Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106042867/sf3018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106042867/sf3018Isup2.hkl |
CCDC reference: 632924
A warming solution containing copper(II) acetate monohydrate (0.181 g, 1.0 mmol) in water (10 ml) was added to a warming solution of di-2-pyridylamine (0.171 g, 1.0 mmol) in methanol (15 ml), and then the solid of malonic acid disodium salt monohydrate (0.084 g, 0.5 mmol) was added. The green solution was slowly evaporated at room temperature. After several days, blue–green crystals were formed. The crystals were filtered off, washed with mother liquor and air-dried.
H atoms bonded to water O atoms were visible in a difference map and were refined with a DFIX (SHELXTL; Sheldrick, 2000b) restraint [O—H = 0.90 (1) Å]. H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93–0.97 Å and an N—H distance of 0.86 Å [Uiso(H) = 1.2Ueq(C,N)].
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Cu(C3H2O4)(C10H8N3)(H2O)]·H2O | Z = 2 |
Mr = 372.82 | F(000) = 382 |
Triclinic, P1 | Dx = 1.695 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2409 (1) Å | Cell parameters from 3443 reflections |
b = 9.6351 (2) Å | θ = 1.9–30.4° |
c = 11.43800 (1) Å | µ = 1.53 mm−1 |
α = 87.815 (1)° | T = 293 K |
β = 71.700 (1)° | Plate, blue–green |
γ = 74.844 (1)° | 0.33 × 0.32 × 0.10 mm |
V = 730.46 (2) Å3 |
Siemens SMART CCD area-detector diffractometer | 4432 independent reflections |
Radiation source: fine-focus sealed tube | 3443 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω scans | θmax = 30.4°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a) | h = −9→10 |
Tmin = 0.599, Tmax = 0.858 | k = −11→13 |
5409 measured reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0652P)2 + 0.0267P] where P = (Fo2 + 2Fc2)/3 |
3945 reflections | (Δ/σ)max = 0.001 |
224 parameters | Δρmax = 0.37 e Å−3 |
4 restraints | Δρmin = −0.53 e Å−3 |
[Cu(C3H2O4)(C10H8N3)(H2O)]·H2O | γ = 74.844 (1)° |
Mr = 372.82 | V = 730.46 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2409 (1) Å | Mo Kα radiation |
b = 9.6351 (2) Å | µ = 1.53 mm−1 |
c = 11.43800 (1) Å | T = 293 K |
α = 87.815 (1)° | 0.33 × 0.32 × 0.10 mm |
β = 71.700 (1)° |
Siemens SMART CCD area-detector diffractometer | 4432 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a) | 3443 reflections with I > 2σ(I) |
Tmin = 0.599, Tmax = 0.858 | Rint = 0.018 |
5409 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 4 restraints |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.37 e Å−3 |
3945 reflections | Δρmin = −0.53 e Å−3 |
224 parameters |
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 | ||
Cu | 0.32750 (3) | 0.72392 (2) | 0.26124 (2) | 0.02562 (9) | |
O1 | 0.3253 (3) | 0.68233 (19) | 0.09718 (14) | 0.0381 (4) | |
O2 | 0.0799 (2) | 0.66796 (18) | 0.33730 (14) | 0.0364 (3) | |
O3 | 0.2227 (3) | 0.5950 (2) | −0.03979 (15) | 0.0435 (4) | |
O4 | −0.1659 (3) | 0.5697 (2) | 0.34784 (16) | 0.0437 (4) | |
O5 | 0.5461 (2) | 0.50946 (16) | 0.27038 (14) | 0.0300 (3) | |
O6 | 0.3125 (3) | 0.3190 (2) | 0.40014 (19) | 0.0540 (5) | |
N1 | 0.5275 (3) | 0.83725 (18) | 0.18613 (16) | 0.0283 (3) | |
N2 | 0.2880 (3) | 0.81266 (18) | 0.42481 (16) | 0.0272 (3) | |
N3 | 0.3603 (3) | 1.02676 (18) | 0.33734 (17) | 0.0317 (4) | |
H5 | 0.3158 | 1.1189 | 0.3471 | 0.038* | |
C1 | 0.6765 (3) | 0.7858 (2) | 0.0790 (2) | 0.0360 (4) | |
H1 | 0.7045 | 0.6893 | 0.0553 | 0.043* | |
C2 | 0.7869 (4) | 0.8690 (3) | 0.0046 (2) | 0.0415 (5) | |
H2 | 0.8915 | 0.8293 | −0.0663 | 0.050* | |
C3 | 0.7389 (4) | 1.0153 (3) | 0.0376 (2) | 0.0394 (5) | |
H3 | 0.8047 | 1.0760 | −0.0145 | 0.047* | |
C4 | 0.5945 (3) | 1.0685 (2) | 0.1471 (2) | 0.0341 (4) | |
H4 | 0.5630 | 1.1653 | 0.1711 | 0.041* | |
C5 | 0.4939 (3) | 0.9747 (2) | 0.22312 (19) | 0.0268 (4) | |
C6 | 0.2886 (3) | 0.9497 (2) | 0.43851 (18) | 0.0265 (4) | |
C7 | 0.2116 (3) | 1.0219 (2) | 0.5553 (2) | 0.0356 (4) | |
H7 | 0.2103 | 1.1179 | 0.5634 | 0.043* | |
C8 | 0.1385 (4) | 0.9486 (3) | 0.6567 (2) | 0.0405 (5) | |
H8 | 0.0843 | 0.9954 | 0.7343 | 0.049* | |
C9 | 0.1452 (4) | 0.8037 (3) | 0.6437 (2) | 0.0407 (5) | |
H9 | 0.1005 | 0.7514 | 0.7120 | 0.049* | |
C10 | 0.2197 (3) | 0.7412 (2) | 0.5272 (2) | 0.0348 (4) | |
H10 | 0.2239 | 0.6450 | 0.5175 | 0.042* | |
C11 | 0.2282 (3) | 0.6048 (2) | 0.06699 (18) | 0.0290 (4) | |
C12 | 0.1167 (4) | 0.5167 (2) | 0.1642 (2) | 0.0343 (4) | |
H12A | 0.0222 | 0.4870 | 0.1328 | 0.041* | |
H12B | 0.2141 | 0.4300 | 0.1738 | 0.041* | |
C13 | 0.0018 (3) | 0.5899 (2) | 0.29054 (18) | 0.0293 (4) | |
H14 | 0.617 (4) | 0.469 (3) | 0.1958 (17) | 0.033 (7)* | |
H13 | 0.632 (4) | 0.526 (4) | 0.300 (3) | 0.063 (10)* | |
H16 | 0.383 (5) | 0.378 (4) | 0.358 (3) | 0.074 (11)* | |
H15 | 0.259 (5) | 0.353 (4) | 0.478 (2) | 0.073 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.02937 (14) | 0.02235 (13) | 0.02621 (13) | −0.01086 (9) | −0.00663 (9) | −0.00120 (8) |
O1 | 0.0500 (9) | 0.0443 (9) | 0.0288 (7) | −0.0263 (8) | −0.0138 (7) | 0.0058 (6) |
O2 | 0.0319 (7) | 0.0420 (9) | 0.0342 (8) | −0.0180 (6) | −0.0001 (6) | −0.0135 (6) |
O3 | 0.0455 (9) | 0.0584 (11) | 0.0277 (8) | −0.0166 (8) | −0.0096 (7) | −0.0075 (7) |
O4 | 0.0378 (8) | 0.0635 (11) | 0.0357 (8) | −0.0300 (8) | −0.0059 (7) | −0.0021 (8) |
O5 | 0.0287 (7) | 0.0304 (7) | 0.0292 (7) | −0.0072 (6) | −0.0069 (6) | −0.0004 (6) |
O6 | 0.0710 (13) | 0.0345 (9) | 0.0466 (10) | −0.0264 (9) | 0.0063 (9) | −0.0085 (8) |
N1 | 0.0313 (8) | 0.0240 (8) | 0.0294 (8) | −0.0107 (6) | −0.0064 (7) | 0.0004 (6) |
N2 | 0.0302 (8) | 0.0246 (8) | 0.0282 (8) | −0.0085 (6) | −0.0095 (6) | −0.0014 (6) |
N3 | 0.0351 (9) | 0.0186 (7) | 0.0383 (9) | −0.0083 (6) | −0.0058 (7) | −0.0020 (6) |
C1 | 0.0392 (11) | 0.0313 (10) | 0.0341 (10) | −0.0123 (9) | −0.0038 (9) | −0.0032 (8) |
C2 | 0.0394 (12) | 0.0446 (13) | 0.0347 (11) | −0.0146 (10) | −0.0007 (9) | 0.0022 (9) |
C3 | 0.0388 (11) | 0.0403 (12) | 0.0432 (12) | −0.0194 (10) | −0.0126 (10) | 0.0137 (10) |
C4 | 0.0364 (10) | 0.0245 (9) | 0.0439 (12) | −0.0128 (8) | −0.0131 (9) | 0.0076 (8) |
C5 | 0.0259 (8) | 0.0225 (8) | 0.0344 (10) | −0.0079 (7) | −0.0116 (7) | 0.0012 (7) |
C6 | 0.0245 (8) | 0.0231 (9) | 0.0322 (9) | −0.0048 (7) | −0.0098 (7) | −0.0039 (7) |
C7 | 0.0343 (10) | 0.0326 (10) | 0.0372 (11) | −0.0054 (8) | −0.0088 (9) | −0.0101 (8) |
C8 | 0.0390 (11) | 0.0469 (13) | 0.0312 (10) | −0.0046 (10) | −0.0093 (9) | −0.0089 (9) |
C9 | 0.0454 (12) | 0.0437 (13) | 0.0288 (10) | −0.0095 (10) | −0.0078 (9) | 0.0040 (9) |
C10 | 0.0425 (11) | 0.0290 (10) | 0.0337 (10) | −0.0119 (9) | −0.0116 (9) | 0.0040 (8) |
C11 | 0.0293 (9) | 0.0287 (9) | 0.0271 (9) | −0.0052 (7) | −0.0077 (7) | −0.0034 (7) |
C12 | 0.0416 (11) | 0.0296 (10) | 0.0323 (10) | −0.0160 (8) | −0.0061 (9) | −0.0067 (8) |
C13 | 0.0300 (9) | 0.0300 (9) | 0.0283 (9) | −0.0109 (8) | −0.0071 (8) | −0.0010 (7) |
Cu—O2 | 1.9368 (15) | C1—C2 | 1.364 (3) |
Cu—O1 | 1.9396 (15) | C1—H1 | 0.9300 |
Cu—N2 | 1.9929 (16) | C2—C3 | 1.397 (4) |
Cu—N1 | 2.0002 (17) | C2—H2 | 0.9300 |
Cu—O5 | 2.2722 (15) | C3—C4 | 1.368 (3) |
O1—C11 | 1.272 (2) | C3—H3 | 0.9300 |
O2—C13 | 1.271 (2) | C4—C5 | 1.411 (3) |
O3—C11 | 1.243 (3) | C4—H4 | 0.9300 |
O4—C13 | 1.247 (3) | C6—C7 | 1.407 (3) |
O5—H14 | 0.887 (17) | C7—C8 | 1.368 (4) |
O5—H13 | 0.848 (18) | C7—H7 | 0.9300 |
O6—H16 | 0.89 (4) | C8—C9 | 1.397 (4) |
O6—H15 | 0.887 (18) | C8—H8 | 0.9300 |
N1—C5 | 1.342 (2) | C9—C10 | 1.368 (3) |
N1—C1 | 1.359 (3) | C9—H9 | 0.9300 |
N2—C6 | 1.337 (2) | C10—H10 | 0.9300 |
N2—C10 | 1.357 (3) | C11—C12 | 1.527 (3) |
N3—C5 | 1.377 (3) | C12—C13 | 1.515 (3) |
N3—C6 | 1.385 (3) | C12—H12A | 0.9700 |
N3—H5 | 0.8600 | C12—H12B | 0.9700 |
O2—Cu—O1 | 91.84 (7) | C3—C4—C5 | 119.1 (2) |
O2—Cu—N2 | 87.37 (7) | C3—C4—H4 | 120.5 |
O1—Cu—N2 | 166.18 (7) | C5—C4—H4 | 120.5 |
O2—Cu—N1 | 163.51 (7) | N1—C5—N3 | 120.26 (17) |
O1—Cu—N1 | 88.80 (7) | N1—C5—C4 | 121.22 (19) |
N2—Cu—N1 | 88.10 (7) | N3—C5—C4 | 118.53 (18) |
O2—Cu—O5 | 97.62 (7) | N2—C6—N3 | 120.91 (17) |
O1—Cu—O5 | 94.39 (7) | N2—C6—C7 | 121.38 (19) |
N2—Cu—O5 | 99.39 (6) | N3—C6—C7 | 117.69 (18) |
N1—Cu—O5 | 98.76 (6) | C8—C7—C6 | 118.9 (2) |
C11—O1—Cu | 127.75 (14) | C8—C7—H7 | 120.6 |
C13—O2—Cu | 128.12 (13) | C6—C7—H7 | 120.6 |
Cu—O5—H14 | 111.7 (17) | C7—C8—C9 | 120.1 (2) |
Cu—O5—H13 | 108 (2) | C7—C8—H8 | 120.0 |
H14—O5—H13 | 105 (3) | C9—C8—H8 | 120.0 |
H16—O6—H15 | 108 (3) | C10—C9—C8 | 117.7 (2) |
C5—N1—C1 | 118.31 (18) | C10—C9—H9 | 121.1 |
C5—N1—Cu | 121.30 (14) | C8—C9—H9 | 121.1 |
C1—N1—Cu | 118.83 (13) | N2—C10—C9 | 123.3 (2) |
C6—N2—C10 | 118.53 (17) | N2—C10—H10 | 118.3 |
C6—N2—Cu | 121.98 (14) | C9—C10—H10 | 118.3 |
C10—N2—Cu | 118.19 (14) | O3—C11—O1 | 122.8 (2) |
C5—N3—C6 | 128.29 (17) | O3—C11—C12 | 117.79 (19) |
C5—N3—H5 | 115.9 | O1—C11—C12 | 119.42 (17) |
C6—N3—H5 | 115.9 | C13—C12—C11 | 116.74 (17) |
N1—C1—C2 | 123.1 (2) | C13—C12—H12A | 108.1 |
N1—C1—H1 | 118.4 | C11—C12—H12A | 108.1 |
C2—C1—H1 | 118.4 | C13—C12—H12B | 108.1 |
C1—C2—C3 | 118.4 (2) | C11—C12—H12B | 108.1 |
C1—C2—H2 | 120.8 | H12A—C12—H12B | 107.3 |
C3—C2—H2 | 120.8 | O4—C13—O2 | 121.28 (19) |
C4—C3—C2 | 119.5 (2) | O4—C13—C12 | 119.25 (18) |
C4—C3—H3 | 120.3 | O2—C13—C12 | 119.45 (17) |
C2—C3—H3 | 120.3 | ||
O2—Cu—O1—C11 | −18.7 (2) | C1—N1—C5—N3 | −172.77 (19) |
N2—Cu—O1—C11 | −105.1 (3) | Cu—N1—C5—N3 | 21.7 (3) |
N1—Cu—O1—C11 | 177.81 (19) | C1—N1—C5—C4 | 6.9 (3) |
O5—Cu—O1—C11 | 79.11 (19) | Cu—N1—C5—C4 | −158.71 (16) |
O1—Cu—O2—C13 | 19.8 (2) | C6—N3—C5—N1 | 19.1 (3) |
N2—Cu—O2—C13 | −174.0 (2) | C6—N3—C5—C4 | −160.5 (2) |
N1—Cu—O2—C13 | 111.8 (3) | C3—C4—C5—N1 | −4.7 (3) |
O5—Cu—O2—C13 | −74.8 (2) | C3—C4—C5—N3 | 175.0 (2) |
O2—Cu—N1—C5 | 33.0 (3) | C10—N2—C6—N3 | 178.72 (19) |
O1—Cu—N1—C5 | 125.44 (16) | Cu—N2—C6—N3 | −14.5 (3) |
N2—Cu—N1—C5 | −41.09 (16) | C10—N2—C6—C7 | −3.0 (3) |
O5—Cu—N1—C5 | −140.30 (16) | Cu—N2—C6—C7 | 163.74 (15) |
O2—Cu—N1—C1 | −132.5 (2) | C5—N3—C6—N2 | −23.3 (3) |
O1—Cu—N1—C1 | −40.05 (17) | C5—N3—C6—C7 | 158.4 (2) |
N2—Cu—N1—C1 | 153.42 (17) | N2—C6—C7—C8 | 1.3 (3) |
O5—Cu—N1—C1 | 54.21 (17) | N3—C6—C7—C8 | 179.6 (2) |
O2—Cu—N2—C6 | −126.71 (16) | C6—C7—C8—C9 | 1.4 (3) |
O1—Cu—N2—C6 | −39.7 (4) | C7—C8—C9—C10 | −2.3 (4) |
N1—Cu—N2—C6 | 37.43 (16) | C6—N2—C10—C9 | 2.2 (3) |
O5—Cu—N2—C6 | 136.00 (15) | Cu—N2—C10—C9 | −165.11 (19) |
O2—Cu—N2—C10 | 40.09 (17) | C8—C9—C10—N2 | 0.5 (4) |
O1—Cu—N2—C10 | 127.1 (3) | Cu—O1—C11—O3 | 173.39 (17) |
N1—Cu—N2—C10 | −155.77 (17) | Cu—O1—C11—C12 | −8.0 (3) |
O5—Cu—N2—C10 | −57.20 (16) | O3—C11—C12—C13 | −139.3 (2) |
C5—N1—C1—C2 | −3.2 (3) | O1—C11—C12—C13 | 42.0 (3) |
Cu—N1—C1—C2 | 162.7 (2) | Cu—O2—C13—O4 | −175.46 (17) |
N1—C1—C2—C3 | −2.7 (4) | Cu—O2—C13—C12 | 6.1 (3) |
C1—C2—C3—C4 | 4.9 (4) | C11—C12—C13—O4 | 140.6 (2) |
C2—C3—C4—C5 | −1.4 (3) | C11—C12—C13—O2 | −41.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H5···O6i | 0.86 | 2.04 | 2.836 (3) | 155 |
O5—H13···O4ii | 0.85 (3) | 1.86 (3) | 2.702 (3) | 173 (2) |
O5—H14···O3iii | 0.89 (2) | 1.82 (2) | 2.706 (2) | 173 (2) |
O6—H15···O4iv | 0.89 (2) | 2.00 (2) | 2.885 (3) | 174 (2) |
O6—H16···O5 | 0.89 (4) | 1.99 (4) | 2.874 (3) | 177 (2) |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z; (iv) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C3H2O4)(C10H8N3)(H2O)]·H2O |
Mr | 372.82 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.2409 (1), 9.6351 (2), 11.43800 (1) |
α, β, γ (°) | 87.815 (1), 71.700 (1), 74.844 (1) |
V (Å3) | 730.46 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.53 |
Crystal size (mm) | 0.33 × 0.32 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000a) |
Tmin, Tmax | 0.599, 0.858 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5409, 4432, 3443 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.713 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.101, 1.05 |
No. of reflections | 3945 |
No. of parameters | 224 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.53 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Sheldrick, 2000b), SHELXTL.
Cu—O2 | 1.9368 (15) | Cu—N1 | 2.0002 (17) |
Cu—O1 | 1.9396 (15) | Cu—O5 | 2.2722 (15) |
Cu—N2 | 1.9929 (16) | ||
O2—Cu—O1 | 91.84 (7) | N2—Cu—N1 | 88.10 (7) |
O2—Cu—N2 | 87.37 (7) | O2—Cu—O5 | 97.62 (7) |
O1—Cu—N2 | 166.18 (7) | O1—Cu—O5 | 94.39 (7) |
O2—Cu—N1 | 163.51 (7) | N2—Cu—O5 | 99.39 (6) |
O1—Cu—N1 | 88.80 (7) | N1—Cu—O5 | 98.76 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H5···O6i | 0.8600 | 2.04000 | 2.836 (3) | 155.00 |
O5—H13···O4ii | 0.85 (3) | 1.86 (3) | 2.702 (3) | 173 (2) |
O5—H14···O3iii | 0.89 (2) | 1.82 (2) | 2.706 (2) | 173 (2) |
O6—H15···O4iv | 0.89 (2) | 2.00 (2) | 2.885 (3) | 174 (2) |
O6—H16···O5 | 0.89 (4) | 1.99 (4) | 2.874 (3) | 177 (2) |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z; (iv) −x, −y+1, −z+1. |
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There has been considerable interest in the design and syntheses of transition metal complexes with the malonate ligand in coordination chemistry, owing to the fact that this type of complex has potential application in molecular-based magnets (Rodriguez-Martín et al., 2001). The malonate dianion generally exhibits bidentate, tridentate or tetradentate coordination modes (Shen et al., 2000). Although some complexes containing mixed malonate and nitrogen-donor ligands have been synthesized and characterized, complexes containing mixed malonate (mal) and di-2-pyridylamine (dpyam) ligands have never been reported. To the best of our knowledge, there are only four reports on structures with malonate/nitrogen-donor ligands, such as phen (1,10-phenanthroline), bpy (2,2'-bipyridyl) and bpym (2,2'-bipyrimidine), namely [Cu(phen)(mal)(H2O)]·1.5H2O, (II) (Kwik et al., 1986), [Cu(bpym)(mal)(H2O)]·H2O, (III) (Rodriguez-Martín et al., 2001), [Cu(bpy)(mal)(H2O)]·H2O, (IV) (Suresh & Bhadbhade, 1997), and [Cu(bpy)(mal)(H2O)]·H2O, (V) (Shen et al., 2000). The first three compounds exhibit mononuclear structures, while the last compound involves a dinuclear unit. In this paper, we report the crystal structure of [Cu(dpyam)(mal)(H2O)]·H2O, (I), in which the three-dimensional network is formed by hydrogen bonds. The ligand dpyam has been selected primarily because of the fact that it also has an NH hydrogen-bond donor function that might form one-, two- or three-dimensional supramolecular architectures. The structure of complex (I) consists of neutral mononuclear [Cu(dpyam)(mal)(H2O)] units (see Fig. 1) and crystallization water molecules. The Cu atom exhibits a slightly distorted square–pyramidal environment, the geometric τ value (Addison et al., 1984) being only 0.045. The CuII ion is bonded to two dpyam N atoms and two carboxylate O atoms from the malonate ligand in the basal plane, and to a water molecule in the apical position (Table 1 and Fig. 1). The Cu atom is displaced by 0.257 (1) Å from the mean basal plane towards the apical position. In the Cu unit, the dihedral angle between the N1/Cu1/N2 and O1/Cu1/O2 planes is 21.3°. The dpyam ligands are not planar, with a dihedral angle of 22.9°. Other related examples of the malonate are compounds (II)–(V). In each of these, the CuII atom exhibits a slightly distorted square–pyramidal geometry, with τ values of 0.057 for (II), 0.006 for (III), 0.061 for (IV) and 0.040 for (V).
The electronic reflectance spectrum of (I) involves two bands at 15 800 and 11 000 cm−1, this spectral character of the compound is consistent with the distorted square–pyramidal geometry with τ = 0.045. The transitions may be assigned as the dz2 → dx2-y2 transition for the low-energy peak and the dxz ≈ dyz → dx2-y2 transition for the high-energy peak. The electronic spectrum of (I) is similar to that found in a complex with similar CuII environment, compound (V) (15 400 and 11 000 cm−1). The IR spectrum of (I) exhibits several characteristic strong bands at 1670–1600 cm−1, which are attributed to C═O stretching modes. The complex molecules are linked to form a three-dimensional network by hydrogen-bonding interactions between the NH group of the dpyam group and the uncoordinated water molecule, and between the coordinated water molecule and the uncoordinated malonate O atoms (Table 2 and Fig. 2). All available hydrogen-bonding donors take part in hydrogen bonds.