Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113018350/fg3291sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113018350/fg3291Isup2.hkl |
CCDC reference: 964756
The ability of first-row transition metals to form complexes with ligands such as phenanthroline (phen), bipyridine (bipy) or acetylacetonate (acac) is well known. These ligands form five- or six-membered rings when coordinated to the metal atom. Many complexes, such as [Cu(bipy)3](ClO4)2, present the metal coordinated to one type of bidentate ligand. In cases such as [Zn(phen)3](ClO4)2.CH3CH2OH.H2O (Wei et al., 2004), the metal presents the conventional octahedral coordination geometry, with similar Zn—N bond lengths [2.142 (5)–2.179 (5) Å]. In contrast, the Cu—N bond lengths in copper complexes such as [Cu(bipy)3](ClO4)2 are more distinct [2.023 (9)–2.444 (10) Å]. In this way, the symmetry tends to be reduced in copper complexes compared with zinc complexes, possibly reflecting the higher asphericity of Cu2+ than Zn2+. If the metal is coordinated to more than one ligand type the local symmetry is reduced as well, for example in the compound [Cu(acac)(bipy)(H2O)]NO3.H2O (Onawumi et al., 2008).
The structures of mixed-ligand complexes of copper(II) with acac and bipy are known and they belong to the class of cytotoxic and antineoplastic compounds marketed as Casiopeinas. Examples are the complexes [Cu(acac)Cl(bipy)][Cu(acac)(bipy)(H2O)]Cl.H2O and [Cu(acac)Br(bipy)].H2O (Onawumi et al., 2011), one with chloride and the other with bromide. The title new mixed-ligand complex (acetylacetonato-κ2O,O')(2,2'-bipyridine-κ2N,N')iodidocopper(II), [Cu(acac)I(bipy)], (I), containing the iodide, is herein presented.
Copper(II) acetylacetonate was obtained as desribed previously (Glidewell, 1994). Single crystals of (I) were obtained from a methanolic solution (50 ml) of copper(II) acetylacetonate (0.10 g), 2,2'-bipyridine (0.06 g) and potassium iodide (0.07 g). The reactants were mixed at 298 K for 2 h and left to crystallize. After 2 d at 298 K, needle-like blue [Green prism given in CIF tables - please clarify] single crystals of (I) were formed and one was chosen for the diffraction experiment. The reaction yield was 68%.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were geometrically fixed, with C—H = 0.93 Å, or 0.96 Å for methyl H, and with Uiso(H) = 1.2Ueq(C), or 0.05 Å2 for methyl H. [Please confirm added text] Methyl H atoms were allowed for considering each methyl as a rigid rotating group.
Complex (I) crystallizes in the triclinic space group P1, with two molecules (A and B) in the asymmetric unit. The CuII cation presents a slightly distorted square-planar coordination geometry, with the I atoms in the axial positions. The torsion angles in molecules A and B (Table 1) indicate that the bipy and acac ligands are approximately in the basal planes of the molecules.
It is interesting to note that the bond lengths and angles involving only the basal atoms are close to each other in both molecules. However, the bond lengths and angles involving the axial Cu—I bonds are different. Additionally, the I1—Cu1—N1 angle is close to the I1—Cu1—N2 angle, but angles I2—Cu2—N21 and I2—Cu2—N22 are clearly different (Table 2). The same effect is observed for the I—Cu—O angles. This is related to the fact that atom I2 is involved in intermolecular C—H···I interactions, and is probably associated with the presence of two molecules in the asymmetric unit.
The mean planes through the acac O atoms and the bipy N atoms of each molecule were calculated, as well as the distances of the Cu and I atoms from these planes. It is interesting to note that the Cu-to-plane distances of the two independent molecules are similar [0.2557 (11) and 0.3461 (12) Å], as are the distances between the I atoms and the appropriate plane [3.1943 (11) and 3.1611 (12) Å, respectively].
The two independent molecules (A and B) of the asymmetric unit of (I) are involved in π–π stacking interactions, which contribute to the formation of the crystal structure. The π–π stacking interactions between neighbouring molecules A and Ai (Fig. 2) involve the bipy groups. The mean plane between the bipy rings of the molecules at (x, y, z) and (-x, -y, -z) are parallel, with an interplanar distance of 3.501 (2) Å. The distance between the centroid of the N1/C1–C5 ring at (x, y, z) and the centroid of the N2/C6–C10 ring at (-x, -y, -z) is 3.737 (2) Å. The π–π stacking interaction between neighbouring molecules B and Bii (Fig. 2) involves the acac groups. The Cu–acac Cu2/O21/O22/C32/C33/C34 rings of the molecules at (x, y, z) and (-x, -y + 1, -z + 1) are parallel, with ring-centroid separations of 3.495 (2) Å. C—H···I interactions (Table 3) also contribute to the crystal packing of (I). As can be seen in Fig. 2, an infinite chain of molecules in the [011] direction is formed by C2—H2···I2 and C3—H3···I2 interactions and the above-mentioned π–π stacking interactions. C—H···I angles close to 120° suggest that these interactions are weak (Wood et al., 2009). C13—H13···I1i (Table 3) interactions also contribute to the crystal packing.
Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012).
Fig. 1. The two independent molecules in the asymmetric unit of (I), with the
atom-numbering scheme. Displacement ellipsoids are drawn at the 50%
probability level. Dashed lines indicate C—H···I interactions? Fig. 2. Part of the crystal structure of (I), showing the chain along the [011] direction built from C—H···I (dashed lines?) and π–π stacking interactions. Displacement ellipsoids are drawn at the 20% probability level. [Symmetry codes: (i) -x, -y, -z; (ii) -x, -y + 1, -z + 1; (iii) x, y + 1, z + 1; (iv) -x, -y + 2, -z + 2.] |
[Cu(C5H7O2)I(C10H8N2)] | V = 1615.04 (6) Å3 |
Mr = 445.75 | Z = 4 |
Triclinic, P1 | F(000) = 868 |
Hall symbol: -P 1 | Dx = 1.833 Mg m−3 |
a = 8.1171 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.4659 (2) Å | µ = 3.27 mm−1 |
c = 18.1340 (4) Å | T = 293 K |
α = 84.990 (2)° | Prism, green |
β = 80.120 (2)° | 0.26 × 0.24 × 0.12 mm |
γ = 76.538 (2)° |
Agilent Gemini diffractometer | 6540 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ω scans | θmax = 29.8°, θmin = 1.8° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −11→11 |
Tmin = 0.678, Tmax = 1.000 | k = −15→15 |
57283 measured reflections | l = −24→25 |
8476 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.022P)2 + 1.1877P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.068 | (Δ/σ)max = 0.003 |
S = 1.05 | Δρmax = 1.02 e Å−3 |
8476 reflections | Δρmin = −1.08 e Å−3 |
383 parameters |
[Cu(C5H7O2)I(C10H8N2)] | γ = 76.538 (2)° |
Mr = 445.75 | V = 1615.04 (6) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.1171 (2) Å | Mo Kα radiation |
b = 11.4659 (2) Å | µ = 3.27 mm−1 |
c = 18.1340 (4) Å | T = 293 K |
α = 84.990 (2)° | 0.26 × 0.24 × 0.12 mm |
β = 80.120 (2)° |
Agilent Gemini diffractometer | 8476 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 6540 reflections with I > 2σ(I) |
Tmin = 0.678, Tmax = 1.000 | Rint = 0.041 |
57283 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.02 e Å−3 |
8476 reflections | Δρmin = −1.08 e Å−3 |
383 parameters |
Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cu1 | −0.11919 (4) | 0.22269 (3) | −0.092482 (19) | 0.03959 (9) | |
I1 | 0.00139 (3) | 0.429446 (19) | −0.148853 (13) | 0.05470 (7) | |
O1 | −0.2516 (2) | 0.2059 (2) | −0.16830 (11) | 0.0488 (5) | |
O2 | −0.3209 (2) | 0.2876 (2) | −0.02190 (11) | 0.0493 (5) | |
N1 | 0.0176 (3) | 0.1799 (2) | −0.00704 (13) | 0.0383 (5) | |
N2 | 0.0798 (3) | 0.0963 (2) | −0.14003 (13) | 0.0383 (5) | |
C1 | −0.0249 (4) | 0.2318 (3) | 0.05908 (16) | 0.0470 (7) | |
H1 | −0.1173 | 0.2973 | 0.0656 | 0.056* | |
C2 | 0.0650 (4) | 0.1904 (3) | 0.11781 (17) | 0.0512 (8) | |
H2 | 0.0344 | 0.2278 | 0.1632 | 0.061* | |
C3 | 0.2003 (4) | 0.0930 (3) | 0.10785 (17) | 0.0501 (8) | |
H3 | 0.2599 | 0.0619 | 0.1472 | 0.06* | |
C4 | 0.2476 (4) | 0.0412 (3) | 0.03926 (17) | 0.0448 (7) | |
H4 | 0.3407 | −0.0237 | 0.0316 | 0.054* | |
C5 | 0.1543 (3) | 0.0876 (2) | −0.01810 (15) | 0.0349 (6) | |
C6 | 0.1930 (3) | 0.0426 (2) | −0.09441 (16) | 0.0364 (6) | |
C7 | 0.3346 (4) | −0.0454 (3) | −0.11979 (18) | 0.0475 (7) | |
H7 | 0.4114 | −0.0823 | −0.0877 | 0.057* | |
C8 | 0.3610 (4) | −0.0779 (3) | −0.1932 (2) | 0.0552 (8) | |
H8 | 0.4564 | −0.1362 | −0.2113 | 0.066* | |
C9 | 0.2442 (4) | −0.0230 (3) | −0.23923 (19) | 0.0541 (8) | |
H9 | 0.2596 | −0.0435 | −0.2888 | 0.065* | |
C10 | 0.1041 (4) | 0.0630 (3) | −0.21056 (17) | 0.0478 (7) | |
H10 | 0.024 | 0.0991 | −0.2413 | 0.057* | |
C11 | −0.4867 (4) | 0.2139 (3) | −0.22950 (18) | 0.0545 (8) | |
H11A | −0.4242 | 0.1392 | −0.2503 | 0.05* | |
H11B | −0.4776 | 0.2783 | −0.2664 | 0.05* | |
H11C | −0.6052 | 0.2111 | −0.2147 | 0.05* | |
C12 | −0.4133 (3) | 0.2343 (2) | −0.16212 (16) | 0.0399 (6) | |
C13 | −0.5241 (4) | 0.2833 (3) | −0.09959 (18) | 0.0471 (7) | |
H13 | −0.6409 | 0.3005 | −0.1018 | 0.056* | |
C14 | −0.4750 (3) | 0.3085 (2) | −0.03466 (17) | 0.0418 (7) | |
C15 | −0.6094 (4) | 0.3652 (3) | 0.0276 (2) | 0.0611 (9) | |
H15A | −0.5911 | 0.3213 | 0.0741 | 0.05* | |
H15B | −0.721 | 0.3638 | 0.0173 | 0.05* | |
H15C | −0.6019 | 0.4469 | 0.031 | 0.05* | |
Cu2 | 0.17330 (4) | 0.30628 (3) | 0.418661 (19) | 0.04041 (9) | |
I2 | 0.14914 (2) | 0.109649 (18) | 0.328411 (11) | 0.04608 (6) | |
O21 | −0.0019 (3) | 0.42908 (19) | 0.38125 (12) | 0.0506 (5) | |
O22 | 0.0290 (3) | 0.28373 (19) | 0.51217 (11) | 0.0494 (5) | |
N21 | 0.3824 (3) | 0.22090 (19) | 0.46330 (12) | 0.0372 (5) | |
N22 | 0.3549 (3) | 0.3497 (2) | 0.33885 (13) | 0.0385 (5) | |
C21 | 0.3821 (4) | 0.1573 (3) | 0.52880 (17) | 0.0457 (7) | |
H21 | 0.2779 | 0.1499 | 0.5572 | 0.055* | |
C22 | 0.5320 (5) | 0.1025 (3) | 0.55533 (19) | 0.0540 (8) | |
H22 | 0.5288 | 0.0597 | 0.6014 | 0.065* | |
C23 | 0.6849 (5) | 0.1117 (3) | 0.5133 (2) | 0.0575 (9) | |
H23 | 0.787 | 0.0745 | 0.5303 | 0.069* | |
C24 | 0.6879 (4) | 0.1762 (3) | 0.4455 (2) | 0.0514 (8) | |
H24 | 0.7915 | 0.1828 | 0.4163 | 0.062* | |
C25 | 0.5327 (3) | 0.2314 (2) | 0.42163 (16) | 0.0381 (6) | |
C26 | 0.5180 (3) | 0.3051 (2) | 0.35106 (16) | 0.0385 (6) | |
C27 | 0.6556 (4) | 0.3285 (3) | 0.30066 (19) | 0.0513 (8) | |
H27 | 0.7672 | 0.2971 | 0.3095 | 0.062* | |
C28 | 0.6242 (5) | 0.3997 (3) | 0.2364 (2) | 0.0582 (9) | |
H28 | 0.7148 | 0.418 | 0.2021 | 0.07* | |
C29 | 0.4587 (5) | 0.4426 (3) | 0.22406 (18) | 0.0552 (8) | |
H29 | 0.4359 | 0.4892 | 0.1808 | 0.066* | |
C30 | 0.3262 (4) | 0.4161 (3) | 0.27625 (17) | 0.0477 (7) | |
H30 | 0.2139 | 0.4453 | 0.2676 | 0.057* | |
C31 | −0.2534 (4) | 0.5764 (3) | 0.3767 (2) | 0.0596 (9) | |
H31A | −0.2523 | 0.5537 | 0.3269 | 0.05* | |
H31B | −0.207 | 0.6466 | 0.3742 | 0.05* | |
H31C | −0.3692 | 0.5934 | 0.4027 | 0.05* | |
C32 | −0.1467 (4) | 0.4753 (3) | 0.41809 (18) | 0.0436 (7) | |
C33 | −0.2062 (4) | 0.4406 (3) | 0.49116 (19) | 0.0505 (8) | |
H33 | −0.3137 | 0.482 | 0.513 | 0.061* | |
C34 | −0.1178 (4) | 0.3491 (3) | 0.53424 (18) | 0.0465 (7) | |
C35 | −0.1937 (5) | 0.3212 (4) | 0.61349 (19) | 0.0648 (10) | |
H35A | −0.1853 | 0.2362 | 0.6212 | 0.05* | |
H35B | −0.3121 | 0.3624 | 0.6225 | 0.05* | |
H35C | −0.1324 | 0.3471 | 0.6474 | 0.05* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02935 (17) | 0.0515 (2) | 0.03531 (19) | −0.00232 (14) | −0.00483 (14) | −0.00631 (15) |
I1 | 0.04142 (11) | 0.05483 (13) | 0.06307 (14) | −0.00741 (9) | −0.00834 (10) | 0.01466 (10) |
O1 | 0.0313 (10) | 0.0688 (14) | 0.0443 (12) | −0.0037 (9) | −0.0069 (9) | −0.0106 (10) |
O2 | 0.0345 (11) | 0.0663 (14) | 0.0436 (12) | −0.0052 (10) | 0.0005 (9) | −0.0130 (10) |
N1 | 0.0347 (12) | 0.0445 (13) | 0.0357 (13) | −0.0082 (10) | −0.0057 (10) | −0.0026 (10) |
N2 | 0.0320 (12) | 0.0461 (13) | 0.0366 (13) | −0.0079 (10) | −0.0030 (10) | −0.0073 (10) |
C1 | 0.0446 (17) | 0.0556 (18) | 0.0385 (16) | −0.0056 (14) | −0.0044 (13) | −0.0084 (14) |
C2 | 0.0532 (19) | 0.067 (2) | 0.0365 (17) | −0.0178 (16) | −0.0081 (14) | −0.0057 (15) |
C3 | 0.0495 (18) | 0.064 (2) | 0.0410 (17) | −0.0192 (16) | −0.0150 (14) | 0.0081 (15) |
C4 | 0.0381 (15) | 0.0488 (17) | 0.0464 (18) | −0.0077 (13) | −0.0099 (13) | 0.0057 (13) |
C5 | 0.0307 (13) | 0.0386 (14) | 0.0361 (14) | −0.0118 (11) | −0.0044 (11) | 0.0033 (11) |
C6 | 0.0283 (13) | 0.0393 (15) | 0.0426 (16) | −0.0113 (11) | −0.0043 (11) | 0.0001 (12) |
C7 | 0.0376 (16) | 0.0484 (17) | 0.0549 (19) | −0.0054 (13) | −0.0075 (14) | −0.0046 (14) |
C8 | 0.0399 (17) | 0.0529 (19) | 0.069 (2) | −0.0035 (14) | 0.0016 (16) | −0.0178 (17) |
C9 | 0.0491 (18) | 0.065 (2) | 0.0481 (19) | −0.0152 (16) | 0.0037 (15) | −0.0208 (16) |
C10 | 0.0410 (16) | 0.063 (2) | 0.0401 (17) | −0.0126 (14) | −0.0040 (13) | −0.0112 (14) |
C11 | 0.0455 (18) | 0.069 (2) | 0.0518 (19) | −0.0139 (16) | −0.0179 (15) | 0.0035 (16) |
C12 | 0.0347 (14) | 0.0386 (15) | 0.0464 (17) | −0.0085 (12) | −0.0111 (12) | 0.0083 (12) |
C13 | 0.0284 (14) | 0.0550 (18) | 0.0542 (19) | −0.0047 (13) | −0.0058 (13) | 0.0028 (15) |
C14 | 0.0335 (14) | 0.0356 (15) | 0.0516 (18) | −0.0047 (12) | 0.0012 (13) | 0.0014 (13) |
C15 | 0.0452 (18) | 0.066 (2) | 0.064 (2) | −0.0054 (16) | 0.0089 (16) | −0.0124 (18) |
Cu2 | 0.03122 (17) | 0.0488 (2) | 0.03593 (19) | −0.00044 (14) | −0.00437 (14) | 0.00176 (15) |
I2 | 0.04460 (11) | 0.05291 (12) | 0.04093 (11) | −0.00439 (9) | −0.01379 (8) | −0.00680 (8) |
O21 | 0.0409 (11) | 0.0566 (13) | 0.0446 (12) | 0.0086 (10) | −0.0073 (9) | −0.0014 (10) |
O22 | 0.0413 (11) | 0.0580 (13) | 0.0417 (12) | −0.0039 (10) | 0.0017 (9) | 0.0011 (10) |
N21 | 0.0390 (12) | 0.0358 (12) | 0.0362 (13) | −0.0026 (10) | −0.0094 (10) | −0.0065 (10) |
N22 | 0.0379 (12) | 0.0397 (13) | 0.0364 (13) | −0.0052 (10) | −0.0061 (10) | −0.0017 (10) |
C21 | 0.0545 (18) | 0.0416 (16) | 0.0393 (16) | −0.0042 (13) | −0.0106 (14) | −0.0044 (13) |
C22 | 0.068 (2) | 0.0427 (17) | 0.052 (2) | −0.0014 (15) | −0.0279 (17) | 0.0000 (14) |
C23 | 0.058 (2) | 0.0481 (19) | 0.071 (2) | −0.0001 (15) | −0.0373 (19) | −0.0055 (17) |
C24 | 0.0387 (16) | 0.0506 (18) | 0.066 (2) | −0.0033 (13) | −0.0158 (15) | −0.0098 (16) |
C25 | 0.0368 (14) | 0.0360 (14) | 0.0429 (16) | −0.0045 (11) | −0.0112 (12) | −0.0095 (12) |
C26 | 0.0377 (15) | 0.0380 (15) | 0.0418 (16) | −0.0085 (12) | −0.0058 (12) | −0.0126 (12) |
C27 | 0.0399 (16) | 0.0554 (19) | 0.060 (2) | −0.0156 (14) | 0.0004 (15) | −0.0126 (16) |
C28 | 0.060 (2) | 0.060 (2) | 0.055 (2) | −0.0273 (17) | 0.0112 (17) | −0.0099 (17) |
C29 | 0.073 (2) | 0.0468 (18) | 0.0442 (18) | −0.0179 (17) | −0.0024 (16) | 0.0029 (14) |
C30 | 0.0519 (18) | 0.0475 (17) | 0.0410 (17) | −0.0061 (14) | −0.0072 (14) | −0.0004 (13) |
C31 | 0.0464 (18) | 0.0526 (19) | 0.078 (2) | 0.0073 (15) | −0.0221 (17) | −0.0173 (17) |
C32 | 0.0347 (15) | 0.0414 (16) | 0.0571 (19) | −0.0032 (12) | −0.0147 (14) | −0.0156 (14) |
C33 | 0.0314 (15) | 0.0544 (19) | 0.062 (2) | −0.0061 (13) | 0.0027 (14) | −0.0144 (16) |
C34 | 0.0394 (16) | 0.0541 (18) | 0.0493 (18) | −0.0187 (14) | 0.0015 (13) | −0.0151 (14) |
C35 | 0.056 (2) | 0.080 (3) | 0.056 (2) | −0.0241 (19) | 0.0133 (17) | −0.0131 (18) |
Cu1—O1 | 1.9316 (19) | Cu2—O22 | 1.923 (2) |
Cu1—O2 | 1.9372 (19) | Cu2—O21 | 1.9230 (19) |
Cu1—N1 | 2.019 (2) | Cu2—N22 | 1.999 (2) |
Cu1—N2 | 2.025 (2) | Cu2—N21 | 2.014 (2) |
Cu1—I1 | 2.8171 (4) | Cu2—I2 | 2.9598 (4) |
O1—C12 | 1.264 (3) | O21—C32 | 1.269 (3) |
O2—C14 | 1.275 (3) | O22—C34 | 1.271 (3) |
N1—C1 | 1.341 (4) | N21—C21 | 1.338 (4) |
N1—C5 | 1.344 (3) | N21—C25 | 1.345 (4) |
N2—C10 | 1.335 (4) | N22—C30 | 1.334 (4) |
N2—C6 | 1.348 (3) | N22—C26 | 1.352 (3) |
C1—C2 | 1.381 (4) | C21—C22 | 1.378 (4) |
C1—H1 | 0.93 | C21—H21 | 0.93 |
C2—C3 | 1.372 (4) | C22—C23 | 1.362 (5) |
C2—H2 | 0.93 | C22—H22 | 0.93 |
C3—C4 | 1.380 (4) | C23—C24 | 1.377 (5) |
C3—H3 | 0.93 | C23—H23 | 0.93 |
C4—C5 | 1.387 (4) | C24—C25 | 1.394 (4) |
C4—H4 | 0.93 | C24—H24 | 0.93 |
C5—C6 | 1.476 (4) | C25—C26 | 1.478 (4) |
C6—C7 | 1.382 (4) | C26—C27 | 1.378 (4) |
C7—C8 | 1.381 (4) | C27—C28 | 1.389 (5) |
C7—H7 | 0.93 | C27—H27 | 0.93 |
C8—C9 | 1.376 (5) | C28—C29 | 1.369 (5) |
C8—H8 | 0.93 | C28—H28 | 0.93 |
C9—C10 | 1.379 (4) | C29—C30 | 1.377 (4) |
C9—H9 | 0.93 | C29—H29 | 0.93 |
C10—H10 | 0.93 | C30—H30 | 0.93 |
C11—C12 | 1.506 (4) | C31—C32 | 1.504 (4) |
C11—H11A | 0.96 | C31—H31A | 0.96 |
C11—H11B | 0.96 | C31—H31B | 0.96 |
C11—H11C | 0.96 | C31—H31C | 0.96 |
C12—C13 | 1.391 (4) | C32—C33 | 1.387 (4) |
C13—C14 | 1.379 (4) | C33—C34 | 1.387 (4) |
C13—H13 | 0.93 | C33—H33 | 0.93 |
C14—C15 | 1.504 (4) | C34—C35 | 1.502 (4) |
C15—H15A | 0.96 | C35—H35A | 0.96 |
C15—H15B | 0.96 | C35—H35B | 0.96 |
C15—H15C | 0.96 | C35—H35C | 0.96 |
O1—Cu1—O2 | 93.32 (8) | O22—Cu2—O21 | 93.11 (9) |
O1—Cu1—N1 | 160.23 (9) | O22—Cu2—N22 | 164.65 (9) |
O2—Cu1—N1 | 89.50 (9) | O21—Cu2—N22 | 91.81 (9) |
O1—Cu1—N2 | 90.21 (9) | O22—Cu2—N21 | 90.44 (9) |
O2—Cu1—N2 | 157.13 (10) | O21—Cu2—N21 | 162.81 (9) |
N1—Cu1—N2 | 79.94 (9) | N22—Cu2—N21 | 80.77 (9) |
O1—Cu1—I1 | 101.11 (7) | O22—Cu2—I2 | 103.84 (7) |
O2—Cu1—I1 | 102.49 (7) | O21—Cu2—I2 | 97.55 (7) |
N1—Cu1—I1 | 97.36 (7) | N22—Cu2—I2 | 89.90 (6) |
N2—Cu1—I1 | 98.97 (7) | N21—Cu2—I2 | 97.91 (6) |
C12—O1—Cu1 | 125.53 (19) | C32—O21—Cu2 | 125.8 (2) |
C14—O2—Cu1 | 125.21 (19) | C34—O22—Cu2 | 125.6 (2) |
C1—N1—C5 | 119.8 (2) | C21—N21—C25 | 119.5 (2) |
C1—N1—Cu1 | 124.74 (19) | C21—N21—Cu2 | 125.8 (2) |
C5—N1—Cu1 | 115.35 (18) | C25—N21—Cu2 | 114.74 (18) |
C10—N2—C6 | 119.4 (2) | C30—N22—C26 | 119.5 (3) |
C10—N2—Cu1 | 125.5 (2) | C30—N22—Cu2 | 125.2 (2) |
C6—N2—Cu1 | 115.07 (18) | C26—N22—Cu2 | 115.32 (19) |
N1—C1—C2 | 121.8 (3) | N21—C21—C22 | 121.8 (3) |
N1—C1—H1 | 119.1 | N21—C21—H21 | 119.1 |
C2—C1—H1 | 119.1 | C22—C21—H21 | 119.1 |
C3—C2—C1 | 118.7 (3) | C23—C22—C21 | 119.2 (3) |
C3—C2—H2 | 120.7 | C23—C22—H22 | 120.4 |
C1—C2—H2 | 120.7 | C21—C22—H22 | 120.4 |
C2—C3—C4 | 119.8 (3) | C22—C23—C24 | 119.8 (3) |
C2—C3—H3 | 120.1 | C22—C23—H23 | 120.1 |
C4—C3—H3 | 120.1 | C24—C23—H23 | 120.1 |
C3—C4—C5 | 119.0 (3) | C23—C24—C25 | 118.8 (3) |
C3—C4—H4 | 120.5 | C23—C24—H24 | 120.6 |
C5—C4—H4 | 120.5 | C25—C24—H24 | 120.6 |
N1—C5—C4 | 120.8 (3) | N21—C25—C24 | 120.9 (3) |
N1—C5—C6 | 114.5 (2) | N21—C25—C26 | 114.9 (2) |
C4—C5—C6 | 124.6 (3) | C24—C25—C26 | 124.2 (3) |
N2—C6—C7 | 121.0 (3) | N22—C26—C27 | 121.4 (3) |
N2—C6—C5 | 114.7 (2) | N22—C26—C25 | 114.2 (2) |
C7—C6—C5 | 124.3 (3) | C27—C26—C25 | 124.4 (3) |
C8—C7—C6 | 119.4 (3) | C26—C27—C28 | 118.7 (3) |
C8—C7—H7 | 120.3 | C26—C27—H27 | 120.6 |
C6—C7—H7 | 120.3 | C28—C27—H27 | 120.6 |
C9—C8—C7 | 119.2 (3) | C29—C28—C27 | 119.4 (3) |
C9—C8—H8 | 120.4 | C29—C28—H28 | 120.3 |
C7—C8—H8 | 120.4 | C27—C28—H28 | 120.3 |
C8—C9—C10 | 118.8 (3) | C28—C29—C30 | 119.4 (3) |
C8—C9—H9 | 120.6 | C28—C29—H29 | 120.3 |
C10—C9—H9 | 120.6 | C30—C29—H29 | 120.3 |
N2—C10—C9 | 122.2 (3) | N22—C30—C29 | 121.7 (3) |
N2—C10—H10 | 118.9 | N22—C30—H30 | 119.2 |
C9—C10—H10 | 118.9 | C29—C30—H30 | 119.2 |
C12—C11—H11A | 109.5 | C32—C31—H31A | 109.5 |
C12—C11—H11B | 109.5 | C32—C31—H31B | 109.5 |
H11A—C11—H11B | 109.5 | H31A—C31—H31B | 109.5 |
C12—C11—H11C | 109.5 | C32—C31—H31C | 109.5 |
H11A—C11—H11C | 109.5 | H31A—C31—H31C | 109.5 |
H11B—C11—H11C | 109.5 | H31B—C31—H31C | 109.5 |
O1—C12—C13 | 125.3 (3) | O21—C32—C33 | 124.9 (3) |
O1—C12—C11 | 115.6 (3) | O21—C32—C31 | 114.5 (3) |
C13—C12—C11 | 119.1 (3) | C33—C32—C31 | 120.6 (3) |
C14—C13—C12 | 125.5 (3) | C32—C33—C34 | 125.1 (3) |
C14—C13—H13 | 117.3 | C32—C33—H33 | 117.4 |
C12—C13—H13 | 117.3 | C34—C33—H33 | 117.4 |
O2—C14—C13 | 125.2 (3) | O22—C34—C33 | 124.9 (3) |
O2—C14—C15 | 115.3 (3) | O22—C34—C35 | 114.7 (3) |
C13—C14—C15 | 119.5 (3) | C33—C34—C35 | 120.4 (3) |
C14—C15—H15A | 109.5 | C34—C35—H35A | 109.5 |
C14—C15—H15B | 109.5 | C34—C35—H35B | 109.5 |
H15A—C15—H15B | 109.5 | H35A—C35—H35B | 109.5 |
C14—C15—H15C | 109.5 | C34—C35—H35C | 109.5 |
H15A—C15—H15C | 109.5 | H35A—C35—H35C | 109.5 |
H15B—C15—H15C | 109.5 | H35B—C35—H35C | 109.5 |
I1—Cu1—N2—N1 | 95.96 (7) | I2—Cu2—N21—N22 | 88.60 (7) |
I1—Cu1—O2—O1 | 102.15 (7) | I2—Cu2—O21—O22 | 104.41 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···I2 | 0.93 | 3.37 | 3.987 (3) | 126 |
C3—H3···I2 | 0.93 | 3.31 | 3.967 (3) | 129 |
C13—H13···I1i | 0.93 | 3.16 | 4.044 (3) | 160 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C5H7O2)I(C10H8N2)] |
Mr | 445.75 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.1171 (2), 11.4659 (2), 18.1340 (4) |
α, β, γ (°) | 84.990 (2), 80.120 (2), 76.538 (2) |
V (Å3) | 1615.04 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.27 |
Crystal size (mm) | 0.26 × 0.24 × 0.12 |
Data collection | |
Diffractometer | Agilent Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.678, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 57283, 8476, 6540 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.700 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.068, 1.05 |
No. of reflections | 8476 |
No. of parameters | 383 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.02, −1.08 |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).
Cu1—O1 | 1.9316 (19) | Cu2—O22 | 1.923 (2) |
Cu1—O2 | 1.9372 (19) | Cu2—O21 | 1.9230 (19) |
Cu1—N1 | 2.019 (2) | Cu2—N22 | 1.999 (2) |
Cu1—N2 | 2.025 (2) | Cu2—N21 | 2.014 (2) |
Cu1—I1 | 2.8171 (4) | Cu2—I2 | 2.9598 (4) |
O1—Cu1—I1 | 101.11 (7) | O22—Cu2—I2 | 103.84 (7) |
O2—Cu1—I1 | 102.49 (7) | O21—Cu2—I2 | 97.55 (7) |
N1—Cu1—I1 | 97.36 (7) | N22—Cu2—I2 | 89.90 (6) |
N2—Cu1—I1 | 98.97 (7) | N21—Cu2—I2 | 97.91 (6) |
I1—Cu1—N2—N1 | 95.96 (7) | I2—Cu2—N21—N22 | 88.60 (7) |
I1—Cu1—O2—O1 | 102.15 (7) | I2—Cu2—O21—O22 | 104.41 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···I2 | 0.93 | 3.37 | 3.987 (3) | 126 |
C3—H3···I2 | 0.93 | 3.31 | 3.967 (3) | 129.2 |
C13—H13···I1i | 0.93 | 3.16 | 4.044 (3) | 159.9 |
Symmetry code: (i) x−1, y, z. |