Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020895/wn6126sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020895/wn6126Isup2.hkl |
CCDC reference: 202291
A solution of dimethylformamide (10 ml) and methanol (5 ml) containing CuI (0.19 g, 1 mmol) and 2,2'-bipyridine (0.16 g, 1 mmol) was refluxed, under atmospheric pressure, for 2 h. After two weeks, dark-brown single crystals of the title compound, (I), were obtained from the green filtrate.
H atoms were placed in calculated positions, with C—H = 0.93 Å, and included in the final cycles of refinement riding on their parent atoms, with Uiso(H) = 1.2Ueq of the carrier atoms.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).
[CuI(C20H16N4)]I | Z = 2 |
Mr = 629.71 | F(000) = 598 |
Triclinic, P1 | Dx = 2.015 Mg m−3 |
a = 10.5450 (16) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 14.299 (3) Å | Cell parameters from 18 reflections |
c = 7.4229 (6) Å | θ = 4.2–11.0° |
α = 95.445 (10)° | µ = 4.04 mm−1 |
β = 98.780 (9)° | T = 298 K |
γ = 108.300 (14)° | Prism, dark brown |
V = 1038.0 (3) Å3 | 0.20 × 0.16 × 0.10 mm |
Rigaku AFC-7S diffractometer | 2818 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 26.0°, θmin = 2.1° |
ω/2θ scans | h = 0→12 |
Absorption correction: ψ scan (North et al., 1968) | k = −17→16 |
Tmin = 0.446, Tmax = 0.668 | l = −9→9 |
4307 measured reflections | 3 standard reflections every 150 reflections |
4074 independent reflections | intensity decay: 0.5% |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0221P)2 + 0.5203P] where P = (Fo2 + 2Fc2)/3 |
4074 reflections | (Δ/σ)max = 0.001 |
244 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
[CuI(C20H16N4)]I | γ = 108.300 (14)° |
Mr = 629.71 | V = 1038.0 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.5450 (16) Å | Mo Kα radiation |
b = 14.299 (3) Å | µ = 4.04 mm−1 |
c = 7.4229 (6) Å | T = 298 K |
α = 95.445 (10)° | 0.20 × 0.16 × 0.10 mm |
β = 98.780 (9)° |
Rigaku AFC-7S diffractometer | 2818 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.013 |
Tmin = 0.446, Tmax = 0.668 | 3 standard reflections every 150 reflections |
4307 measured reflections | intensity decay: 0.5% |
4074 independent reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.53 e Å−3 |
4074 reflections | Δρmin = −0.66 e Å−3 |
244 parameters |
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 | ||
I1 | 0.12786 (3) | 0.26626 (2) | 0.91724 (4) | 0.04460 (9) | |
I2 | 0.62770 (4) | 0.22026 (3) | 0.87871 (6) | 0.07493 (13) | |
Cu | 0.13972 (5) | 0.27068 (3) | 0.56041 (7) | 0.03710 (13) | |
N1 | 0.3087 (3) | 0.3877 (2) | 0.6269 (4) | 0.0372 (8) | |
N2 | 0.0795 (3) | 0.3712 (2) | 0.4101 (4) | 0.0373 (8) | |
N3 | −0.0339 (3) | 0.1591 (2) | 0.4726 (5) | 0.0391 (8) | |
N4 | 0.2084 (4) | 0.1732 (2) | 0.4061 (5) | 0.0391 (8) | |
C1 | 0.2992 (4) | 0.4733 (3) | 0.5752 (6) | 0.0391 (10) | |
C2 | 0.4032 (5) | 0.5632 (3) | 0.6439 (6) | 0.0544 (13) | |
H2 | 0.3938 | 0.6227 | 0.6137 | 0.065* | |
C3 | 0.5197 (5) | 0.5641 (4) | 0.7562 (7) | 0.0610 (14) | |
H3 | 0.5898 | 0.6240 | 0.8016 | 0.073* | |
C4 | 0.5324 (5) | 0.4767 (4) | 0.8009 (6) | 0.0541 (13) | |
H4 | 0.6123 | 0.4756 | 0.8722 | 0.065* | |
C5 | 0.4231 (5) | 0.3896 (3) | 0.7374 (6) | 0.0472 (11) | |
H5 | 0.4293 | 0.3303 | 0.7728 | 0.057* | |
C6 | 0.1742 (5) | 0.4629 (3) | 0.4445 (5) | 0.0379 (9) | |
C7 | 0.1530 (5) | 0.5396 (3) | 0.3564 (6) | 0.0504 (12) | |
H7 | 0.2200 | 0.6021 | 0.3782 | 0.060* | |
C8 | 0.0319 (6) | 0.5223 (4) | 0.2366 (6) | 0.0528 (12) | |
H8 | 0.0151 | 0.5737 | 0.1799 | 0.063* | |
C9 | −0.0628 (5) | 0.4297 (4) | 0.2018 (6) | 0.0517 (12) | |
H9 | −0.1447 | 0.4166 | 0.1203 | 0.062* | |
C10 | −0.0356 (5) | 0.3555 (3) | 0.2890 (6) | 0.0446 (10) | |
H10 | −0.0998 | 0.2918 | 0.2627 | 0.053* | |
C11 | −0.0291 (4) | 0.0832 (3) | 0.3552 (5) | 0.0382 (10) | |
C12 | −0.1468 (5) | 0.0043 (3) | 0.2782 (6) | 0.0505 (12) | |
H12 | −0.1432 | −0.0491 | 0.1997 | 0.061* | |
C13 | −0.2699 (5) | 0.0060 (4) | 0.3195 (6) | 0.0565 (14) | |
H13 | −0.3501 | −0.0452 | 0.2651 | 0.068* | |
C14 | −0.2729 (5) | 0.0829 (4) | 0.4400 (7) | 0.0550 (13) | |
H14 | −0.3546 | 0.0844 | 0.4704 | 0.066* | |
C15 | −0.1526 (4) | 0.1585 (3) | 0.5161 (6) | 0.0461 (11) | |
H15 | −0.1541 | 0.2105 | 0.6001 | 0.055* | |
C16 | 0.1073 (4) | 0.0906 (3) | 0.3189 (5) | 0.0380 (10) | |
C17 | 0.1337 (5) | 0.0176 (3) | 0.2078 (6) | 0.0485 (12) | |
H17 | 0.0635 | −0.0404 | 0.1513 | 0.058* | |
C18 | 0.2637 (6) | 0.0319 (4) | 0.1823 (6) | 0.0576 (13) | |
H18 | 0.2825 | −0.0161 | 0.1077 | 0.069* | |
C20 | 0.3337 (5) | 0.1854 (3) | 0.3796 (6) | 0.0488 (11) | |
H20 | 0.4034 | 0.2428 | 0.4400 | 0.059* | |
C19 | 0.3661 (6) | 0.1176 (4) | 0.2676 (7) | 0.0576 (13) | |
H19 | 0.4550 | 0.1295 | 0.2501 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.04720 (19) | 0.04357 (16) | 0.03842 (16) | 0.00970 (13) | 0.00667 (13) | 0.00554 (12) |
I2 | 0.0480 (2) | 0.0557 (2) | 0.1142 (3) | 0.01393 (17) | 0.0076 (2) | 0.0045 (2) |
Cu | 0.0333 (3) | 0.0300 (2) | 0.0426 (3) | 0.0049 (2) | 0.0044 (2) | 0.0043 (2) |
N1 | 0.035 (2) | 0.0361 (18) | 0.0367 (18) | 0.0072 (15) | 0.0069 (16) | 0.0035 (14) |
N2 | 0.042 (2) | 0.0361 (18) | 0.0332 (18) | 0.0121 (16) | 0.0060 (16) | 0.0070 (14) |
N3 | 0.034 (2) | 0.0372 (18) | 0.041 (2) | 0.0060 (15) | 0.0038 (16) | 0.0077 (15) |
N4 | 0.040 (2) | 0.0330 (17) | 0.044 (2) | 0.0115 (15) | 0.0081 (17) | 0.0080 (15) |
C1 | 0.042 (2) | 0.034 (2) | 0.037 (2) | 0.0041 (18) | 0.013 (2) | 0.0058 (17) |
C2 | 0.058 (3) | 0.037 (2) | 0.054 (3) | −0.003 (2) | 0.011 (3) | 0.001 (2) |
C3 | 0.054 (3) | 0.055 (3) | 0.050 (3) | −0.013 (2) | 0.011 (3) | 0.003 (2) |
C4 | 0.029 (2) | 0.078 (4) | 0.039 (3) | −0.001 (2) | 0.005 (2) | 0.001 (2) |
C5 | 0.042 (3) | 0.052 (3) | 0.041 (2) | 0.007 (2) | 0.007 (2) | 0.007 (2) |
C6 | 0.050 (3) | 0.034 (2) | 0.035 (2) | 0.0160 (19) | 0.018 (2) | 0.0088 (17) |
C7 | 0.072 (4) | 0.037 (2) | 0.048 (3) | 0.020 (2) | 0.022 (3) | 0.015 (2) |
C8 | 0.075 (4) | 0.057 (3) | 0.041 (3) | 0.037 (3) | 0.017 (3) | 0.014 (2) |
C9 | 0.060 (3) | 0.070 (3) | 0.038 (2) | 0.037 (3) | 0.011 (2) | 0.014 (2) |
C10 | 0.040 (3) | 0.053 (3) | 0.040 (2) | 0.017 (2) | 0.003 (2) | 0.005 (2) |
C11 | 0.043 (2) | 0.035 (2) | 0.029 (2) | 0.0051 (18) | −0.0023 (18) | 0.0115 (17) |
C12 | 0.059 (3) | 0.037 (2) | 0.041 (3) | 0.002 (2) | −0.004 (2) | 0.0054 (19) |
C13 | 0.043 (3) | 0.055 (3) | 0.049 (3) | −0.008 (2) | −0.010 (2) | 0.016 (2) |
C14 | 0.031 (3) | 0.064 (3) | 0.062 (3) | 0.007 (2) | −0.003 (2) | 0.020 (3) |
C15 | 0.037 (3) | 0.048 (3) | 0.046 (3) | 0.008 (2) | 0.004 (2) | 0.008 (2) |
C16 | 0.046 (3) | 0.034 (2) | 0.029 (2) | 0.0103 (18) | −0.0020 (18) | 0.0094 (16) |
C17 | 0.066 (3) | 0.037 (2) | 0.038 (2) | 0.017 (2) | −0.001 (2) | 0.0019 (18) |
C18 | 0.076 (4) | 0.065 (3) | 0.042 (3) | 0.040 (3) | 0.009 (3) | 0.007 (2) |
C20 | 0.049 (3) | 0.044 (3) | 0.053 (3) | 0.013 (2) | 0.013 (2) | 0.011 (2) |
C19 | 0.057 (3) | 0.072 (3) | 0.056 (3) | 0.033 (3) | 0.018 (3) | 0.020 (3) |
I1—Cu | 2.6765 (6) | C7—H7 | 0.930 |
Cu—N1 | 1.980 (3) | C8—C9 | 1.358 (7) |
Cu—N3 | 1.981 (3) | C8—H8 | 0.930 |
Cu—N4 | 2.089 (3) | C9—C10 | 1.376 (6) |
Cu—N2 | 2.092 (3) | C9—H9 | 0.930 |
N1—C5 | 1.342 (5) | C10—H10 | 0.930 |
N1—C1 | 1.345 (5) | C11—C12 | 1.386 (6) |
N2—C10 | 1.337 (5) | C11—C16 | 1.477 (6) |
N2—C6 | 1.347 (5) | C12—C13 | 1.385 (7) |
N3—C15 | 1.337 (5) | C12—H12 | 0.930 |
N3—C11 | 1.344 (5) | C13—C14 | 1.362 (7) |
N4—C20 | 1.325 (6) | C13—H13 | 0.930 |
N4—C16 | 1.344 (5) | C14—C15 | 1.378 (6) |
C1—C2 | 1.392 (6) | C14—H14 | 0.930 |
C1—C6 | 1.470 (6) | C15—H15 | 0.930 |
C2—C3 | 1.371 (7) | C16—C17 | 1.391 (6) |
C2—H2 | 0.930 | C17—C18 | 1.366 (7) |
C3—C4 | 1.363 (7) | C17—H17 | 0.930 |
C3—H3 | 0.930 | C18—C19 | 1.372 (7) |
C4—C5 | 1.387 (6) | C18—H18 | 0.930 |
C4—H4 | 0.930 | C20—C19 | 1.374 (6) |
C5—H5 | 0.930 | C20—H20 | 0.930 |
C6—C7 | 1.388 (6) | C19—H19 | 0.930 |
C7—C8 | 1.378 (7) | ||
N1—Cu—N3 | 174.53 (14) | C8—C7—H7 | 120.3 |
N1—Cu—N4 | 99.80 (14) | C6—C7—H7 | 120.3 |
N3—Cu—N4 | 80.29 (14) | C9—C8—C7 | 119.5 (4) |
N1—Cu—N2 | 80.06 (13) | C9—C8—H8 | 120.3 |
N3—Cu—N2 | 94.87 (14) | C7—C8—H8 | 120.3 |
N4—Cu—N2 | 113.89 (13) | C8—C9—C10 | 119.0 (5) |
N1—Cu—I1 | 90.53 (10) | C8—C9—H9 | 120.5 |
N3—Cu—I1 | 94.00 (10) | C10—C9—H9 | 120.5 |
N4—Cu—I1 | 123.04 (9) | N2—C10—C9 | 122.6 (4) |
N2—Cu—I1 | 123.07 (9) | N2—C10—H10 | 118.7 |
C5—N1—C1 | 119.0 (4) | C9—C10—H10 | 118.7 |
C5—N1—Cu | 124.5 (3) | N3—C11—C12 | 120.4 (4) |
C1—N1—Cu | 115.9 (3) | N3—C11—C16 | 115.5 (4) |
C10—N2—C6 | 118.7 (4) | C12—C11—C16 | 124.1 (4) |
C10—N2—Cu | 128.9 (3) | C13—C12—C11 | 119.2 (4) |
C6—N2—Cu | 112.4 (3) | C13—C12—H12 | 120.4 |
C15—N3—C11 | 119.9 (4) | C11—C12—H12 | 120.4 |
C15—N3—Cu | 123.9 (3) | C14—C13—C12 | 119.7 (4) |
C11—N3—Cu | 116.1 (3) | C14—C13—H13 | 120.1 |
C20—N4—C16 | 118.6 (4) | C12—C13—H13 | 120.1 |
C20—N4—Cu | 128.5 (3) | C13—C14—C15 | 118.8 (5) |
C16—N4—Cu | 112.8 (3) | C13—C14—H14 | 120.6 |
N1—C1—C2 | 120.4 (4) | C15—C14—H14 | 120.6 |
N1—C1—C6 | 115.1 (3) | N3—C15—C14 | 121.9 (5) |
C2—C1—C6 | 124.5 (4) | N3—C15—H15 | 119.1 |
C3—C2—C1 | 119.9 (5) | C14—C15—H15 | 119.1 |
C3—C2—H2 | 120.1 | N4—C16—C17 | 120.9 (4) |
C1—C2—H2 | 120.1 | N4—C16—C11 | 115.1 (4) |
C4—C3—C2 | 119.7 (4) | C17—C16—C11 | 124.0 (4) |
C4—C3—H3 | 120.1 | C18—C17—C16 | 119.4 (4) |
C2—C3—H3 | 120.1 | C18—C17—H17 | 120.3 |
C3—C4—C5 | 118.3 (5) | C16—C17—H17 | 120.3 |
C3—C4—H4 | 120.8 | C17—C18—C19 | 119.5 (5) |
C5—C4—H4 | 120.8 | C17—C18—H18 | 120.3 |
N1—C5—C4 | 122.5 (5) | C19—C18—H18 | 120.3 |
N1—C5—H5 | 118.8 | N4—C20—C19 | 123.4 (5) |
C4—C5—H5 | 118.8 | N4—C20—H20 | 118.3 |
N2—C6—C7 | 120.9 (4) | C19—C20—H20 | 118.3 |
N2—C6—C1 | 115.3 (3) | C18—C19—C20 | 118.1 (5) |
C7—C6—C1 | 123.8 (4) | C18—C19—H19 | 120.9 |
C8—C7—C6 | 119.3 (4) | C20—C19—H19 | 120.9 |
Experimental details
Crystal data | |
Chemical formula | [CuI(C20H16N4)]I |
Mr | 629.71 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 10.5450 (16), 14.299 (3), 7.4229 (6) |
α, β, γ (°) | 95.445 (10), 98.780 (9), 108.300 (14) |
V (Å3) | 1038.0 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.04 |
Crystal size (mm) | 0.20 × 0.16 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.446, 0.668 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4307, 4074, 2818 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.066, 1.01 |
No. of reflections | 4074 |
No. of parameters | 244 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.66 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1985), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), WinGX (Farrugia, 1999).
I1—Cu | 2.6765 (6) | Cu—N4 | 2.089 (3) |
Cu—N1 | 1.980 (3) | Cu—N2 | 2.092 (3) |
Cu—N3 | 1.981 (3) | ||
N1—Cu—N3 | 174.53 (14) | N4—Cu—N2 | 113.89 (13) |
N1—Cu—N4 | 99.80 (14) | N1—Cu—I1 | 90.53 (10) |
N3—Cu—N4 | 80.29 (14) | N3—Cu—I1 | 94.00 (10) |
N1—Cu—N2 | 80.06 (13) | N4—Cu—I1 | 123.04 (9) |
N3—Cu—N2 | 94.87 (14) | N2—Cu—I1 | 123.07 (9) |
The structure of the title compound, (I), consists of CuII complex cations and iodide anions. The CuII atom has a compressed trigonal–bipyramidal coordination geometry. The Cu—N bonds [1.980 (3) and 1.981 (3) Å] in the axial directions are significantly shorter than the Cu—N bonds [2.092 (3) and 2.089 (3) Å] in the equatorial plane. The C···I2 distance of 3.833 (5) Å and the C5—H5—I2 angle of 144° suggest weak C—H···I hydrogen bonding between the iodide ion and the pyridine ring. Separations of 3.308 (15) Å and 3.377 (5) Å between parallel bipyridine planes indicate significant π–π stacking. A rather short C···C contact of 3.190 (7) Å is observed between neighboring molecules in the crystal.