A novel centrosymmetric chair-like dimer, bis(2,2′-bipyridine)-1κ
2N,
N′;3κ
2N,
N′-tetra-μ-chloro-1:2κ
2Cl;2:3κ
2Cl;3:4κ
2Cl;1:4κ
2Cl-tetracopper(I), [Cu
4Cl
4(C
10H
8N
2)
2], has been solvothermally synthesized and structurally characterized. The complex self-assembles into a three-dimensional network
via C—H
Cl hydrogen bonds, π–π stacking and weak Cu
Cl electrostatic interactions.
Supporting information
CCDC reference: 163877
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT and SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Crystal data top
[Cu4Cl4(C10H8N2)2] | Z = 1 |
Mr = 708.33 | F(000) = 348 |
Triclinic, P1 | Dx = 2.055 Mg m−3 |
a = 7.4252 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.4231 (7) Å | Cell parameters from 1649 reflections |
c = 9.4957 (9) Å | θ = 2.4–25.0° |
α = 64.253 (2)° | µ = 4.15 mm−1 |
β = 74.117 (2)° | T = 293 K |
γ = 88.504 (2)° | Plate, purple |
V = 572.28 (9) Å3 | 0.15 × 0.15 × 0.10 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 2006 independent reflections |
Radiation source: fine-focus sealed tube | 1596 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.526, Tmax = 0.661 | k = −11→8 |
2994 measured reflections | l = −11→9 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.162 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.104P)2 + 0.663P] where P = (Fo2 + 2Fc2)/3 |
2006 reflections | (Δ/σ)max = 0.001 |
146 parameters | Δρmax = 0.90 e Å−3 |
0 restraints | Δρmin = −0.84 e Å−3 |
Special details top
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 | 0.36488 (12) | 0.37281 (9) | 0.76046 (9) | 0.0564 (4) | |
Cu2 | 0.27638 (12) | 0.55493 (9) | 0.46479 (10) | 0.0557 (3) | |
Cl1 | 0.1289 (2) | 0.33153 (19) | 0.6406 (2) | 0.0523 (4) | |
Cl2 | 0.4053 (2) | 0.78493 (18) | 0.2887 (2) | 0.0518 (4) | |
N1 | 0.2068 (7) | 0.2786 (6) | 1.0056 (6) | 0.0446 (12) | |
N2 | 0.3850 (6) | 0.5683 (6) | 0.7967 (6) | 0.0397 (11) | |
C1 | 0.1200 (10) | 0.1323 (8) | 1.1047 (8) | 0.0550 (16) | |
H1A | 0.1354 | 0.0562 | 1.0660 | 0.066* | |
C2 | 0.0090 (10) | 0.0902 (8) | 1.2617 (8) | 0.0586 (18) | |
H2A | −0.0520 | −0.0119 | 1.3266 | 0.070* | |
C3 | −0.0109 (10) | 0.1998 (8) | 1.3214 (8) | 0.0544 (16) | |
H3A | −0.0825 | 0.1726 | 1.4283 | 0.065* | |
C4 | 0.0765 (9) | 0.3504 (8) | 1.2213 (7) | 0.0491 (15) | |
H4A | 0.0614 | 0.4272 | 1.2592 | 0.059* | |
C5 | 0.1868 (8) | 0.3884 (7) | 1.0642 (7) | 0.0384 (12) | |
C6 | 0.2898 (8) | 0.5478 (6) | 0.9489 (6) | 0.0368 (12) | |
C7 | 0.2915 (9) | 0.6699 (7) | 0.9929 (8) | 0.0455 (14) | |
H7A | 0.2251 | 0.6543 | 1.0978 | 0.055* | |
C8 | 0.3911 (10) | 0.8139 (8) | 0.8816 (8) | 0.0522 (16) | |
H8A | 0.3937 | 0.8963 | 0.9103 | 0.063* | |
C9 | 0.4873 (9) | 0.8342 (8) | 0.7267 (8) | 0.0483 (14) | |
H9A | 0.5557 | 0.9307 | 0.6490 | 0.058* | |
C10 | 0.4807 (9) | 0.7103 (7) | 0.6889 (8) | 0.0455 (14) | |
H10B | 0.5453 | 0.7250 | 0.5840 | 0.055* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0737 (6) | 0.0552 (6) | 0.0444 (5) | 0.0022 (4) | −0.0044 (4) | −0.0331 (4) |
Cu2 | 0.0681 (6) | 0.0521 (5) | 0.0497 (5) | −0.0014 (4) | −0.0079 (4) | −0.0303 (4) |
Cl1 | 0.0543 (9) | 0.0551 (9) | 0.0513 (9) | −0.0020 (7) | −0.0133 (7) | −0.0276 (8) |
Cl2 | 0.0597 (10) | 0.0452 (9) | 0.0524 (9) | 0.0068 (7) | −0.0105 (7) | −0.0270 (7) |
N1 | 0.052 (3) | 0.045 (3) | 0.044 (3) | 0.009 (2) | −0.017 (2) | −0.025 (2) |
N2 | 0.036 (3) | 0.049 (3) | 0.043 (3) | 0.009 (2) | −0.012 (2) | −0.029 (2) |
C1 | 0.066 (4) | 0.052 (4) | 0.054 (4) | 0.005 (3) | −0.017 (3) | −0.030 (3) |
C2 | 0.064 (4) | 0.053 (4) | 0.048 (4) | 0.004 (3) | −0.019 (3) | −0.012 (3) |
C3 | 0.062 (4) | 0.060 (4) | 0.035 (3) | 0.006 (3) | −0.008 (3) | −0.019 (3) |
C4 | 0.061 (4) | 0.055 (4) | 0.042 (3) | 0.016 (3) | −0.017 (3) | −0.031 (3) |
C5 | 0.039 (3) | 0.047 (3) | 0.040 (3) | 0.011 (2) | −0.015 (2) | −0.027 (3) |
C6 | 0.043 (3) | 0.044 (3) | 0.035 (3) | 0.011 (2) | −0.018 (2) | −0.024 (3) |
C7 | 0.056 (4) | 0.048 (4) | 0.046 (3) | 0.008 (3) | −0.015 (3) | −0.033 (3) |
C8 | 0.064 (4) | 0.051 (4) | 0.060 (4) | 0.008 (3) | −0.027 (3) | −0.036 (3) |
C9 | 0.048 (3) | 0.049 (4) | 0.054 (4) | 0.003 (3) | −0.016 (3) | −0.028 (3) |
C10 | 0.048 (3) | 0.048 (4) | 0.045 (3) | 0.003 (3) | −0.010 (3) | −0.026 (3) |
Geometric parameters (Å, º) top
Cu1—N1 | 2.085 (5) | N2—C6 | 1.353 (7) |
Cu1—N2 | 2.032 (5) | C1—C2 | 1.375 (10) |
Cu1—Cl1 | 2.4556 (18) | C2—C3 | 1.365 (10) |
Cu1—Cl2i | 2.3184 (17) | C3—C4 | 1.370 (10) |
Cu2—Cl1 | 2.1176 (18) | C4—C5 | 1.382 (8) |
Cu2—Cl2 | 2.1196 (18) | C5—C6 | 1.487 (8) |
Cu1—Cu2 | 2.8327 (12) | C6—C7 | 1.386 (8) |
Cu1—Cu2i | 2.8008 (12) | C7—C8 | 1.372 (9) |
N1—C1 | 1.337 (8) | C8—C9 | 1.378 (9) |
N1—C5 | 1.360 (7) | C9—C10 | 1.368 (9) |
N2—C10 | 1.343 (8) | | |
| | | |
N1—Cu1—N2 | 81.2 (2) | Cu2—Cl2—Cu1i | 78.12 (6) |
N2—Cu1—Cl2i | 129.91 (14) | C1—N1—C5 | 118.4 (5) |
N1—Cu1—Cl2i | 112.52 (14) | C1—N1—Cu1 | 129.1 (4) |
N2—Cu1—Cl1 | 121.91 (14) | C5—N1—Cu1 | 112.4 (4) |
N1—Cu1—Cl1 | 100.12 (15) | C10—N2—C6 | 118.4 (5) |
Cl2i—Cu1—Cl1 | 103.44 (6) | C10—N2—Cu1 | 127.6 (4) |
N2—Cu1—Cu2i | 94.02 (14) | C6—N2—Cu1 | 114.0 (4) |
N1—Cu1—Cu2i | 146.96 (15) | N1—C1—C2 | 122.5 (6) |
Cl2i—Cu1—Cu2i | 47.78 (5) | C3—C2—C1 | 119.3 (7) |
Cl1—Cu1—Cu2i | 109.85 (5) | C2—C3—C4 | 119.0 (6) |
N2—Cu1—Cu2 | 90.95 (14) | C3—C4—C5 | 120.1 (6) |
N1—Cu1—Cu2 | 132.93 (14) | N1—C5—C4 | 120.7 (6) |
Cl2i—Cu1—Cu2 | 107.93 (5) | N1—C5—C6 | 115.8 (5) |
Cl1—Cu1—Cu2 | 46.54 (4) | C4—C5—C6 | 123.5 (5) |
Cu2i—Cu1—Cu2 | 79.51 (3) | N2—C6—C7 | 120.9 (5) |
Cl1—Cu2—Cl2 | 175.93 (8) | N2—C6—C5 | 116.4 (5) |
Cl1—Cu2—Cu1i | 129.58 (6) | C7—C6—C5 | 122.7 (5) |
Cl2—Cu2—Cu1i | 54.10 (5) | C8—C7—C6 | 120.0 (6) |
Cl1—Cu2—Cu1 | 57.32 (5) | C7—C8—C9 | 118.9 (6) |
Cl2—Cu2—Cu1 | 125.25 (6) | C10—C9—C8 | 119.0 (6) |
Cu1i—Cu2—Cu1 | 100.49 (3) | N2—C10—C9 | 122.9 (6) |
Cu2—Cl1—Cu1 | 76.15 (6) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |