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In the neutral title complex, [Cu(C3H2O4)(C5H8N2)2(H2O)]·2H2O or [Cu(mal)(dmp)2(H2O)]·2H2O (mal is malon­ate and dmp is 3,5-di­methyl-1H-pyrazole), the CuII ion, in a slightly distorted square-pyramidal geometry, is coordinated by two O atoms of the bidentate malonate, the O atom of the water ligand and two N atoms from the two 3,5-di­methyl­pyrazole ligands. The mean Cu—N bond length is 2.007 (6) Å, longer than the Cu—Omal bonds [1.950 (5) Å]. The apical position is occupied by a relatively strongly coordinated water mol­ecule [Cu—Owater 2.288 (5) Å]. The crystal structure is characterized by the layer motif of a hydrogen-bonded network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101015116/da1196sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101015116/da1196Isup2.hkl
Contains datablock I

CCDC reference: 179252

Comment top

The self-assembly of ordered supramolecular arrays in the solid state using non-covalent forces such as hydrogen bonding (Braga & Grepioni, 2000; Fan et al., 1994; Prins et al., 1998) and ππ stacking (Amabilino et al., 1994) is a rapidly expanding field. Cooperative intermolecular interactions that may be encouraged through alignment of molecules in certain ways in the solid state can result in novel magnetic, conductive and nonlinear-optical properties. Traditionally, organic chemistry (Whitesides et al., 1995) has been the domain of crystal engineering through hydrogen bonding, but transition metal coordination chemistry (our present interest) can also exploit hydrogen bonding if prudent ligand design is practized (Bernhardt, 1999).

The malonate ion (abbreviated as mal) is a versatile ligand frequently used for designing complexes with desired magnetic properties (Ruiz-Perez et al., 2000), and it is also useful as a building block in metal-containing supramolecules. Since the mal ion has four potential proton acceptors but no proton donors, ligands with proton donors may be introduced in order to create potential building blocks for supramolecular assemblies. Therefore, we have synthesized and crystallized the title compound, (I), a new mixed-ligand copper complex containing mal, H2O and 3,5-dimethyl-1H-pyrazole (abbreviated as dmp), which is a proton donor as well as an important ligand in coordination chemistry (Ardizzoia et al., 1996). \sch

The crystal structure of (I) consists of the neutral [Cu(mal)(dmp)2H2O] complex and two uncoordinated water molecules. Fig. 1 shows a perspective view of (I) together with the atom-numbering scheme. The geometry of the five-coordinate CuN2O3 core is a slightly distorted square pyramid. The basal sites are occupied by two dmp N atoms and two mal carboxylate O atoms. The apical position is occupied by a relatively strongly coordinated water molecule [Cu—O1W 2.288 (5) Å], which is 2.495 (6) Å from the mean basal plane defined by O1—O3—N1—N3. The coordination geometry around the CuII ion is similar to that of two reported CuN2O3-type complexes, [Cu(mal)(phen)H2O] (Kwik et al., 1986) and [Cu(mal)(bpy)H2O] (Lu et al., 1996) (phen is 1,10-phenanthroline and bpy is 4,4'-bipyridine *Query*). Although phen and bpy are bidentate N-ligands, structurally different from the N-ligand dmp in (I), the structural likeness may indicate that dmp has similar π-acceptor properties.

The two dmp ligands are located cis to each other in the basal plane, in an antisymmetrical mode. The planes of the two pyrazole rings form dihedral angles of 40.1 (4) and 32.0 (3)° with the basal plane. The six-membered chelate ring of mal is in a boat conformation. Atoms Cu1 and C2 are displaced by 0.71 (1) and 0.32 (1) Å, respectively, from the least-squares plane of O1—O3—C1—C3.

As expected, the molecules of (I) are hydrogen bonded to each other to form a supramolecular array. In this array, H atoms from the coordinated water ligand link to a carbonyl O atom of an adjacent molecule via a strong O1W—H1WA···O4 hydrogen bond, with an O···O distance of 2.719 (8) Å (Table 1), leading to the formation of an infinite zigzag supramolecular chain along the (001) direction, as shown in Fig. 2. These supramolecular chains are further joined into an extended two-dimensional supramolecular layer parallel to the [011] plane by a stronger hydrogen-bonded bridge between one carbonyl O atom, one uncoordinated H2O molecule and one coordinated H2O molecule, e.g. O2···H3WB—O3W···H1WB—O1W, but there is no hydrogen bonding between the layers (Fig 3). Therefore, the complex crystal may be characterized as a two-dimensional hydrogen-bonded network.

An important point to emerge from the above crystal analysis is that metal complexes containing mal may assemble into interesting hydrogen-bonded supramolecular networks due to the potential boat shape and four proton acceptors of mal, if ligands with proton donors are introduced to the mal-containing metal complex. These complexes can be useful new building blocks for crystal engineering.

Related literature top

For related literature, see: Amabilino et al. (1994); Ardizzoia et al. (1996); Bernhardt (1999); Braga & Grepioni (2000); Fan et al. (1994); Flack (1983); Kwik et al. (1986); Lu et al. (1996); Prins et al. (1998); Ruiz-Perez, Sanchiz, Molina, Lloret & Julve (2000); Whitesides et al. (1995).

Experimental top

To an aqueous solution of H2mal (100 ml, 1 mmol l-1), Cu(OH)2 powder (1 mmol) and dmp solid (2 mmol) were slowly added with stirring; the mixture was stirred for 15 min at 323 K. Blue polyhedral crystals of (I) appeared within 3 d (70% yield).

Refinement top

H atoms attached to C atoms were placed in their optimized positions with Uiso fixed at 0.08 Å2; the N—H and water H atoms were located in difference Fourier maps and were included in fixed positions. Although the Flack parameter (Flack, 1983) is zero within one s.u., note that this is based on only a few Bijvoet pairs and may be unreliable.

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL.

Figures top
[Figure 1] Fig. 1. A perspective view of (I) drawn with 40% probability displacement ellipsoids. Water H atoms are shown as small spheres of arbitrary radii; other H atoms have been omitted for clarity.
[Figure 2] Fig. 2. A fragment of a one-dimensional supramolecular chain in (I), along (001); the uncoordinated water molecules have been omitted.
[Figure 3] Fig. 3. A view of the hydrogen-bonded supramolecular plane parallel to [110], showing the layer structure.
Aquabis(3,5-dimethyl-1H-pyrazole-N2)(malonato-O,O')copper(II) dihydrate top
Crystal data top
[Cu(C3H2O4)(C5H8N2)2(H2O)]·2H2ODx = 1.426 Mg m3
Mr = 411.90Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21Cell parameters from 25 reflections
a = 24.000 (7) Åθ = 7.5–15.0°
b = 8.531 (3) ŵ = 1.18 mm1
c = 9.369 (2) ÅT = 293 K
V = 1918.2 (10) Å3Prism, blue
Z = 40.46 × 0.36 × 0.32 mm
F(000) = 860
Data collection top
Siemens P4
diffractometer
1654 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.033
Graphite monochromatorθmax = 29.0°, θmin = 2.4°
ω scansh = 132
Absorption correction: empirical (using intensity measurements)
via ψ-scan (North et al., 1968)
k = 011
Tmin = 0.523, Tmax = 0.686l = 012
2821 measured reflections2 standard reflections every 120 min
2705 independent reflections intensity decay: none
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)] = 0.059H-atom parameters constrained
wR(F2) = 0.157 w = 1/[σ2(Fo2) + (0.0781P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2705 reflectionsΔρmax = 0.36 e Å3
226 parametersΔρmin = 0.43 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.01 (3)
Crystal data top
[Cu(C3H2O4)(C5H8N2)2(H2O)]·2H2OV = 1918.2 (10) Å3
Mr = 411.90Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 24.000 (7) ŵ = 1.18 mm1
b = 8.531 (3) ÅT = 293 K
c = 9.369 (2) Å0.46 × 0.36 × 0.32 mm
Data collection top
Siemens P4
diffractometer
1654 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements)
via ψ-scan (North et al., 1968)
Rint = 0.033
Tmin = 0.523, Tmax = 0.6862 standard reflections every 120 min
2821 measured reflections intensity decay: none
2705 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.157Δρmax = 0.36 e Å3
S = 1.03Δρmin = 0.43 e Å3
2705 reflectionsAbsolute structure: Flack (1983)
226 parametersAbsolute structure parameter: 0.01 (3)
1 restraint
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
Cu10.38077 (3)0.39341 (9)0.66382 (10)0.0428 (2)
O10.3854 (2)0.2900 (6)0.4781 (6)0.0522 (13)
O20.4431 (3)0.1827 (7)0.3248 (7)0.0738 (18)
O30.4157 (2)0.5794 (6)0.5835 (6)0.0547 (14)
O40.4661 (3)0.7059 (7)0.4239 (8)0.078 (2)
O1W0.4538 (2)0.2349 (6)0.7258 (7)0.0667 (17)
H1WA0.47490.22070.83240.080*
H1WB0.44360.16300.67290.080*
O2W0.3742 (3)0.0620 (8)0.4225 (11)0.093 (3)
H2WA0.39700.01080.46010.080*
H2WB0.37980.16400.42770.080*
O3W0.5405 (3)0.0925 (6)0.1910 (8)0.070 (2)
H3WA0.52450.11300.10130.080*
H3WB0.50840.12760.23900.080*
N10.3144 (2)0.2557 (7)0.7012 (6)0.0493 (16)
N20.3171 (2)0.1039 (7)0.6535 (10)0.0563 (16)
H20.35680.10200.62120.080*
N30.3830 (2)0.5051 (7)0.8518 (7)0.0460 (14)
N40.3898 (2)0.6638 (7)0.8566 (8)0.0480 (15)
H40.39710.72500.77660.080*
C10.4496 (3)0.5828 (9)0.4771 (9)0.0497 (18)
C20.4716 (3)0.4283 (8)0.4167 (10)0.056 (2)
H2A0.50310.39740.47290.080*
H2B0.48500.44900.32200.080*
C30.4310 (3)0.2908 (9)0.4073 (9)0.0487 (18)
C40.2706 (4)0.0248 (10)0.7018 (13)0.078 (3)
C50.2381 (4)0.1267 (10)0.7758 (12)0.076 (3)
H5A0.20330.10460.82190.080*
C60.2665 (3)0.2714 (11)0.7744 (10)0.061 (2)
C70.2641 (5)0.1458 (9)0.659 (2)0.131 (6)
H7A0.23020.18710.69860.080*
H7B0.26290.15350.55710.080*
H7C0.29520.20470.69490.080*
C80.2469 (4)0.4246 (10)0.8346 (13)0.085 (3)
H8A0.27450.50360.81710.080*
H8B0.21240.45470.79040.080*
H8C0.24140.41350.93560.080*
C90.3782 (3)0.4600 (10)0.9886 (9)0.0504 (18)
C100.3814 (3)0.5909 (10)1.0759 (9)0.061 (2)
H10A0.37760.59211.17790.080*
C110.3900 (3)0.7181 (9)0.9909 (10)0.055 (2)
C120.3709 (4)0.2921 (11)1.0263 (11)0.073 (3)
H12A0.37080.23010.94080.080*
H12B0.40080.25871.08710.080*
H12C0.33610.27921.07520.080*
C130.3972 (5)0.8885 (10)1.0208 (15)0.089 (3)
H13A0.40300.94460.93320.080*
H13B0.36450.92781.06750.080*
H13C0.42890.90261.08200.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0377 (4)0.0479 (4)0.0430 (4)0.0044 (4)0.0032 (6)0.0039 (6)
O10.042 (3)0.062 (3)0.052 (3)0.004 (2)0.001 (3)0.007 (3)
O20.075 (4)0.078 (4)0.068 (4)0.010 (3)0.009 (4)0.033 (4)
O30.062 (4)0.049 (3)0.053 (3)0.004 (2)0.024 (3)0.004 (3)
O40.089 (4)0.060 (4)0.086 (5)0.008 (3)0.044 (4)0.015 (4)
O1W0.061 (3)0.060 (3)0.080 (4)0.010 (3)0.034 (3)0.017 (3)
O2W0.079 (5)0.066 (4)0.136 (7)0.015 (3)0.028 (5)0.008 (5)
O3W0.079 (4)0.060 (3)0.071 (6)0.007 (3)0.029 (4)0.003 (3)
N10.046 (3)0.059 (4)0.043 (4)0.012 (3)0.004 (3)0.002 (3)
N20.045 (3)0.059 (3)0.065 (4)0.016 (3)0.013 (5)0.005 (4)
N30.041 (3)0.046 (3)0.050 (4)0.003 (3)0.002 (3)0.001 (3)
N40.050 (4)0.041 (3)0.053 (4)0.001 (3)0.000 (3)0.003 (3)
C10.042 (4)0.057 (5)0.049 (4)0.006 (3)0.005 (3)0.006 (4)
C20.040 (4)0.068 (5)0.059 (5)0.002 (4)0.019 (4)0.001 (4)
C30.042 (4)0.062 (5)0.042 (4)0.011 (4)0.004 (3)0.001 (4)
C40.053 (4)0.070 (5)0.111 (10)0.028 (4)0.032 (5)0.018 (6)
C50.055 (5)0.092 (7)0.083 (7)0.015 (5)0.006 (5)0.029 (6)
C60.046 (4)0.083 (5)0.053 (5)0.005 (4)0.005 (4)0.003 (5)
C70.101 (9)0.072 (6)0.218 (16)0.043 (6)0.077 (13)0.023 (13)
C80.051 (5)0.122 (8)0.083 (7)0.007 (6)0.011 (5)0.001 (7)
C90.049 (4)0.057 (4)0.045 (4)0.007 (4)0.005 (4)0.002 (4)
C100.057 (5)0.082 (6)0.045 (4)0.003 (5)0.003 (4)0.007 (4)
C110.056 (5)0.053 (4)0.055 (5)0.002 (4)0.012 (4)0.006 (4)
C120.093 (7)0.069 (6)0.058 (5)0.001 (5)0.001 (5)0.008 (5)
C130.108 (8)0.065 (6)0.096 (9)0.007 (6)0.016 (7)0.009 (6)
Geometric parameters (Å, º) top
Cu1—O31.946 (5)N3—N41.365 (9)
Cu1—O11.954 (6)N4—C111.341 (11)
Cu1—N32.003 (6)C1—C21.528 (10)
Cu1—N12.010 (6)C2—C31.527 (11)
Cu1—O1W2.288 (5)C4—C51.359 (14)
O1—C31.278 (9)C4—C71.517 (14)
O2—C31.238 (9)C5—C61.410 (11)
O3—C11.287 (9)C6—C81.499 (12)
O4—C11.229 (9)C9—C101.386 (12)
N1—C61.346 (9)C9—C121.486 (13)
N1—N21.372 (9)C10—C111.361 (12)
N2—C41.380 (10)C11—C131.491 (12)
N3—C91.343 (10)
O3—Cu1—O189.9 (2)O4—C1—C2118.4 (7)
O3—Cu1—N386.6 (2)O3—C1—C2119.1 (7)
O1—Cu1—N3175.0 (2)C3—C2—C1117.6 (6)
O3—Cu1—N1152.3 (3)O2—C3—O1121.4 (8)
O1—Cu1—N186.4 (2)O2—C3—C2117.3 (7)
N3—Cu1—N198.4 (2)O1—C3—C2121.3 (7)
O3—Cu1—O1W104.5 (2)C5—C4—N2108.6 (7)
O1—Cu1—O1W85.1 (2)C5—C4—C7133.5 (9)
N3—Cu1—O1W92.2 (2)N2—C4—C7117.8 (10)
N1—Cu1—O1W102.5 (2)C4—C5—C6106.2 (8)
C3—O1—Cu1120.6 (5)N1—C6—C5109.3 (8)
C1—O3—Cu1126.2 (5)N1—C6—C8123.1 (8)
C6—N1—N2107.5 (6)C5—C6—C8127.5 (8)
C6—N1—Cu1135.1 (6)N3—C9—C10109.2 (7)
N2—N1—Cu1117.2 (5)N3—C9—C12120.8 (7)
N1—N2—C4108.4 (7)C10—C9—C12130.0 (8)
C9—N3—N4105.2 (6)C11—C10—C9107.7 (8)
C9—N3—Cu1134.5 (5)N4—C11—C10105.9 (7)
N4—N3—Cu1120.3 (5)N4—C11—C13120.9 (9)
C11—N4—N3112.0 (7)C10—C11—C13133.2 (10)
O4—C1—O3122.5 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O4i1.131.772.719 (8)139
O1W—H1WB···O3Wii0.832.222.815 (7)129
O2W—H2WA···O20.902.232.816 (10)122
O2W—H2WA···O10.902.403.059 (9)130
O2W—H2WB···O4iii0.882.352.965 (9)127
O3W—H3WA···O4iv0.942.283.041 (10)138
O3W—H3WB···O20.941.822.762 (9)175
N2—H2···O11.002.202.812 (9)118
N4—H4···O30.932.242.731 (9)112
Symmetry codes: (i) x+1, y+1, z+1/2; (ii) x+1, y, z+1/2; (iii) x, y1, z; (iv) x+1, y+1, z1/2.

Experimental details

Crystal data
Chemical formula[Cu(C3H2O4)(C5H8N2)2(H2O)]·2H2O
Mr411.90
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)293
a, b, c (Å)24.000 (7), 8.531 (3), 9.369 (2)
V3)1918.2 (10)
Z4
Radiation typeMo Kα
µ (mm1)1.18
Crystal size (mm)0.46 × 0.36 × 0.32
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
via ψ-scan (North et al., 1968)
Tmin, Tmax0.523, 0.686
No. of measured, independent and
observed [I > 2σ(I)] reflections
2821, 2705, 1654
Rint0.033
(sin θ/λ)max1)0.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.157, 1.03
No. of reflections2705
No. of parameters226
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.36, 0.43
Absolute structureFlack (1983)
Absolute structure parameter0.01 (3)

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O4i1.131.772.719 (8)139
O1W—H1WB···O3Wii0.832.222.815 (7)129
O2W—H2WA···O20.902.232.816 (10)122
O2W—H2WA···O10.902.403.059 (9)130
O2W—H2WB···O4iii0.882.352.965 (9)127
O3W—H3WA···O4iv0.942.283.041 (10)138
O3W—H3WB···O20.941.822.762 (9)175
N2—H2···O11.002.202.812 (9)118
N4—H4···O30.932.242.731 (9)112
Symmetry codes: (i) x+1, y+1, z+1/2; (ii) x+1, y, z+1/2; (iii) x, y1, z; (iv) x+1, y+1, z1/2.
 

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