Two polymorphs of bis(1,10-phenanthroline-[kappa]²N,N')copper(I) iodide

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.

S1. Comment

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 π–π 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 Cu^I centre, or whether the Cu is four-coordinate, with the I⁻ forming part of an ionic matrix. The majority of Cu^I 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 Cu^I 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 Cu^I 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 Cu^II 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⁻.

S2. Experimental

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.

S3. Refinement

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

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

	Fig. 1. The trigonal-bipyramidal coordination of bis(dafone)copper(I) iodide, (II) (Kulkarni et al., 2002).
	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.
	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 π–π interactions between the phenanthroline rings.

(Ia) bis(1,10-phenanthroline-κ²N,N')copper(I) iodide

Crystal data

[Cu(C12H8N2)2]I	Dx = 1.817 Mg m^−3
Mr = 550.85	Melting point: decomposition, greater than 373K K
Orthorhombic, Pban	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2b	Cell parameters from 1677 reflections
a = 14.215 (4) Å	θ = 2.9–26.7°
b = 7.458 (2) Å	µ = 2.64 mm^−1
c = 9.493 (3) Å	T = 293 K
V = 1006.4 (5) Å^3	Plate, black
Z = 2	0.30 × 0.15 × 0.05 mm
F(000) = 540

Data collection

Bruker CCD area-detector diffractometer	1178 independent reflections
Radiation source: sealed tube	892 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −18→18
Tmin = 0.526, Tmax = 0.876	k = −9→9
5578 measured reflections	l = −12→7

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.24	w = 1/[σ^2(Fo^2) + (0.0406P)^2 + 0.9045P] where P = (Fo^2 + 2Fc^2)/3
1178 reflections	(Δ/σ)max < 0.001
70 parameters	Δρmax = 1.20 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.8560 (4)	0.1123 (7)	0.7455 (4)	0.0689 (13)
H1	0.7983	0.0838	0.7049	0.083*
C2	0.9359 (4)	0.0860 (7)	0.6671 (5)	0.0799 (15)
H2	0.9320	0.0455	0.5747	0.096*
C3	1.0205 (4)	0.1201 (7)	0.7270 (6)	0.0795 (16)
H3	1.0756	0.1007	0.6762	0.095*
C4	1.0249 (3)	0.1829 (7)	0.8618 (5)	0.0652 (12)
C5	0.9408 (3)	0.2126 (5)	0.9312 (4)	0.0493 (9)
C6	1.1094 (4)	0.2177 (7)	0.9354 (7)	0.0838 (17)
H6	1.1666	0.1943	0.8915	0.101*
N	0.8564 (2)	0.1751 (5)	0.8739 (3)	0.0555 (8)
Cu	0.7500	0.2500	1.0000	0.0667 (3)
I	0.7500	0.7500	0.5000	0.0654 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.071 (3)	0.087 (4)	0.049 (2)	−0.009 (3)	0.004 (2)	−0.011 (2)
C2	0.086 (4)	0.097 (4)	0.057 (2)	−0.006 (3)	0.022 (3)	−0.016 (2)
C3	0.078 (4)	0.076 (4)	0.084 (3)	0.000 (3)	0.040 (3)	−0.006 (3)
C4	0.053 (3)	0.064 (3)	0.078 (3)	−0.001 (2)	0.019 (2)	0.004 (2)
C5	0.050 (2)	0.044 (2)	0.054 (2)	−0.0001 (16)	0.0047 (18)	0.0048 (16)
C6	0.048 (3)	0.075 (4)	0.129 (5)	0.000 (2)	0.015 (3)	−0.009 (3)
N	0.0498 (19)	0.075 (2)	0.0418 (15)	−0.0039 (17)	0.0028 (15)	−0.0053 (16)
Cu	0.0445 (6)	0.1076 (9)	0.0480 (5)	0.000	0.000	0.000
I	0.0415 (3)	0.0977 (5)	0.0571 (4)	0.000	0.000	0.000

Geometric parameters (Å, º)

C1—N	1.306 (5)	C3—H3	0.9300
C1—C2	1.372 (6)	C4—C5	1.383 (6)
C1—H1	0.9300	C4—C6	1.414 (7)
C2—C3	1.355 (7)	C5—N	1.347 (5)
C2—H2	0.9300	C6—H6	0.9300
C3—C4	1.365 (7)	N—Cu	2.008 (3)
N—C1—C2	123.6 (5)	C4—C5—C5^i	120.1 (3)
N—C1—H1	118.2	C6^i—C6—C4	121.8 (3)
C2—C1—H1	118.2	C6^i—C6—H6	119.1
C3—C2—C1	118.8 (4)	C4—C6—H6	119.1
C3—C2—H2	120.6	C1—N—C5	117.1 (4)
C1—C2—H2	120.6	C1—N—Cu	130.8 (3)
C2—C3—C4	119.9 (5)	C5—N—Cu	111.9 (3)
C2—C3—H3	120.1	N^i—Cu—N^ii	147.7 (2)
C4—C3—H3	120.1	N^i—Cu—N^iii	106.80 (19)
C3—C4—C5	117.6 (5)	N^ii—Cu—N^iii	82.28 (19)
C3—C4—C6	124.4 (5)	N^i—Cu—N	82.28 (19)
C5—C4—C6	118.0 (5)	N^ii—Cu—N	106.80 (19)
N—C5—C4	123.0 (4)	N^iii—Cu—N	147.7 (2)
N—C5—C5^i	116.9 (2)
N—C1—C2—C3	2.6 (8)	C2—C1—N—Cu	172.3 (4)
C1—C2—C3—C4	−1.3 (8)	C4—C5—N—C1	−1.8 (6)
C2—C3—C4—C5	−1.3 (7)	C5^i—C5—N—C1	177.6 (4)
C2—C3—C4—C6	178.0 (5)	C4—C5—N—Cu	−176.4 (3)
C3—C4—C5—N	2.9 (7)	C5^i—C5—N—Cu	3.0 (5)
C6—C4—C5—N	−176.4 (4)	C1—N—Cu—N^i	−174.7 (5)
C3—C4—C5—C5^i	−176.5 (5)	C5—N—Cu—N^i	−1.07 (19)
C6—C4—C5—C5^i	4.2 (7)	C1—N—Cu—N^ii	−26.5 (4)
C3—C4—C6—C6^i	178.4 (7)	C5—N—Cu—N^ii	147.1 (3)
C5—C4—C6—C6^i	−2.3 (10)	C1—N—Cu—N^iii	75.9 (4)
C2—C1—N—C5	−1.1 (7)	C5—N—Cu—N^iii	−110.4 (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

Crystal data

[Cu(C12H8N2)2]I	Dx = 1.689 Mg m^−3
Mr = 550.85	Melting point: decomposition, greater than 373K K
Orthorhombic, Ccca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2b 2bc	Cell parameters from 1677 reflections
a = 16.2547 (7) Å	θ = 1.4–28.8°
b = 29.4171 (13) Å	µ = 2.45 mm^−1
c = 18.1262 (8) Å	T = 293 K
V = 8667.3 (7) Å^3	Bladed, dark purple
Z = 16	0.4 × 0.3 × 0.3 mm
F(000) = 4320

Data collection

Bruker CCD area-detector diffractometer	5435 independent reflections
Radiation source: fine-focus sealed tube	2945 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ϕ and ω scans	θmax = 28.8°, θmin = 1.4°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −22→21
Tmin = 0.375, Tmax = 0.484	k = −38→39
49326 measured reflections	l = −23→23

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.107	w = 1/[s^2(Fo^2) + (0.0406P)^2 + 6.4435P] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
5435 reflections	Δρmax = 0.37 e Å^−3
274 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00000 (1)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C2'	0.8378 (2)	0.68781 (13)	0.3827 (2)	0.1028 (12)
H2'	0.8881	0.6800	0.3617	0.123*
C2	1.0079 (2)	0.64030 (11)	0.63142 (19)	0.0892 (10)
H2	0.9726	0.6616	0.6524	0.107*
C3'	0.7866 (3)	0.71731 (15)	0.3446 (2)	0.1012 (15)
H3'	0.8028	0.7289	0.2992	0.145*
C3	1.0822 (3)	0.63158 (12)	0.6667 (2)	0.0977 (11)
H3	1.0953	0.6464	0.7104	0.117*
C4	1.1356 (2)	0.60112 (13)	0.6366 (2)	0.0910 (10)
H4	1.1853	0.5949	0.6599	0.109*
C4'	0.7132 (2)	0.72909 (13)	0.3736 (2)	0.1043 (12)
H4'	0.6786	0.7487	0.3481	0.125*
C5'	0.6893 (2)	0.71162 (11)	0.44248 (19)	0.0808 (9)
C5	1.11512 (18)	0.57918 (10)	0.57027 (17)	0.0705 (8)
C6	1.1671 (2)	0.54766 (12)	0.5334 (2)	0.0942 (11)
H6	1.2183	0.5408	0.5535	0.113*
C6'	0.6138 (2)	0.72202 (14)	0.4782 (3)	0.1050 (12)
H6'	0.5773	0.7420	0.4556	0.126*
C7'	0.5938 (2)	0.70387 (14)	0.5435 (2)	0.1035 (12)
H7'	0.5444	0.7121	0.5658	0.124*
C7	1.1442 (2)	0.52766 (13)	0.4707 (2)	0.0923 (10)
H7	1.1805	0.5079	0.4472	0.111*
C8	1.06547 (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'	0.5802	0.6584	0.6715	0.118*
C9	1.0373 (2)	0.51483 (12)	0.37360 (19)	0.0895 (10)
H9	1.0708	0.4945	0.3483	0.107*
C10'	0.6823 (3)	0.62118 (12)	0.6764 (2)	0.1052 (12)
H10'	0.6707	0.6072	0.7212	0.126*
C10	0.9609 (2)	0.52460 (14)	0.34801 (19)	0.0969 (11)
H10	0.9416	0.5112	0.3049	0.116*
C11	0.91194 (18)	0.55465 (12)	0.38667 (18)	0.0904 (10)
H11	0.8596	0.5608	0.3684	0.108*
C11'	0.7553 (2)	0.61113 (12)	0.63876 (19)	0.0927 (11)
H11'	0.7915	0.5903	0.6596	0.111*
C12	1.01227 (16)	0.56637 (10)	0.47381 (17)	0.0602 (7)
C12'	0.74379 (17)	0.68126 (10)	0.47703 (19)	0.0674 (8)
C13	1.03782 (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)
N1	0.98474 (14)	0.62001 (8)	0.56971 (13)	0.0702 (6)
N2'	0.77507 (15)	0.62990 (8)	0.57505 (14)	0.0730 (7)
N2	0.93517 (13)	0.57531 (8)	0.44844 (13)	0.0710 (6)
Cu	0.87799 (2)	0.623557 (13)	0.51168 (2)	0.08789 (18)
I1	0.7500	0.5000	0.750599 (14)	0.07188 (12)
I2	1.0000	0.7500	0.7500	0.07215 (14)
I3	1.0000	0.7500	0.2500	0.07597 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2'	0.076 (2)	0.143 (3)	0.090 (3)	−0.001 (2)	0.005 (2)	0.032 (2)
C2	0.105 (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)
C3	0.114 (3)	0.101 (3)	0.078 (2)	0.002 (2)	−0.021 (2)	−0.016 (2)
C4	0.086 (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)
C5	0.0677 (18)	0.0737 (19)	0.0702 (19)	0.0059 (16)	−0.0116 (16)	0.0059 (15)
C6	0.069 (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)
C7	0.070 (2)	0.108 (3)	0.099 (3)	0.0293 (19)	0.005 (2)	−0.016 (2)
C8	0.0581 (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)
C9	0.082 (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)
C10	0.066 (2)	0.151 (3)	0.074 (2)	−0.012 (2)	0.0085 (18)	−0.036 (2)
C11	0.0547 (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)
C12	0.0529 (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)
C13	0.0641 (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)
N1	0.0760 (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)
N2	0.0574 (14)	0.0927 (18)	0.0630 (15)	0.0047 (13)	0.0020 (12)	−0.0056 (13)
Cu	0.0715 (3)	0.1059 (4)	0.0863 (3)	0.0307 (2)	0.0031 (2)	0.0017 (2)
I1	0.06453 (19)	0.0843 (2)	0.0668 (2)	0.00965 (13)	0.000	0.000
I2	0.0823 (3)	0.0617 (2)	0.0724 (3)	0.000	0.000	0.000
I3	0.0531 (2)	0.1079 (3)	0.0670 (3)	0.000	0.000	0.000

Geometric parameters (Å, º)

C2'—N1'	1.333 (4)	C8—C12	1.400 (4)
C2'—C3'	1.387 (5)	C8—C9	1.410 (4)
C2'—H2'	0.9300	C8'—C9'	1.394 (5)
C2—N1	1.323 (4)	C8'—C13'	1.406 (4)
C2—C3	1.390 (4)	C9'—C10'	1.355 (5)
C2—H2	0.9300	C9'—H9'	0.9300
C3'—C4'	1.348 (5)	C9—C10	1.357 (5)
C3'—H3'	0.9300	C9—H9	0.9300
C3—C4	1.361 (5)	C10'—C11'	1.400 (4)
C3—H3	0.9300	C10'—H10'	0.9300
C4—C5	1.405 (4)	C10—C11	1.380 (4)
C4—H4	0.9300	C10—H10	0.9300
C4'—C5'	1.405 (5)	C11—N2	1.329 (4)
C4'—H4'	0.9300	C11—H11	0.9300
C5'—C12'	1.405 (4)	C11'—N2'	1.320 (4)
C5'—C6'	1.421 (5)	C11'—H11'	0.9300
C5—C13	1.406 (4)	C12—N2	1.361 (3)
C5—C6	1.421 (4)	C12—C13	1.428 (4)
C6—C7	1.333 (5)	C12'—N1'	1.358 (3)
C6—H6	0.9300	C12'—C13'	1.430 (4)
C6'—C7'	1.338 (5)	C13—N1	1.366 (3)
C6'—H6'	0.9300	C13'—N2'	1.363 (3)
C7'—C8'	1.427 (5)	N1'—Cu	2.037 (2)
C7'—H7'	0.9300	N1—Cu	2.032 (2)
C7—C8	1.425 (4)	N2'—Cu	2.038 (2)
C7—H7	0.9300	N2—Cu	2.048 (2)
N1'—C2'—C3'	123.0 (3)	C10—C9—C8	119.4 (3)
N1'—C2'—H2'	118.5	C10—C9—H9	120.3
C3'—C2'—H2'	118.5	C8—C9—H9	120.3
N1—C2—C3	123.6 (3)	C9'—C10'—C11'	119.4 (3)
N1—C2—H2	118.2	C9'—C10'—H10'	120.3
C3—C2—H2	118.2	C11'—C10'—H10'	120.3
C4'—C3'—C2'	119.8 (4)	C9—C10—C11	119.3 (3)
C4'—C3'—H3'	120.1	C9—C10—H10	120.3
C2'—C3'—H3'	120.1	C11—C10—H10	120.3
C4—C3—C2	119.5 (3)	N2—C11—C10	123.9 (3)
C4—C3—H3	120.3	N2—C11—H11	118.1
C2—C3—H3	120.3	C10—C11—H11	118.1
C3—C4—C5	119.6 (3)	N2'—C11'—C10'	122.9 (3)
C3—C4—H4	120.2	N2'—C11'—H11'	118.5
C5—C4—H4	120.2	C10'—C11'—H11'	118.5
C3'—C4'—C5'	119.8 (3)	N2—C12—C8	122.7 (3)
C3'—C4'—H4'	120.1	N2—C12—C13	117.3 (3)
C5'—C4'—H4'	120.1	C8—C12—C13	120.0 (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—C4	117.1 (3)	N1—C13—C5	123.0 (3)
C13—C5—C6	118.8 (3)	N1—C13—C12	117.5 (2)
C4—C5—C6	124.2 (3)	C5—C13—C12	119.5 (3)
C7—C6—C5	121.5 (3)	N2'—C13'—C8'	122.8 (3)
C7—C6—H6	119.2	N2'—C13'—C12'	117.4 (3)
C5—C6—H6	119.2	C8'—C13'—C12'	119.8 (3)
C7'—C6'—C5'	121.8 (3)	C2'—N1'—C12'	117.5 (3)
C7'—C6'—H6'	119.1	C2'—N1'—Cu	130.7 (2)
C5'—C6'—H6'	119.1	C12'—N1'—Cu	111.7 (2)
C6'—C7'—C8'	121.3 (3)	C2—N1—C13	117.3 (3)
C6'—C7'—H7'	119.4	C2—N1—Cu	131.1 (2)
C8'—C7'—H7'	119.4	C13—N1—Cu	111.46 (19)
C6—C7—C8	121.5 (3)	C11'—N2'—C13'	117.7 (3)
C6—C7—H7	119.2	C11'—N2'—Cu	130.9 (2)
C8—C7—H7	119.2	C13'—N2'—Cu	111.3 (2)
C12—C8—C9	117.4 (3)	C11—N2—C12	117.3 (3)
C12—C8—C7	118.6 (3)	C11—N2—Cu	131.3 (2)
C9—C8—C7	124.0 (3)	C12—N2—Cu	111.27 (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—N2	82.33 (9)
C10'—C9'—H9'	120.0	N1'—Cu—N2	111.48 (11)
C8'—C9'—H9'	120.0	N2'—Cu—N2	138.73 (10)
N1'—C2'—C3'—C4'	−0.2 (7)	C5'—C12'—C13'—C8'	−2.0 (5)
N1—C2—C3—C4	1.0 (6)	C3'—C2'—N1'—C12'	1.3 (5)
C2—C3—C4—C5	0.4 (6)	C3'—C2'—N1'—Cu	175.5 (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'—Cu	−178.0 (2)
C3—C4—C5—C13	−2.0 (5)	C13'—C12'—N1'—Cu	2.2 (3)
C3—C4—C5—C6	178.5 (3)	C3—C2—N1—C13	−0.6 (5)
C13—C5—C6—C7	0.1 (5)	C3—C2—N1—Cu	175.5 (3)
C4—C5—C6—C7	179.6 (4)	C5—C13—N1—C2	−1.2 (4)
C4'—C5'—C6'—C7'	179.1 (4)	C12—C13—N1—C2	178.5 (3)
C12'—C5'—C6'—C7'	0.2 (6)	C5—C13—N1—Cu	−178.0 (2)
C5'—C6'—C7'—C8'	−1.6 (7)	C12—C13—N1—Cu	1.8 (3)
C5—C6—C7—C8	−2.0 (6)	C10'—C11'—N2'—C13'	0.7 (5)
C6—C7—C8—C12	1.4 (5)	C10'—C11'—N2'—Cu	177.0 (3)
C6—C7—C8—C9	−178.5 (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'—Cu	−178.6 (2)
C13'—C8'—C9'—C10'	−1.0 (5)	C12'—C13'—N2'—Cu	2.4 (3)
C7'—C8'—C9'—C10'	179.1 (4)	C10—C11—N2—C12	0.9 (5)
C12—C8—C9—C10	−0.5 (5)	C10—C11—N2—Cu	175.6 (3)
C7—C8—C9—C10	179.4 (3)	C8—C12—N2—C11	−1.9 (4)
C8'—C9'—C10'—C11'	0.1 (6)	C13—C12—N2—C11	178.9 (3)
C8—C9—C10—C11	−0.5 (6)	C8—C12—N2—Cu	−177.7 (2)
C9—C10—C11—N2	0.3 (6)	C13—C12—N2—Cu	3.1 (3)
C9'—C10'—C11'—N2'	0.0 (6)	C2—N1—Cu—N1'	70.2 (3)
C9—C8—C12—N2	1.7 (4)	C13—N1—Cu—N1'	−113.5 (2)
C7—C8—C12—N2	−178.2 (3)	C2—N1—Cu—N2'	−35.7 (3)
C9—C8—C12—C13	−179.1 (3)	C13—N1—Cu—N2'	140.49 (19)
C7—C8—C12—C13	1.0 (4)	C2—N1—Cu—N2	−176.3 (3)
C4'—C5'—C12'—N1'	2.8 (5)	C13—N1—Cu—N2	−0.04 (19)
C6'—C5'—C12'—N1'	−178.3 (3)	C2'—N1'—Cu—N1	66.9 (4)
C4'—C5'—C12'—C13'	−177.3 (3)	C12'—N1'—Cu—N1	−118.7 (2)
C6'—C5'—C12'—C13'	1.6 (5)	C2'—N1'—Cu—N2'	−175.2 (3)
C4—C5—C13—N1	2.5 (4)	C12'—N1'—Cu—N2'	−0.7 (2)
C6—C5—C13—N1	−178.0 (3)	C2'—N1'—Cu—N2	−35.6 (3)
C4—C5—C13—C12	−177.3 (3)	C12'—N1'—Cu—N2	138.9 (2)
C6—C5—C13—C12	2.2 (4)	C11'—N2'—Cu—N1	−38.6 (3)
N2—C12—C13—N1	−3.4 (4)	C13'—N2'—Cu—N1	137.9 (2)
C8—C12—C13—N1	177.4 (2)	C11'—N2'—Cu—N1'	−177.4 (3)
N2—C12—C13—C5	176.4 (3)	C13'—N2'—Cu—N1'	−0.9 (2)
C8—C12—C13—C5	−2.8 (4)	C11'—N2'—Cu—N2	68.6 (4)
C9'—C8'—C13'—N2'	1.8 (5)	C13'—N2'—Cu—N2	−114.9 (2)
C7'—C8'—C13'—N2'	−178.3 (3)	C11—N2—Cu—N1	−176.7 (3)
C9'—C8'—C13'—C12'	−179.3 (3)	C12—N2—Cu—N1	−1.68 (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)