In the title compound, [Cu(C15H11N3)2](ClO4)2·0.5H2O, the 2,2':6',2''-terpyridine (terpy) ligand coordinates to the CuII ion as a terdentate chelating ligand, giving a complex cation with compressed octahedral geometry. The [Cu(terpy)2]2+ cations have crystallographically imposed C2 symmetry.
Supporting information
CCDC reference: 170860
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- Disorder in solvent or counterion
- R factor = 0.063
- wR factor = 0.191
- Data-to-parameter ratio = 11.6
checkCIF results
No syntax errors found
Alert Level B:
PLAT_112 Alert B ADDSYM Detects Additional (Pseudo) Symm. Elem. C
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 31.00 Perc.
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and _chemical_formula_moiety. This is
usually due to the moiety formula being in the wrong format.
Atom count from _chemical_formula_sum: C30 H24 Cl2 Cu1 N6 O9
Atom count from _chemical_formula_moiety:C30 H23 Cl2 Cu1 N6 O8.5
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check
1.0 mmol of [Cu(H2O)6](ClO4)2 was dissolved in distilled H2O and added
to a solution of 1.0 mmoles of 2,2':6',2''-terpyridine in 25 ml of DMSO. The
mixture was stirred for 1 h and left to evaporate until blue crystals were
obtained.
H atoms were located in a difference Fourier map and made to ride on C or O
atoms (C—H = 0.96 Å and O—H = 0.85 Å) with a fixed isotropic
displacement parameter 1.2 times that of the parent atom. The perchlorate
anion is disordered over at least two orientations, related approximately by
twofold rotation about the Cl1—O1 bond. Half-occupancy sites were refined
for two positions of O3 and O4, without geometrical constraints. A broad range
of Cl—O distances was obtained, with average close to accepted values;
angles at Cl are not all close to normal tetrahedral values, but no further
disorder was resolved. Refinement of the site-occupation factor for the water
O atom revealed a partial occupation close to 1/2, which was then kept fixed
to this value in the final refinement.
Data collection: XSCANS (Siemens, 1993); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
Bis(2,2:6,2-terpyridine)copper(II) diperchlorate monohydrated
top
Crystal data top
[Cu(C15H11N3)2](ClO4)2·0.5H2O | Dx = 1.559 Mg m−3 |
Mr = 746.99 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 30 reflections |
a = 12.551 (2) Å | θ = 3.5–12.5° |
c = 40.418 (5) Å | µ = 0.92 mm−1 |
V = 6367.0 (16) Å3 | T = 293 K |
Z = 8 | Prism, green |
F(000) = 3048 | 0.6 × 0.5 × 0.4 mm |
Data collection top
Siemens P4/PC diffractometer | 1368 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.062 |
Graphite monochromator | θmax = 25.0°, θmin = 1.5° |
ω/2θ scans | h = 0→14 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→14 |
Tmin = 0.637, Tmax = 0.693 | l = 0→48 |
3081 measured reflections | 3 standard reflections every 97 reflections |
2808 independent reflections | intensity decay: <3% |
Refinement top
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)] = 0.063 | H-atom parameters not refined |
wR(F2) = 0.191 | w = 1/[σ2(Fo2) + (0.1064P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.88 | (Δ/σ)max = 0.019 |
2808 reflections | Δρmax = 0.36 e Å−3 |
243 parameters | Δρmin = −0.43 e Å−3 |
18 restraints | Extinction correction: SHELXL |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: none |
Crystal data top
[Cu(C15H11N3)2](ClO4)2·0.5H2O | Z = 8 |
Mr = 746.99 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.92 mm−1 |
a = 12.551 (2) Å | T = 293 K |
c = 40.418 (5) Å | 0.6 × 0.5 × 0.4 mm |
V = 6367.0 (16) Å3 | |
Data collection top
Siemens P4/PC diffractometer | 1368 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.062 |
Tmin = 0.637, Tmax = 0.693 | 3 standard reflections every 97 reflections |
3081 measured reflections | intensity decay: <3% |
2808 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 18 restraints |
wR(F2) = 0.191 | H-atom parameters not refined |
S = 0.88 | Δρmax = 0.36 e Å−3 |
2808 reflections | Δρmin = −0.43 e Å−3 |
243 parameters | |
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 | Occ. (<1) |
Cu | 0.5000 | 0.2500 | 0.12793 (3) | 0.0473 (4) | |
N1 | 0.4331 (4) | 0.0944 (4) | 0.11615 (12) | 0.0527 (13) | |
C2 | 0.4293 (4) | 0.0748 (4) | 0.08399 (16) | 0.0489 (14) | |
C3 | 0.3963 (5) | −0.0221 (6) | 0.07150 (18) | 0.0635 (18) | |
H3 | 0.3960 | −0.0347 | 0.0481 | 0.076* | |
C4 | 0.3635 (6) | −0.0995 (6) | 0.0938 (2) | 0.076 (2) | |
H4 | 0.3389 | −0.1674 | 0.0860 | 0.091* | |
C5 | 0.3664 (6) | −0.0794 (6) | 0.1265 (2) | 0.072 (2) | |
H5 | 0.3451 | −0.1333 | 0.1420 | 0.086* | |
C6 | 0.4002 (5) | 0.0180 (5) | 0.13738 (17) | 0.0593 (17) | |
H6 | 0.4006 | 0.0328 | 0.1607 | 0.071* | |
N1' | 0.5000 | 0.2500 | 0.07860 (17) | 0.0499 (17) | |
C2' | 0.4650 (4) | 0.1631 (5) | 0.06249 (15) | 0.0489 (15) | |
C3' | 0.4618 (6) | 0.1623 (6) | 0.02858 (18) | 0.071 (2) | |
H3' | 0.4334 | 0.1018 | 0.0171 | 0.085* | |
C4' | 0.5000 | 0.2500 | 0.0113 (2) | 0.080 (3) | |
H4' | 0.5000 | 0.2500 | −0.0125 | 0.096* | |
N11 | 0.6585 (4) | 0.1849 (4) | 0.14048 (12) | 0.0501 (12) | |
C12 | 0.6767 (5) | 0.1818 (4) | 0.17290 (15) | 0.0483 (14) | |
C13 | 0.7747 (5) | 0.1474 (5) | 0.18539 (18) | 0.0635 (18) | |
H13 | 0.7872 | 0.1463 | 0.2088 | 0.076* | |
C14 | 0.8521 (5) | 0.1151 (6) | 0.1636 (2) | 0.073 (2) | |
H14 | 0.9194 | 0.0898 | 0.1717 | 0.088* | |
C15 | 0.8334 (6) | 0.1184 (6) | 0.1302 (2) | 0.072 (2) | |
H15 | 0.8875 | 0.0975 | 0.1148 | 0.086* | |
C16 | 0.7354 (5) | 0.1532 (5) | 0.11942 (17) | 0.0583 (17) | |
H16 | 0.7210 | 0.1550 | 0.0961 | 0.070* | |
N11' | 0.5000 | 0.2500 | 0.17764 (15) | 0.0445 (16) | |
C12' | 0.5865 (5) | 0.2169 (5) | 0.19417 (15) | 0.0492 (15) | |
C13' | 0.5893 (5) | 0.2164 (5) | 0.22814 (16) | 0.0628 (18) | |
H13' | 0.6522 | 0.1943 | 0.2397 | 0.075* | |
C14' | 0.5000 | 0.2500 | 0.2455 (2) | 0.074 (3) | |
H14' | 0.5000 | 0.2500 | 0.2692 | 0.089* | |
Cl1 | 0.74847 (18) | 0.0418 (2) | 0.03063 (6) | 0.0864 (7) | |
O1 | 0.6623 (5) | 0.0005 (6) | 0.04936 (18) | 0.131 (3) | |
O2 | 0.7261 (7) | 0.0500 (11) | −0.0015 (2) | 0.185 (4) | |
O3 | 0.832 (2) | 0.048 (3) | 0.0496 (4) | 0.184 (11) | 0.50 |
O4 | 0.7575 (15) | 0.1563 (9) | 0.0376 (3) | 0.126 (6) | 0.50 |
O3B | 0.767 (2) | −0.053 (3) | 0.0194 (8) | 0.240 (10) | 0.50 |
O4B | 0.8400 (11) | −0.0177 (18) | 0.0345 (6) | 0.144 (8) | 0.50 |
O5 | 0.7081 (13) | 0.2616 (11) | −0.0373 (3) | 0.142 (6) | 0.50 |
H5A | 0.7428 | 0.3186 | −0.0338 | 0.080* | 0.50 |
H5B | 0.7443 | 0.2126 | −0.0281 | 0.080* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.0340 (6) | 0.0339 (6) | 0.0739 (7) | −0.0008 (5) | 0.000 | 0.000 |
N1 | 0.035 (3) | 0.053 (3) | 0.070 (3) | 0.003 (2) | −0.008 (2) | −0.008 (3) |
C2 | 0.034 (3) | 0.036 (3) | 0.076 (4) | 0.001 (3) | 0.000 (3) | −0.006 (3) |
C3 | 0.054 (4) | 0.059 (5) | 0.078 (4) | −0.009 (3) | −0.003 (3) | −0.016 (3) |
C4 | 0.061 (5) | 0.047 (4) | 0.119 (7) | −0.015 (4) | 0.004 (4) | −0.009 (4) |
C5 | 0.057 (5) | 0.047 (4) | 0.111 (6) | −0.009 (3) | 0.004 (4) | 0.013 (4) |
C6 | 0.042 (4) | 0.055 (4) | 0.082 (4) | 0.002 (3) | 0.007 (3) | 0.002 (3) |
N1' | 0.039 (4) | 0.040 (4) | 0.072 (4) | −0.001 (3) | 0.000 | 0.000 |
C2' | 0.036 (3) | 0.044 (4) | 0.067 (4) | 0.000 (3) | −0.005 (3) | −0.006 (3) |
C3' | 0.073 (5) | 0.056 (5) | 0.084 (5) | 0.004 (4) | −0.012 (4) | −0.010 (4) |
C4' | 0.110 (10) | 0.075 (8) | 0.055 (5) | 0.000 (7) | 0.000 | 0.000 |
N11 | 0.043 (3) | 0.033 (3) | 0.075 (3) | −0.003 (2) | −0.005 (2) | 0.001 (2) |
C12 | 0.044 (4) | 0.033 (3) | 0.068 (4) | −0.003 (3) | −0.005 (3) | −0.002 (3) |
C13 | 0.043 (4) | 0.063 (5) | 0.085 (5) | 0.005 (3) | −0.012 (3) | 0.002 (4) |
C14 | 0.040 (4) | 0.073 (5) | 0.107 (6) | 0.011 (4) | −0.010 (4) | 0.000 (4) |
C15 | 0.058 (5) | 0.057 (5) | 0.101 (6) | 0.005 (4) | 0.020 (4) | −0.006 (4) |
C16 | 0.052 (4) | 0.048 (4) | 0.075 (4) | 0.002 (3) | 0.008 (3) | −0.006 (3) |
N11' | 0.038 (4) | 0.039 (4) | 0.057 (4) | 0.000 (3) | 0.000 | 0.000 |
C12' | 0.045 (4) | 0.038 (3) | 0.065 (4) | −0.002 (3) | −0.002 (3) | 0.001 (3) |
C13' | 0.054 (4) | 0.062 (5) | 0.073 (5) | −0.001 (3) | −0.011 (3) | 0.006 (3) |
C14' | 0.081 (8) | 0.088 (8) | 0.055 (5) | −0.013 (7) | 0.000 | 0.000 |
Cl1 | 0.0682 (14) | 0.1097 (17) | 0.0812 (14) | 0.0108 (13) | 0.0044 (11) | 0.0031 (12) |
O1 | 0.089 (5) | 0.153 (7) | 0.151 (6) | 0.020 (5) | 0.045 (4) | 0.062 (5) |
O2 | 0.156 (8) | 0.304 (13) | 0.095 (5) | −0.056 (8) | −0.026 (5) | 0.035 (6) |
O3 | 0.138 (17) | 0.32 (3) | 0.092 (10) | −0.063 (18) | −0.037 (11) | −0.019 (15) |
O4 | 0.218 (17) | 0.042 (6) | 0.118 (10) | −0.039 (8) | 0.065 (10) | −0.028 (6) |
O3B | 0.19 (2) | 0.25 (2) | 0.28 (2) | 0.003 (19) | −0.096 (17) | −0.067 (19) |
O4B | 0.028 (7) | 0.174 (18) | 0.23 (2) | 0.046 (9) | 0.014 (10) | 0.079 (15) |
O5 | 0.189 (17) | 0.087 (10) | 0.152 (12) | −0.007 (10) | 0.000 (12) | 0.017 (9) |
Geometric parameters (Å, º) top
Cu—N1' | 1.994 (7) | N11—C12 | 1.331 (7) |
Cu—N11' | 2.009 (6) | N11—C16 | 1.347 (8) |
Cu—N1 | 2.178 (5) | C12—C13 | 1.398 (8) |
Cu—N1i | 2.178 (5) | C12—C12' | 1.489 (8) |
Cu—N11 | 2.210 (5) | C13—C14 | 1.373 (9) |
Cu—N11i | 2.210 (5) | C14—C15 | 1.367 (10) |
N1—C2 | 1.324 (7) | C15—C16 | 1.376 (10) |
N1—C6 | 1.351 (8) | N11'—C12'i | 1.341 (6) |
C2—C3 | 1.380 (8) | N11'—C12' | 1.341 (6) |
C2—C2' | 1.478 (8) | C12'—C13' | 1.373 (9) |
C3—C4 | 1.388 (10) | C13'—C14' | 1.387 (8) |
C4—C5 | 1.346 (10) | C14'—C13'i | 1.387 (8) |
C5—C6 | 1.368 (10) | Cl1—O3B | 1.29 (3) |
N1'—C2' | 1.344 (6) | Cl1—O3 | 1.30 (2) |
N1'—C2'i | 1.344 (6) | Cl1—O2 | 1.333 (8) |
C2'—C3' | 1.371 (9) | Cl1—O4B | 1.378 (12) |
C3'—C4' | 1.389 (8) | Cl1—O1 | 1.418 (6) |
C4'—C3'i | 1.389 (8) | Cl1—O4 | 1.468 (10) |
| | | |
N1'—Cu—N11' | 180.0 | C3'—C2'—C2 | 125.0 (6) |
N1'—Cu—N1 | 77.37 (14) | C2'—C3'—C4' | 119.2 (7) |
N11'—Cu—N1 | 102.63 (14) | C3'i—C4'—C3' | 119.5 (9) |
N1'—Cu—N1i | 77.37 (14) | C12—N11—C16 | 119.4 (6) |
N11'—Cu—N1i | 102.63 (14) | C12—N11—Cu | 113.0 (4) |
N1—Cu—N1i | 154.7 (3) | C16—N11—Cu | 127.5 (4) |
N1'—Cu—N11 | 103.26 (14) | N11—C12—C13 | 121.0 (6) |
N11'—Cu—N11 | 76.74 (14) | N11—C12—C12' | 115.5 (5) |
N1—Cu—N11 | 93.78 (18) | C13—C12—C12' | 123.5 (6) |
N1i—Cu—N11 | 91.97 (18) | C14—C13—C12 | 118.8 (6) |
N1'—Cu—N11i | 103.26 (14) | C15—C14—C13 | 120.2 (7) |
N11'—Cu—N11i | 76.74 (14) | C14—C15—C16 | 118.5 (6) |
N1—Cu—N11i | 91.97 (18) | N11—C16—C15 | 122.2 (6) |
N1i—Cu—N11i | 93.78 (18) | C12'i—N11'—C12' | 120.2 (7) |
N11—Cu—N11i | 153.5 (3) | C12'i—N11'—Cu | 119.9 (3) |
C2—N1—C6 | 118.7 (6) | C12'—N11'—Cu | 119.9 (3) |
C2—N1—Cu | 113.3 (4) | N11'—C12'—C13' | 121.3 (6) |
C6—N1—Cu | 127.9 (4) | N11'—C12'—C12 | 114.8 (5) |
N1—C2—C3 | 122.3 (6) | C13'—C12'—C12 | 123.8 (6) |
N1—C2—C2' | 115.3 (5) | C12'—C13'—C14' | 118.9 (7) |
C3—C2—C2' | 122.5 (6) | C13'—C14'—C13'i | 119.3 (9) |
C2—C3—C4 | 117.9 (7) | O3B—Cl1—O3 | 96.9 (16) |
C5—C4—C3 | 119.9 (7) | O2—Cl1—O4B | 109.1 (12) |
C4—C5—C6 | 119.4 (7) | O3B—Cl1—O1 | 89.2 (16) |
N1—C6—C5 | 121.7 (7) | O3—Cl1—O1 | 108.8 (11) |
C2'—N1'—C2'i | 122.1 (7) | O2—Cl1—O1 | 112.8 (5) |
C2'—N1'—Cu | 119.0 (4) | O4B—Cl1—O1 | 112.2 (8) |
C2'i—N1'—Cu | 119.0 (4) | O2—Cl1—O4 | 97.3 (8) |
N1'—C2'—C3' | 119.9 (6) | O4B—Cl1—O4 | 116.4 (12) |
N1'—C2'—C2 | 115.0 (5) | O1—Cl1—O4 | 108.3 (6) |
| | | |
N1'—Cu—N1—C2 | 2.6 (4) | N1'—Cu—N11—C12 | 177.6 (3) |
N11'—Cu—N1—C2 | −177.4 (4) | N11'—Cu—N11—C12 | −2.4 (3) |
N1i—Cu—N1—C2 | 2.6 (4) | N1—Cu—N11—C12 | −104.5 (4) |
N11—Cu—N1—C2 | −100.2 (4) | N1i—Cu—N11—C12 | 100.1 (4) |
N11i—Cu—N1—C2 | 105.7 (4) | N1'—Cu—N11—C16 | −0.1 (5) |
N1'—Cu—N1—C6 | 180.0 (5) | N11'—Cu—N11—C16 | 179.9 (5) |
N11'—Cu—N1—C6 | 0.0 (5) | N1—Cu—N11—C16 | 77.8 (5) |
N1i—Cu—N1—C6 | 180.0 (5) | N1i—Cu—N11—C16 | −77.5 (5) |
N11—Cu—N1—C6 | 77.2 (5) | N11i—Cu—N11—C16 | 179.9 (5) |
N11i—Cu—N1—C6 | −76.9 (5) | C16—N11—C12—C13 | 0.8 (9) |
C6—N1—C2—C3 | −2.1 (9) | Cu—N11—C12—C13 | −177.1 (5) |
Cu—N1—C2—C3 | 175.6 (5) | C16—N11—C12—C12' | −179.2 (5) |
C6—N1—C2—C2' | 179.0 (5) | Cu—N11—C12—C12' | 2.9 (6) |
Cu—N1—C2—C2' | −3.3 (6) | N11—C12—C13—C14 | −0.9 (10) |
N1—C2—C3—C4 | 1.7 (10) | C12'—C12—C13—C14 | 179.0 (6) |
C2'—C2—C3—C4 | −179.5 (6) | C12—C13—C14—C15 | 1.0 (11) |
C2—C3—C4—C5 | −1.1 (11) | C13—C14—C15—C16 | −0.9 (11) |
C3—C4—C5—C6 | 1.0 (11) | C12—N11—C16—C15 | −0.7 (9) |
C2—N1—C6—C5 | 1.9 (9) | Cu—N11—C16—C15 | 176.9 (5) |
Cu—N1—C6—C5 | −175.4 (5) | C14—C15—C16—N11 | 0.8 (10) |
C4—C5—C6—N1 | −1.3 (10) | N1—Cu—N11'—C12'i | −87.6 (3) |
N1—Cu—N1'—C2' | −1.3 (3) | N1i—Cu—N11'—C12'i | 92.4 (3) |
N1i—Cu—N1'—C2' | 178.7 (3) | N11—Cu—N11'—C12'i | −178.6 (3) |
N11—Cu—N1'—C2' | 89.6 (3) | N11i—Cu—N11'—C12'i | 1.4 (3) |
N11i—Cu—N1'—C2' | −90.4 (3) | N1—Cu—N11'—C12' | 92.4 (3) |
N1—Cu—N1'—C2'i | 178.7 (3) | N1i—Cu—N11'—C12' | −87.6 (3) |
N1i—Cu—N1'—C2'i | −1.3 (3) | N11—Cu—N11'—C12' | 1.4 (3) |
N11—Cu—N1'—C2'i | −90.4 (3) | N11i—Cu—N11'—C12' | −178.6 (3) |
N11i—Cu—N1'—C2'i | 89.6 (3) | C12'i—N11'—C12'—C13' | −0.3 (4) |
C2'i—N1'—C2'—C3' | −1.6 (4) | Cu—N11'—C12'—C13' | 179.7 (4) |
Cu—N1'—C2'—C3' | 178.4 (4) | C12'i—N11'—C12'—C12 | 179.7 (6) |
C2'i—N1'—C2'—C2 | −180.0 (6) | Cu—N11'—C12'—C12 | −0.3 (6) |
Cu—N1'—C2'—C2 | 0.0 (6) | N11—C12—C12'—N11' | −1.9 (7) |
N1—C2—C2'—N1' | 2.3 (7) | C13—C12—C12'—N11' | 178.1 (5) |
C3—C2—C2'—N1' | −176.6 (5) | N11—C12—C12'—C13' | 178.1 (5) |
N1—C2—C2'—C3' | −176.0 (6) | C13—C12—C12'—C13' | −1.8 (10) |
C3—C2—C2'—C3' | 5.1 (10) | N11'—C12'—C13'—C14' | 0.7 (9) |
N1'—C2'—C3'—C4' | 3.1 (9) | C12—C12'—C13'—C14' | −179.3 (5) |
C2—C2'—C3'—C4' | −178.7 (5) | C12'—C13'—C14'—C13'i | −0.3 (4) |
C2'—C3'—C4'—C3'i | −1.5 (4) | | |
Symmetry code: (i) −x+1, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O3Bii | 0.85 | 1.74 | 2.55 (4) | 158 |
O5—H5B···O2 | 0.85 | 2.32 | 3.032 (19) | 142 |
Symmetry code: (ii) x, y+1/2, −z. |
Experimental details
Crystal data |
Chemical formula | [Cu(C15H11N3)2](ClO4)2·0.5H2O |
Mr | 746.99 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 293 |
a, c (Å) | 12.551 (2), 40.418 (5) |
V (Å3) | 6367.0 (16) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.6 × 0.5 × 0.4 |
|
Data collection |
Diffractometer | Siemens P4/PC diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.637, 0.693 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3081, 2808, 1368 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.191, 0.88 |
No. of reflections | 2808 |
No. of parameters | 243 |
No. of restraints | 18 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.36, −0.43 |
Selected geometric parameters (Å, º) topCu—N1' | 1.994 (7) | Cu—N1 | 2.178 (5) |
Cu—N11' | 2.009 (6) | Cu—N11 | 2.210 (5) |
| | | |
N1'—Cu—N11' | 180.0 | N1—Cu—N11 | 93.78 (18) |
N1'—Cu—N1 | 77.37 (14) | N11—Cu—N11i | 153.5 (3) |
N11'—Cu—N1 | 102.63 (14) | N1—C2—C2' | 115.3 (5) |
N1—Cu—N1i | 154.7 (3) | N1'—C2'—C2 | 115.0 (5) |
N1'—Cu—N11 | 103.26 (14) | N11—C12—C12' | 115.5 (5) |
N11'—Cu—N11 | 76.74 (14) | N11'—C12'—C12 | 114.8 (5) |
| | | |
N1—C2—C2'—N1' | 2.3 (7) | N11—C12—C12'—N11' | −1.9 (7) |
Symmetry code: (i) −x+1, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O3Bii | 0.85 | 1.74 | 2.55 (4) | 157.5 |
O5—H5B···O2 | 0.85 | 2.32 | 3.032 (19) | 141.9 |
Symmetry code: (ii) x, y+1/2, −z. |
Several studies have been carried out on the structures and magnetic properties of copper(II) complexes with 2,2':6',2''-terpyridine (terpy) (Allmann et al., 1978; Folgado et al., 1990). In one of these studies (Folgado et al., 1990), the crystal structures and/or magnetic properties of some [Cu(terpy)2]2+ salts were determined. Although the X-ray and EPR study revealed that the high-temperature phase of [Cu(terpy)2](PF6)2, (II), was compressed octahedral, at low temperature, the structure contains elongated CuN6 octahedra with an orthorhombic component. The EPR powder data for [Cu(terpy)2](ClO4)2, (I), show the same magnetic behavior as (II), but the crystal structure of the former was not determined. In this paper, we report the crystal structure of [Cu(terpy)2]2+(ClO4)2. 0.5 H2O, (I), at 273 K.
Compound (I) consists of octahedral [Cu(terpy)2]2+, with Cu, N1', C4', H4', N11', C14' and H14' in sites with a twofold symmetry axis, two [ClO4]- anions in general positions, and a water molecule with half occupancy. The terpy ligand coordinates to the metal ion as a meriodonal terdentate ligand. As a consequence of the rigid structure of the terpy ligand the Cu—N distances with the central pyridine ring are significantly shorter giving a compressed octahedral geometry in agreement with the high-temperature structure expected by the previous EPR study.