Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101015116/da1196sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101015116/da1196Isup2.hkl |
CCDC reference: 179252
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).
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).
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.
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.
[Cu(C3H2O4)(C5H8N2)2(H2O)]·2H2O | Dx = 1.426 Mg m−3 |
Mr = 411.90 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 25 reflections |
a = 24.000 (7) Å | θ = 7.5–15.0° |
b = 8.531 (3) Å | µ = 1.18 mm−1 |
c = 9.369 (2) Å | T = 293 K |
V = 1918.2 (10) Å3 | Prism, blue |
Z = 4 | 0.46 × 0.36 × 0.32 mm |
F(000) = 860 |
Siemens P4 diffractometer | 1654 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 29.0°, θmin = 2.4° |
ω scans | h = −1→32 |
Absorption correction: empirical (using intensity measurements) via ψ-scan (North et al., 1968) | k = 0→11 |
Tmin = 0.523, Tmax = 0.686 | l = 0→12 |
2821 measured reflections | 2 standard reflections every 120 min |
2705 independent reflections | intensity decay: none |
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)] = 0.059 | H-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 reflections | Δρmax = 0.36 e Å−3 |
226 parameters | Δρmin = −0.43 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (3) |
[Cu(C3H2O4)(C5H8N2)2(H2O)]·2H2O | V = 1918.2 (10) Å3 |
Mr = 411.90 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 24.000 (7) Å | µ = 1.18 mm−1 |
b = 8.531 (3) Å | T = 293 K |
c = 9.369 (2) Å | 0.46 × 0.36 × 0.32 mm |
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 = 0.686 | 2 standard reflections every 120 min |
2821 measured reflections | intensity decay: none |
2705 independent reflections |
R[F2 > 2σ(F2)] = 0.059 | H-atom parameters constrained |
wR(F2) = 0.157 | Δρmax = 0.36 e Å−3 |
S = 1.03 | Δρmin = −0.43 e Å−3 |
2705 reflections | Absolute structure: Flack (1983) |
226 parameters | Absolute structure parameter: −0.01 (3) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.38077 (3) | 0.39341 (9) | 0.66382 (10) | 0.0428 (2) | |
O1 | 0.3854 (2) | 0.2900 (6) | 0.4781 (6) | 0.0522 (13) | |
O2 | 0.4431 (3) | 0.1827 (7) | 0.3248 (7) | 0.0738 (18) | |
O3 | 0.4157 (2) | 0.5794 (6) | 0.5835 (6) | 0.0547 (14) | |
O4 | 0.4661 (3) | 0.7059 (7) | 0.4239 (8) | 0.078 (2) | |
O1W | 0.4538 (2) | 0.2349 (6) | 0.7258 (7) | 0.0667 (17) | |
H1WA | 0.4749 | 0.2207 | 0.8324 | 0.080* | |
H1WB | 0.4436 | 0.1630 | 0.6729 | 0.080* | |
O2W | 0.3742 (3) | −0.0620 (8) | 0.4225 (11) | 0.093 (3) | |
H2WA | 0.3970 | 0.0108 | 0.4601 | 0.080* | |
H2WB | 0.3798 | −0.1640 | 0.4277 | 0.080* | |
O3W | 0.5405 (3) | 0.0925 (6) | 0.1910 (8) | 0.070 (2) | |
H3WA | 0.5245 | 0.1130 | 0.1013 | 0.080* | |
H3WB | 0.5084 | 0.1276 | 0.2390 | 0.080* | |
N1 | 0.3144 (2) | 0.2557 (7) | 0.7012 (6) | 0.0493 (16) | |
N2 | 0.3171 (2) | 0.1039 (7) | 0.6535 (10) | 0.0563 (16) | |
H2 | 0.3568 | 0.1020 | 0.6212 | 0.080* | |
N3 | 0.3830 (2) | 0.5051 (7) | 0.8518 (7) | 0.0460 (14) | |
N4 | 0.3898 (2) | 0.6638 (7) | 0.8566 (8) | 0.0480 (15) | |
H4 | 0.3971 | 0.7250 | 0.7766 | 0.080* | |
C1 | 0.4496 (3) | 0.5828 (9) | 0.4771 (9) | 0.0497 (18) | |
C2 | 0.4716 (3) | 0.4283 (8) | 0.4167 (10) | 0.056 (2) | |
H2A | 0.5031 | 0.3974 | 0.4729 | 0.080* | |
H2B | 0.4850 | 0.4490 | 0.3220 | 0.080* | |
C3 | 0.4310 (3) | 0.2908 (9) | 0.4073 (9) | 0.0487 (18) | |
C4 | 0.2706 (4) | 0.0248 (10) | 0.7018 (13) | 0.078 (3) | |
C5 | 0.2381 (4) | 0.1267 (10) | 0.7758 (12) | 0.076 (3) | |
H5A | 0.2033 | 0.1046 | 0.8219 | 0.080* | |
C6 | 0.2665 (3) | 0.2714 (11) | 0.7744 (10) | 0.061 (2) | |
C7 | 0.2641 (5) | −0.1458 (9) | 0.659 (2) | 0.131 (6) | |
H7A | 0.2302 | −0.1871 | 0.6986 | 0.080* | |
H7B | 0.2629 | −0.1535 | 0.5571 | 0.080* | |
H7C | 0.2952 | −0.2047 | 0.6949 | 0.080* | |
C8 | 0.2469 (4) | 0.4246 (10) | 0.8346 (13) | 0.085 (3) | |
H8A | 0.2745 | 0.5036 | 0.8171 | 0.080* | |
H8B | 0.2124 | 0.4547 | 0.7904 | 0.080* | |
H8C | 0.2414 | 0.4135 | 0.9356 | 0.080* | |
C9 | 0.3782 (3) | 0.4600 (10) | 0.9886 (9) | 0.0504 (18) | |
C10 | 0.3814 (3) | 0.5909 (10) | 1.0759 (9) | 0.061 (2) | |
H10A | 0.3776 | 0.5921 | 1.1779 | 0.080* | |
C11 | 0.3900 (3) | 0.7181 (9) | 0.9909 (10) | 0.055 (2) | |
C12 | 0.3709 (4) | 0.2921 (11) | 1.0263 (11) | 0.073 (3) | |
H12A | 0.3708 | 0.2301 | 0.9408 | 0.080* | |
H12B | 0.4008 | 0.2587 | 1.0871 | 0.080* | |
H12C | 0.3361 | 0.2792 | 1.0752 | 0.080* | |
C13 | 0.3972 (5) | 0.8885 (10) | 1.0208 (15) | 0.089 (3) | |
H13A | 0.4030 | 0.9446 | 0.9332 | 0.080* | |
H13B | 0.3645 | 0.9278 | 1.0675 | 0.080* | |
H13C | 0.4289 | 0.9026 | 1.0820 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0377 (4) | 0.0479 (4) | 0.0430 (4) | −0.0044 (4) | 0.0032 (6) | −0.0039 (6) |
O1 | 0.042 (3) | 0.062 (3) | 0.052 (3) | −0.004 (2) | −0.001 (3) | −0.007 (3) |
O2 | 0.075 (4) | 0.078 (4) | 0.068 (4) | 0.010 (3) | 0.009 (4) | −0.033 (4) |
O3 | 0.062 (4) | 0.049 (3) | 0.053 (3) | −0.004 (2) | 0.024 (3) | −0.004 (3) |
O4 | 0.089 (4) | 0.060 (4) | 0.086 (5) | 0.008 (3) | 0.044 (4) | 0.015 (4) |
O1W | 0.061 (3) | 0.060 (3) | 0.080 (4) | 0.010 (3) | −0.034 (3) | −0.017 (3) |
O2W | 0.079 (5) | 0.066 (4) | 0.136 (7) | 0.015 (3) | −0.028 (5) | −0.008 (5) |
O3W | 0.079 (4) | 0.060 (3) | 0.071 (6) | 0.007 (3) | 0.029 (4) | 0.003 (3) |
N1 | 0.046 (3) | 0.059 (4) | 0.043 (4) | −0.012 (3) | 0.004 (3) | 0.002 (3) |
N2 | 0.045 (3) | 0.059 (3) | 0.065 (4) | −0.016 (3) | −0.013 (5) | 0.005 (4) |
N3 | 0.041 (3) | 0.046 (3) | 0.050 (4) | −0.003 (3) | 0.002 (3) | −0.001 (3) |
N4 | 0.050 (4) | 0.041 (3) | 0.053 (4) | 0.001 (3) | 0.000 (3) | −0.003 (3) |
C1 | 0.042 (4) | 0.057 (5) | 0.049 (4) | 0.006 (3) | 0.005 (3) | 0.006 (4) |
C2 | 0.040 (4) | 0.068 (5) | 0.059 (5) | 0.002 (4) | 0.019 (4) | −0.001 (4) |
C3 | 0.042 (4) | 0.062 (5) | 0.042 (4) | 0.011 (4) | −0.004 (3) | −0.001 (4) |
C4 | 0.053 (4) | 0.070 (5) | 0.111 (10) | −0.028 (4) | −0.032 (5) | 0.018 (6) |
C5 | 0.055 (5) | 0.092 (7) | 0.083 (7) | −0.015 (5) | 0.006 (5) | 0.029 (6) |
C6 | 0.046 (4) | 0.083 (5) | 0.053 (5) | −0.005 (4) | 0.005 (4) | 0.003 (5) |
C7 | 0.101 (9) | 0.072 (6) | 0.218 (16) | −0.043 (6) | −0.077 (13) | 0.023 (13) |
C8 | 0.051 (5) | 0.122 (8) | 0.083 (7) | 0.007 (6) | 0.011 (5) | 0.001 (7) |
C9 | 0.049 (4) | 0.057 (4) | 0.045 (4) | −0.007 (4) | −0.005 (4) | −0.002 (4) |
C10 | 0.057 (5) | 0.082 (6) | 0.045 (4) | −0.003 (5) | −0.003 (4) | −0.007 (4) |
C11 | 0.056 (5) | 0.053 (4) | 0.055 (5) | −0.002 (4) | 0.012 (4) | −0.006 (4) |
C12 | 0.093 (7) | 0.069 (6) | 0.058 (5) | −0.001 (5) | 0.001 (5) | 0.008 (5) |
C13 | 0.108 (8) | 0.065 (6) | 0.096 (9) | 0.007 (6) | 0.016 (7) | −0.009 (6) |
Cu1—O3 | 1.946 (5) | N3—N4 | 1.365 (9) |
Cu1—O1 | 1.954 (6) | N4—C11 | 1.341 (11) |
Cu1—N3 | 2.003 (6) | C1—C2 | 1.528 (10) |
Cu1—N1 | 2.010 (6) | C2—C3 | 1.527 (11) |
Cu1—O1W | 2.288 (5) | C4—C5 | 1.359 (14) |
O1—C3 | 1.278 (9) | C4—C7 | 1.517 (14) |
O2—C3 | 1.238 (9) | C5—C6 | 1.410 (11) |
O3—C1 | 1.287 (9) | C6—C8 | 1.499 (12) |
O4—C1 | 1.229 (9) | C9—C10 | 1.386 (12) |
N1—C6 | 1.346 (9) | C9—C12 | 1.486 (13) |
N1—N2 | 1.372 (9) | C10—C11 | 1.361 (12) |
N2—C4 | 1.380 (10) | C11—C13 | 1.491 (12) |
N3—C9 | 1.343 (10) | ||
O3—Cu1—O1 | 89.9 (2) | O4—C1—C2 | 118.4 (7) |
O3—Cu1—N3 | 86.6 (2) | O3—C1—C2 | 119.1 (7) |
O1—Cu1—N3 | 175.0 (2) | C3—C2—C1 | 117.6 (6) |
O3—Cu1—N1 | 152.3 (3) | O2—C3—O1 | 121.4 (8) |
O1—Cu1—N1 | 86.4 (2) | O2—C3—C2 | 117.3 (7) |
N3—Cu1—N1 | 98.4 (2) | O1—C3—C2 | 121.3 (7) |
O3—Cu1—O1W | 104.5 (2) | C5—C4—N2 | 108.6 (7) |
O1—Cu1—O1W | 85.1 (2) | C5—C4—C7 | 133.5 (9) |
N3—Cu1—O1W | 92.2 (2) | N2—C4—C7 | 117.8 (10) |
N1—Cu1—O1W | 102.5 (2) | C4—C5—C6 | 106.2 (8) |
C3—O1—Cu1 | 120.6 (5) | N1—C6—C5 | 109.3 (8) |
C1—O3—Cu1 | 126.2 (5) | N1—C6—C8 | 123.1 (8) |
C6—N1—N2 | 107.5 (6) | C5—C6—C8 | 127.5 (8) |
C6—N1—Cu1 | 135.1 (6) | N3—C9—C10 | 109.2 (7) |
N2—N1—Cu1 | 117.2 (5) | N3—C9—C12 | 120.8 (7) |
N1—N2—C4 | 108.4 (7) | C10—C9—C12 | 130.0 (8) |
C9—N3—N4 | 105.2 (6) | C11—C10—C9 | 107.7 (8) |
C9—N3—Cu1 | 134.5 (5) | N4—C11—C10 | 105.9 (7) |
N4—N3—Cu1 | 120.3 (5) | N4—C11—C13 | 120.9 (9) |
C11—N4—N3 | 112.0 (7) | C10—C11—C13 | 133.2 (10) |
O4—C1—O3 | 122.5 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4i | 1.13 | 1.77 | 2.719 (8) | 139 |
O1W—H1WB···O3Wii | 0.83 | 2.22 | 2.815 (7) | 129 |
O2W—H2WA···O2 | 0.90 | 2.23 | 2.816 (10) | 122 |
O2W—H2WA···O1 | 0.90 | 2.40 | 3.059 (9) | 130 |
O2W—H2WB···O4iii | 0.88 | 2.35 | 2.965 (9) | 127 |
O3W—H3WA···O4iv | 0.94 | 2.28 | 3.041 (10) | 138 |
O3W—H3WB···O2 | 0.94 | 1.82 | 2.762 (9) | 175 |
N2—H2···O1 | 1.00 | 2.20 | 2.812 (9) | 118 |
N4—H4···O3 | 0.93 | 2.24 | 2.731 (9) | 112 |
Symmetry codes: (i) −x+1, −y+1, z+1/2; (ii) −x+1, −y, z+1/2; (iii) x, y−1, z; (iv) −x+1, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C3H2O4)(C5H8N2)2(H2O)]·2H2O |
Mr | 411.90 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 293 |
a, b, c (Å) | 24.000 (7), 8.531 (3), 9.369 (2) |
V (Å3) | 1918.2 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.18 |
Crystal size (mm) | 0.46 × 0.36 × 0.32 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.523, 0.686 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2821, 2705, 1654 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.157, 1.03 |
No. of reflections | 2705 |
No. of parameters | 226 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.43 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.01 (3) |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4i | 1.13 | 1.77 | 2.719 (8) | 139 |
O1W—H1WB···O3Wii | 0.83 | 2.22 | 2.815 (7) | 129 |
O2W—H2WA···O2 | 0.90 | 2.23 | 2.816 (10) | 122 |
O2W—H2WA···O1 | 0.90 | 2.40 | 3.059 (9) | 130 |
O2W—H2WB···O4iii | 0.88 | 2.35 | 2.965 (9) | 127 |
O3W—H3WA···O4iv | 0.94 | 2.28 | 3.041 (10) | 138 |
O3W—H3WB···O2 | 0.94 | 1.82 | 2.762 (9) | 175 |
N2—H2···O1 | 1.00 | 2.20 | 2.812 (9) | 118 |
N4—H4···O3 | 0.93 | 2.24 | 2.731 (9) | 112 |
Symmetry codes: (i) −x+1, −y+1, z+1/2; (ii) −x+1, −y, z+1/2; (iii) x, y−1, z; (iv) −x+1, −y+1, z−1/2. |
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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 π–π 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.