supplementary materials
Aquabis(dichloroacetato-![[kappa]](/logos/entities/kappa_rmgif.gif)
O)(1,10-phenanthroline-2N,N')copper(II)
A mixture of Cu(CH3COO)2*3H2O(204 mg, 1 mmol) and 1,10-phenanthroline
(185 mg, 1 mmol) in methanol(30 ml) was placed in a Teflon-lined stainless steel Parr
bomb that was heated at 403 K for 48 h. The bomb was then cooled down to the
room temperature, the solution was filtered. The solvent was removed from the
filtrate under vacuum, and the solid residue was recrystallized from diethyl
ether; blue crystals suitable for X-Ray diffraction study were obtained.
Yield, 0.760 g, 83%. m.p. 573 K. Analysis, calculated for
C16H12Cl4CuN2O5: C 46.73, H 2.94, N 6.81; found: C 46.95,
H 2.56, N
7.07%. The elemental analyses were performed with a Perkine Elemer PE2400II
instrument.
C-bound H atoms were geometrically positioned (C—H 0.93–0.97 Å) and
refined as riding, with Uiso(H)=1.2Ueq(C).
The water H atoms were located on a Fourier map and isotropically refined
with the distance restraints O—H=0.85 (2) Å.
Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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).
Aquabis(dichloroacetato-
κO)(1,10-phenanthroline-
κ2N,
N')copper(II)
top
Crystal data top
| [Cu(C2HCl2O2)2(C12H8N2)(H2O)] | Z = 2 |
| Mr = 517.62 | F(000) = 518 |
| Triclinic, P1 | Dx = 1.806 Mg m−3 |
| a = 8.2701 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 10.8883 (11) Å | Cell parameters from 1923 reflections |
| c = 12.0125 (12) Å | θ = 2.3–27.1° |
| α = 67.439 (1)° | µ = 1.74 mm−1 |
| β = 77.585 (2)° | T = 273 K |
| γ = 73.776 (2)° | Block, colorless |
| V = 952.02 (16) Å3 | 0.32 × 0.25 × 0.21 mm |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 3346 independent reflections |
| Radiation source: fine-focus sealed tube | 2539 reflections with I > 2σ(I) |
| graphite | Rint = 0.064 |
| φ and ω scans | θmax = 25.1°, θmin = 1.9° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −9→8 |
| Tmin = 0.606, Tmax = 0.711 | k = −12→12 |
| 5043 measured reflections | l = −14→14 |
Refinement top
| 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.046P)2]
where P = (Fo2 + 2Fc2)/3 |
| 3346 reflections | (Δ/σ)max < 0.001 |
| 261 parameters | Δρmax = 0.63 e Å−3 |
| 3 restraints | Δρmin = −0.51 e Å−3 |
Crystal data top
| [Cu(C2HCl2O2)2(C12H8N2)(H2O)] | γ = 73.776 (2)° |
| Mr = 517.62 | V = 952.02 (16) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.2701 (8) Å | Mo Kα radiation |
| b = 10.8883 (11) Å | µ = 1.74 mm−1 |
| c = 12.0125 (12) Å | T = 273 K |
| α = 67.439 (1)° | 0.32 × 0.25 × 0.21 mm |
| β = 77.585 (2)° | |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 3346 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 2539 reflections with I > 2σ(I) |
| Tmin = 0.606, Tmax = 0.711 | Rint = 0.064 |
| 5043 measured reflections | θmax = 25.1° |
Refinement top
| R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.106 | Δρmax = 0.63 e Å−3 |
| S = 1.00 | Δρmin = −0.51 e Å−3 |
| 3346 reflections | Absolute structure: ? |
| 261 parameters | Flack parameter: ? |
| 3 restraints | Rogers parameter: ? |
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| | x | y | z | Uiso*/Ueq | |
| Cu1 | 0.23680 (6) | 0.74569 (4) | 0.41387 (4) | 0.03375 (16) | |
| Cl4 | 0.12884 (15) | 0.83880 (10) | 0.01776 (9) | 0.0498 (3) | |
| Cl3 | 0.18005 (19) | 0.55281 (11) | 0.05837 (10) | 0.0653 (4) | |
| Cl1 | 0.66991 (17) | 0.90846 (12) | 0.08639 (11) | 0.0717 (4) | |
| Cl2 | 0.5908 (2) | 0.69108 (14) | 0.04161 (11) | 0.0831 (5) | |
| O3 | 0.1567 (3) | 0.7463 (2) | 0.2733 (2) | 0.0399 (6) | |
| C5 | 0.2814 (4) | 0.9060 (3) | 0.5379 (3) | 0.0310 (8) | |
| O5 | 0.1749 (4) | 0.5698 (3) | 0.5130 (2) | 0.0471 (7) | |
| N2 | 0.1747 (4) | 0.9522 (3) | 0.3541 (2) | 0.0324 (7) | |
| N1 | 0.3082 (4) | 0.7741 (3) | 0.5489 (3) | 0.0343 (7) | |
| C9 | 0.0716 (5) | 1.1808 (4) | 0.2276 (3) | 0.0447 (10) | |
| H9 | 0.0263 | 1.2392 | 0.1564 | 0.054* | |
| O2 | 0.7530 (4) | 0.6097 (3) | 0.2708 (2) | 0.0586 (8) | |
| C13 | 0.6067 (5) | 0.6806 (4) | 0.2683 (3) | 0.0344 (8) | |
| C16 | 0.0957 (5) | 0.6794 (3) | 0.1249 (3) | 0.0340 (8) | |
| H16 | −0.0272 | 0.6861 | 0.1432 | 0.041* | |
| C11 | 0.2127 (6) | 1.1856 (4) | 0.4993 (4) | 0.0471 (10) | |
| H11 | 0.1873 | 1.2779 | 0.4887 | 0.056* | |
| C15 | 0.1639 (5) | 0.6447 (3) | 0.2447 (3) | 0.0341 (8) | |
| O4 | 0.2088 (4) | 0.5243 (3) | 0.3049 (2) | 0.0609 (9) | |
| C14 | 0.5542 (5) | 0.7783 (4) | 0.1437 (3) | 0.0357 (9) | |
| H14 | 0.4330 | 0.8198 | 0.1536 | 0.043* | |
| C1 | 0.3872 (5) | 0.6806 (4) | 0.6436 (3) | 0.0447 (10) | |
| H1 | 0.4132 | 0.5893 | 0.6509 | 0.054* | |
| C12 | 0.2859 (6) | 1.0935 (4) | 0.5985 (4) | 0.0510 (11) | |
| H12 | 0.3130 | 1.1242 | 0.6531 | 0.061* | |
| C8 | 0.1025 (5) | 1.2327 (4) | 0.3051 (3) | 0.0421 (10) | |
| H8 | 0.0766 | 1.3264 | 0.2879 | 0.051* | |
| C10 | 0.1075 (5) | 1.0398 (4) | 0.2542 (3) | 0.0398 (9) | |
| H10 | 0.0836 | 1.0063 | 0.2004 | 0.048* | |
| C6 | 0.2062 (5) | 1.0040 (3) | 0.4314 (3) | 0.0306 (8) | |
| C7 | 0.1742 (5) | 1.1436 (4) | 0.4118 (3) | 0.0368 (9) | |
| C4 | 0.3223 (5) | 0.9501 (4) | 0.6208 (3) | 0.0390 (9) | |
| C2 | 0.4306 (6) | 0.7160 (4) | 0.7297 (4) | 0.0506 (11) | |
| H2 | 0.4810 | 0.6482 | 0.7955 | 0.061* | |
| O1 | 0.5012 (4) | 0.6801 (3) | 0.3559 (2) | 0.0634 (9) | |
| C3 | 0.4009 (6) | 0.8478 (4) | 0.7199 (3) | 0.0477 (10) | |
| H3 | 0.4321 | 0.8710 | 0.7779 | 0.057* | |
| H5A | 0.192 (6) | 0.535 (3) | 0.458 (2) | 0.065 (16)* | |
| H5B | 0.194 (6) | 0.509 (3) | 0.5816 (15) | 0.068 (15)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cu1 | 0.0471 (3) | 0.0207 (2) | 0.0318 (3) | −0.00140 (19) | −0.0107 (2) | −0.00826 (19) |
| Cl4 | 0.0728 (8) | 0.0307 (5) | 0.0416 (6) | −0.0135 (5) | −0.0179 (5) | −0.0005 (4) |
| Cl3 | 0.1158 (11) | 0.0350 (6) | 0.0486 (6) | −0.0027 (6) | −0.0209 (6) | −0.0222 (5) |
| Cl1 | 0.0801 (9) | 0.0472 (7) | 0.0746 (8) | −0.0293 (6) | −0.0338 (7) | 0.0168 (6) |
| Cl2 | 0.1151 (12) | 0.0745 (9) | 0.0677 (8) | 0.0119 (8) | −0.0340 (8) | −0.0440 (7) |
| O3 | 0.0622 (18) | 0.0227 (13) | 0.0366 (14) | −0.0029 (12) | −0.0151 (13) | −0.0119 (11) |
| C5 | 0.034 (2) | 0.0258 (19) | 0.0303 (18) | −0.0034 (15) | −0.0046 (16) | −0.0087 (15) |
| O5 | 0.073 (2) | 0.0312 (15) | 0.0346 (16) | −0.0132 (15) | −0.0142 (15) | −0.0038 (14) |
| N2 | 0.0419 (19) | 0.0222 (16) | 0.0315 (16) | −0.0044 (13) | −0.0051 (14) | −0.0090 (13) |
| N1 | 0.0420 (18) | 0.0271 (17) | 0.0326 (16) | −0.0042 (14) | −0.0059 (14) | −0.0104 (13) |
| C9 | 0.058 (3) | 0.026 (2) | 0.039 (2) | −0.0008 (18) | −0.014 (2) | −0.0011 (17) |
| O2 | 0.0396 (17) | 0.0558 (19) | 0.0453 (16) | 0.0073 (15) | −0.0018 (14) | 0.0063 (14) |
| C13 | 0.037 (2) | 0.029 (2) | 0.037 (2) | −0.0090 (17) | −0.0027 (18) | −0.0108 (17) |
| C16 | 0.041 (2) | 0.0239 (19) | 0.0350 (19) | −0.0038 (16) | −0.0062 (17) | −0.0094 (16) |
| C11 | 0.066 (3) | 0.029 (2) | 0.052 (2) | −0.010 (2) | −0.010 (2) | −0.018 (2) |
| C15 | 0.041 (2) | 0.024 (2) | 0.034 (2) | −0.0025 (16) | −0.0069 (17) | −0.0084 (16) |
| O4 | 0.113 (3) | 0.0235 (15) | 0.0449 (16) | 0.0005 (16) | −0.0331 (17) | −0.0086 (13) |
| C14 | 0.032 (2) | 0.030 (2) | 0.039 (2) | −0.0029 (16) | −0.0048 (17) | −0.0088 (16) |
| C1 | 0.060 (3) | 0.024 (2) | 0.044 (2) | −0.0006 (19) | −0.018 (2) | −0.0048 (17) |
| C12 | 0.072 (3) | 0.043 (3) | 0.051 (3) | −0.018 (2) | −0.008 (2) | −0.026 (2) |
| C8 | 0.051 (3) | 0.0200 (19) | 0.047 (2) | −0.0035 (17) | −0.007 (2) | −0.0049 (17) |
| C10 | 0.051 (2) | 0.030 (2) | 0.035 (2) | −0.0034 (18) | −0.0145 (18) | −0.0065 (17) |
| C6 | 0.034 (2) | 0.0242 (19) | 0.0298 (18) | −0.0039 (15) | 0.0009 (15) | −0.0097 (15) |
| C7 | 0.040 (2) | 0.0229 (19) | 0.042 (2) | −0.0055 (16) | −0.0010 (18) | −0.0088 (17) |
| C4 | 0.044 (2) | 0.039 (2) | 0.036 (2) | −0.0094 (18) | −0.0024 (18) | −0.0149 (18) |
| C2 | 0.063 (3) | 0.043 (3) | 0.040 (2) | −0.005 (2) | −0.020 (2) | −0.006 (2) |
| O1 | 0.0491 (19) | 0.083 (2) | 0.0386 (16) | 0.0057 (16) | −0.0020 (15) | −0.0158 (16) |
| C3 | 0.057 (3) | 0.052 (3) | 0.038 (2) | −0.010 (2) | −0.014 (2) | −0.016 (2) |
Geometric parameters (Å, °) top
| Cu1—O3 | 1.939 (2) | C13—O1 | 1.213 (4) |
| Cu1—O5 | 1.971 (2) | C13—C14 | 1.536 (5) |
| Cu1—N1 | 1.994 (3) | C16—C15 | 1.531 (5) |
| Cu1—N2 | 2.027 (3) | C16—H16 | 0.9800 |
| Cu1—O1 | 2.152 (3) | C11—C12 | 1.359 (6) |
| Cl4—C16 | 1.774 (3) | C11—C7 | 1.417 (5) |
| Cl3—C16 | 1.759 (4) | C11—H11 | 0.9300 |
| Cl1—C14 | 1.767 (4) | C15—O4 | 1.223 (4) |
| Cl2—C14 | 1.753 (4) | C14—H14 | 0.9800 |
| O3—C15 | 1.261 (4) | C1—C2 | 1.374 (5) |
| C5—N1 | 1.348 (4) | C1—H1 | 0.9300 |
| C5—C4 | 1.394 (5) | C12—C4 | 1.432 (5) |
| C5—C6 | 1.444 (5) | C12—H12 | 0.9300 |
| O5—H5A | 0.85 (3) | C8—C7 | 1.410 (5) |
| O5—H5B | 0.85 (3) | C8—H8 | 0.9300 |
| N2—C10 | 1.331 (4) | C10—H10 | 0.9300 |
| N2—C6 | 1.355 (4) | C6—C7 | 1.401 (5) |
| N1—C1 | 1.348 (4) | C4—C3 | 1.411 (5) |
| C9—C8 | 1.355 (5) | C2—C3 | 1.349 (5) |
| C9—C10 | 1.399 (5) | C2—H2 | 0.9300 |
| C9—H9 | 0.9300 | C3—H3 | 0.9300 |
| O2—C13 | 1.240 (5) | | |
| | | |
| Cl1···Cl4i | 3.306 (2) | Cg1···Cg2iii | 3.734 (2) |
| Cl2···Cl3ii | 3.278 (2) | | |
| | | |
| O3—Cu1—O5 | 91.06 (10) | O4—C15—O3 | 127.3 (3) |
| O3—Cu1—N1 | 171.76 (11) | O4—C15—C16 | 117.8 (3) |
| O5—Cu1—N1 | 95.86 (11) | O3—C15—C16 | 114.7 (3) |
| O3—Cu1—N2 | 90.28 (11) | C13—C14—Cl2 | 110.9 (3) |
| O5—Cu1—N2 | 149.53 (12) | C13—C14—Cl1 | 109.3 (2) |
| N1—Cu1—N2 | 81.49 (11) | Cl2—C14—Cl1 | 110.0 (2) |
| O3—Cu1—O1 | 95.15 (11) | C13—C14—H14 | 108.9 |
| O5—Cu1—O1 | 101.24 (12) | Cl2—C14—H14 | 108.9 |
| N1—Cu1—O1 | 87.88 (12) | Cl1—C14—H14 | 108.9 |
| N2—Cu1—O1 | 108.94 (12) | N1—C1—C2 | 122.1 (4) |
| C15—O3—Cu1 | 127.3 (2) | N1—C1—H1 | 118.9 |
| N1—C5—C4 | 124.2 (3) | C2—C1—H1 | 119.0 |
| N1—C5—C6 | 115.7 (3) | C11—C12—C4 | 121.4 (4) |
| C4—C5—C6 | 120.1 (3) | C11—C12—H12 | 119.3 |
| Cu1—O5—H5A | 99 (2) | C4—C12—H12 | 119.3 |
| Cu1—O5—H5B | 137 (3) | C9—C8—C7 | 119.6 (3) |
| H5A—O5—H5B | 111 (3) | C9—C8—H8 | 120.2 |
| C10—N2—C6 | 117.7 (3) | C7—C8—H8 | 120.2 |
| C10—N2—Cu1 | 129.8 (3) | N2—C10—C9 | 121.9 (4) |
| C6—N2—Cu1 | 112.5 (2) | N2—C10—H10 | 119.0 |
| C1—N1—C5 | 117.1 (3) | C9—C10—H10 | 119.1 |
| C1—N1—Cu1 | 128.6 (3) | N2—C6—C7 | 124.1 (3) |
| C5—N1—Cu1 | 114.1 (2) | N2—C6—C5 | 116.1 (3) |
| C8—C9—C10 | 120.4 (4) | C7—C6—C5 | 119.8 (3) |
| C8—C9—H9 | 119.8 | C6—C7—C8 | 116.3 (3) |
| C10—C9—H9 | 119.8 | C6—C7—C11 | 118.9 (3) |
| O1—C13—O2 | 125.7 (4) | C8—C7—C11 | 124.7 (3) |
| O1—C13—C14 | 117.0 (3) | C5—C4—C3 | 116.3 (3) |
| O2—C13—C14 | 117.3 (3) | C5—C4—C12 | 118.5 (3) |
| C15—C16—Cl3 | 113.0 (3) | C3—C4—C12 | 125.2 (3) |
| C15—C16—Cl4 | 112.4 (2) | C3—C2—C1 | 120.8 (3) |
| Cl3—C16—Cl4 | 109.30 (19) | C3—C2—H2 | 119.6 |
| C15—C16—H16 | 107.3 | C1—C2—H2 | 119.6 |
| Cl3—C16—H16 | 107.3 | C13—O1—Cu1 | 144.6 (3) |
| Cl4—C16—H16 | 107.3 | C2—C3—C4 | 119.4 (3) |
| C12—C11—C7 | 121.2 (4) | C2—C3—H3 | 120.3 |
| C12—C11—H11 | 119.4 | C4—C3—H3 | 120.3 |
| C7—C11—H11 | 119.4 | | |
| Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z+2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C16—H16···O2iv | 0.98 | 2.24 | 3.118 (5) | 149 |
| O5—H5B···O2v | 0.85 (2) | 1.81 (2) | 2.654 (3) | 174 (3) |
| O5—H5A···O4 | 0.85 (2) | 1.86 (2) | 2.673 (4) | 159 (3) |
| Symmetry codes: (iv) x−1, y, z; (v) −x+1, −y+1, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C16—H16···O2i | 0.98 | 2.24 | 3.118 (5) | 149 |
| O5—H5B···O2ii | 0.85 (2) | 1.81 (2) | 2.654 (3) | 174 (3) |
| O5—H5A···O4 | 0.85 (2) | 1.86 (2) | 2.673 (4) | 159 (3) |
| Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1. |
The authors thank the Postgraduate Foundation of Taishan University for
financial support (grant No. Y07–2–15).
Lin, M. M., Wei, H. H. & Lee, G. H. (2001). Polyhedron, 20, 3057–3063.
Múdra, M., Moncol', J., Švorec, J., Melník, M., Lönnecke, P., Glowiak, T. & Kirmse, R. (2003). Inorg. Chem. Commun. 6, 1259–1265.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Zhu, L.-G. & Xiao, H.-P. (2006). Acta Cryst. E62, m2061–m2063.
O hydrogen bonds link the molecules into centrosymmetric dimers. The crystal packing also exhibits weak intermolecular C-H![[pi]](/logos/entities/pi_rmgif.gif)
-![[Figure 1]](./cv2493fig1thm.gif)
Dichloroacetic acid and its derivatives are biologically active compounds which have been widely studied because of their fascinating topologies and potential applications as functional materials (Múdra et al., 2003; Lin et al., 2001; Zhu et al., 2006;). In our study of this field, we selected 1,10-phenanthroline as the co-ligand to continue our exploration to the Cu complexes with the dichloroacetic acid ligand. Herein we report the structure of the title complex (I).
In (I) (Fig. 1), the Cu ion has a distorted square-pyramidal coordination. Two N atoms from 1,10-phenanthroline ligand and two oxygen atoms from a dichloroacetic acid ligand form a basal plane, and an aqua atom occupy the axial apical position. Intermolecular O—H···O hydrogen bonds (Table 2) link the molecules into centrosymmetric dimers. The crystal packing exhibits also weak intermolecular C—H···O hydrogen bonds, π–π interactions and short intermolecular Cl···Cl contacts (Table 1).