Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011333/wn6019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011333/wn6019Isup2.hkl |
CCDC reference: 170880
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.036
- wR factor = 0.098
- Data-to-parameter ratio = 10.3
checkCIF results
No syntax errors foundGLOBAL _publ field problems
Alert Level A:
PUBL_002 Alert A The contact author's address is missing, _publ_contact_author_address. ADDSYM reports no extra symmetry
1 Alert Level A = Potentially serious problem
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A mixture of CuO (0.080 g, 2.0 mmol), [H2pydc]·H2O (0.185 g, 1.0 mmol) and H2O (16 ml) in a molar ratio of ca 2:1:890 was sealed in a 25 ml stainless-steel reactor with Teflon liner. The reaction system was heated at 443 K for 72 h. Slowly cooling the system to room temperature yielded needle-like green crystals of the complex and some blue–green precipitate. The organic H atoms were positioned geometrically (C—H bond fixed at 0.96 Å) and allowed to ride on their parent C atoms before the final cycle of refinement. The hydrate H atoms were located from difference maps and refined with isotropic displacement parameters.
Data collection: SMART (Siemens, 1994); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: XPREP (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.
Fig. 1. The structure of [Cu(Hpydc)2]·2H2O. Displacement ellipsoids are plotted at the 50% probability level. | |
Fig. 2. Packing diagram of [Cu(Hpydc)2]·2H2O. Dashed lines indicate the hydrogen bonds. |
[Cu(C7H4NO4)2]·2H2O | Z = 2 |
Mr = 431.80 | F(000) = 438 |
Triclinic, P1 | Dx = 1.820 Mg m−3 |
a = 7.212 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.139 (3) Å | Cell parameters from 4087 reflections |
c = 11.337 (5) Å | θ = 1.9–25.0° |
α = 73.67 (3)° | µ = 1.45 mm−1 |
β = 82.67 (3)° | T = 293 K |
γ = 85.04 (3)° | Needle, green |
V = 787.8 (5) Å3 | 0.42 × 0.10 × 0.04 mm |
SMART CCD diffractometer | 2754 independent reflections |
Radiation source: fine-focus sealed tube | 2345 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −8→6 |
Tmin = 0.586, Tmax = 0.944 | k = −11→12 |
4087 measured reflections | l = −13→13 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0527P)2 + 0.4456P] where P = (Fo2 + 2Fc2)/3 |
2754 reflections | (Δ/σ)max = 0.001 |
268 parameters | Δρmax = 0.61 e Å−3 |
6 restraints | Δρmin = −0.33 e Å−3 |
[Cu(C7H4NO4)2]·2H2O | γ = 85.04 (3)° |
Mr = 431.80 | V = 787.8 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.212 (3) Å | Mo Kα radiation |
b = 10.139 (3) Å | µ = 1.45 mm−1 |
c = 11.337 (5) Å | T = 293 K |
α = 73.67 (3)° | 0.42 × 0.10 × 0.04 mm |
β = 82.67 (3)° |
SMART CCD diffractometer | 2754 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2345 reflections with I > 2σ(I) |
Tmin = 0.586, Tmax = 0.944 | Rint = 0.017 |
4087 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 6 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.61 e Å−3 |
2754 reflections | Δρmin = −0.33 e Å−3 |
268 parameters |
Experimental. Empirical, from equivalent reflections (XEMP in SHELXTL; Siemens, 1994) |
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 | 1.27541 (5) | 1.49224 (3) | 0.25191 (3) | 0.03307 (15) | |
O1 | 1.2538 (3) | 1.4647 (2) | 0.43016 (17) | 0.0368 (5) | |
O2 | 1.2721 (3) | 1.5772 (2) | 0.56913 (18) | 0.0444 (5) | |
O3 | 1.6457 (4) | 2.0310 (2) | 0.3902 (2) | 0.0534 (6) | |
O4 | 1.5974 (4) | 2.1257 (2) | 0.1930 (2) | 0.0534 (6) | |
H4A | 1.607 (6) | 2.211 (3) | 0.208 (4) | 0.081 (14)* | |
O5 | 1.2745 (3) | 1.5269 (2) | 0.07431 (17) | 0.0355 (5) | |
O6 | 1.1984 (3) | 1.4340 (2) | −0.06682 (18) | 0.0394 (5) | |
O7 | 0.9924 (4) | 0.8422 (2) | 0.3087 (2) | 0.0517 (6) | |
H7A | 0.979 (6) | 0.760 (3) | 0.291 (4) | 0.079 (14)* | |
O8 | 1.0782 (5) | 0.9119 (3) | 0.1063 (3) | 0.0798 (10) | |
O01 | 0.9524 (3) | 1.6088 (2) | 0.26439 (19) | 0.0358 (5) | |
H01A | 0.907 (5) | 1.615 (4) | 0.193 (2) | 0.062 (12)* | |
H01B | 0.869 (4) | 1.555 (3) | 0.322 (3) | 0.064 (12)* | |
O02 | 1.6122 (3) | 1.3612 (2) | 0.2347 (2) | 0.0435 (5) | |
H02A | 1.646 (5) | 1.362 (4) | 0.309 (2) | 0.063 (12)* | |
H02B | 1.686 (5) | 1.423 (3) | 0.176 (3) | 0.064 (12)* | |
N1 | 1.3952 (3) | 1.6618 (2) | 0.2473 (2) | 0.0288 (5) | |
N2 | 1.1834 (3) | 1.3128 (2) | 0.2575 (2) | 0.0300 (5) | |
C11 | 1.2989 (4) | 1.5657 (3) | 0.4626 (2) | 0.0307 (6) | |
C12 | 1.3909 (4) | 1.6795 (3) | 0.3611 (2) | 0.0280 (6) | |
C13 | 1.4613 (4) | 1.7935 (3) | 0.3799 (3) | 0.0312 (6) | |
H13A | 1.4584 | 1.8035 | 0.4592 | 0.037* | |
C14 | 1.5364 (4) | 1.8928 (3) | 0.2778 (3) | 0.0301 (6) | |
C15 | 1.5437 (4) | 1.8727 (3) | 0.1610 (3) | 0.0345 (6) | |
H15A | 1.5969 | 1.9368 | 0.0918 | 0.041* | |
C16 | 1.4709 (4) | 1.7564 (3) | 0.1490 (2) | 0.0323 (6) | |
H16A | 1.4744 | 1.7433 | 0.0708 | 0.039* | |
C17 | 1.6002 (4) | 2.0233 (3) | 0.2941 (3) | 0.0359 (7) | |
C21 | 1.2142 (4) | 1.4312 (3) | 0.0412 (2) | 0.0306 (6) | |
C22 | 1.1656 (4) | 1.3025 (3) | 0.1436 (2) | 0.0280 (6) | |
C23 | 1.1163 (4) | 1.1824 (3) | 0.1244 (3) | 0.0327 (6) | |
H23A | 1.1007 | 1.1779 | 0.0455 | 0.039* | |
C24 | 1.0903 (4) | 1.0683 (3) | 0.2259 (3) | 0.0340 (6) | |
C25 | 1.1122 (4) | 1.0791 (3) | 0.3419 (3) | 0.0364 (7) | |
H25A | 1.0970 | 1.0032 | 0.4104 | 0.044* | |
C26 | 1.1566 (5) | 1.2032 (3) | 0.3555 (3) | 0.0378 (7) | |
H26A | 1.1682 | 1.2109 | 0.4340 | 0.045* | |
C27 | 1.0492 (5) | 0.9338 (3) | 0.2068 (3) | 0.0409 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0532 (3) | 0.0268 (2) | 0.0222 (2) | −0.01591 (16) | −0.00435 (15) | −0.00754 (14) |
O1 | 0.0578 (13) | 0.0306 (11) | 0.0248 (10) | −0.0177 (9) | −0.0060 (9) | −0.0068 (8) |
O2 | 0.0680 (15) | 0.0474 (13) | 0.0223 (10) | −0.0271 (11) | −0.0006 (9) | −0.0114 (9) |
O3 | 0.0734 (17) | 0.0470 (14) | 0.0487 (14) | −0.0196 (12) | −0.0122 (12) | −0.0202 (11) |
O4 | 0.0873 (19) | 0.0309 (12) | 0.0455 (14) | −0.0212 (12) | −0.0097 (12) | −0.0100 (11) |
O5 | 0.0546 (13) | 0.0307 (11) | 0.0236 (10) | −0.0155 (9) | −0.0031 (9) | −0.0079 (8) |
O6 | 0.0597 (14) | 0.0409 (12) | 0.0214 (10) | −0.0145 (10) | −0.0056 (9) | −0.0108 (9) |
O7 | 0.0668 (16) | 0.0323 (12) | 0.0601 (16) | −0.0182 (11) | 0.0061 (12) | −0.0204 (12) |
O8 | 0.152 (3) | 0.0427 (15) | 0.0544 (17) | −0.0150 (17) | −0.0312 (18) | −0.0180 (13) |
O01 | 0.0489 (13) | 0.0309 (11) | 0.0297 (11) | −0.0141 (9) | −0.0051 (9) | −0.0076 (9) |
O02 | 0.0686 (15) | 0.0351 (12) | 0.0307 (12) | −0.0225 (11) | −0.0075 (11) | −0.0083 (10) |
N1 | 0.0378 (13) | 0.0263 (12) | 0.0238 (11) | −0.0054 (10) | −0.0044 (9) | −0.0077 (9) |
N2 | 0.0418 (13) | 0.0276 (12) | 0.0227 (11) | −0.0091 (10) | −0.0006 (10) | −0.0092 (10) |
C11 | 0.0382 (15) | 0.0320 (15) | 0.0228 (14) | −0.0086 (12) | −0.0072 (11) | −0.0050 (12) |
C12 | 0.0342 (14) | 0.0266 (14) | 0.0237 (13) | −0.0042 (11) | −0.0062 (11) | −0.0055 (11) |
C13 | 0.0392 (16) | 0.0308 (15) | 0.0280 (14) | −0.0063 (12) | −0.0056 (12) | −0.0129 (12) |
C14 | 0.0330 (14) | 0.0260 (14) | 0.0332 (15) | −0.0049 (11) | −0.0032 (11) | −0.0103 (12) |
C15 | 0.0439 (17) | 0.0295 (15) | 0.0296 (15) | −0.0092 (13) | 0.0005 (12) | −0.0070 (12) |
C16 | 0.0452 (16) | 0.0292 (15) | 0.0242 (14) | −0.0066 (12) | −0.0023 (12) | −0.0093 (12) |
C17 | 0.0359 (16) | 0.0357 (16) | 0.0394 (17) | −0.0098 (13) | 0.0021 (13) | −0.0158 (14) |
C21 | 0.0376 (15) | 0.0313 (15) | 0.0240 (14) | −0.0059 (12) | −0.0022 (11) | −0.0086 (12) |
C22 | 0.0310 (14) | 0.0293 (14) | 0.0254 (14) | −0.0060 (11) | −0.0009 (11) | −0.0098 (11) |
C23 | 0.0404 (16) | 0.0342 (16) | 0.0286 (14) | −0.0057 (12) | −0.0063 (12) | −0.0149 (12) |
C24 | 0.0349 (15) | 0.0320 (15) | 0.0383 (16) | −0.0035 (12) | −0.0048 (12) | −0.0139 (13) |
C25 | 0.0499 (18) | 0.0294 (15) | 0.0286 (15) | −0.0104 (13) | 0.0038 (12) | −0.0068 (12) |
C26 | 0.0553 (19) | 0.0353 (16) | 0.0251 (14) | −0.0144 (14) | 0.0005 (13) | −0.0105 (13) |
C27 | 0.0500 (19) | 0.0285 (16) | 0.0489 (19) | −0.0008 (14) | −0.0142 (15) | −0.0144 (14) |
Cu—O5 | 1.945 (2) | O02—H02B | 0.920 (19) |
Cu—O1 | 1.948 (2) | N1—C16 | 1.339 (4) |
Cu—N2 | 1.972 (2) | N1—C12 | 1.347 (3) |
Cu—N1 | 1.975 (2) | N2—C26 | 1.340 (4) |
O1—C11 | 1.260 (3) | N2—C22 | 1.347 (3) |
O2—C11 | 1.235 (3) | C11—C12 | 1.512 (4) |
O2—O02i | 2.716 (3) | C12—C13 | 1.381 (4) |
O2—O01ii | 2.736 (3) | C13—C14 | 1.387 (4) |
O3—C17 | 1.202 (4) | C13—H13A | 0.9300 |
O4—C17 | 1.313 (4) | C14—C15 | 1.390 (4) |
O4—O02iii | 2.575 (3) | C14—C17 | 1.504 (4) |
O4—H4A | 0.939 (19) | C15—C16 | 1.379 (4) |
O5—C21 | 1.262 (3) | C15—H15A | 0.9300 |
O6—C21 | 1.236 (3) | C16—H16A | 0.9300 |
O6—O02iv | 2.721 (3) | C21—C22 | 1.516 (4) |
O6—O01v | 2.764 (3) | C22—C23 | 1.378 (4) |
O7—C27 | 1.306 (4) | C23—C24 | 1.390 (4) |
O7—O01vi | 2.600 (3) | C23—H23A | 0.9300 |
O7—H7A | 0.929 (19) | C24—C25 | 1.379 (4) |
O8—C27 | 1.210 (4) | C24—C27 | 1.499 (4) |
O01—H01A | 0.900 (19) | C25—C26 | 1.378 (4) |
O01—H01B | 0.918 (19) | C25—H25A | 0.9300 |
O02—H02A | 0.908 (19) | C26—H26A | 0.9300 |
O5—Cu—O1 | 174.94 (9) | C12—C13—H13A | 120.7 |
O5—Cu—N2 | 83.63 (9) | C14—C13—H13A | 120.7 |
O1—Cu—N2 | 96.47 (9) | C13—C14—C15 | 119.3 (2) |
O5—Cu—N1 | 97.05 (9) | C13—C14—C17 | 119.8 (3) |
O1—Cu—N1 | 83.40 (9) | C15—C14—C17 | 120.9 (3) |
N2—Cu—N1 | 173.73 (10) | C16—C15—C14 | 119.1 (3) |
C11—O1—Cu | 114.43 (17) | C16—C15—H15A | 120.4 |
C11—O2—O02i | 151.7 (2) | C14—C15—H15A | 120.4 |
C11—O2—O01ii | 116.58 (19) | N1—C16—C15 | 121.5 (3) |
O02i—O2—O01ii | 87.39 (9) | N1—C16—H16A | 119.2 |
C17—O4—O02iii | 112.48 (19) | C15—C16—H16A | 119.2 |
C17—O4—H4A | 112 (3) | O3—C17—O4 | 124.9 (3) |
O02iii—O4—H4A | 2 (3) | O3—C17—C14 | 122.7 (3) |
C21—O5—Cu | 114.81 (17) | O4—C17—C14 | 112.4 (3) |
C21—O6—O02iv | 112.72 (19) | O6—C21—O5 | 125.0 (3) |
C21—O6—O01v | 159.0 (2) | O6—C21—C22 | 119.0 (2) |
O02iv—O6—O01v | 86.75 (9) | O5—C21—C22 | 115.9 (2) |
C27—O7—O01vi | 110.48 (19) | N2—C22—C23 | 121.9 (2) |
C27—O7—H7A | 109 (3) | N2—C22—C21 | 113.7 (2) |
O01vi—O7—H7A | 1 (3) | C23—C22—C21 | 124.3 (2) |
H01A—O01—H01B | 102 (3) | C22—C23—C24 | 118.3 (3) |
H02A—O02—H02B | 106 (3) | C22—C23—H23A | 120.8 |
C16—N1—C12 | 119.6 (2) | C24—C23—H23A | 120.8 |
C16—N1—Cu | 128.61 (19) | C25—C24—C23 | 119.3 (3) |
C12—N1—Cu | 111.75 (18) | C25—C24—C27 | 121.1 (3) |
C26—N2—C22 | 119.7 (2) | C23—C24—C27 | 119.5 (3) |
C26—N2—Cu | 128.11 (19) | C26—C25—C24 | 119.6 (3) |
C22—N2—Cu | 111.84 (18) | C26—C25—H25A | 120.2 |
O2—C11—O1 | 124.8 (3) | C24—C25—H25A | 120.2 |
O2—C11—C12 | 119.2 (2) | N2—C26—C25 | 121.1 (3) |
O1—C11—C12 | 116.0 (2) | N2—C26—H26A | 119.5 |
N1—C12—C13 | 121.9 (2) | C25—C26—H26A | 119.5 |
N1—C12—C11 | 113.7 (2) | O8—C27—O7 | 124.2 (3) |
C13—C12—C11 | 124.4 (2) | O8—C27—C24 | 121.8 (3) |
C12—C13—C14 | 118.5 (2) | O7—C27—C24 | 113.8 (3) |
Symmetry codes: (i) −x+3, −y+3, −z+1; (ii) −x+2, −y+3, −z+1; (iii) x, y+1, z; (iv) −x+3, −y+3, −z; (v) −x+2, −y+3, −z; (vi) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C7H4NO4)2]·2H2O |
Mr | 431.80 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.212 (3), 10.139 (3), 11.337 (5) |
α, β, γ (°) | 73.67 (3), 82.67 (3), 85.04 (3) |
V (Å3) | 787.8 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.45 |
Crystal size (mm) | 0.42 × 0.10 × 0.04 |
Data collection | |
Diffractometer | SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.586, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4087, 2754, 2345 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.098, 1.04 |
No. of reflections | 2754 |
No. of parameters | 268 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.61, −0.33 |
Computer programs: SMART (Siemens, 1994), SMART and SAINT (Siemens, 1994), XPREP (Siemens, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Cu—O5 | 1.945 (2) | O2—O01ii | 2.736 (3) |
Cu—O1 | 1.948 (2) | O4—O02iii | 2.575 (3) |
Cu—N2 | 1.972 (2) | O6—O02iv | 2.721 (3) |
Cu—N1 | 1.975 (2) | O6—O01v | 2.764 (3) |
O2—O02i | 2.716 (3) | O7—O01vi | 2.600 (3) |
O5—Cu—O1 | 174.94 (9) | C11—O1—Cu | 114.43 (17) |
O5—Cu—N2 | 83.63 (9) | C21—O5—Cu | 114.81 (17) |
O1—Cu—N2 | 96.47 (9) | C16—N1—Cu | 128.61 (19) |
O5—Cu—N1 | 97.05 (9) | C12—N1—Cu | 111.75 (18) |
O1—Cu—N1 | 83.40 (9) | C26—N2—Cu | 128.11 (19) |
N2—Cu—N1 | 173.73 (10) | C22—N2—Cu | 111.84 (18) |
Symmetry codes: (i) −x+3, −y+3, −z+1; (ii) −x+2, −y+3, −z+1; (iii) x, y+1, z; (iv) −x+3, −y+3, −z; (v) −x+2, −y+3, −z; (vi) x, y−1, z. |
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Research into transition metal complexes has been rapidly expanding because of their fascinating structural diversity and potential applications as functional materials and enzymes (Li et al., 1998). The key step in the design of polymeric transition metal complexes is to select suitable multidentate bridging ligands containing certain features, such as flexibility, versatile binding modes and the ability to form hydrogen bonds. With these criteria in mind, we chose pyridine-2,5-dicarboxylic acid as ligand. It reacts with transition metals or rare earths; a series of novel complexes having infinite or discrete structures has been obtained and reported (Liang et al., 2000, 2001). In this paper, we report the synthesis and crystal structure of a mononuclear copper(II) compound, (I), i.e. [Cu(Hpydc)2]·2H2O, (I), where pydc is pyridine-2,4-dicarboxylate.
The coordination complex [Cu(Hpydc)2]·2H2O was prepared by the hydrothermal reaction of CuO and H2pydc in H2O. The crystallographic analysis reveals that the compound is a discrete [Cu(Hpydc)22(H2O)] molecule, in which the CuII atom is coordinated by the two N and two O atoms of two Hpydc ligands to form a distorted planar four-coordinate geometry, as shown in Fig. 1. There is a weak interaction between the Cu and hydrate O atoms, with an average Cu—O distance of 2.602 Å. Other Cu—O and Cu—N distances are listed in Table 1, as are N—Cu—N, O—Cu—O and O—Cu—N angles. The molecules are connected by hydrogen-bonding interactions between the carboxylate groups and H2O, with an average O···O distance of 2.675 Å, to form a three-dimensional network, as shown in Fig. 2.