Two [Cu₂I₂]-based coordination polymers of 1,3-bis­(pyridin-4-yl)propane

Solvothermal reactions of Cu₂(OH)₂CO₃ with 1,3-bis­(pyridin-4-yl)propane (bpp) in the presence of aqueous ammonia in 4-iodo­toluene/CH₃CN or 1,4-diiodo­benzene/CH₃CN afforded two [Cu₂I₂]-based coordination polymers, namely catena-poly[[[di-[mu]-iodido-dicopper(I)]-bis­[[mu]-1,3-bis­(pyridin-4-yl)propane-[kappa]²N:N']] p-toluidine tetra­solvate], {[Cu₂I₂(C₁₃H₁₄N₂)₂]·4C₇H₉N}_n, (I), and the analogous 1,4-diiodo­benzene monosolvate, {[Cu₂I₂(C₁₃H₁₄N₂)₂]·C₆H₄I₂}_n, (II). The [Cu₂I₂] unit of (I) lies on a centre of symmetry at the mid-point of the two I atoms, while that of (II) has a twofold axis running through the I...I line. In (I) and (II), each Cu centre is tetra­hedrally coordinated by two [mu]-I and two N atoms from two different bpp ligands. Each rhomboid [Cu₂I₂] unit can be considered as a four-connecting node linked to the symmetry-related [Cu₂I₂] units via two pairs of bpp ligands to form a one-dimensional double chain along the c axis. The dimensions of the [Cu₂I₂(bpp)₂]₂ rings in (I) and (II) are different, which may be due to the presence of different guest solvent mol­ecules in the structures. In (I), one p-toluidine mol­ecule, derived from an Ullmann coupling reaction of 4-iodo­toluene with ammonia, inter­acts with the [Cu₂I₂] cluster fragment through N-H...I hydrogen bonds, while the two p-toluidine molecules interact via N-H...N hydrogen bonds. In (II), two I atoms of each 1,4-diiodo­benzene mol­ecule are linked to the I atoms of the [Cu₂I₂] fragments from a neighbouring chain via I...I secondary inter­actions.

S1. Comment

In recent years, the construction of cluster-based coordination polymers has received much interest due to their structural diversity (Fujita, 1998; Blake, Champness et al., 1999; Leininger et al., 2000; Naumov et al., 2002; Tulsky et al., 2003; Wang et al., 2008), and their applications in storage and separation processes (Ma et al., 2007; Cotton et al., 2004; Chatterjee et al., 2004; Rosi et al., 2003), magnetism (Kahn, 2000), catalysis (Fujita et al., 1994; Pan et al., 2003; Hasegawa et al., 2007; Lin & Wu, 2007) and other potential uses (Beauvais et al., 2000; Horcajada et al., 2006). Cu^I salts are used in reactions with N-donor ligands to form cluster-based coordination polymers of various structural motifs such as rhomboid [Cu₂I₂] dimers (Biradha et al., 2000; Hu et al., 2006; Graham & Pike, 2000; Thébault et al., 2006; Niu et al., 2006; Araki et al., 2005), cubane [Cu₄I₄] tetramers (Blake et al., 2001), zigzag [CuI]_n or [Cu₃I₄]_n^n- chains (Graham & Pike, 2000; Thébault et al., 2006; Cheng et al., 2004), double-stranded [Cu₂I₂]_n ladders or ribbons (Graham & Pike, 2000; Thébault et al., 2006; Cheng et al., 2004), and two-dimensional [CuI]_n layers (Thébault et al., 2006; Peng et al., 2005; Blake, Brooks et al., 1999). Many factors like reaction temperature, pH value and the symmetry of the ligands can exert great influence on the construction and structure of [Cu_xI_x]-based coordination polymers, but solvent effects on the assembly and structure of such polymers have been less well explored (Chen et al., 2008). Herein, we report the crystal structures of two [Cu₂I₂]-based coordination polymers, {[Cu₂I₂(bpp)₂].4p-toluidine}_n, (I), and {[Cu₂I₂(bpp)₂].p-diiodobenzene}_n, (II), which were obtained from solvothermal reactions of Cu₂(OH)₂CO₃ with 1,3-bis(pyridin-4-yl)propane (bpp) and aqueous ammonia in 4-iodotoluene/CH₃CN and p-diiodobenzene/CH₃CN, respectively.

The asymmetric unit of (I) contains half a [Cu₂I₂(bpp)₂] dimeric molecule and two p-toluidine solvent molecules (Fig. 1), while that of (II) consists of half a [Cu₂I₂(bpp)₂] dimeric molecule and half a p-diiodobenzene solvent molecule (Fig. 2). In the dimeric molecules of (I) and (II), each Cu atom is tetrahedrally coordinated by two µ-I and two N atoms from two different bpp ligands. The dimer of (I) lies on a centre of symmetry at the midpoint of atoms I1 and I1ⁱ [symmetry code: (i) -x, -y, -z + 1], while that of (II) has a twofold screw axis running along the I1···I2 line. Each rhomboid [Cu₂I₂] unit can be viewed as a four-connecting node linking symmetry-equivalent [Cu₂I₂] units via two pairs of bpp ligands to afford a one-dimensional double chain along the c axis. [Fig. 3 for (I) and Fig. 4 for (II)].

The mean Cu1···Cu1ⁱ distance in (I) [2.7366 (19) Å] is slightly shorter than that observed in [Cu₂I₂L₄]_n [L is 3-methylpyridine, 2.781 (2) Å; Rath et al. 1986] but longer than those found in [Cu₂I₂L₄]_n [L is pyridine, 2.699 (5) Å; Dyason et al. 1984] and [Cu₂I₂L₄]_n [L is 3,5-dimethylpyridine, 2.687 (3) Å; Healy et al. 1983]. The length of the Cu···Cu contact (3.654 Å) in (II) precludes any metal–metal interaction. The mean Cu—I bond length in (I) [2.6608 (9) Å] (Table 1) is comparable with that in {[Cu₂I₂(bpp)₂].2aniline}_n [2.6674 (19) Å; Chen et al., 2008] but shorter than those in (II) [2.7392 (8) Å] or {[Cu₂I₂(bpe)₂].Am}_n [Am is aniline, 2.7939 (15) Å; Am is p-toluidine, 2.7415 (11) Å; Yang et al. 2011]. The average Cu—N bond length of 2.051 (2) Å in (I) is longer than those observed in (II) [2.027 (4) Å] or {[Cu₂I₂(bpe)₂].Am}_n [Am is aniline, 2.006 (2) Å; Am is p-toluidine, 2.014 (3) Å], but slightly shorter than those in {[Cu₂I₂(bpp)₂].2aniline}_n [2.064 (7) Å] and [Cu₂I₂L₄]_n [L is 3,5-dimethylpyridine, 2.06 (3) Å; Healy et al. 1983].

Each bpp ligand in (I) and (II) adopts a trans–trans configuration (Chen et al. 2008). However, as the pyridyl rings are rotated around the Cu—N direction, the bpp ligand in (I) is not planar, with a dihedral angle of 70.6° between the two pyridyl groups, while that of (II) is approximately planar, with a dihedral angle of 12.5° between the two pyridyl groups. The N1···N2 separation (9.595 Å) in (I) is shorter than that in (II) (10.178 Å). On the other hand, the one-dimensional chains in (I) and (II) may be viewed as a sequence of 28-membered [Cu₂I₂(bpp)]₂ metallomacrocycle rings (Perera et al., 2010; Chan et al., 2009), which are constructed of two [Cu₂I₂] and two bpp ligands. The dimensions of these metallomacrocycle rings in (I) and (II) are roughly 12.96 × 8.27 Å and 13.76 × 7.79 Å, respectively. These differences may be ascribed to solvent effects, which greatly influence the structures of [Cu₂I₂]-based coordination polymers (Blake et al., 2001; Chen et al., 2008; Yang et al., 2011).

In the formation of (I) and (II), Cu^II may be reduced by bpp and/or iodide and the resulting Cu^I may combine iodides to produce the [Cu₂I₂] species (Yang et al. 2011). The latter have then been captured by bpp ligands to yield the [Cu₂I₂]-based frameworks of (I) and (II). In (I), the p-toluidine guest molecules have been generated in situ through an Ullmann coupling reaction of 4-iodotoluene with ammonia (Chen et al. 2008).

In (I), two p-toluidine molecules interact with each other via intermolecular hydrogen bonds between two amino groups (N4—H4···N3; Table 2). The NH₂ group of one p-toluidine molecule binds the I atom of the [Cu₂I₂] fragment through an intermolecular hydrogen bond (N3—H3···I1), while its methyl group interacts with two pyridyl groups of the bpp ligands of a neighbouring chain via C14—H14···π interactions [H···pyridyl centroid = 2.893 and 3.225 Å; symmetry codes (-x + 1, -y, -z + 1) and (x - 1, y, z - 1), respectively] (Ciunik & Desiraju, 2001), thereby forming a two-dimensional network (Fig. 3).

In (II), the two I atoms of each p-diiodobenzene molecule interact with the I atoms of the [Cu₂I₂] fragments from an adjacent chain via an I···I(-x, -y + 1, -z) secondary interaction (3.620 Å). The methylene group of the bpp ligand in such a chain interacts with a pyridyl group of the bpp ligand of a neighbouring chain via C8—H8···π(1/2 - x, 3/2 - y, -z + 2) interactions (H···pyridyl centroid = 3.174 Å), affording another two-dimensional network (Fig. 4).

Related literature

For related literature, see: Araki et al. (2005); Beauvais et al. (2000); Biradha et al. (2000); Blake et al. (2001); Blake, Brooks, Champness, Cooke, Deveson, Fenske, Hubberstey, Li & Schröder (1999); Blake, Champness, Hubberstey, Li, Withersby & Schröder (1999); Chan et al. (2009); Chatterjee et al. (2004); Chen et al. (2008); Cheng et al. (2004); Ciunik & Desiraju (2001); Cotton et al. (2004); Dyason et al. (1984); Fujita (1998); Fujita et al. (1994); Graham & Pike (2000); Hasegawa et al. (2007); Healy et al. (1983); Horcajada et al. (2006); Hu et al. (2006); Kahn (2000); Leininger et al. (2000); Lin & Wu (2007); Ma et al. (2007); Naumov et al. (2002); Niu et al. (2006); Pan et al. (2003); Peng et al. (2005); Perera et al. (2010); Rath et al. (1986); Rosi et al. (2003); Thébault et al. (2006); Tulsky et al. (2003); Wang et al. (2008); Yang et al. (2011).

S2. Experimental

Cu₂(OH)₂CO₃ (22 mg, 0.1 mmol), bpp (20 mg, 0.1 mmol), 4-iodotoluene (150 mg, 0.7 mmol), aqueous ammonia (25%, 1.5 ml) and CH₃CN (0.5 ml) were added to a Pyrex glass tube (15 cm in length, 7 mm in inner diameter). The tube was sealed and heated in an oven at 423 K for 70 h, and then cooled to room temperature at a rate of 5 K per 100 min to form red blocks [Yellow prism in CIF - please clarify] of {[Cu₂I₂(bpp)₂].4p-toluidine}_n, (I), which were collected by filtration, washed with CH₃CN and dried in air (yield: 21 mg, 30% based on bpp). Analysis, found: C 53.59, H 5.29, N 9.20%; calculated for C₂₇H₃₂CuIN₄: C 53.78, H 5.35, N 9.29%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3427 (w), 3380 (w), 3301 (w), 3209 (w), 3022 (w), 2926 (w), 2860 (w), 1608 (s), 1514 (s), 1421(m), 1262 (m), 1220 (m), 1011 (w), 809 (s), 610 (w), 512 (m).

Cu₂(OH)₂CO₃ (22 mg, 0.1 mmol), bpp (20 mg, 0.1 mmol), p-diiodobenzene (33 mg, 0.1 mmol), aqueous ammonia (25%, 0.2 ml) and CH₃CN (1.5 ml) were added to a Pyrex glass tube (15 cm in length, 7 mm in inner diameter). The tube was sealed and heated in an oven at 423 K for 70 h, and then cooled to room temperature at a rate of 5 K per 100 min to form red [Orange in CIF - please clarify] blocks of {[Cu₂I₂(bpp)₂].p-diiodobenzene}_n (II), which were collected by filtration, washed with CH₃CN, and dried in air (yield: 0.021 g, 30% based on bpp). Analysis, found: C 34.69, H 2.89, N 5.10%; calculated for C₁₆H₁₆CuI₂N₂: C 34.71, H 2.91, N 5.06%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3425 (w), 3378 (w), 3206 (w), 3021 (w), 2923 (w), 2856 (w), 1602 (s), 1509 (s), 1417 (s), 1258 (m), 1218 (m), 1008 (w), 805 (s), 613 (w), 512 (m).

S3. Refinement

All H atoms were placed in geometrically idealized positions, with C—H = 0.98 for methyl groups, 0.99 for methylene groups and 0.95 Å for phenyl groups, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) for phenyl groups and U_iso(H) = 1.5U_eq(C) for methyl groups.

Computing details

For both compounds, data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x, -y, -z + 1; (ii) x, y, z + 1; (iii) -x, -y, -z.]
	Fig. 2. The molecular structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x, y, -z + 1/2; (ii) -x, y, -z + 3/2; (iii) x, y, z - 1.]
	Fig. 3. A view of the two-dimensional network of (I), extending along the ac plane. Dashed lines indicate N—H···N and N—H···I hydrogen bonds and C—H···π interactions. (In the electronic version of the journal, atom colour codes are: Cu cyan, I pink, N blue, C grey and H green.)
	Fig. 4. A view of the two-dimensional network of (II), extending along the ac plane. Dashed lines indicate I···I secondary interactions and C—H···π interactions. [In the electronic version of the journal, atom colour codes are: Cu cyan, I pink, N blue, C grey and H green.)

(I) catena-poly[[[di-µ-iodido-dicopper(I)]- bis[µ-1,3-bis(pyridin-4-yl)propane-κ²N:N']] p-toluidine tetrasolvate]

Crystal data

[Cu2I2(C13H14N2)2]·4C7H9N	Z = 1
Mr = 1206.02	F(000) = 608
Triclinic, P1	Dx = 1.525 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.119 (2) Å	Cell parameters from 6516 reflections
b = 12.370 (3) Å	θ = 3.1–27.5°
c = 12.962 (3) Å	µ = 2.03 mm^−1
α = 103.19 (3)°	T = 223 K
β = 111.06 (3)°	Prism, yellow
γ = 109.30 (3)°	0.60 × 0.60 × 0.40 mm
V = 1313.4 (5) Å^3

Data collection

Rigaku Saturn 724+ CCD area-detector diffractometer	5891 independent reflections
Radiation source: fine-focus sealed tube	4782 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (Jacobson, 1998)	h = −12→13
Tmin = 0.376, Tmax = 0.498	k = −15→15
12464 measured reflections	l = −16→12

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0292P)^2] where P = (Fo^2 + 2Fc^2)/3
5891 reflections	(Δ/σ)max = 0.001
300 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.77 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.

TITL t in P-1 CELL 0.71073 10.1194 12.3695 12.9620 103.189 111.059 109.304 ZERR 2.00 0.0020 0.0025 0.0026 0.030 0.030 0.030 L A T T 1 SFAC C H N CU I UNIT 54 64 8 2 2

omit -1 - 1 2 omit -1 3 0 omit 0 1 2 omit -2 1 0 omit -1 - 2 2 omit -1 - 2 3 omit 1 - 2 1 omit -1 - 2 1 omit -3 - 3 14 omit -3 - 4 4 omit -2 - 2 2 omit -2 2 0

L.S. 10 BOND $h HTAB N3 I1 HTAB N4 N3 acta bond size 0.6 0.6 0.4 temp -50 FMAP 2 PLAN -5

WGHT 0.029200 FVAR 0.23618 CU1 4 0.128385 0.115425 0.559364 11.00000 0.03476 0.03237 = 0.02291 0.01181 0.01599 0.01367 I1 5 0.168864 - 0.088121 0.525253 11.00000 0.03066 0.03232 = 0.03433 0.01086 0.01424 0.01318 N1 3 0.233529 0.214234 0.479626 11.00000 0.02982 0.02719 = 0.02526 0.01170 0.01475 0.01205 N2 3 0.239216 0.215935 - 0.258629 11.00000 0.02742 0.02545 = 0.01932 0.00846 0.01203 0.01060 N3 3 0.619629 0.076251 0.683350 11.00000 0.04417 0.04907 = 0.05260 0.02292 0.02520 0.01992 AFIX 3 H3A 2 0.522859 0.030021 0.630840 11.00000 - 1.20000 H3B 2 0.672808 0.071091 0.646080 11.00000 - 1.20000 AFIX 0 N4 3 0.746379 0.372027 0.815126 11.00000 0.05491 0.04771 = 0.06703 0.02633 0.03337 0.02122 AFIX 3 H4B 2 0.698809 0.296777 0.765106 11.00000 - 1.20000 H4C 2 0.768909 0.388577 0.888476 11.00000 - 1.20000 AFIX 0 C1 1 0.180553 0.286942 0.433409 11.00000 0.02785 0.03772 = 0.03336 0.01885 0.01623 0.01618 AFIX 43 H1 2 0.090398 0.290614 0.435930 11.00000 - 1.20000 AFIX 0 C2 1 0.251621 0.356429 0.382483 11.00000 0.03533 0.03750 = 0.03029 0.02042 0.01536 0.01968 AFIX 43 H2 2 0.209870 0.406368 0.351659 11.00000 - 1.20000 AFIX 0 C3 1 0.383231 0.353741 0.376093 11.00000 0.03088 0.02456 = 0.01467 0.00337 0.01054 0.00467 C4 1 0.438785 0.279767 0.424049 11.00000 0.04364 0.04567 = 0.04750 0.02638 0.03187 0.02449 AFIX 43 H4A 2 0.528984 0.275187 0.422497 11.00000 - 1.20000 AFIX 0 C5 1 0.362700 0.212158 0.474486 11.00000 0.04407 0.04244 = 0.04933 0.02945 0.03042 0.02718 AFIX 43 H5 2 0.403301 0.162382 0.506707 11.00000 - 1.20000 AFIX 0 C6 1 0.459859 0.426373 0.317281 11.00000 0.03622 0.02781 = 0.02043 0.00765 0.01541 0.00513 AFIX 23 H6A 2 0.573396 0.448647 0.354524 11.00000 - 1.20000 H6B 2 0.449572 0.503763 0.330598 11.00000 - 1.20000 AFIX 0 C7 1 0.383570 0.351376 0.181923 11.00000 0.03159 0.02410 = 0.02155 0.00718 0.01378 0.00716 AFIX 23 H7A 2 0.391728 0.273116 0.168309 11.00000 - 1.20000 H7B 2 0.270596 0.330871 0.144115 11.00000 - 1.20000 AFIX 0 C8 1 0.465329 0.425309 0.124398 11.00000 0.03527 0.02737 = 0.02033 0.00685 0.01355 0.00453 AFIX 23 H8A 2 0.459703 0.504585 0.140196 11.00000 - 1.20000 H8B 2 0.577728 0.444027 0.161120 11.00000 - 1.20000 AFIX 0 C9 1 0.389385 0.354525 - 0.009385 11.00000 0.02834 0.02246 = 0.01977 0.00888 0.01175 0.00356 C10 1 0.250887 0.351323 - 0.087729 11.00000 0.03525 0.03115 = 0.02828 0.00891 0.02012 0.01571 AFIX 43 H10 2 0.204489 0.396108 - 0.057714 11.00000 - 1.20000 AFIX 0 C11 1 0.181038 0.283012 - 0.209068 11.00000 0.02876 0.03401 = 0.02337 0.01073 0.01204 0.01449 AFIX 43 H11 2 0.087656 0.283288 - 0.259993 11.00000 - 1.20000 AFIX 0 C12 1 0.373793 0.219793 - 0.183336 11.00000 0.03131 0.03207 = 0.02884 0.01140 0.01553 0.01750 AFIX 43 H12 2 0.418260 0.174622 - 0.215531 11.00000 - 1.20000 AFIX 0 C13 1 0.450274 0.286753 - 0.060959 11.00000 0.02961 0.03266 = 0.02621 0.01298 0.01026 0.01445 AFIX 43 H13 2 0.544691 0.286385 - 0.012062 11.00000 - 1.20000 AFIX 0 C14 1 0.877591 0.033769 1.136800 11.00000 0.07346 0.06191 = 0.05052 0.02022 0.02965 0.02533 AFIX 137 H14A 2 0.827712 0.060614 1.181891 11.00000 - 1.50000 H14B 2 0.991204 0.087893 1.180355 11.00000 - 1.50000 H14C 2 0.857856 - 0.051259 1.126312 11.00000 - 1.50000 AFIX 0 C15 1 0.808876 0.040105 1.014739 11.00000 0.05060 0.02926 = 0.04444 0.01106 0.02552 0.01746 C16 1 0.647155 - 0.007183 0.944339 11.00000 0.04852 0.03189 = 0.06260 0.02074 0.03850 0.01763 AFIX 43 H16 2 0.578393 - 0.046855 0.971798 11.00000 - 1.20000 AFIX 0 C17 1 0.582924 0.001892 0.834667 11.00000 0.03166 0.03971 = 0.06318 0.02355 0.02732 0.01767 AFIX 43 H17 2 0.472160 - 0.030801 0.789374 11.00000 - 1.20000 AFIX 0 C18 1 0.681326 0.059119 0.791061 11.00000 0.03635 0.02960 = 0.04767 0.01437 0.02339 0.01563 C19 1 0.843674 0.105175 0.860261 11.00000 0.03737 0.04274 = 0.05931 0.02317 0.02953 0.01378 AFIX 43 H19 2 0.912762 0.143589 0.832481 11.00000 - 1.20000 AFIX 0 C20 1 0.905649 0.095252 0.970335 11.00000 0.03270 0.04083 = 0.05358 0.01502 0.01776 0.00760 AFIX 43 H20 2 1.016252 0.126930 1.015571 11.00000 - 1.20000 AFIX 0 C21 1 1.218404 0.675724 0.722564 11.00000 0.05628 0.09080 = 0.09825 0.06395 0.04770 0.04356 AFIX 137 H21A 2 1.222247 0.625790 0.655134 11.00000 - 1.50000 H21B 2 1.322719 0.717795 0.792518 11.00000 - 1.50000 H21C 2 1.186414 0.737110 0.702525 11.00000 - 1.50000 AFIX 0 C22 1 1.100134 0.592615 0.749761 11.00000 0.03577 0.04811 = 0.06081 0.03252 0.02301 0.02765 C23 1 1.092589 0.635504 0.855409 11.00000 0.03649 0.03346 = 0.04967 0.01293 0.01009 0.01668 AFIX 43 H23 2 1.167091 0.716444 0.913021 11.00000 - 1.20000 AFIX 0 C24 1 0.979558 0.563036 0.877840 11.00000 0.04800 0.04044 = 0.03908 0.01347 0.02005 0.02557 AFIX 43 H24 2 0.977575 0.595385 0.950009 11.00000 - 1.20000 AFIX 0 C25 1 0.867926 0.442666 0.795813 11.00000 0.04072 0.03598 = 0.04766 0.01847 0.01982 0.02472 C26 1 0.875306 0.398196 0.691417 11.00000 0.04670 0.03092 = 0.04699 0.00893 0.01430 0.02183 AFIX 43 H26 2 0.801652 0.316735 0.634594 11.00000 - 1.20000 AFIX 0 C27 1 0.989904 0.471946 0.668979 11.00000 0.05863 0.05752 = 0.04231 0.02300 0.02851 0.04157 AFIX 43 H27 2 0.992724 0.439195 0.597278 11.00000 - 1.20000

HKLF 4

REM t in P-1 REM R1 = 0.0304 for 4782 F_o > 4sig(F_o) and 0.0385 for all 5891 data REM 300 parameters refined using 0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.12838 (4)	0.11542 (3)	0.55936 (3)	0.02952 (9)
I1	0.16886 (2)	−0.088121 (18)	0.525253 (17)	0.03362 (7)
N1	0.2335 (2)	0.2142 (2)	0.47963 (19)	0.0268 (5)
N2	0.2392 (2)	0.2159 (2)	−0.25863 (18)	0.0242 (5)
N3	0.6196 (3)	0.0763 (3)	0.6833 (2)	0.0476 (7)
H3A	0.5229	0.0300	0.6308	0.057*
H3B	0.6728	0.0711	0.6461	0.057*
N4	0.7464 (3)	0.3720 (3)	0.8151 (3)	0.0549 (8)
H4B	0.6988	0.2968	0.7651	0.066*
H4C	0.7689	0.3886	0.8885	0.066*
C1	0.1806 (3)	0.2869 (3)	0.4334 (2)	0.0310 (6)
H1	0.0904	0.2906	0.4359	0.037*
C2	0.2516 (3)	0.3564 (3)	0.3825 (2)	0.0320 (6)
H2	0.2099	0.4064	0.3517	0.038*
C3	0.3832 (3)	0.3537 (3)	0.3761 (2)	0.0268 (6)
C4	0.4388 (3)	0.2798 (3)	0.4240 (3)	0.0392 (7)
H4A	0.5290	0.2752	0.4225	0.047*
C5	0.3627 (3)	0.2122 (3)	0.4745 (3)	0.0379 (7)
H5	0.4033	0.1624	0.5067	0.045*
C6	0.4599 (3)	0.4264 (3)	0.3173 (2)	0.0307 (6)
H6A	0.5734	0.4486	0.3545	0.037*
H6B	0.4496	0.5038	0.3306	0.037*
C7	0.3836 (3)	0.3514 (3)	0.1819 (2)	0.0274 (6)
H7A	0.3917	0.2731	0.1683	0.033*
H7B	0.2706	0.3309	0.1441	0.033*
C8	0.4653 (3)	0.4253 (3)	0.1244 (2)	0.0310 (6)
H8A	0.4597	0.5046	0.1402	0.037*
H8B	0.5777	0.4440	0.1611	0.037*
C9	0.3894 (3)	0.3545 (2)	−0.0094 (2)	0.0257 (6)
C10	0.2509 (3)	0.3513 (3)	−0.0877 (2)	0.0302 (6)
H10	0.2045	0.3961	−0.0577	0.036*
C11	0.1810 (3)	0.2830 (3)	−0.2091 (2)	0.0289 (6)
H11	0.0877	0.2833	−0.2600	0.035*
C12	0.3738 (3)	0.2198 (3)	−0.1833 (2)	0.0295 (6)
H12	0.4183	0.1746	−0.2155	0.035*
C13	0.4503 (3)	0.2868 (3)	−0.0610 (2)	0.0301 (6)
H13	0.5447	0.2864	−0.0121	0.036*
C14	0.8776 (5)	0.0338 (4)	1.1368 (3)	0.0639 (10)
H14A	0.8277	0.0606	1.1819	0.096*
H14B	0.9912	0.0879	1.1804	0.096*
H14C	0.8579	−0.0513	1.1263	0.096*
C15	0.8089 (4)	0.0401 (3)	1.0147 (3)	0.0413 (7)
C16	0.6472 (4)	−0.0072 (3)	0.9443 (3)	0.0433 (8)
H16	0.5784	−0.0469	0.9718	0.052*
C17	0.5829 (3)	0.0019 (3)	0.8347 (3)	0.0421 (8)
H17	0.4722	−0.0308	0.7894	0.051*
C18	0.6813 (3)	0.0591 (3)	0.7911 (3)	0.0367 (7)
C19	0.8437 (3)	0.1052 (3)	0.8603 (3)	0.0450 (8)
H19	0.9128	0.1436	0.8325	0.054*
C20	0.9056 (4)	0.0953 (3)	0.9703 (3)	0.0468 (8)
H20	1.0163	0.1269	1.0156	0.056*
C21	1.2184 (4)	0.6757 (4)	0.7226 (4)	0.0695 (12)
H21A	1.2222	0.6258	0.6551	0.104*
H21B	1.3227	0.7178	0.7925	0.104*
H21C	1.1864	0.7371	0.7025	0.104*
C22	1.1001 (3)	0.5926 (3)	0.7498 (3)	0.0433 (8)
C23	1.0926 (4)	0.6355 (3)	0.8554 (3)	0.0438 (8)
H23	1.1671	0.7164	0.9130	0.053*
C24	0.9796 (4)	0.5630 (3)	0.8778 (3)	0.0415 (7)
H24	0.9776	0.5954	0.9500	0.050*
C25	0.8679 (4)	0.4427 (3)	0.7958 (3)	0.0392 (7)
C26	0.8753 (4)	0.3982 (3)	0.6914 (3)	0.0442 (8)
H26	0.8017	0.3167	0.6346	0.053*
C27	0.9899 (4)	0.4719 (3)	0.6690 (3)	0.0459 (8)
H27	0.9927	0.4392	0.5973	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03476 (18)	0.0324 (2)	0.02291 (19)	0.01367 (16)	0.01599 (15)	0.01181 (17)
I1	0.03066 (10)	0.03232 (12)	0.03433 (12)	0.01318 (9)	0.01424 (8)	0.01086 (9)
N1	0.0298 (11)	0.0272 (13)	0.0253 (12)	0.0120 (10)	0.0147 (10)	0.0117 (11)
N2	0.0274 (11)	0.0254 (13)	0.0193 (12)	0.0106 (10)	0.0120 (9)	0.0085 (10)
N3	0.0442 (15)	0.0491 (18)	0.0526 (18)	0.0199 (14)	0.0252 (14)	0.0229 (16)
N4	0.0549 (17)	0.0477 (19)	0.067 (2)	0.0212 (15)	0.0334 (16)	0.0263 (17)
C1	0.0279 (13)	0.0377 (17)	0.0334 (16)	0.0162 (13)	0.0162 (12)	0.0189 (15)
C2	0.0353 (14)	0.0375 (18)	0.0303 (16)	0.0197 (14)	0.0154 (12)	0.0204 (15)
C3	0.0309 (13)	0.0246 (15)	0.0147 (13)	0.0047 (12)	0.0105 (11)	0.0034 (12)
C4	0.0436 (17)	0.046 (2)	0.0475 (19)	0.0245 (16)	0.0319 (15)	0.0264 (17)
C5	0.0441 (16)	0.0424 (19)	0.0493 (19)	0.0272 (15)	0.0304 (15)	0.0295 (17)
C6	0.0362 (14)	0.0278 (16)	0.0204 (14)	0.0051 (13)	0.0154 (12)	0.0076 (13)
C7	0.0316 (13)	0.0241 (15)	0.0215 (14)	0.0072 (12)	0.0138 (11)	0.0072 (13)
C8	0.0353 (14)	0.0274 (16)	0.0203 (14)	0.0045 (13)	0.0136 (12)	0.0069 (13)
C9	0.0283 (13)	0.0225 (15)	0.0198 (14)	0.0036 (11)	0.0118 (11)	0.0089 (12)
C10	0.0353 (14)	0.0312 (16)	0.0283 (16)	0.0157 (13)	0.0201 (12)	0.0089 (14)
C11	0.0288 (13)	0.0340 (17)	0.0234 (15)	0.0145 (13)	0.0120 (11)	0.0107 (14)
C12	0.0313 (14)	0.0321 (16)	0.0288 (16)	0.0175 (13)	0.0155 (12)	0.0114 (14)
C13	0.0296 (13)	0.0327 (17)	0.0262 (15)	0.0145 (13)	0.0103 (12)	0.0130 (14)
C14	0.073 (3)	0.062 (3)	0.051 (2)	0.025 (2)	0.030 (2)	0.020 (2)
C15	0.0506 (18)	0.0293 (18)	0.044 (2)	0.0175 (16)	0.0255 (16)	0.0111 (16)
C16	0.0485 (18)	0.0319 (18)	0.063 (2)	0.0176 (16)	0.0385 (17)	0.0207 (18)
C17	0.0317 (15)	0.0397 (19)	0.063 (2)	0.0177 (15)	0.0273 (15)	0.0235 (18)
C18	0.0363 (15)	0.0296 (17)	0.0477 (19)	0.0156 (14)	0.0234 (14)	0.0144 (16)
C19	0.0374 (16)	0.043 (2)	0.059 (2)	0.0138 (15)	0.0295 (16)	0.0232 (18)
C20	0.0327 (16)	0.041 (2)	0.054 (2)	0.0076 (15)	0.0178 (15)	0.0150 (18)
C21	0.056 (2)	0.091 (3)	0.098 (3)	0.044 (2)	0.048 (2)	0.064 (3)
C22	0.0358 (16)	0.048 (2)	0.061 (2)	0.0276 (16)	0.0230 (16)	0.033 (2)
C23	0.0365 (16)	0.0335 (19)	0.050 (2)	0.0167 (15)	0.0101 (15)	0.0129 (17)
C24	0.0480 (18)	0.040 (2)	0.0391 (19)	0.0256 (17)	0.0200 (15)	0.0135 (17)
C25	0.0407 (16)	0.0360 (19)	0.048 (2)	0.0247 (16)	0.0198 (15)	0.0185 (17)
C26	0.0467 (18)	0.0309 (18)	0.047 (2)	0.0218 (16)	0.0143 (16)	0.0089 (17)
C27	0.059 (2)	0.058 (2)	0.042 (2)	0.042 (2)	0.0285 (17)	0.0230 (19)

Geometric parameters (Å, º)

Cu1—N1	2.050 (2)	C9—C10	1.385 (4)
Cu1—N2^i	2.051 (2)	C10—C11	1.374 (4)
Cu1—I1	2.6470 (7)	C10—H10	0.9400
Cu1—I1^ii	2.6746 (9)	C11—H11	0.9400
Cu1—Cu1^ii	2.7366 (19)	C12—C13	1.377 (4)
I1—Cu1^ii	2.6746 (9)	C12—H12	0.9400
N1—C1	1.338 (3)	C13—H13	0.9400
N1—C5	1.341 (3)	C14—C15	1.515 (4)
N2—C12	1.338 (3)	C14—H14A	0.9700
N2—C11	1.341 (3)	C14—H14B	0.9700
N2—Cu1^iii	2.051 (2)	C14—H14C	0.9700
N3—C18	1.407 (4)	C15—C20	1.378 (4)
N3—H3A	0.8499	C15—C16	1.380 (4)
N3—H3B	0.8500	C16—C17	1.383 (4)
N4—C25	1.396 (4)	C16—H16	0.9400
N4—H4B	0.8500	C17—C18	1.390 (4)
N4—H4C	0.8499	C17—H17	0.9400
C1—C2	1.372 (4)	C18—C19	1.385 (4)
C1—H1	0.9400	C19—C20	1.390 (4)
C2—C3	1.374 (4)	C19—H19	0.9400
C2—H2	0.9400	C20—H20	0.9400
C3—C4	1.374 (4)	C21—C22	1.506 (5)
C3—C6	1.505 (3)	C21—H21A	0.9700
C4—C5	1.380 (4)	C21—H21B	0.9700
C4—H4A	0.9400	C21—H21C	0.9700
C5—H5	0.9400	C22—C27	1.384 (5)
C6—C7	1.531 (4)	C22—C23	1.390 (5)
C6—H6A	0.9800	C23—C24	1.370 (4)
C6—H6B	0.9800	C23—H23	0.9400
C7—C8	1.527 (3)	C24—C25	1.388 (5)
C7—H7A	0.9800	C24—H24	0.9400
C7—H7B	0.9800	C25—C26	1.378 (5)
C8—C9	1.506 (4)	C26—C27	1.388 (5)
C8—H8A	0.9800	C26—H26	0.9400
C8—H8B	0.9800	C27—H27	0.9400
C9—C13	1.382 (4)
N1—Cu1—N2^i	110.41 (9)	C11—C10—H10	119.8
N1—Cu1—I1	107.30 (7)	C9—C10—H10	119.8
N2^i—Cu1—I1	107.55 (7)	N2—C11—C10	123.4 (2)
N1—Cu1—I1^ii	107.16 (6)	N2—C11—H11	118.3
N2^i—Cu1—I1^ii	106.24 (7)	C10—C11—H11	118.3
I1—Cu1—I1^ii	118.11 (4)	N2—C12—C13	123.1 (2)
N1—Cu1—Cu1^ii	125.17 (7)	N2—C12—H12	118.4
N2^i—Cu1—Cu1^ii	124.41 (7)	C13—C12—H12	118.4
I1—Cu1—Cu1^ii	59.55 (3)	C12—C13—C9	120.6 (2)
I1^ii—Cu1—Cu1^ii	58.56 (3)	C12—C13—H13	119.7
Cu1—I1—Cu1^ii	61.89 (4)	C9—C13—H13	119.7
C1—N1—C5	116.4 (2)	C15—C14—H14A	109.5
C1—N1—Cu1	122.11 (17)	C15—C14—H14B	109.5
C5—N1—Cu1	121.42 (17)	H14A—C14—H14B	109.5
C12—N2—C11	116.4 (2)	C15—C14—H14C	109.5
C12—N2—Cu1^iii	122.18 (18)	H14A—C14—H14C	109.5
C11—N2—Cu1^iii	121.38 (16)	H14B—C14—H14C	109.5
C18—N3—H3A	120.0	C20—C15—C16	117.2 (3)
C18—N3—H3B	111.5	C20—C15—C14	121.3 (3)
H3A—N3—H3B	105.4	C16—C15—C14	121.5 (3)
C25—N4—H4B	110.0	C15—C16—C17	122.1 (3)
C25—N4—H4C	115.2	C15—C16—H16	118.9
H4B—N4—H4C	120.3	C17—C16—H16	118.9
N1—C1—C2	123.1 (2)	C16—C17—C18	120.3 (3)
N1—C1—H1	118.5	C16—C17—H17	119.8
C2—C1—H1	118.5	C18—C17—H17	119.8
C1—C2—C3	120.7 (2)	C19—C18—C17	117.9 (3)
C1—C2—H2	119.7	C19—C18—N3	120.6 (3)
C3—C2—H2	119.7	C17—C18—N3	121.4 (3)
C4—C3—C2	116.5 (2)	C18—C19—C20	120.8 (3)
C4—C3—C6	122.1 (2)	C18—C19—H19	119.6
C2—C3—C6	121.4 (2)	C20—C19—H19	119.6
C3—C4—C5	120.3 (3)	C15—C20—C19	121.6 (3)
C3—C4—H4A	119.9	C15—C20—H20	119.2
C5—C4—H4A	119.9	C19—C20—H20	119.2
N1—C5—C4	123.0 (2)	C22—C21—H21A	109.5
N1—C5—H5	118.5	C22—C21—H21B	109.5
C4—C5—H5	118.5	H21A—C21—H21B	109.5
C3—C6—C7	111.6 (2)	C22—C21—H21C	109.5
C3—C6—H6A	109.3	H21A—C21—H21C	109.5
C7—C6—H6A	109.3	H21B—C21—H21C	109.5
C3—C6—H6B	109.3	C27—C22—C23	116.9 (3)
C7—C6—H6B	109.3	C27—C22—C21	121.7 (3)
H6A—C6—H6B	108.0	C23—C22—C21	121.4 (4)
C8—C7—C6	110.8 (2)	C24—C23—C22	121.8 (3)
C8—C7—H7A	109.5	C24—C23—H23	119.1
C6—C7—H7A	109.5	C22—C23—H23	119.1
C8—C7—H7B	109.5	C23—C24—C25	121.1 (3)
C6—C7—H7B	109.5	C23—C24—H24	119.4
H7A—C7—H7B	108.1	C25—C24—H24	119.4
C9—C8—C7	111.7 (2)	C26—C25—C24	117.8 (3)
C9—C8—H8A	109.3	C26—C25—N4	121.1 (3)
C7—C8—H8A	109.3	C24—C25—N4	121.0 (3)
C9—C8—H8B	109.3	C25—C26—C27	120.9 (3)
C7—C8—H8B	109.3	C25—C26—H26	119.5
H8A—C8—H8B	107.9	C27—C26—H26	119.5
C13—C9—C10	116.1 (2)	C22—C27—C26	121.5 (3)
C13—C9—C8	122.5 (2)	C22—C27—H27	119.2
C10—C9—C8	121.3 (2)	C26—C27—H27	119.2
C11—C10—C9	120.3 (2)

Symmetry codes: (i) x, y, z+1; (ii) −x, −y, −z+1; (iii) x, y, z−1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···I1	0.85	2.99	3.793 (3)	158
N4—H4B···N3	0.85	2.41	3.228 (4)	160

(II) catena-poly[[[di-µ-iodido-dicopper(I)]- bis[µ-1,3-bis(pyridin-4-yl)propane-κ²N:N']] 1,4-diiodobenzene monosolvate]

Crystal data

[Cu2I2(C13H14N2)2]·C6H4I2	F(000) = 2088
Mr = 1107.30	Dx = 2.195 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6485 reflections
a = 17.700 (4) Å	θ = 3.1–25.4°
b = 14.604 (3) Å	µ = 4.98 mm^−1
c = 13.757 (3) Å	T = 223 K
β = 109.53 (3)°	Block, orange
V = 3351.4 (12) Å^3	0.54 × 0.40 × 0.38 mm
Z = 4

Data collection

Rigaku Saturn 724+ CCD area-detector diffractometer	3058 independent reflections
Radiation source: fine-focus sealed tube	2902 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 25.4°, θmin = 3.1°
Absorption correction: multi-scan (Jacobson, 1998)	h = −21→19
Tmin = 0.174, Tmax = 0.253	k = −17→17
15742 measured reflections	l = −14→16

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 11.4239P] where P = (Fo^2 + 2Fc^2)/3
3058 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.84 e Å^−3
0 restraints	Δρmin = −1.67 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
Cu1	0.10953 (3)	0.86540 (4)	0.29705 (4)	0.03457 (16)
I1	0.0000	0.72585 (3)	0.2500	0.02780 (12)
I2	0.0000	1.00533 (2)	0.2500	0.02788 (12)
I3	0.02316 (2)	0.34964 (2)	0.00902 (2)	0.04574 (12)
N1	0.1660 (2)	0.8730 (2)	0.4512 (3)	0.0287 (8)
C1	0.2453 (3)	0.8665 (4)	0.4956 (4)	0.0512 (14)
H1	0.2764	0.8571	0.4529	0.061*
C2	0.2843 (3)	0.8727 (4)	0.6002 (4)	0.0500 (14)
H2	0.3405	0.8680	0.6265	0.060*
C3	0.2421 (2)	0.8856 (3)	0.6666 (3)	0.0260 (8)
C4	0.1604 (3)	0.8928 (4)	0.6214 (4)	0.0413 (11)
H4	0.1280	0.9017	0.6626	0.050*
C5	0.1258 (3)	0.8870 (4)	0.5160 (3)	0.0431 (12)
H5	0.0699	0.8934	0.4878	0.052*
C6	0.2859 (3)	0.8911 (3)	0.7811 (3)	0.0311 (9)
H6A	0.3175	0.9477	0.7953	0.037*
H6B	0.3235	0.8398	0.8009	0.037*
C7	0.2335 (3)	0.8896 (3)	0.8497 (3)	0.0290 (9)
H7A	0.2004	0.9449	0.8376	0.035*
H7B	0.1977	0.8364	0.8321	0.035*
C8	0.2856 (3)	0.8847 (3)	0.9629 (3)	0.0307 (9)
H8A	0.3211	0.8315	0.9722	0.037*
H8B	0.3196	0.9394	0.9794	0.037*
C14	0.0102 (3)	0.3565 (3)	0.1554 (3)	0.0328 (10)
C15	0.0055 (3)	0.4391 (3)	0.2027 (3)	0.0361 (10)
H15	0.0096	0.4948	0.1705	0.043*
C16	0.0053 (3)	0.2745 (3)	0.2030 (4)	0.0386 (10)
H16	0.0093	0.2188	0.1708	0.046*
C9	0.2412 (3)	0.8776 (3)	1.0401 (3)	0.0269 (9)
C10	0.1592 (3)	0.8817 (4)	1.0146 (3)	0.0392 (11)
H10	0.1266	0.8886	0.9454	0.047*
C13	0.2845 (3)	0.8666 (3)	1.1438 (4)	0.0384 (11)
H13	0.3407	0.8633	1.1655	0.046*
C11	0.1250 (3)	0.8755 (4)	1.0911 (4)	0.0460 (13)
H11	0.0689	0.8787	1.0714	0.055*
N2	0.1666 (2)	0.8653 (2)	1.1913 (3)	0.0282 (8)
C12	0.2460 (3)	0.8606 (3)	1.2149 (3)	0.0357 (11)
H12	0.2773	0.8526	1.2845	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0327 (3)	0.0491 (4)	0.0230 (3)	0.0004 (2)	0.0108 (2)	0.0002 (2)
I1	0.0253 (2)	0.0317 (2)	0.0251 (2)	0.000	0.00676 (16)	0.000
I2	0.0221 (2)	0.0302 (2)	0.0303 (2)	0.000	0.00736 (16)	0.000
I3	0.0515 (2)	0.0593 (2)	0.0322 (2)	0.00667 (15)	0.02174 (16)	0.00379 (13)
N1	0.0264 (19)	0.0337 (19)	0.0254 (19)	0.0002 (14)	0.0077 (15)	0.0000 (14)
C1	0.034 (3)	0.099 (4)	0.024 (2)	0.017 (3)	0.013 (2)	−0.004 (2)
C2	0.021 (2)	0.103 (5)	0.024 (2)	0.015 (2)	0.005 (2)	0.000 (2)
C3	0.029 (2)	0.027 (2)	0.024 (2)	0.0036 (16)	0.0112 (17)	0.0020 (15)
C4	0.028 (2)	0.071 (3)	0.030 (2)	0.003 (2)	0.017 (2)	0.001 (2)
C5	0.021 (2)	0.081 (4)	0.026 (2)	0.001 (2)	0.0060 (19)	0.001 (2)
C6	0.030 (2)	0.040 (2)	0.022 (2)	0.0036 (18)	0.0078 (18)	0.0012 (17)
C7	0.031 (2)	0.037 (2)	0.019 (2)	0.0056 (18)	0.0087 (17)	0.0028 (16)
C8	0.030 (2)	0.044 (2)	0.019 (2)	0.0024 (18)	0.0087 (18)	0.0006 (17)
C14	0.032 (2)	0.043 (3)	0.025 (2)	0.0016 (18)	0.0130 (19)	0.0011 (17)
C15	0.041 (3)	0.035 (2)	0.032 (2)	−0.0001 (19)	0.013 (2)	0.0049 (18)
C16	0.040 (3)	0.037 (3)	0.039 (2)	0.0025 (19)	0.013 (2)	−0.0014 (19)
C9	0.031 (2)	0.026 (2)	0.024 (2)	0.0023 (16)	0.0103 (18)	0.0001 (15)
C10	0.028 (2)	0.068 (3)	0.019 (2)	0.006 (2)	0.0043 (18)	0.001 (2)
C13	0.023 (2)	0.066 (3)	0.025 (2)	0.002 (2)	0.0071 (19)	0.005 (2)
C11	0.020 (2)	0.084 (4)	0.030 (3)	0.005 (2)	0.004 (2)	0.004 (2)
N2	0.0256 (19)	0.037 (2)	0.0238 (18)	0.0003 (14)	0.0101 (15)	0.0004 (14)
C12	0.031 (3)	0.056 (3)	0.019 (2)	0.0031 (19)	0.0061 (19)	0.0061 (18)

Geometric parameters (Å, º)

Cu1—N1	2.023 (4)	C7—H7A	0.9800
Cu1—N2^i	2.030 (4)	C7—H7B	0.9800
Cu1—I1	2.7371 (8)	C8—C9	1.521 (6)
Cu1—I2	2.7412 (8)	C8—H8A	0.9800
I1—Cu1^ii	2.7371 (8)	C8—H8B	0.9800
I2—Cu1^ii	2.7412 (8)	C14—C16	1.381 (6)
I3—C14	2.103 (4)	C14—C15	1.387 (6)
N1—C5	1.328 (6)	C15—C15^ii	1.378 (9)
N1—C1	1.335 (6)	C15—H15	0.9400
C1—C2	1.375 (7)	C16—C16^ii	1.368 (9)
C1—H1	0.9400	C16—H16	0.9400
C2—C3	1.373 (6)	C9—C10	1.376 (6)
C2—H2	0.9400	C9—C13	1.384 (6)
C3—C4	1.374 (6)	C10—C11	1.381 (7)
C3—C6	1.507 (6)	C10—H10	0.9400
C4—C5	1.376 (6)	C13—C12	1.369 (6)
C4—H4	0.9400	C13—H13	0.9400
C5—H5	0.9400	C11—N2	1.336 (6)
C6—C7	1.528 (6)	C11—H11	0.9400
C6—H6A	0.9800	N2—C12	1.334 (6)
C6—H6B	0.9800	N2—Cu1^iii	2.030 (4)
C7—C8	1.524 (5)	C12—H12	0.9400
N1—Cu1—N2^i	124.21 (15)	C6—C7—H7B	109.6
N1—Cu1—I1	110.57 (10)	H7A—C7—H7B	108.1
N2^i—Cu1—I1	108.22 (10)	C9—C8—C7	116.1 (4)
N1—Cu1—I2	105.60 (10)	C9—C8—H8A	108.3
N2^i—Cu1—I2	108.25 (10)	C7—C8—H8A	108.3
I1—Cu1—I2	96.32 (3)	C9—C8—H8B	108.3
Cu1—I1—Cu1^ii	83.76 (3)	C7—C8—H8B	108.3
Cu1^ii—I2—Cu1	83.60 (3)	H8A—C8—H8B	107.4
C5—N1—C1	114.9 (4)	C16—C14—C15	120.6 (4)
C5—N1—Cu1	121.6 (3)	C16—C14—I3	117.2 (3)
C1—N1—Cu1	123.4 (3)	C15—C14—I3	122.3 (3)
N1—C1—C2	123.9 (4)	C15^ii—C15—C14	119.5 (3)
N1—C1—H1	118.1	C15^ii—C15—H15	120.2
C2—C1—H1	118.1	C14—C15—H15	120.2
C3—C2—C1	120.7 (4)	C16^ii—C16—C14	119.9 (3)
C3—C2—H2	119.6	C16^ii—C16—H16	120.0
C1—C2—H2	119.6	C14—C16—H16	120.0
C2—C3—C4	115.8 (4)	C10—C9—C13	116.2 (4)
C2—C3—C6	119.9 (4)	C10—C9—C8	124.5 (4)
C4—C3—C6	124.4 (4)	C13—C9—C8	119.3 (4)
C3—C4—C5	120.1 (4)	C9—C10—C11	119.8 (4)
C3—C4—H4	119.9	C9—C10—H10	120.1
C5—C4—H4	119.9	C11—C10—H10	120.1
N1—C5—C4	124.6 (4)	C12—C13—C9	120.5 (4)
N1—C5—H5	117.7	C12—C13—H13	119.8
C4—C5—H5	117.7	C9—C13—H13	119.8
C3—C6—C7	116.0 (3)	N2—C11—C10	124.3 (4)
C3—C6—H6A	108.3	N2—C11—H11	117.9
C7—C6—H6A	108.3	C10—C11—H11	117.9
C3—C6—H6B	108.3	C12—N2—C11	115.4 (4)
C7—C6—H6B	108.3	C12—N2—Cu1^iii	124.1 (3)
H6A—C6—H6B	107.4	C11—N2—Cu1^iii	120.4 (3)
C8—C7—C6	110.3 (3)	N2—C12—C13	123.9 (4)
C8—C7—H7A	109.6	N2—C12—H12	118.0
C6—C7—H7A	109.6	C13—C12—H12	118.0
C8—C7—H7B	109.6

Symmetry codes: (i) x, y, z−1; (ii) −x, y, −z+1/2; (iii) x, y, z+1.