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The crystal structure of the title complex, [CuI(C20H16N4)]I, was first determined and reported by Barclay et al. [J. Chem. Soc. (1963), pp. 5691–5699]. We present here a redetermin­ation, of greatly improved precision, in which the H-atom positions have been located.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020895/wn6126sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020895/wn6126Isup2.hkl
Contains datablock I

CCDC reference: 202291

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.025
  • wR factor = 0.066
  • Data-to-parameter ratio = 16.7

checkCIF results

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ADDSYM reports no extra symmetry








Comment top

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 ππ stacking. A rather short C···C contact of 3.190 (7) Å is observed between neighboring molecules in the crystal.

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of the structure of (I), shown with 30% probability displacement ellipsoids. The dashed line indicates the weak hydrogen bond.
[Figure 2] Fig. 2. A packing diagram, showing ππ aromatic stacking between neighboring molecules.
(I) top
Crystal data top
[CuI(C20H16N4)]IZ = 2
Mr = 629.71F(000) = 598
Triclinic, P1Dx = 2.015 Mg m3
a = 10.5450 (16) ÅMo Kα radiation, λ = 0.71069 Å
b = 14.299 (3) ÅCell parameters from 18 reflections
c = 7.4229 (6) Åθ = 4.2–11.0°
α = 95.445 (10)°µ = 4.04 mm1
β = 98.780 (9)°T = 298 K
γ = 108.300 (14)°Prism, dark brown
V = 1038.0 (3) Å30.20 × 0.16 × 0.10 mm
Data collection top
Rigaku AFC-7S
diffractometer
2818 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.013
Graphite monochromatorθmax = 26.0°, θmin = 2.1°
ω/2θ scansh = 012
Absorption correction: ψ scan
(North et al., 1968)
k = 1716
Tmin = 0.446, Tmax = 0.668l = 99
4307 measured reflections3 standard reflections every 150 reflections
4074 independent reflections intensity decay: 0.5%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-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 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
[CuI(C20H16N4)]Iγ = 108.300 (14)°
Mr = 629.71V = 1038.0 (3) Å3
Triclinic, P1Z = 2
a = 10.5450 (16) ÅMo Kα radiation
b = 14.299 (3) ŵ = 4.04 mm1
c = 7.4229 (6) ÅT = 298 K
α = 95.445 (10)°0.20 × 0.16 × 0.10 mm
β = 98.780 (9)°
Data collection top
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 = 0.6683 standard reflections every 150 reflections
4307 measured reflections intensity decay: 0.5%
4074 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.066H-atom parameters constrained
S = 1.01Δρmax = 0.53 e Å3
4074 reflectionsΔρmin = 0.66 e Å3
244 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
xyzUiso*/Ueq
I10.12786 (3)0.26626 (2)0.91724 (4)0.04460 (9)
I20.62770 (4)0.22026 (3)0.87871 (6)0.07493 (13)
Cu0.13972 (5)0.27068 (3)0.56041 (7)0.03710 (13)
N10.3087 (3)0.3877 (2)0.6269 (4)0.0372 (8)
N20.0795 (3)0.3712 (2)0.4101 (4)0.0373 (8)
N30.0339 (3)0.1591 (2)0.4726 (5)0.0391 (8)
N40.2084 (4)0.1732 (2)0.4061 (5)0.0391 (8)
C10.2992 (4)0.4733 (3)0.5752 (6)0.0391 (10)
C20.4032 (5)0.5632 (3)0.6439 (6)0.0544 (13)
H20.39380.62270.61370.065*
C30.5197 (5)0.5641 (4)0.7562 (7)0.0610 (14)
H30.58980.62400.80160.073*
C40.5324 (5)0.4767 (4)0.8009 (6)0.0541 (13)
H40.61230.47560.87220.065*
C50.4231 (5)0.3896 (3)0.7374 (6)0.0472 (11)
H50.42930.33030.77280.057*
C60.1742 (5)0.4629 (3)0.4445 (5)0.0379 (9)
C70.1530 (5)0.5396 (3)0.3564 (6)0.0504 (12)
H70.22000.60210.37820.060*
C80.0319 (6)0.5223 (4)0.2366 (6)0.0528 (12)
H80.01510.57370.17990.063*
C90.0628 (5)0.4297 (4)0.2018 (6)0.0517 (12)
H90.14470.41660.12030.062*
C100.0356 (5)0.3555 (3)0.2890 (6)0.0446 (10)
H100.09980.29180.26270.053*
C110.0291 (4)0.0832 (3)0.3552 (5)0.0382 (10)
C120.1468 (5)0.0043 (3)0.2782 (6)0.0505 (12)
H120.14320.04910.19970.061*
C130.2699 (5)0.0060 (4)0.3195 (6)0.0565 (14)
H130.35010.04520.26510.068*
C140.2729 (5)0.0829 (4)0.4400 (7)0.0550 (13)
H140.35460.08440.47040.066*
C150.1526 (4)0.1585 (3)0.5161 (6)0.0461 (11)
H150.15410.21050.60010.055*
C160.1073 (4)0.0906 (3)0.3189 (5)0.0380 (10)
C170.1337 (5)0.0176 (3)0.2078 (6)0.0485 (12)
H170.06350.04040.15130.058*
C180.2637 (6)0.0319 (4)0.1823 (6)0.0576 (13)
H180.28250.01610.10770.069*
C200.3337 (5)0.1854 (3)0.3796 (6)0.0488 (11)
H200.40340.24280.44000.059*
C190.3661 (6)0.1176 (4)0.2676 (7)0.0576 (13)
H190.45500.12950.25010.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.04720 (19)0.04357 (16)0.03842 (16)0.00970 (13)0.00667 (13)0.00554 (12)
I20.0480 (2)0.0557 (2)0.1142 (3)0.01393 (17)0.0076 (2)0.0045 (2)
Cu0.0333 (3)0.0300 (2)0.0426 (3)0.0049 (2)0.0044 (2)0.0043 (2)
N10.035 (2)0.0361 (18)0.0367 (18)0.0072 (15)0.0069 (16)0.0035 (14)
N20.042 (2)0.0361 (18)0.0332 (18)0.0121 (16)0.0060 (16)0.0070 (14)
N30.034 (2)0.0372 (18)0.041 (2)0.0060 (15)0.0038 (16)0.0077 (15)
N40.040 (2)0.0330 (17)0.044 (2)0.0115 (15)0.0081 (17)0.0080 (15)
C10.042 (2)0.034 (2)0.037 (2)0.0041 (18)0.013 (2)0.0058 (17)
C20.058 (3)0.037 (2)0.054 (3)0.003 (2)0.011 (3)0.001 (2)
C30.054 (3)0.055 (3)0.050 (3)0.013 (2)0.011 (3)0.003 (2)
C40.029 (2)0.078 (4)0.039 (3)0.001 (2)0.005 (2)0.001 (2)
C50.042 (3)0.052 (3)0.041 (2)0.007 (2)0.007 (2)0.007 (2)
C60.050 (3)0.034 (2)0.035 (2)0.0160 (19)0.018 (2)0.0088 (17)
C70.072 (4)0.037 (2)0.048 (3)0.020 (2)0.022 (3)0.015 (2)
C80.075 (4)0.057 (3)0.041 (3)0.037 (3)0.017 (3)0.014 (2)
C90.060 (3)0.070 (3)0.038 (2)0.037 (3)0.011 (2)0.014 (2)
C100.040 (3)0.053 (3)0.040 (2)0.017 (2)0.003 (2)0.005 (2)
C110.043 (2)0.035 (2)0.029 (2)0.0051 (18)0.0023 (18)0.0115 (17)
C120.059 (3)0.037 (2)0.041 (3)0.002 (2)0.004 (2)0.0054 (19)
C130.043 (3)0.055 (3)0.049 (3)0.008 (2)0.010 (2)0.016 (2)
C140.031 (3)0.064 (3)0.062 (3)0.007 (2)0.003 (2)0.020 (3)
C150.037 (3)0.048 (3)0.046 (3)0.008 (2)0.004 (2)0.008 (2)
C160.046 (3)0.034 (2)0.029 (2)0.0103 (18)0.0020 (18)0.0094 (16)
C170.066 (3)0.037 (2)0.038 (2)0.017 (2)0.001 (2)0.0019 (18)
C180.076 (4)0.065 (3)0.042 (3)0.040 (3)0.009 (3)0.007 (2)
C200.049 (3)0.044 (3)0.053 (3)0.013 (2)0.013 (2)0.011 (2)
C190.057 (3)0.072 (3)0.056 (3)0.033 (3)0.018 (3)0.020 (3)
Geometric parameters (Å, º) top
I1—Cu2.6765 (6)C7—H70.930
Cu—N11.980 (3)C8—C91.358 (7)
Cu—N31.981 (3)C8—H80.930
Cu—N42.089 (3)C9—C101.376 (6)
Cu—N22.092 (3)C9—H90.930
N1—C51.342 (5)C10—H100.930
N1—C11.345 (5)C11—C121.386 (6)
N2—C101.337 (5)C11—C161.477 (6)
N2—C61.347 (5)C12—C131.385 (7)
N3—C151.337 (5)C12—H120.930
N3—C111.344 (5)C13—C141.362 (7)
N4—C201.325 (6)C13—H130.930
N4—C161.344 (5)C14—C151.378 (6)
C1—C21.392 (6)C14—H140.930
C1—C61.470 (6)C15—H150.930
C2—C31.371 (7)C16—C171.391 (6)
C2—H20.930C17—C181.366 (7)
C3—C41.363 (7)C17—H170.930
C3—H30.930C18—C191.372 (7)
C4—C51.387 (6)C18—H180.930
C4—H40.930C20—C191.374 (6)
C5—H50.930C20—H200.930
C6—C71.388 (6)C19—H190.930
C7—C81.378 (7)
N1—Cu—N3174.53 (14)C8—C7—H7120.3
N1—Cu—N499.80 (14)C6—C7—H7120.3
N3—Cu—N480.29 (14)C9—C8—C7119.5 (4)
N1—Cu—N280.06 (13)C9—C8—H8120.3
N3—Cu—N294.87 (14)C7—C8—H8120.3
N4—Cu—N2113.89 (13)C8—C9—C10119.0 (5)
N1—Cu—I190.53 (10)C8—C9—H9120.5
N3—Cu—I194.00 (10)C10—C9—H9120.5
N4—Cu—I1123.04 (9)N2—C10—C9122.6 (4)
N2—Cu—I1123.07 (9)N2—C10—H10118.7
C5—N1—C1119.0 (4)C9—C10—H10118.7
C5—N1—Cu124.5 (3)N3—C11—C12120.4 (4)
C1—N1—Cu115.9 (3)N3—C11—C16115.5 (4)
C10—N2—C6118.7 (4)C12—C11—C16124.1 (4)
C10—N2—Cu128.9 (3)C13—C12—C11119.2 (4)
C6—N2—Cu112.4 (3)C13—C12—H12120.4
C15—N3—C11119.9 (4)C11—C12—H12120.4
C15—N3—Cu123.9 (3)C14—C13—C12119.7 (4)
C11—N3—Cu116.1 (3)C14—C13—H13120.1
C20—N4—C16118.6 (4)C12—C13—H13120.1
C20—N4—Cu128.5 (3)C13—C14—C15118.8 (5)
C16—N4—Cu112.8 (3)C13—C14—H14120.6
N1—C1—C2120.4 (4)C15—C14—H14120.6
N1—C1—C6115.1 (3)N3—C15—C14121.9 (5)
C2—C1—C6124.5 (4)N3—C15—H15119.1
C3—C2—C1119.9 (5)C14—C15—H15119.1
C3—C2—H2120.1N4—C16—C17120.9 (4)
C1—C2—H2120.1N4—C16—C11115.1 (4)
C4—C3—C2119.7 (4)C17—C16—C11124.0 (4)
C4—C3—H3120.1C18—C17—C16119.4 (4)
C2—C3—H3120.1C18—C17—H17120.3
C3—C4—C5118.3 (5)C16—C17—H17120.3
C3—C4—H4120.8C17—C18—C19119.5 (5)
C5—C4—H4120.8C17—C18—H18120.3
N1—C5—C4122.5 (5)C19—C18—H18120.3
N1—C5—H5118.8N4—C20—C19123.4 (5)
C4—C5—H5118.8N4—C20—H20118.3
N2—C6—C7120.9 (4)C19—C20—H20118.3
N2—C6—C1115.3 (3)C18—C19—C20118.1 (5)
C7—C6—C1123.8 (4)C18—C19—H19120.9
C8—C7—C6119.3 (4)C20—C19—H19120.9

Experimental details

Crystal data
Chemical formula[CuI(C20H16N4)]I
Mr629.71
Crystal system, space groupTriclinic, 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)
V3)1038.0 (3)
Z2
Radiation typeMo Kα
µ (mm1)4.04
Crystal size (mm)0.20 × 0.16 × 0.10
Data collection
DiffractometerRigaku AFC-7S
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.446, 0.668
No. of measured, independent and
observed [I > 2σ(I)] reflections
4307, 4074, 2818
Rint0.013
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.066, 1.01
No. of reflections4074
No. of parameters244
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
I1—Cu2.6765 (6)Cu—N42.089 (3)
Cu—N11.980 (3)Cu—N22.092 (3)
Cu—N31.981 (3)
N1—Cu—N3174.53 (14)N4—Cu—N2113.89 (13)
N1—Cu—N499.80 (14)N1—Cu—I190.53 (10)
N3—Cu—N480.29 (14)N3—Cu—I194.00 (10)
N1—Cu—N280.06 (13)N4—Cu—I1123.04 (9)
N3—Cu—N294.87 (14)N2—Cu—I1123.07 (9)
 

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