), which is formed via Cu1 and O5—H5D···O4v hydrogen bonds (Fig. 2b). No hydrogen bonds are observed between the two-dimensional layers; the interlayer spaces are occupied alternately by a methyl group of the upper layer and another one from the layer below (Fig. 3b).

In summary, a comparison with the previously reported methylmalonate Cu complex (Pasan et al., 2007) reveals that (I) has some similarities in the connectivity of its two-dimensional layered structure, but its interlayer structure is different. Not only the methyl groups but also hydrogen bonds separate the layers. The interlayer spaces are occupied by methyl groups of the layers above and below and by water molecules. The chemically similar complex poly[aqua-µ3-2,2-dimethylmalonato-zinc(II)] (Guo & Zhao, 2006) and (II) are isotypic, and they both have the same structure topology. It might be possible that the differences in conditions during the synthesis and the packing efficiency requirements of the different extended structures are responsible for the different coordination environments of the two complexes.

Experimental top

Complex (I) was prepared under continuous stirring, with successive addition of dimethylmalonic acid (0.53 g, 4 mmol), CaCO3 (0.30 g, 3 mmol) and Cu(NO3)2.6H2O (0.48 g, 2 mmol) to distilled water (25 ml) at room temperature. After filtration, slow evaporation over a period of 2 d at room temperature provided blue prism crystals of (I).

Complex (II) was prepared under continuous stirring, with successive addition of dimethylmalonic acid (0.53 g, 4 mmol), Na2CO3 (0.22 g, 2 mmol), Cu(NO3)2.6H2O (0.48 g, 2 mmol) and barium nitrate (0.52 g, 2 mmol) to distilled water (20 ml) at room temperature. After filtration, slow evaporation over a period of 3 d at room temperature provided blue prism crystals of (II).

Refinement top

Initially, the structure of (I) refined poorly, with R1 = 0.115 [I > 2σ(I)] and 0.119 (all data), wR2 = 0.260, highest peak 5.50 e Å-3 and deepest hole -0.77 e Å-3. The TwinRotMat routine in PLATON (Spek, 2009) indicated the presence of non-merohedral twinning in the data, with a twin law of (-1 0 0/0 -1 0/0.783 0 1), which corresponds with a twofold rotation about (001). A reflection file in HKLF 5 format (SHELXL97; Sheldrick, 2008) with twin contributions added to the original reflection file was used in the final refinement. 813 of the 1507 reflections had twin contributions. The twin fraction refined to 0.330 (1). The number of Friedel pairs for (I) is 506.

The H atoms of the water molecules were found in difference Fourier maps. However, during refinement they were fixed at O—H = 0.85 Å with Uiso(H) = 1.2Ueq(O). The H atoms of the C—H groups were treated as riding, with C—H = 0.96 Å, and with Uiso(H) = 1.5Ueq(C). The initial refinement of (I) led to a C2—C5 bond length of 1.576 (11) Å, so a bond-length restraint of 1.540 (4) Å was applied to this bond in the final refinement.

Computing details top

For both compounds, data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structures of (a) (I) and (b) (II), showing the atom-numbering schemes and the CuII coordination environment. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes for (I): (i) -x + 2, y + 1/2, -z + 1; (ii) -x + 1, y + 1/2, -z + 1. Symmetry codes for (II): (i) x, -y + 3/2, z + 1/2; (ii) -x, y + 1/2, -z + 1/2.]
[Figure 2] Fig. 2. Packing diagrams for (a) (I), in the direction of the ab plane and viewed down the c axis, and (b) (II), in the direction of the bc plane and viewed down the a axis, showing the two-dimensional polymeric layers. Hydrogen-bonding interactions are shown as dashed lines for the intralayers.
[Figure 3] Fig. 3. (a) A packing diagram for (I), viewed down the c axis, showing the hydrogen-bonding interactions as dashed lines for the interlayers. The H atoms of the methyl groups have been omitted for clarity. (b) A packing diagram for (II), viewed down the a axis, showing how the interlayer spaces are occupied alternately by a methyl group of the upper layer and another one from the layer below.
(I) Poly[[aqua-µ3-2,2-dimethylmalonato-copper(II)] monohydrate] top
Crystal data top
[Cu(C5H3O4)(H2O)]·H2OF(000) = 234
Mr = 229.67Dx = 2.008 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 3084 reflections
a = 7.0202 (14) Åθ = 3.0–28.2°
b = 5.6645 (11) ŵ = 2.86 mm1
c = 9.938 (2) ÅT = 294 K
β = 106.06 (3)°Prism, blue
V = 379.76 (13) Å30.18 × 0.06 × 0.04 mm
Z = 2
Data collection top
Rigaku Saturn CCD area-detector
diffractometer
1467 independent reflections
Radiation source: rotating anode1177 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.060
Detector resolution: 28.162 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = 99
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
k = 77
Tmin = 0.793, Tmax = 0.887l = 512
3098 measured reflections
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)] = 0.056H-atom parameters constrained
wR(F2) = 0.152 w = 1/[σ2(Fo2) + (0.083P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
1467 reflectionsΔρmax = 1.22 e Å3
112 parametersΔρmin = 0.68 e Å3
2 restraintsAbsolute structure: Flack (1983), with 506 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (7)
Crystal data top
[Cu(C5H3O4)(H2O)]·H2OV = 379.76 (13) Å3
Mr = 229.67Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.0202 (14) ŵ = 2.86 mm1
b = 5.6645 (11) ÅT = 294 K
c = 9.938 (2) Å0.18 × 0.06 × 0.04 mm
β = 106.06 (3)°
Data collection top
Rigaku Saturn CCD area-detector
diffractometer
1467 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
1177 reflections with I > 2σ(I)
Tmin = 0.793, Tmax = 0.887Rint = 0.060
3098 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.152Δρmax = 1.22 e Å3
S = 1.01Δρmin = 0.68 e Å3
1467 reflectionsAbsolute structure: Flack (1983), with 506 Friedel pairs
112 parametersAbsolute structure parameter: 0.02 (7)
2 restraints
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
Cu10.71353 (17)0.2703 (6)0.40364 (9)0.0405 (3)
C10.9846 (15)0.0508 (17)0.6435 (12)0.040 (2)
C20.840 (2)0.1369 (15)0.7258 (11)0.043 (2)
C30.6294 (15)0.0539 (19)0.6429 (12)0.041 (2)
C40.8900 (17)0.0208 (16)0.8721 (9)0.0438 (19)
H4A0.88860.14780.86220.066*
H4B0.79350.06710.91910.066*
H4C1.01930.07110.92590.066*
C50.841 (2)0.4091 (15)0.7355 (11)0.042 (2)
H5A0.76500.45810.79740.063*
H5B0.78370.47470.64410.063*
H5C0.97490.46380.77090.063*
O10.9530 (10)0.1131 (16)0.5165 (8)0.0402 (15)
O21.1290 (10)0.0676 (15)0.7062 (8)0.0422 (16)
O30.5589 (11)0.1164 (16)0.5151 (8)0.0441 (17)
O40.5249 (10)0.0611 (15)0.7023 (7)0.0443 (16)
O50.6565 (13)0.0422 (13)0.2489 (7)0.0520 (15)
H5D0.68950.17800.28510.062*
H5E0.58470.05170.16470.062*
O60.4235 (18)0.065 (3)0.0227 (11)0.114 (4)
H6A0.31600.11120.07980.136*
H6B0.50250.01480.06900.136*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0364 (4)0.0426 (5)0.0425 (4)0.0005 (8)0.0111 (4)0.0016 (6)
C10.042 (5)0.030 (5)0.046 (6)0.006 (4)0.009 (4)0.004 (4)
C20.034 (5)0.049 (7)0.043 (5)0.001 (6)0.006 (5)0.004 (5)
C30.035 (5)0.038 (6)0.050 (6)0.005 (4)0.014 (4)0.008 (5)
C40.037 (4)0.056 (5)0.039 (4)0.005 (5)0.011 (5)0.002 (4)
C50.046 (6)0.041 (6)0.044 (5)0.001 (7)0.022 (6)0.002 (4)
O10.037 (4)0.047 (4)0.038 (4)0.001 (3)0.013 (3)0.001 (3)
O20.040 (4)0.042 (4)0.043 (4)0.004 (3)0.010 (3)0.001 (3)
O30.042 (4)0.044 (4)0.045 (4)0.006 (3)0.010 (3)0.004 (3)
O40.043 (4)0.046 (4)0.044 (4)0.006 (3)0.012 (3)0.006 (3)
O50.050 (4)0.049 (4)0.056 (4)0.001 (4)0.014 (4)0.005 (3)
O60.077 (7)0.177 (12)0.078 (6)0.017 (10)0.007 (6)0.035 (8)
Geometric parameters (Å, º) top
Cu1—O11.958 (7)C3—O31.278 (14)
Cu1—O2i1.981 (7)C4—H4A0.9600
Cu1—O4ii1.961 (7)C4—H4B0.9600
Cu1—O31.958 (8)C4—H4C0.9600
Cu1—O52.306 (7)C5—H5A0.9600
C1—O21.231 (13)C5—H5B0.9600
C1—O11.270 (13)C5—H5C0.9600
C1—C21.550 (17)O5—H5D0.8537
C2—C41.545 (13)O5—H5E0.8502
C2—C51.545 (12)O6—H6A0.8499
C2—C31.550 (16)O6—H6B0.8620
C3—O41.246 (13)
O3—Cu1—O189.8 (2)O3—C3—C2119.6 (9)
O3—Cu1—O4ii89.8 (3)C2—C4—H4A109.5
O1—Cu1—O4ii177.3 (4)C2—C4—H4B109.5
O3—Cu1—O2i178.7 (4)H4A—C4—H4B109.5
O1—Cu1—O2i90.3 (3)C2—C4—H4C109.5
O4ii—Cu1—O2i90.1 (2)H4A—C4—H4C109.5
O3—Cu1—O590.8 (3)H4B—C4—H4C109.5
O1—Cu1—O589.8 (3)C2—C5—H5A109.5
O4ii—Cu1—O592.9 (3)C2—C5—H5B109.5
O2i—Cu1—O590.5 (3)H5A—C5—H5B109.5
O2—C1—O1123.2 (10)C2—C5—H5C109.5
O2—C1—C2118.2 (10)H5A—C5—H5C109.5
O1—C1—C2118.5 (9)H5B—C5—H5C109.5
C4—C2—C5111.7 (10)C1—O1—Cu1125.6 (6)
C4—C2—C3107.9 (10)C1—O2—Cu1iii118.7 (7)
C5—C2—C3108.9 (12)C3—O3—Cu1124.2 (7)
C4—C2—C1110.5 (10)C3—O4—Cu1iv121.8 (7)
C5—C2—C1110.7 (12)Cu1—O5—H5D115.7
C3—C2—C1107.0 (8)Cu1—O5—H5E130.6
O4—C3—O3119.9 (9)H5D—O5—H5E112.1
O4—C3—C2120.3 (10)H6A—O6—H6B109.1
O2—C1—C2—C48.8 (13)C2—C1—O1—Cu110.0 (13)
O1—C1—C2—C4173.9 (9)O3—Cu1—O1—C128.8 (8)
O2—C1—C2—C5115.5 (12)O2i—Cu1—O1—C1149.9 (9)
O1—C1—C2—C561.9 (14)O5—Cu1—O1—C1119.6 (9)
O2—C1—C2—C3126.0 (10)O1—C1—O2—Cu1iii14.3 (14)
O1—C1—C2—C356.6 (11)C2—C1—O2—Cu1iii168.5 (7)
C4—C2—C3—O48.2 (14)O4—C3—O3—Cu1173.9 (7)
C5—C2—C3—O4113.3 (12)C2—C3—O3—Cu110.4 (14)
C1—C2—C3—O4127.0 (11)O1—Cu1—O3—C328.4 (8)
C4—C2—C3—O3176.1 (9)O4ii—Cu1—O3—C3149.0 (9)
C5—C2—C3—O362.4 (14)O5—Cu1—O3—C3118.1 (9)
C1—C2—C3—O357.2 (12)O3—C3—O4—Cu1iv18.2 (14)
O2—C1—O1—Cu1172.8 (7)C2—C3—O4—Cu1iv166.1 (7)
Symmetry codes: (i) x+2, y+1/2, z+1; (ii) x+1, y+1/2, z+1; (iii) x+2, y1/2, z+1; (iv) x+1, y1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H6B···O4v0.862.343.009 (13)135
O6—H6A···O2vi0.852.182.907 (13)143
O5—H5E···O60.851.892.745 (13)179
O5—H5D···O2iii0.852.543.310 (11)151
Symmetry codes: (iii) x+2, y1/2, z+1; (v) x, y, z1; (vi) x1, y, z1.
(II) poly[aqua-µ3-2,2-dimethylmalonato-copper(II)] top
Crystal data top
[Cu(C5H3O4)(H2O)]F(000) = 428
Mr = 211.65Dx = 2.085 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1386 reflections
a = 8.7697 (18) Åθ = 2.4–27.8°
b = 8.5492 (17) ŵ = 3.21 mm1
c = 9.3313 (19) ÅT = 294 K
β = 105.42 (3)°Prism, blue
V = 674.4 (2) Å30.12 × 0.08 × 0.08 mm
Z = 4
Data collection top
Rigaku Saturn CCD area-detector
diffractometer
1183 independent reflections
Radiation source: rotating anode1083 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.048
Detector resolution: 27.782 pixels mm-1θmax = 25.0°, θmin = 3.3°
ω scansh = 910
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
k = 1010
Tmin = 0.745, Tmax = 0.773l = 1111
4871 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.039P)2 + 0.4683P]
where P = (Fo2 + 2Fc2)/3
1183 reflections(Δ/σ)max = 0.001
100 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
[Cu(C5H3O4)(H2O)]V = 674.4 (2) Å3
Mr = 211.65Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.7697 (18) ŵ = 3.21 mm1
b = 8.5492 (17) ÅT = 294 K
c = 9.3313 (19) Å0.12 × 0.08 × 0.08 mm
β = 105.42 (3)°
Data collection top
Rigaku Saturn CCD area-detector
diffractometer
1183 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
1083 reflections with I > 2σ(I)
Tmin = 0.745, Tmax = 0.773Rint = 0.048
4871 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.086H-atom parameters constrained
S = 1.11Δρmax = 0.50 e Å3
1183 reflectionsΔρmin = 0.30 e Å3
100 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
Cu10.16128 (5)0.63669 (5)0.37478 (5)0.02629 (19)
O10.2113 (3)0.7083 (3)0.1956 (3)0.0298 (6)
O20.2551 (3)0.6697 (3)0.0255 (3)0.0278 (6)
O30.0724 (3)0.4483 (3)0.2725 (3)0.0286 (6)
O40.0719 (3)0.2466 (3)0.1248 (3)0.0281 (6)
O50.1980 (3)0.5221 (3)0.5630 (3)0.0284 (6)
H5D0.14680.43840.56580.034*
H5E0.19400.59170.62700.034*
C10.2423 (4)0.6203 (4)0.0976 (4)0.0253 (8)
C20.2703 (4)0.4443 (4)0.1317 (4)0.0267 (8)
C30.1273 (4)0.3752 (4)0.1786 (4)0.0252 (8)
C40.2962 (5)0.3580 (4)0.0035 (4)0.0304 (9)
H4A0.20460.37020.08610.046*
H4B0.31340.24890.01950.046*
H4C0.38700.40070.02880.046*
C50.4191 (4)0.4274 (5)0.2630 (4)0.0320 (8)
H5A0.43870.31860.28620.048*
H5B0.40290.48100.34820.048*
H5C0.50830.47200.23650.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0304 (3)0.0247 (3)0.0246 (3)0.00144 (17)0.0088 (2)0.00082 (16)
O10.0387 (15)0.0260 (14)0.0256 (13)0.0008 (11)0.0102 (11)0.0008 (11)
O20.0331 (14)0.0260 (13)0.0253 (13)0.0003 (11)0.0097 (11)0.0001 (10)
O30.0303 (14)0.0281 (14)0.0282 (14)0.0019 (11)0.0094 (11)0.0019 (11)
O40.0303 (14)0.0232 (13)0.0316 (13)0.0022 (10)0.0098 (11)0.0025 (11)
O50.0352 (14)0.0237 (13)0.0261 (13)0.0020 (11)0.0080 (11)0.0016 (10)
C10.0223 (19)0.0279 (19)0.026 (2)0.0035 (14)0.0064 (15)0.0034 (15)
C20.0243 (19)0.0278 (19)0.0280 (19)0.0000 (15)0.0071 (15)0.0006 (15)
C30.0278 (19)0.0253 (19)0.0214 (19)0.0028 (14)0.0047 (15)0.0046 (14)
C40.036 (2)0.025 (2)0.033 (2)0.0004 (15)0.0143 (17)0.0031 (15)
C50.029 (2)0.033 (2)0.034 (2)0.0017 (16)0.0075 (16)0.0045 (17)
Geometric parameters (Å, º) top
Cu1—O31.928 (2)C1—C21.544 (5)
Cu1—O11.937 (2)C2—C41.530 (5)
Cu1—O51.961 (2)C2—C51.541 (5)
Cu1—O2i1.969 (2)C2—C31.551 (5)
Cu1—O4ii2.251 (2)C4—H4A0.9600
O1—C11.268 (4)C4—H4B0.9600
O2—C11.256 (4)C4—H4C0.9600
O3—C31.271 (4)C5—H5A0.9600
O4—C31.252 (4)C5—H5B0.9600
O5—H5D0.8491C5—H5C0.9600
O5—H5E0.8501
O3—Cu1—O189.50 (10)C4—C2—C1110.5 (3)
O3—Cu1—O588.54 (10)C5—C2—C1108.1 (3)
O1—Cu1—O5155.47 (11)C4—C2—C3111.0 (3)
O3—Cu1—O2i178.31 (11)C5—C2—C3108.5 (3)
O1—Cu1—O2i88.87 (11)C1—C2—C3109.5 (3)
O5—Cu1—O2i92.76 (10)O4—C3—O3122.1 (3)
O3—Cu1—O4ii95.83 (10)O4—C3—C2118.5 (3)
O1—Cu1—O4ii106.50 (10)O3—C3—C2119.4 (3)
O5—Cu1—O4ii98.02 (10)C2—C4—H4A109.5
O2i—Cu1—O4ii85.06 (10)C2—C4—H4B109.5
C1—O1—Cu1125.2 (2)H4A—C4—H4B109.5
C1—O2—Cu1iii125.9 (2)C2—C4—H4C109.5
C3—O3—Cu1125.1 (2)H4A—C4—H4C109.5
C3—O4—Cu1iv128.4 (2)H4B—C4—H4C109.5
Cu1—O5—H5D119.1C2—C5—H5A109.5
Cu1—O5—H5E104.6C2—C5—H5B109.5
H5D—O5—H5E116.6H5A—C5—H5B109.5
O2—C1—O1123.2 (3)C2—C5—H5C109.5
O2—C1—C2117.9 (3)H5A—C5—H5C109.5
O1—C1—C2118.8 (3)H5B—C5—H5C109.5
C4—C2—C5109.3 (3)
O3—Cu1—O1—C129.5 (3)O1—C1—C2—C563.8 (4)
O5—Cu1—O1—C155.9 (4)O2—C1—C2—C3127.4 (3)
O2i—Cu1—O1—C1150.0 (3)O1—C1—C2—C354.2 (4)
O4ii—Cu1—O1—C1125.5 (3)Cu1iv—O4—C3—O316.4 (5)
O1—Cu1—O3—C337.5 (3)Cu1iv—O4—C3—C2165.3 (2)
O5—Cu1—O3—C3118.0 (3)Cu1—O3—C3—O4174.1 (2)
O4ii—Cu1—O3—C3144.1 (3)Cu1—O3—C3—C24.2 (4)
Cu1iii—O2—C1—O123.1 (5)C4—C2—C3—O413.2 (4)
Cu1iii—O2—C1—C2158.5 (2)C5—C2—C3—O4106.9 (4)
Cu1—O1—C1—O2171.0 (2)C1—C2—C3—O4135.5 (3)
Cu1—O1—C1—C210.7 (4)C4—C2—C3—O3168.4 (3)
O2—C1—C2—C44.9 (4)C5—C2—C3—O371.6 (4)
O1—C1—C2—C4176.7 (3)C1—C2—C3—O346.1 (4)
O2—C1—C2—C5114.7 (4)
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x, y+3/2, z1/2; (iv) x, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5D···O4v0.851.852.678 (3)164
O5—H5E···O1i0.851.822.604 (3)153
Symmetry codes: (i) x, y+3/2, z+1/2; (v) x, y+1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formula[Cu(C5H3O4)(H2O)]·H2O[Cu(C5H3O4)(H2O)]
Mr229.67211.65
Crystal system, space groupMonoclinic, P21Monoclinic, P21/c
Temperature (K)294294
a, b, c (Å)7.0202 (14), 5.6645 (11), 9.938 (2)8.7697 (18), 8.5492 (17), 9.3313 (19)
β (°) 106.06 (3) 105.42 (3)
V3)379.76 (13)674.4 (2)
Z24
Radiation typeMo KαMo Kα
µ (mm1)2.863.21
Crystal size (mm)0.18 × 0.06 × 0.040.12 × 0.08 × 0.08
Data collection
DiffractometerRigaku Saturn CCD area-detector
diffractometer
Rigaku Saturn CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku/MSC, 2005)
Multi-scan
(CrystalClear; Rigaku/MSC, 2005)
Tmin, Tmax0.793, 0.8870.745, 0.773
No. of measured, independent and
observed [I > 2σ(I)] reflections
3098, 1467, 1177 4871, 1183, 1083
Rint0.0600.048
(sin θ/λ)max1)0.6510.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.152, 1.01 0.035, 0.086, 1.11
No. of reflections14671183
No. of parameters112100
No. of restraints20
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.22, 0.680.50, 0.30
Absolute structureFlack (1983), with 506 Friedel pairs?
Absolute structure parameter0.02 (7)?

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) for (I) top
Cu1—O11.958 (7)C1—O21.231 (13)
Cu1—O2i1.981 (7)C1—O11.270 (13)
Cu1—O4ii1.961 (7)C3—O41.246 (13)
Cu1—O31.958 (8)C3—O31.278 (14)
Cu1—O52.306 (7)
O3—Cu1—O189.8 (2)O3—Cu1—O590.8 (3)
O3—Cu1—O4ii89.8 (3)O1—Cu1—O589.8 (3)
O1—Cu1—O4ii177.3 (4)O4ii—Cu1—O592.9 (3)
O3—Cu1—O2i178.7 (4)O2i—Cu1—O590.5 (3)
O1—Cu1—O2i90.3 (3)O2—C1—O1123.2 (10)
O4ii—Cu1—O2i90.1 (2)O4—C3—O3119.9 (9)
O1—C1—O2—Cu1iii14.3 (14)O3—C3—O4—Cu1iv18.2 (14)
Symmetry codes: (i) x+2, y+1/2, z+1; (ii) x+1, y+1/2, z+1; (iii) x+2, y1/2, z+1; (iv) x+1, y1/2, z+1.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O6—H6B···O4v0.862.343.009 (13)135
O6—H6A···O2vi0.852.182.907 (13)143
O5—H5E···O60.851.892.745 (13)179
O5—H5D···O2iii0.852.543.310 (11)151
Symmetry codes: (iii) x+2, y1/2, z+1; (v) x, y, z1; (vi) x1, y, z1.
Selected geometric parameters (Å, º) for (II) top
Cu1—O31.928 (2)O1—C11.268 (4)
Cu1—O11.937 (2)O2—C11.256 (4)
Cu1—O51.961 (2)O3—C31.271 (4)
Cu1—O2i1.969 (2)O4—C31.252 (4)
Cu1—O4ii2.251 (2)
O3—Cu1—O189.50 (10)O3—Cu1—O4ii95.83 (10)
O3—Cu1—O588.54 (10)O1—Cu1—O4ii106.50 (10)
O1—Cu1—O5155.47 (11)O5—Cu1—O4ii98.02 (10)
O3—Cu1—O2i178.31 (11)O2i—Cu1—O4ii85.06 (10)
O1—Cu1—O2i88.87 (11)O2—C1—O1123.2 (3)
O5—Cu1—O2i92.76 (10)O4—C3—O3122.1 (3)
Cu1iii—O2—C1—O123.1 (5)Cu1iv—O4—C3—O316.4 (5)
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x, y+3/2, z1/2; (iv) x, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O5—H5D···O4v0.851.852.678 (3)164.1
O5—H5E···O1i0.851.822.604 (3)152.9
Symmetry codes: (i) x, y+3/2, z+1/2; (v) x, y+1/2, z+1/2.
 

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