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The title complex, [Cu(C12H8N2)2]I, (I), has been crystallized in two polymorphic forms, both containing four-coordinate copper. Both forms are orthorhombic, with form (Ia) crystallizing in the primitive space group Pban and form (Ib) in the c-centred space group Ccca. In (Ia), the complex cation and the I- anion both have 222 crystallographic symmetry, and in (Ib), the complex cation has approximate 222 symmetry, with the I- counter-ion distributed over three special positions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102020590/ta1392sup1.cif
Contains datablocks global, Ia, Ib

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020590/ta1392Iasup2.hkl
Contains datablock Ia

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020590/ta1392Ibsup3.hkl
Contains datablock Ib

CCDC references: 204023; 204024

Comment top

Bis(1,10-phenanthroline-κ2N,N')copper(I) iodide, [Cu(C12H8N2)2]I, (I), and other halo-forms, have been prepared and employed in the preparation of a range of halo(amine)copper organophosphonate materials. The latter are the subject of a forthcoming publication, and will not be discussed in detail here. However, the phosphonates themselves produced unexpected supramolecular structures, in which it was believed that compound (I) and the organophosphonic acid were unchanged, and had merely produced an associated structure through favourable opportunities for ππ and hydrogen-bonding interactions. Thus, the structural observations of the resulting phosphonates prompted us to investigate the structure of (I). \sch

There appear to be conflicting views on the structure of (I). These relate to the nature of the coordination of the I and the question of whether it is bound, producing a five-coordinate CuI centre, or whether the Cu is four-coordinate, with the I forming part of an ionic matrix. The majority of CuI complexes are four-coordinate, and indeed, (I) was originally thought to be ionic (Jardine et al., 1970), because it gave conducting solutions in nitrobenzene (which has an equivalent conductance of 30.8 mho in 10−3 M solution). However, there are exceptions to this four-coordinate rule, for example, the corresponding five-coordinate dafone complex, (II) (Kulkarni et al., 2002; Fig. 1).

Single-crystal structural analysis confirms that (I) is an ionic compound and that it exists in at least two polymorphic forms, (Ia) and (Ib). Both polymorphs are orthorhombic, with form (Ia) crystallizing in space group Pban and form (Ib) in Ccca. In polymorph (Ia), the copper complex has crystallographic 222 symmetry, with the Cu atom occupying a 222 site and the I counterion occupying a general position (Fig. 2a). In polymorph (Ib), the copper complex has approximate 222 symmetry, with the I distributed over a twofold site and two 222 sites (see Fig. 2 b). There are significant differences in the geometry about the Cu atom in the two forms. Whilst each Cu atom is four-coordinate, the dihedral angles between the two planes made up of the Cu and the two phenanthroline N atoms are 43.30 (4)° in form (Ia) and 61.80 (4)° in form (Ib). Thus, the geometry of (Ia) is midway between square-planar and tetrahedral, and (Ib) is closer to tetrahedral.

The packing diagrams for the two polymorphs are shown in Figs. 3a and 3 b. As can be seen, both crystals contain ribbons of [Cu(C12H8N2)2]+ cations, together with unassociated I counterions, which are positioned in the voids. The copper complex cations are associated with their identical neighbours through stacking of the aromatic rings of the phenanthroline in an `offset' manner. This occurs to maximize attractive electrostatic interactions between the positively charged σ frameworks and the negatively charged π electrons, and has been observed for a number of similar systems (Hunter, 1994; Nord, 1985). The minimum distance between overlapping phenanthroline rings is approximately 3.550 Å in form (Ia) and 3.414–3.707 Å in form (Ib). The angle between phenanthroline ring planes in the latter is 4.40 (4)°.

The bonding about the Cu atom in (Ia) and (Ib) is typical of this class of compounds (Jardine, 1970). Phenanthroline ligands generally form four-coordinate complexes with CuI ions, due to steric interactions between the α H atoms of the amine ligand (Simmons et al., 1987). Therefore, if a [Cu(C12H8N2)2]+ cation takes a quasi-square-planar stereochemistry, the four N atoms are expected to have a flattened tetrahedral disposition and the Ni—Cu—Nii or N—Cu—Niii angles should be in the range 150–160° [symmetry codes: (i) x, 1/2 − y, 2 − z; (ii) 3/2 − x, 1/2 − y, z; (iii) 3/2 − x, y, 2 − z Please check these added symops are correct], with no significant differences between the four Cu—N (C12H8N2) distances (Murphy, Murphy et al., 1997 or Murphy, Nagle et al., 1997?). This is the case in (Ia). However, the corresponding angles (N1—Cu—N1' and N2—Cu—N2') in (Ib) are considerably smaller, at approximately 138°, and the Cu—N distances (Tables 1 and 2) are all slightly different.

Other CuI complexes with bidentate amine ligands show different structures. The corresponding dafone complex, (II) (Fig. 1), has trigonal-bipyramidal coordination about the Cu atom, coordinating two dafone molecules and an I. The N atoms of the dafone ligand have a larger `bite' size (2.99 Å) compared with phenanthroline (2.65 Å), and it can expand the coordination number from four to five because it does not have the steric strain normally associated with phenanthroline in metal complexes (Kulkarni et al., 2002). By comparison, the analogous CuII derivative, [CuI(C12H8N2)2]I·H2O (Nagle & Hathaway, 1991), has a distorted trigonal-bipyramidal copper centre which bonds to four N atoms from two phenanthroline molecules and an I.

Experimental top

Compound (I) was synthesized following the procedure of Tartarini (1933). Solid 1,10-phenanthroline monohydrate (1.80 g) was added to an aqueous solution of copper(II) sulfate pentahydrate (1.25 g, 50 ml). Solid potassium iodide (2 g) was then added to this stirred solution, which turned a mustard-yellow colour. The solution was then diluted with sodium sulfite (12.6 g, 250 ml) and brought to the boil, whence a purple precipitate was deposited. The solid was filtered off, washed with water and dried over P2O5 prior to recrystallization from ethanol.

Refinement top

H atoms were treated as riding, with C—H distances of 0.93 Å. Is this added text OK? The peak of highest electron density in the final difference map of (Ia) occurs at (3/4, 0.88, 1/2) and is about 1 Å away from the I counterion.

Computing details top

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXTL (Bruker, 2001). Program(s) used to refine structure: SHELXTL for (Ia); SHELXL97 (Sheldrick, 1997) for (Ib). For both compounds, molecular graphics: SHELXTL and ZORTEP (Zsolnai, 1994); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The trigonal-bipyramidal coordination of bis(dafone)copper(I) iodide, (II) (Kulkarni et al., 2002).
[Figure 2] Fig. 2. Views of the molecular units of (a) polymorph (Ia) and (b) polymorph (Ib). Symmetry codes (i), (ii) and (iii) are as given in Table 1. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. Packing diagrams (viewed along the a axis) for (a) polymorph (Ia) and (b) polymorph (Ib), showing the distribution of the I ions within the ionic matrix and the ππ interactions between the phenanthroline rings.
(Ia) bis(1,10-phenanthroline-κ2N,N')copper(I) iodide top
Crystal data top
[Cu(C12H8N2)2]IDx = 1.817 Mg m3
Mr = 550.85Melting point: decomposition, greater than 373K K
Orthorhombic, PbanMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2bCell parameters from 1677 reflections
a = 14.215 (4) Åθ = 2.9–26.7°
b = 7.458 (2) ŵ = 2.64 mm1
c = 9.493 (3) ÅT = 293 K
V = 1006.4 (5) Å3Plate, black
Z = 20.30 × 0.15 × 0.05 mm
F(000) = 540
Data collection top
Bruker CCD area-detector
diffractometer
1178 independent reflections
Radiation source: sealed tube892 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ϕ and ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1818
Tmin = 0.526, Tmax = 0.876k = 99
5578 measured reflectionsl = 127
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.24 w = 1/[σ2(Fo2) + (0.0406P)2 + 0.9045P]
where P = (Fo2 + 2Fc2)/3
1178 reflections(Δ/σ)max < 0.001
70 parametersΔρmax = 1.20 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
[Cu(C12H8N2)2]IV = 1006.4 (5) Å3
Mr = 550.85Z = 2
Orthorhombic, PbanMo Kα radiation
a = 14.215 (4) ŵ = 2.64 mm1
b = 7.458 (2) ÅT = 293 K
c = 9.493 (3) Å0.30 × 0.15 × 0.05 mm
Data collection top
Bruker CCD area-detector
diffractometer
1178 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
892 reflections with I > 2σ(I)
Tmin = 0.526, Tmax = 0.876Rint = 0.031
5578 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.119H-atom parameters constrained
S = 1.24Δρmax = 1.20 e Å3
1178 reflectionsΔρmin = 0.32 e Å3
70 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
C10.8560 (4)0.1123 (7)0.7455 (4)0.0689 (13)
H10.79830.08380.70490.083*
C20.9359 (4)0.0860 (7)0.6671 (5)0.0799 (15)
H20.93200.04550.57470.096*
C31.0205 (4)0.1201 (7)0.7270 (6)0.0795 (16)
H31.07560.10070.67620.095*
C41.0249 (3)0.1829 (7)0.8618 (5)0.0652 (12)
C50.9408 (3)0.2126 (5)0.9312 (4)0.0493 (9)
C61.1094 (4)0.2177 (7)0.9354 (7)0.0838 (17)
H61.16660.19430.89150.101*
N0.8564 (2)0.1751 (5)0.8739 (3)0.0555 (8)
Cu0.75000.25001.00000.0667 (3)
I0.75000.75000.50000.0654 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.071 (3)0.087 (4)0.049 (2)0.009 (3)0.004 (2)0.011 (2)
C20.086 (4)0.097 (4)0.057 (2)0.006 (3)0.022 (3)0.016 (2)
C30.078 (4)0.076 (4)0.084 (3)0.000 (3)0.040 (3)0.006 (3)
C40.053 (3)0.064 (3)0.078 (3)0.001 (2)0.019 (2)0.004 (2)
C50.050 (2)0.044 (2)0.054 (2)0.0001 (16)0.0047 (18)0.0048 (16)
C60.048 (3)0.075 (4)0.129 (5)0.000 (2)0.015 (3)0.009 (3)
N0.0498 (19)0.075 (2)0.0418 (15)0.0039 (17)0.0028 (15)0.0053 (16)
Cu0.0445 (6)0.1076 (9)0.0480 (5)0.0000.0000.000
I0.0415 (3)0.0977 (5)0.0571 (4)0.0000.0000.000
Geometric parameters (Å, º) top
C1—N1.306 (5)C3—H30.9300
C1—C21.372 (6)C4—C51.383 (6)
C1—H10.9300C4—C61.414 (7)
C2—C31.355 (7)C5—N1.347 (5)
C2—H20.9300C6—H60.9300
C3—C41.365 (7)N—Cu2.008 (3)
N—C1—C2123.6 (5)C4—C5—C5i120.1 (3)
N—C1—H1118.2C6i—C6—C4121.8 (3)
C2—C1—H1118.2C6i—C6—H6119.1
C3—C2—C1118.8 (4)C4—C6—H6119.1
C3—C2—H2120.6C1—N—C5117.1 (4)
C1—C2—H2120.6C1—N—Cu130.8 (3)
C2—C3—C4119.9 (5)C5—N—Cu111.9 (3)
C2—C3—H3120.1Ni—Cu—Nii147.7 (2)
C4—C3—H3120.1Ni—Cu—Niii106.80 (19)
C3—C4—C5117.6 (5)Nii—Cu—Niii82.28 (19)
C3—C4—C6124.4 (5)Ni—Cu—N82.28 (19)
C5—C4—C6118.0 (5)Nii—Cu—N106.80 (19)
N—C5—C4123.0 (4)Niii—Cu—N147.7 (2)
N—C5—C5i116.9 (2)
N—C1—C2—C32.6 (8)C2—C1—N—Cu172.3 (4)
C1—C2—C3—C41.3 (8)C4—C5—N—C11.8 (6)
C2—C3—C4—C51.3 (7)C5i—C5—N—C1177.6 (4)
C2—C3—C4—C6178.0 (5)C4—C5—N—Cu176.4 (3)
C3—C4—C5—N2.9 (7)C5i—C5—N—Cu3.0 (5)
C6—C4—C5—N176.4 (4)C1—N—Cu—Ni174.7 (5)
C3—C4—C5—C5i176.5 (5)C5—N—Cu—Ni1.07 (19)
C6—C4—C5—C5i4.2 (7)C1—N—Cu—Nii26.5 (4)
C3—C4—C6—C6i178.4 (7)C5—N—Cu—Nii147.1 (3)
C5—C4—C6—C6i2.3 (10)C1—N—Cu—Niii75.9 (4)
C2—C1—N—C51.1 (7)C5—N—Cu—Niii110.4 (3)
Symmetry codes: (i) x, y+1/2, z+2; (ii) x+3/2, y+1/2, z; (iii) x+3/2, y, z+2.
(Ib) bis(1,10-phenanthroline-κ2N,N')copper(I) iodide top
Crystal data top
[Cu(C12H8N2)2]IDx = 1.689 Mg m3
Mr = 550.85Melting point: decomposition, greater than 373K K
Orthorhombic, CccaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2b 2bcCell parameters from 1677 reflections
a = 16.2547 (7) Åθ = 1.4–28.8°
b = 29.4171 (13) ŵ = 2.45 mm1
c = 18.1262 (8) ÅT = 293 K
V = 8667.3 (7) Å3Bladed, dark purple
Z = 160.4 × 0.3 × 0.3 mm
F(000) = 4320
Data collection top
Bruker CCD area-detector
diffractometer
5435 independent reflections
Radiation source: fine-focus sealed tube2945 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ϕ and ω scansθmax = 28.8°, θmin = 1.4°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 2221
Tmin = 0.375, Tmax = 0.484k = 3839
49326 measured reflectionsl = 2323
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.107 w = 1/[s2(Fo2) + (0.0406P)2 + 6.4435P]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
5435 reflectionsΔρmax = 0.37 e Å3
274 parametersΔρmin = 0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00000 (1)
Crystal data top
[Cu(C12H8N2)2]IV = 8667.3 (7) Å3
Mr = 550.85Z = 16
Orthorhombic, CccaMo Kα radiation
a = 16.2547 (7) ŵ = 2.45 mm1
b = 29.4171 (13) ÅT = 293 K
c = 18.1262 (8) Å0.4 × 0.3 × 0.3 mm
Data collection top
Bruker CCD area-detector
diffractometer
5435 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
2945 reflections with I > 2σ(I)
Tmin = 0.375, Tmax = 0.484Rint = 0.030
49326 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 0.98Δρmax = 0.37 e Å3
5435 reflectionsΔρmin = 0.25 e Å3
274 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
C2'0.8378 (2)0.68781 (13)0.3827 (2)0.1028 (12)
H2'0.88810.68000.36170.123*
C21.0079 (2)0.64030 (11)0.63142 (19)0.0892 (10)
H20.97260.66160.65240.107*
C3'0.7866 (3)0.71731 (15)0.3446 (2)0.1012 (15)
H3'0.80280.72890.29920.145*
C31.0822 (3)0.63158 (12)0.6667 (2)0.0977 (11)
H31.09530.64640.71040.117*
C41.1356 (2)0.60112 (13)0.6366 (2)0.0910 (10)
H41.18530.59490.65990.109*
C4'0.7132 (2)0.72909 (13)0.3736 (2)0.1043 (12)
H4'0.67860.74870.34810.125*
C5'0.6893 (2)0.71162 (11)0.44248 (19)0.0808 (9)
C51.11512 (18)0.57918 (10)0.57027 (17)0.0705 (8)
C61.1671 (2)0.54766 (12)0.5334 (2)0.0942 (11)
H61.21830.54080.55350.113*
C6'0.6138 (2)0.72202 (14)0.4782 (3)0.1050 (12)
H6'0.57730.74200.45560.126*
C7'0.5938 (2)0.70387 (14)0.5435 (2)0.1035 (12)
H7'0.54440.71210.56580.124*
C71.1442 (2)0.52766 (13)0.4707 (2)0.0923 (10)
H71.18050.50790.44720.111*
C81.06547 (17)0.53581 (10)0.43879 (16)0.0694 (8)
C8'0.64659 (19)0.67213 (11)0.57956 (19)0.0794 (9)
C9'0.6288 (2)0.65142 (13)0.6469 (2)0.0985 (11)
H9'0.58020.65840.67150.118*
C91.0373 (2)0.51483 (12)0.37360 (19)0.0895 (10)
H91.07080.49450.34830.107*
C10'0.6823 (3)0.62118 (12)0.6764 (2)0.1052 (12)
H10'0.67070.60720.72120.126*
C100.9609 (2)0.52460 (14)0.34801 (19)0.0969 (11)
H100.94160.51120.30490.116*
C110.91194 (18)0.55465 (12)0.38667 (18)0.0904 (10)
H110.85960.56080.36840.108*
C11'0.7553 (2)0.61113 (12)0.63876 (19)0.0927 (11)
H11'0.79150.59030.65960.111*
C121.01227 (16)0.56637 (10)0.47381 (17)0.0602 (7)
C12'0.74379 (17)0.68126 (10)0.47703 (19)0.0674 (8)
C131.03782 (17)0.58919 (9)0.53950 (15)0.0610 (7)
C13'0.72166 (18)0.66072 (10)0.54574 (17)0.0663 (7)
N1'0.81822 (14)0.67013 (9)0.44814 (14)0.0769 (7)
N10.98474 (14)0.62001 (8)0.56971 (13)0.0702 (6)
N2'0.77507 (15)0.62990 (8)0.57505 (14)0.0730 (7)
N20.93517 (13)0.57531 (8)0.44844 (13)0.0710 (6)
Cu0.87799 (2)0.623557 (13)0.51168 (2)0.08789 (18)
I10.75000.50000.750599 (14)0.07188 (12)
I21.00000.75000.75000.07215 (14)
I31.00000.75000.25000.07597 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C2'0.076 (2)0.143 (3)0.090 (3)0.001 (2)0.005 (2)0.032 (2)
C20.105 (3)0.082 (2)0.081 (2)0.015 (2)0.008 (2)0.0162 (19)
C3'0.093 (3)0.168 (4)0.103 (3)0.006 (3)0.011 (2)0.065 (3)
C30.114 (3)0.101 (3)0.078 (2)0.002 (2)0.021 (2)0.016 (2)
C40.086 (2)0.103 (3)0.085 (2)0.006 (2)0.0251 (19)0.003 (2)
C4'0.091 (3)0.117 (3)0.105 (3)0.003 (2)0.030 (2)0.039 (2)
C5'0.072 (2)0.080 (2)0.090 (2)0.0082 (17)0.0180 (18)0.0098 (18)
C50.0677 (18)0.0737 (19)0.0702 (19)0.0059 (16)0.0116 (16)0.0059 (15)
C60.069 (2)0.115 (3)0.099 (3)0.029 (2)0.015 (2)0.008 (2)
C6'0.084 (3)0.110 (3)0.121 (3)0.037 (2)0.020 (3)0.002 (3)
C7'0.076 (2)0.122 (3)0.113 (3)0.031 (2)0.005 (2)0.007 (3)
C70.070 (2)0.108 (3)0.099 (3)0.0293 (19)0.005 (2)0.016 (2)
C80.0581 (16)0.081 (2)0.0691 (19)0.0048 (15)0.0121 (15)0.0037 (16)
C8'0.072 (2)0.084 (2)0.082 (2)0.0139 (17)0.0086 (17)0.0091 (18)
C9'0.094 (3)0.109 (3)0.092 (3)0.020 (2)0.028 (2)0.012 (2)
C90.082 (2)0.110 (3)0.076 (2)0.000 (2)0.0244 (19)0.025 (2)
C10'0.130 (3)0.103 (3)0.083 (2)0.013 (2)0.034 (2)0.009 (2)
C100.066 (2)0.151 (3)0.074 (2)0.012 (2)0.0085 (18)0.036 (2)
C110.0547 (18)0.142 (3)0.075 (2)0.0002 (18)0.0031 (16)0.021 (2)
C11'0.111 (3)0.087 (2)0.080 (2)0.027 (2)0.018 (2)0.0110 (19)
C120.0529 (15)0.0701 (18)0.0577 (17)0.0013 (13)0.0071 (13)0.0047 (15)
C12'0.0593 (17)0.073 (2)0.0700 (19)0.0035 (14)0.0112 (16)0.0007 (17)
C130.0641 (16)0.0584 (16)0.0606 (18)0.0033 (13)0.0009 (14)0.0066 (14)
C13'0.0649 (17)0.0668 (18)0.0672 (19)0.0066 (15)0.0006 (15)0.0079 (15)
N1'0.0633 (15)0.0945 (19)0.0728 (16)0.0059 (13)0.0024 (13)0.0128 (14)
N10.0760 (15)0.0680 (15)0.0668 (16)0.0134 (12)0.0044 (12)0.0055 (13)
N2'0.0774 (16)0.0730 (17)0.0687 (16)0.0165 (13)0.0079 (13)0.0049 (13)
N20.0574 (14)0.0927 (18)0.0630 (15)0.0047 (13)0.0020 (12)0.0056 (13)
Cu0.0715 (3)0.1059 (4)0.0863 (3)0.0307 (2)0.0031 (2)0.0017 (2)
I10.06453 (19)0.0843 (2)0.0668 (2)0.00965 (13)0.0000.000
I20.0823 (3)0.0617 (2)0.0724 (3)0.0000.0000.000
I30.0531 (2)0.1079 (3)0.0670 (3)0.0000.0000.000
Geometric parameters (Å, º) top
C2'—N1'1.333 (4)C8—C121.400 (4)
C2'—C3'1.387 (5)C8—C91.410 (4)
C2'—H2'0.9300C8'—C9'1.394 (5)
C2—N11.323 (4)C8'—C13'1.406 (4)
C2—C31.390 (4)C9'—C10'1.355 (5)
C2—H20.9300C9'—H9'0.9300
C3'—C4'1.348 (5)C9—C101.357 (5)
C3'—H3'0.9300C9—H90.9300
C3—C41.361 (5)C10'—C11'1.400 (4)
C3—H30.9300C10'—H10'0.9300
C4—C51.405 (4)C10—C111.380 (4)
C4—H40.9300C10—H100.9300
C4'—C5'1.405 (5)C11—N21.329 (4)
C4'—H4'0.9300C11—H110.9300
C5'—C12'1.405 (4)C11'—N2'1.320 (4)
C5'—C6'1.421 (5)C11'—H11'0.9300
C5—C131.406 (4)C12—N21.361 (3)
C5—C61.421 (4)C12—C131.428 (4)
C6—C71.333 (5)C12'—N1'1.358 (3)
C6—H60.9300C12'—C13'1.430 (4)
C6'—C7'1.338 (5)C13—N11.366 (3)
C6'—H6'0.9300C13'—N2'1.363 (3)
C7'—C8'1.427 (5)N1'—Cu2.037 (2)
C7'—H7'0.9300N1—Cu2.032 (2)
C7—C81.425 (4)N2'—Cu2.038 (2)
C7—H70.9300N2—Cu2.048 (2)
N1'—C2'—C3'123.0 (3)C10—C9—C8119.4 (3)
N1'—C2'—H2'118.5C10—C9—H9120.3
C3'—C2'—H2'118.5C8—C9—H9120.3
N1—C2—C3123.6 (3)C9'—C10'—C11'119.4 (3)
N1—C2—H2118.2C9'—C10'—H10'120.3
C3—C2—H2118.2C11'—C10'—H10'120.3
C4'—C3'—C2'119.8 (4)C9—C10—C11119.3 (3)
C4'—C3'—H3'120.1C9—C10—H10120.3
C2'—C3'—H3'120.1C11—C10—H10120.3
C4—C3—C2119.5 (3)N2—C11—C10123.9 (3)
C4—C3—H3120.3N2—C11—H11118.1
C2—C3—H3120.3C10—C11—H11118.1
C3—C4—C5119.6 (3)N2'—C11'—C10'122.9 (3)
C3—C4—H4120.2N2'—C11'—H11'118.5
C5—C4—H4120.2C10'—C11'—H11'118.5
C3'—C4'—C5'119.8 (3)N2—C12—C8122.7 (3)
C3'—C4'—H4'120.1N2—C12—C13117.3 (3)
C5'—C4'—H4'120.1C8—C12—C13120.0 (2)
C4'—C5'—C12'117.0 (3)N1'—C12'—C5'122.8 (3)
C4'—C5'—C6'124.4 (3)N1'—C12'—C13'117.2 (3)
C12'—C5'—C6'118.5 (3)C5'—C12'—C13'119.9 (3)
C13—C5—C4117.1 (3)N1—C13—C5123.0 (3)
C13—C5—C6118.8 (3)N1—C13—C12117.5 (2)
C4—C5—C6124.2 (3)C5—C13—C12119.5 (3)
C7—C6—C5121.5 (3)N2'—C13'—C8'122.8 (3)
C7—C6—H6119.2N2'—C13'—C12'117.4 (3)
C5—C6—H6119.2C8'—C13'—C12'119.8 (3)
C7'—C6'—C5'121.8 (3)C2'—N1'—C12'117.5 (3)
C7'—C6'—H6'119.1C2'—N1'—Cu130.7 (2)
C5'—C6'—H6'119.1C12'—N1'—Cu111.7 (2)
C6'—C7'—C8'121.3 (3)C2—N1—C13117.3 (3)
C6'—C7'—H7'119.4C2—N1—Cu131.1 (2)
C8'—C7'—H7'119.4C13—N1—Cu111.46 (19)
C6—C7—C8121.5 (3)C11'—N2'—C13'117.7 (3)
C6—C7—H7119.2C11'—N2'—Cu130.9 (2)
C8—C7—H7119.2C13'—N2'—Cu111.3 (2)
C12—C8—C9117.4 (3)C11—N2—C12117.3 (3)
C12—C8—C7118.6 (3)C11—N2—Cu131.3 (2)
C9—C8—C7124.0 (3)C12—N2—Cu111.27 (19)
C9'—C8'—C13'117.2 (3)N1—Cu—N1'137.28 (10)
C9'—C8'—C7'124.2 (3)N1—Cu—N2'114.46 (10)
C13'—C8'—C7'118.6 (3)N1'—Cu—N2'82.27 (10)
C10'—C9'—C8'119.9 (3)N1—Cu—N282.33 (9)
C10'—C9'—H9'120.0N1'—Cu—N2111.48 (11)
C8'—C9'—H9'120.0N2'—Cu—N2138.73 (10)
N1'—C2'—C3'—C4'0.2 (7)C5'—C12'—C13'—C8'2.0 (5)
N1—C2—C3—C41.0 (6)C3'—C2'—N1'—C12'1.3 (5)
C2—C3—C4—C50.4 (6)C3'—C2'—N1'—Cu175.5 (3)
C2'—C3'—C4'—C5'0.4 (6)C5'—C12'—N1'—C2'2.7 (5)
C3'—C4'—C5'—C12'1.6 (6)C13'—C12'—N1'—C2'177.5 (3)
C3'—C4'—C5'—C6'179.6 (4)C5'—C12'—N1'—Cu178.0 (2)
C3—C4—C5—C132.0 (5)C13'—C12'—N1'—Cu2.2 (3)
C3—C4—C5—C6178.5 (3)C3—C2—N1—C130.6 (5)
C13—C5—C6—C70.1 (5)C3—C2—N1—Cu175.5 (3)
C4—C5—C6—C7179.6 (4)C5—C13—N1—C21.2 (4)
C4'—C5'—C6'—C7'179.1 (4)C12—C13—N1—C2178.5 (3)
C12'—C5'—C6'—C7'0.2 (6)C5—C13—N1—Cu178.0 (2)
C5'—C6'—C7'—C8'1.6 (7)C12—C13—N1—Cu1.8 (3)
C5—C6—C7—C82.0 (6)C10'—C11'—N2'—C13'0.7 (5)
C6—C7—C8—C121.4 (5)C10'—C11'—N2'—Cu177.0 (3)
C6—C7—C8—C9178.5 (4)C8'—C13'—N2'—C11'1.6 (5)
C6'—C7'—C8'—C9'178.9 (4)C12'—C13'—N2'—C11'179.4 (3)
C6'—C7'—C8'—C13'1.2 (6)C8'—C13'—N2'—Cu178.6 (2)
C13'—C8'—C9'—C10'1.0 (5)C12'—C13'—N2'—Cu2.4 (3)
C7'—C8'—C9'—C10'179.1 (4)C10—C11—N2—C120.9 (5)
C12—C8—C9—C100.5 (5)C10—C11—N2—Cu175.6 (3)
C7—C8—C9—C10179.4 (3)C8—C12—N2—C111.9 (4)
C8'—C9'—C10'—C11'0.1 (6)C13—C12—N2—C11178.9 (3)
C8—C9—C10—C110.5 (6)C8—C12—N2—Cu177.7 (2)
C9—C10—C11—N20.3 (6)C13—C12—N2—Cu3.1 (3)
C9'—C10'—C11'—N2'0.0 (6)C2—N1—Cu—N1'70.2 (3)
C9—C8—C12—N21.7 (4)C13—N1—Cu—N1'113.5 (2)
C7—C8—C12—N2178.2 (3)C2—N1—Cu—N2'35.7 (3)
C9—C8—C12—C13179.1 (3)C13—N1—Cu—N2'140.49 (19)
C7—C8—C12—C131.0 (4)C2—N1—Cu—N2176.3 (3)
C4'—C5'—C12'—N1'2.8 (5)C13—N1—Cu—N20.04 (19)
C6'—C5'—C12'—N1'178.3 (3)C2'—N1'—Cu—N166.9 (4)
C4'—C5'—C12'—C13'177.3 (3)C12'—N1'—Cu—N1118.7 (2)
C6'—C5'—C12'—C13'1.6 (5)C2'—N1'—Cu—N2'175.2 (3)
C4—C5—C13—N12.5 (4)C12'—N1'—Cu—N2'0.7 (2)
C6—C5—C13—N1178.0 (3)C2'—N1'—Cu—N235.6 (3)
C4—C5—C13—C12177.3 (3)C12'—N1'—Cu—N2138.9 (2)
C6—C5—C13—C122.2 (4)C11'—N2'—Cu—N138.6 (3)
N2—C12—C13—N13.4 (4)C13'—N2'—Cu—N1137.9 (2)
C8—C12—C13—N1177.4 (2)C11'—N2'—Cu—N1'177.4 (3)
N2—C12—C13—C5176.4 (3)C13'—N2'—Cu—N1'0.9 (2)
C8—C12—C13—C52.8 (4)C11'—N2'—Cu—N268.6 (4)
C9'—C8'—C13'—N2'1.8 (5)C13'—N2'—Cu—N2114.9 (2)
C7'—C8'—C13'—N2'178.3 (3)C11—N2—Cu—N1176.7 (3)
C9'—C8'—C13'—C12'179.3 (3)C12—N2—Cu—N11.68 (19)
C7'—C8'—C13'—C12'0.7 (5)C11—N2—Cu—N1'38.6 (3)
N1'—C12'—C13'—N2'3.2 (4)C12—N2—Cu—N1'136.4 (2)
C5'—C12'—C13'—N2'177.0 (3)C11—N2—Cu—N2'64.6 (3)
N1'—C12'—C13'—C8'177.8 (3)C12—N2—Cu—N2'120.4 (2)

Experimental details

(Ia)(Ib)
Crystal data
Chemical formula[Cu(C12H8N2)2]I[Cu(C12H8N2)2]I
Mr550.85550.85
Crystal system, space groupOrthorhombic, PbanOrthorhombic, Ccca
Temperature (K)293293
a, b, c (Å)14.215 (4), 7.458 (2), 9.493 (3)16.2547 (7), 29.4171 (13), 18.1262 (8)
V3)1006.4 (5)8667.3 (7)
Z216
Radiation typeMo KαMo Kα
µ (mm1)2.642.45
Crystal size (mm)0.30 × 0.15 × 0.050.4 × 0.3 × 0.3
Data collection
DiffractometerBruker CCD area-detector
diffractometer
Bruker CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.526, 0.8760.375, 0.484
No. of measured, independent and
observed [I > 2σ(I)] reflections
5578, 1178, 892 49326, 5435, 2945
Rint0.0310.030
(sin θ/λ)max1)0.6510.678
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.119, 1.24 0.035, 0.107, 0.98
No. of reflections11785435
No. of parameters70274
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.20, 0.320.37, 0.25

Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXTL (Bruker, 2001), SHELXL97 (Sheldrick, 1997), SHELXTL and ZORTEP (Zsolnai, 1994).

Selected geometric parameters (Å, º) for (Ia) top
C1—N1.306 (5)N—Cu2.008 (3)
C5—N1.347 (5)
N—C1—C2123.6 (5)C1—N—Cu130.8 (3)
N—C5—C4123.0 (4)C5—N—Cu111.9 (3)
N—C5—C5i116.9 (2)Ni—Cu—N82.28 (19)
C4—C5—C5i120.1 (3)Nii—Cu—N106.80 (19)
C6i—C6—C4121.8 (3)Niii—Cu—N147.7 (2)
C1—N—C5117.1 (4)
Symmetry codes: (i) x, y+1/2, z+2; (ii) x+3/2, y+1/2, z; (iii) x+3/2, y, z+2.
Selected geometric parameters (Å, º) for (Ib) top
C2'—N1'1.333 (4)C13—N11.366 (3)
C2—N11.323 (4)C13'—N2'1.363 (3)
C11—N21.329 (4)N1'—Cu2.037 (2)
C11'—N2'1.320 (4)N1—Cu2.032 (2)
C12—N21.361 (3)N2'—Cu2.038 (2)
C12'—N1'1.358 (3)N2—Cu2.048 (2)
N1'—C2'—C3'123.0 (3)C2—N1—C13117.3 (3)
N1—C2—C3123.6 (3)C2—N1—Cu131.1 (2)
N2—C11—C10123.9 (3)C13—N1—Cu111.46 (19)
N2'—C11'—C10'122.9 (3)C11'—N2'—C13'117.7 (3)
N2—C12—C8122.7 (3)C11'—N2'—Cu130.9 (2)
N2—C12—C13117.3 (3)C13'—N2'—Cu111.3 (2)
N1'—C12'—C5'122.8 (3)C11—N2—C12117.3 (3)
N1'—C12'—C13'117.2 (3)C11—N2—Cu131.3 (2)
N1—C13—C5123.0 (3)C12—N2—Cu111.27 (19)
N1—C13—C12117.5 (2)N1—Cu—N1'137.28 (10)
N2'—C13'—C8'122.8 (3)N1—Cu—N2'114.46 (10)
N2'—C13'—C12'117.4 (3)N1'—Cu—N2'82.27 (10)
C2'—N1'—C12'117.5 (3)N1—Cu—N282.33 (9)
C2'—N1'—Cu130.7 (2)N1'—Cu—N2111.48 (11)
C12'—N1'—Cu111.7 (2)N2'—Cu—N2138.73 (10)
 

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