supplementary materials
Dichlorido(1,10-phenanthroline)copper(II)
A mixture of 1,10-phenanthroline (0.161 g, 0.001 mol) and CuCl2 (0.135 g, 0.001 mol) was added to methanol (20 ml), and the mixture was heated at 365 K for 5 h under reflux with stirring. The resulting solution was then filtered and single crystals suitable for X-ray diffraction analysis formed after a week by slow evaporation of the solvent.
All H atoms were located at calculated positions and refined as riding on their parent C atoms with the C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
Dichlorido(1,10-phenanthroline)copper(II)
top
Crystal data top
| [CuCl2(C12H8N2)] | F(000) = 628 |
| Mr = 314.65 | Dx = 1.743 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 3375 reflections |
| a = 8.000 (5) Å | θ = 1.0–28.3° |
| b = 15.669 (8) Å | µ = 2.24 mm−1 |
| c = 11.348 (5) Å | T = 293 K |
| β = 122.53 (3)° | Block, blue |
| V = 1199.3 (12) Å3 | 0.26 × 0.07 × 0.06 mm |
| Z = 4 | |
Data collection top
Bruker SMART CCD
diffractometer | 1510 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.042 |
| Graphite monochromator | θmax = 25.5°, θmin = 2.5° |
| phi and ω scans | h = −9→9 |
| 7416 measured reflections | k = −18→18 |
| 2220 independent reflections | l = −13→13 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.091 | H-atom parameters constrained |
| S = 0.99 | w = 1/[σ2(Fo2) + (0.0486P)2]
where P = (Fo2 + 2Fc2)/3 |
| 2220 reflections | (Δ/σ)max = 0.001 |
| 162 parameters | Δρmax = 0.26 e Å−3 |
| 0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
| [CuCl2(C12H8N2)] | V = 1199.3 (12) Å3 |
| Mr = 314.65 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.000 (5) Å | µ = 2.24 mm−1 |
| b = 15.669 (8) Å | T = 293 K |
| c = 11.348 (5) Å | 0.26 × 0.07 × 0.06 mm |
| β = 122.53 (3)° | |
Data collection top
Bruker SMART CCD
diffractometer | 1510 reflections with I > 2σ(I) |
| 7416 measured reflections | Rint = 0.042 |
| 2220 independent reflections | θmax = 25.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.091 | Δρmax = 0.26 e Å−3 |
| S = 0.99 | Δρmin = −0.32 e Å−3 |
| 2220 reflections | Absolute structure: ? |
| 162 parameters | Flack parameter: ? |
| 0 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 | 0.73800 (6) | 0.22097 (2) | 0.95569 (4) | 0.04570 (17) | |
| Cl1 | 0.57194 (15) | 0.31386 (6) | 0.99943 (11) | 0.0681 (3) | |
| Cl2 | 0.92896 (14) | 0.27755 (5) | 0.89018 (11) | 0.0621 (3) | |
| N1 | 0.5460 (4) | 0.12799 (16) | 0.8272 (3) | 0.0438 (7) | |
| N2 | 0.8850 (4) | 0.11559 (17) | 1.0788 (3) | 0.0456 (7) | |
| C1 | 0.3787 (5) | 0.1347 (2) | 0.7024 (4) | 0.0508 (9) | |
| H1 | 0.3393 | 0.1885 | 0.6621 | 0.055 (10)* | |
| C2 | 0.2612 (5) | 0.0655 (2) | 0.6306 (4) | 0.0591 (10) | |
| H2 | 0.1457 | 0.0728 | 0.5432 | 0.074 (12)* | |
| C3 | 0.3154 (5) | −0.0135 (2) | 0.6880 (4) | 0.0550 (10) | |
| H3 | 0.2374 | −0.0606 | 0.6402 | 0.060 (10)* | |
| C4 | 0.4892 (5) | −0.0243 (2) | 0.8191 (4) | 0.0452 (8) | |
| C5 | 0.6006 (5) | 0.04917 (19) | 0.8855 (3) | 0.0398 (7) | |
| C6 | 0.5560 (5) | −0.1041 (2) | 0.8883 (4) | 0.0539 (9) | |
| H6 | 0.4798 | −0.1528 | 0.8468 | 0.066 (11)* | |
| C7 | 0.7274 (5) | −0.1107 (2) | 1.0122 (4) | 0.0564 (10) | |
| H7 | 0.7685 | −0.1639 | 1.0547 | 0.069 (12)* | |
| C8 | 0.8498 (5) | −0.0375 (2) | 1.0818 (4) | 0.0481 (8) | |
| C9 | 1.0331 (5) | −0.0415 (3) | 1.2071 (4) | 0.0587 (10) | |
| H9 | 1.0841 | −0.0936 | 1.2513 | 0.057 (10)* | |
| C10 | 1.1382 (6) | 0.0321 (3) | 1.2647 (4) | 0.0596 (10) | |
| H10 | 1.2618 | 0.0301 | 1.3477 | 0.065 (11)* | |
| C11 | 1.0576 (5) | 0.1093 (2) | 1.1984 (3) | 0.0542 (9) | |
| H11 | 1.1290 | 0.1590 | 1.2401 | 0.047 (9)* | |
| C12 | 0.7828 (5) | 0.0422 (2) | 1.0188 (3) | 0.0420 (8) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cu1 | 0.0442 (3) | 0.0321 (2) | 0.0536 (3) | −0.00146 (18) | 0.0216 (2) | −0.00104 (19) |
| Cl1 | 0.0739 (7) | 0.0533 (6) | 0.0802 (7) | 0.0106 (5) | 0.0436 (6) | −0.0022 (5) |
| Cl2 | 0.0557 (6) | 0.0442 (5) | 0.0879 (7) | 0.0035 (4) | 0.0397 (5) | 0.0093 (5) |
| N1 | 0.0454 (16) | 0.0361 (15) | 0.0458 (16) | −0.0035 (13) | 0.0219 (14) | 0.0025 (13) |
| N2 | 0.0447 (16) | 0.0437 (16) | 0.0436 (16) | 0.0004 (13) | 0.0206 (14) | −0.0038 (13) |
| C1 | 0.050 (2) | 0.045 (2) | 0.053 (2) | 0.0025 (17) | 0.0241 (18) | 0.0037 (17) |
| C2 | 0.050 (2) | 0.061 (3) | 0.051 (2) | −0.0022 (19) | 0.0165 (19) | −0.0053 (19) |
| C3 | 0.046 (2) | 0.048 (2) | 0.062 (3) | −0.0079 (17) | 0.023 (2) | −0.0093 (19) |
| C4 | 0.046 (2) | 0.0351 (18) | 0.063 (2) | −0.0001 (15) | 0.0349 (18) | −0.0065 (16) |
| C5 | 0.0423 (18) | 0.0372 (18) | 0.0472 (19) | 0.0015 (15) | 0.0289 (16) | 0.0014 (15) |
| C6 | 0.054 (2) | 0.0359 (19) | 0.077 (3) | 0.0008 (17) | 0.039 (2) | −0.0028 (18) |
| C7 | 0.062 (3) | 0.039 (2) | 0.079 (3) | 0.0106 (18) | 0.045 (2) | 0.0073 (19) |
| C8 | 0.053 (2) | 0.044 (2) | 0.057 (2) | 0.0087 (17) | 0.0355 (18) | 0.0054 (17) |
| C9 | 0.057 (2) | 0.061 (3) | 0.060 (2) | 0.019 (2) | 0.033 (2) | 0.018 (2) |
| C10 | 0.051 (2) | 0.077 (3) | 0.044 (2) | 0.019 (2) | 0.0209 (19) | 0.010 (2) |
| C11 | 0.045 (2) | 0.063 (2) | 0.046 (2) | −0.0009 (19) | 0.0181 (18) | −0.0077 (19) |
| C12 | 0.0442 (19) | 0.0400 (19) | 0.0479 (19) | 0.0046 (15) | 0.0289 (16) | 0.0022 (16) |
Geometric parameters (Å, º) top
| Cu1—N1 | 2.049 (3) | C4—C5 | 1.402 (4) |
| Cu1—N2 | 2.072 (3) | C4—C6 | 1.419 (5) |
| Cu1—Cl1 | 2.1998 (13) | C5—C12 | 1.433 (5) |
| Cu1—Cl2 | 2.2122 (14) | C6—C7 | 1.340 (5) |
| N1—C1 | 1.330 (4) | C6—H6 | 0.930 |
| N1—C5 | 1.357 (4) | C7—C8 | 1.437 (5) |
| N2—C11 | 1.320 (4) | C7—H7 | 0.930 |
| N2—C12 | 1.362 (4) | C8—C9 | 1.391 (5) |
| C1—C2 | 1.379 (5) | C8—C12 | 1.396 (5) |
| C1—H1 | 0.930 | C9—C10 | 1.368 (6) |
| C2—C3 | 1.357 (5) | C9—H9 | 0.930 |
| C2—H2 | 0.930 | C10—C11 | 1.387 (5) |
| C3—C4 | 1.397 (5) | C10—H10 | 0.930 |
| C3—H3 | 0.930 | C11—H11 | 0.930 |
| | | |
| N1—Cu1—N2 | 81.35 (11) | N1—C5—C4 | 122.7 (3) |
| N1—Cu1—Cl1 | 108.56 (9) | N1—C5—C12 | 117.5 (3) |
| N2—Cu1—Cl1 | 124.60 (8) | C4—C5—C12 | 119.8 (3) |
| N1—Cu1—Cl2 | 115.78 (9) | C7—C6—C4 | 121.1 (3) |
| N2—Cu1—Cl2 | 107.56 (9) | C7—C6—H6 | 119.4 |
| Cl1—Cu1—Cl2 | 114.87 (5) | C4—C6—H6 | 119.5 |
| C1—N1—C5 | 117.8 (3) | C6—C7—C8 | 121.7 (3) |
| C1—N1—Cu1 | 129.9 (2) | C6—C7—H7 | 119.4 |
| C5—N1—Cu1 | 112.3 (2) | C8—C7—H7 | 118.9 |
| C11—N2—C12 | 117.8 (3) | C9—C8—C12 | 117.8 (3) |
| C11—N2—Cu1 | 130.8 (2) | C9—C8—C7 | 123.9 (3) |
| C12—N2—Cu1 | 111.4 (2) | C12—C8—C7 | 118.2 (3) |
| N1—C1—C2 | 122.9 (3) | C10—C9—C8 | 119.4 (4) |
| N1—C1—H1 | 118.4 | C10—C9—H9 | 120.2 |
| C2—C1—H1 | 118.7 | C8—C9—H9 | 120.4 |
| C3—C2—C1 | 119.6 (4) | C9—C10—C11 | 119.3 (4) |
| C3—C2—H2 | 120.2 | C9—C10—H10 | 120.1 |
| C1—C2—H2 | 120.3 | C11—C10—H10 | 120.6 |
| C2—C3—C4 | 120.0 (3) | N2—C11—C10 | 123.1 (4) |
| C2—C3—H3 | 120.2 | N2—C11—H11 | 118.5 |
| C4—C3—H3 | 119.8 | C10—C11—H11 | 118.3 |
| C3—C4—C5 | 117.0 (3) | N2—C12—C8 | 122.6 (3) |
| C3—C4—C6 | 124.0 (3) | N2—C12—C5 | 117.4 (3) |
| C5—C4—C6 | 119.0 (3) | C8—C12—C5 | 120.0 (3) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···Cl2i | 0.93 | 2.88 | 3.572 (3) | 132 |
| C3—H3···Cl2ii | 0.93 | 2.80 | 3.669 (3) | 157 |
| C7—H7···Cl2iii | 0.93 | 2.79 | 3.513 (3) | 135 |
| Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+2, −y, −z+2. |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···Cl2i | 0.93 | 2.88 | 3.572 (3) | 132.4 |
| C3—H3···Cl2ii | 0.93 | 2.80 | 3.669 (3) | 156.5 |
| C7—H7···Cl2iii | 0.93 | 2.79 | 3.513 (3) | 135.2 |
| Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+2, −y, −z+2. |
The author is grateful for the support from the Key Laboratory of Coordination Chemistry, JingGangShan University, China.
Bruker (1997). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Viossat, B., Gaucher, J. F., Mazurier, A., Selkti, M. & Tomas, A. (1998). Z. Kristallogr. New Cryst. Struct. 213, 329–330.
Wang, S., Li, Y., Wang, E., Luan, G., Hu, C., Hu, N. & Jia, H. (2002). J. Solid State Chem. 167, 402–406.
Cl contacts and ![[pi]](/logos/entities/pi_rmgif.gif)
-![[Figure 1]](./bi2255fig1thm.gif)
![[Figure 2]](./bi2255fig2thm.gif)
As shown in Fig. 1, the title compound is a monomeric complex in which the CuII atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from one 1,10-phenanthroline ligand and two Cl atoms. In the crystal structure, molecules form intermolecular C—H···Cl contacts and π-π stacking interactions (Fig. 2). The dihedral angle and centroid-to-centroid distance between rings [C4–C8, C12] and [C1–C5, N1]i (symmetry code: (i) 1 − x, 1 − y, 1 − z) are 1.4° and 3.803 Å, respectively. Between rings [C4–C8, C12] and [C8–C12, N2]ii (symmetry code: (ii) 2 − x, 1 − y, 1 − z), the corresponding measurements are 3.0° and 3.671 Å.