Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109017107/em3023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109017107/em3023Isup2.hkl |
CCDC reference: 742226
A solution formed by mixing a 0.1 M warm solution of CuSO4 (10 ml, 1 mmol) and tacn.3HBr in 10 ml of methanol and 10 ml of water (0.22 ml, 2 mmol) was mixed with a 0.1 M warm solution of K2[Pd(CN)4] (10 ml, 1 mmol). The resulting precipitate was dissolved by addition of a concentrated aqueous solution of ammonia (25%). Finally, the solution was filtered and left to crystallize at ambient temperature (291 K). The first single crystals appeared as blue prisms after one day. Analysis found (Mr 1580.28): C 26.95, H 4.05, N 21.05%; calculated: C 27.36, H 3.95, N 21.27. FT–IR (cm-1, KBr): ν(OH): 3507 (s), 3437 (s); ν(NH): 3302 (s); ν(CH): 2959 (m), 2924 (m); ν(CN): 2183 (vs), 2145 (vs); δ(OH2): 1651 (m); δ(CH2) [δ or \v?]: 1485 (m), 1454 (m); ν(C—N): 1153 (w); ν(C—C): 1099 (m).
All H-atom positions were calculated using the appropriate riding model with Uiso values of 1.2 times Ueq of the parent atoms, and with C—H distances of 0.99 and N—H distances of 0.93 Å. H atoms that belong to the water molecule were not modelled. During the solving of the structure, in the Fourier difference map several peaks appeared that could be assigned to the N and C atoms of the tacn ligand. By careful assignment of the observed maxima in the electron map to the N and C atoms two different orientations could be modelled. The site occupation factors were freely refined, giving a major occupancy of 50.6 (10)%.
Cyano complexes exhibit great structural variability due to the bridging ability of the cyano ligand. This structural variability allied with the presence of paramagnetic central atoms makes cyanocomplexes popular among chemists and physicists as materials exhibiting various interesting magnetic properties (Lescouezec et al., 2005; Ohba & Okawa, 2000; Garde et al., 2008; Bernhardt et al., 2005; Klokishner et al., 2007; Herrera et al., 2008).
In construction of low-dimensional cyano complexes, the so-called `brick and mortar' method can be applied (Willet et al., 1993), in which a metallic central atom coordinated by suitable blocking ligand(s) acts as the `brick' and the cyanide complex anion is used as the `mortar'. Previously, following these ideas we have prepared, structurally characterized and studied the magnetic properties of several low-dimensional cyanide complexes in which various bidentate ligands were used (Hanko et al., 2007; Kuchár et al., 2004, 2003). These complexes are also interesting as models for studies of the role of hydrogen bonds in mediating magnetic exchange interactions.
As a continuation of our effort to prepare one-dimensional cyano complexes, we have decided to use a cyclic triaza ligand, 1,4,7-triazacyclononane (tacn). This tridentate ligand, connected to a CuII central atom, affords mainly five-coordination (Han et al., 2004; Wang et al., 2004), thus leaving two coordination sites free for the polymerization process during crystallization. As a result of our synthetic procedure using tacn.3HBr, prepared according to the literature (White et al., 1979), we have isolated the title compound, (I).
The crystal structure of (I) is essentially ionic (Figs. 1–3). It is built up of positively charged 2,4-ribbons exhibiting composition [Cu(tacn)(NC)2—Pd(CN)2—Cu(tacn)]n2n+ and running along the (100) direction, bromide anions, electroneutral 2,2-CT chains [Cu(tacn)(NC)—Pd(CN)2—(CN)–] running along the (001) direction and one water molecule of crystallization. An alternative view of the structure is that it is formed of the abovementioned chains, with ribbons running perpendicularly between the chains, and with bromide anions and water molecules of crystallization placed in the free space between the chains and ribbons.
This type of 2,4-ribbon incorporating cyanide ligands and CuII central atoms has not been described previously, but a similar ribbon structural motif was found in [Mn6(tptz)6(MeOH)4(DMF)2W4(CN)32]8.2H2O.2.3MeOH [tptz is 2,4,6-tris(2-pyridyl)-1,3,5-triazine and DMF is N,N-dimethylformamide; Zhao et al., 2007). On the other hand, chains built up of cyano complex anions and CuII ions are not uncommon; as examples, Cu(en)2Ni(CN)4 or Cu(dmen)2Pd(CN)4 can be mentioned (en and dmen are ??; Seitz et al., 2001; Kuchár et al., 2004). The presence of both one-dimensional structural motifs within the same structure is, however, a unique feature of this structure.
Both the ribbon and the chain parts of the structure contain five-coordinated CuII ions. As expected, three coordination sites are occupied by the blocking tacn ligand, with Cu—N bonds within the range 1.917 (11)–2.216 (4) Å and with intrachelate N—Cu—N angles of 83.38 (17), 83.47 (18) and 83.7 (2)° (Table 1). The remaining two coordination sites around the CuII central ions are occupied by N atoms from bridging cyanide ligands with Cu—N distances in the range 1.976 (4)–1.998 (4) Å. As calculated following the suggestion of Addison et al. (1984), the τ parameters of atoms Cu1 (chain) and Cu2 are 0.98 and 1/3, respectively, indicating that the polyhedron around atom Cu1 is close to ideal trigonal bipyramidal while that around atom Cu2 is closer to square pyramidal. The geometric parameters within the tacn ligands are as expected (Schwindinger et al., 1980).
There are three crystallographically independent PdII ions in the structure. Each of them occupies a special position (centre of symmetry). All PdII ions exhibit square-planar coordination by four cyano ligands with a mean Pd—C bond length of 2.004 (3) Å; this value is close to that of 1.994 (1) found in [Cu(tn)Pd(CN)4] (tn is 1,3-diaminopropane; Legendre et al., 2008). All of the cyanide ligands within the ribbon exhibit bridging character, while amongst those in the [Pd(CN)4]2- anion within the chain, two are terminal and two link Cu and Pd ions. The C≡N bonds are from the range 1.126 (7)–1.151 (7) Å, which are normal values (Legendre et al., 2008). The Cu—N≡C angles formed by bridging cyanide ligands exhibit values in the range 167.1 (4)—177.6 (5)°. The presence of both bridging and terminal cyanide ligands in the structure was also detected by IR spectroscopy; in the spectrum there are absorption bands at 2183 and 2145 cm-1, which were attributed to the stretching vibrations of the bridging (higher wavenumbers) and terminal cyanide ligands. The absorption band at higher wavenumbers exhibits greater intensity, in line with the larger number of bridging cyanide ligands in the structure.
There is one non-coordinated bromide anion that occupies a general position, which hydrogen bonds to NH groups of the tacn ligands (Table 2). Two unique crystallographic positions are occupied by the O atom of the water molecule, one on a centre of symmetry, which is half occupied, and the other in a general position, 1.432 (2) Å away, with one-quarter occupancy. The water molecule, N atoms from the tacn ligands and terminal n atoms from the cyanide groups are involved in N—H···O and N—H···N(≡C) hydrogen bonds, respectively (Table 2 and Fig. 3).
N—H···N(≡C) hydrogen bonds connect the electroneutral chains to one another as well as to the chains of negatively charged ribbons, with N···N distances in the range 2.942 (6)–3.282 (11) Å. The water molecule interacts via an N—H···O hydrogen-bond interaction with H atoms from the electroneutral chain. At the same time, the O1B···Br1 (2.992 Å) and O1A···Br1 distances (3.249 and 3.384 Å), respectively, suggest the presence of further hydrogen-bonding interactions. The bromide anions form further weak hydrogen-bonding interactions of the N—H···Br type, with H···Br distances in the range 2.35–2.66 Å.
For related literature, see: Addison et al. (1984); Bernhardt et al. (2005); Garde et al. (2008); Han et al. (2004); Hanko et al. (2007); Herrera et al. (2008); Klokishner et al. (2007); Kuchár et al. (2003, 2004); Legendre et al. (2008); Lescouezec et al. (2005); Ohba & Okawa (2000); Schwindinger et al. (1980); Seitz et al. (2001); Wang et al. (2004); White et al. (1979); Willet et al. (1993); Zhao et al. (2007).
Data collection: X-AREA (Stoe & Cie, 2003); cell refinement: X-AREA (Stoe & Cie, 2003); data reduction: X-AREA (Stoe & Cie, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Cu2Pd(CN)4(C6H15N3)2]Br2·[Cu2Pd2(CN)8(C6H15N3)2]·H2O | Z = 1 |
Mr = 1580.28 | F(000) = 778 |
Triclinic, P1 | Dx = 1.943 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3214 (8) Å | Cell parameters from 39615 reflections |
b = 12.9466 (14) Å | θ = 1.9–30.7° |
c = 14.5178 (16) Å | µ = 4.05 mm−1 |
α = 83.699 (9)° | T = 193 K |
β = 84.378 (9)° | Column, blue |
γ = 82.878 (9)° | 0.40 × 0.12 × 0.10 mm |
V = 1352.3 (3) Å3 |
Stoe IPDS-II diffractometer | 5903 independent reflections |
Radiation source: fine-focus sealed tube | 4826 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
Detector resolution: 150 pixels mm-1 | θmax = 27.0°, θmin = 2.0° |
ω–scans | h = −9→7 |
Absorption correction: multi-scan (WinGX; Farrugia, 1999) | k = −16→16 |
Tmin = 0.410, Tmax = 0.667 | l = −18→18 |
22649 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0643P)2 + 2.2827P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
5903 reflections | Δρmax = 1.18 e Å−3 |
394 parameters | Δρmin = −1.36 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0047 (6) |
[Cu2Pd(CN)4(C6H15N3)2]Br2·[Cu2Pd2(CN)8(C6H15N3)2]·H2O | γ = 82.878 (9)° |
Mr = 1580.28 | V = 1352.3 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.3214 (8) Å | Mo Kα radiation |
b = 12.9466 (14) Å | µ = 4.05 mm−1 |
c = 14.5178 (16) Å | T = 193 K |
α = 83.699 (9)° | 0.40 × 0.12 × 0.10 mm |
β = 84.378 (9)° |
Stoe IPDS-II diffractometer | 5903 independent reflections |
Absorption correction: multi-scan (WinGX; Farrugia, 1999) | 4826 reflections with I > 2σ(I) |
Tmin = 0.410, Tmax = 0.667 | Rint = 0.062 |
22649 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.18 e Å−3 |
5903 reflections | Δρmin = −1.36 e Å−3 |
394 parameters |
Experimental. For CHNS analysis: CHNS Elemental Analyzer Flash EA 1112; Thermo Finnigan For FT–IR: Nicolet Avatar 330 FT–IR, in KBr |
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. H-atoms of water molecules of crystallization not included 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pd1 | 0.0000 | 0.5000 | 0.5000 | 0.02885 (14) | |
Pd2 | 0.0000 | 0.5000 | 1.0000 | 0.02774 (14) | |
Pd3 | 0.0000 | 0.0000 | 0.5000 | 0.03002 (14) | |
Br1 | −1.05503 (10) | −0.07867 (5) | 0.81959 (5) | 0.05234 (19) | |
Cu1 | 0.35590 (9) | 0.28367 (4) | 0.75330 (4) | 0.02838 (15) | |
Cu2 | −0.48752 (9) | −0.21174 (4) | 0.67676 (4) | 0.03105 (16) | |
N1 | 0.1897 (6) | 0.3507 (3) | 0.6570 (3) | 0.0313 (9) | |
N2 | 0.3545 (7) | 0.6193 (4) | 0.4729 (3) | 0.0399 (10) | |
N3 | 0.3444 (8) | 0.5838 (4) | 1.0675 (4) | 0.0469 (12) | |
N4 | 0.2267 (7) | 0.3702 (3) | 0.8491 (3) | 0.0365 (10) | |
N5 | −0.2899 (7) | −0.1428 (4) | 0.5994 (3) | 0.0367 (10) | |
N6 | 0.3216 (7) | −0.1416 (3) | 0.5962 (3) | 0.0364 (10) | |
N7 | 0.2894 (7) | 0.1245 (3) | 0.8068 (3) | 0.0384 (10) | |
H7 | 0.1625 | 0.1214 | 0.8146 | 0.046* | |
N8 | 0.5775 (7) | 0.2447 (4) | 0.8283 (3) | 0.0414 (11) | |
H8 | 0.5822 | 0.2962 | 0.8676 | 0.050* | |
N9 | 0.5187 (6) | 0.2066 (3) | 0.6550 (3) | 0.0322 (9) | |
H9 | 0.5204 | 0.2495 | 0.5993 | 0.039* | |
C1 | 0.1184 (7) | 0.4021 (4) | 0.6001 (3) | 0.0301 (10) | |
C2 | 0.2244 (8) | 0.5763 (4) | 0.4831 (4) | 0.0341 (11) | |
C3 | 0.2222 (8) | 0.5525 (4) | 1.0409 (4) | 0.0340 (11) | |
C4 | 0.1489 (7) | 0.4169 (4) | 0.9044 (3) | 0.0319 (10) | |
C5 | −0.1823 (8) | −0.0933 (4) | 0.5632 (4) | 0.0344 (11) | |
C6 | 0.2058 (8) | −0.0918 (4) | 0.5601 (4) | 0.0323 (11) | |
C7 | 0.3713 (10) | 0.1111 (4) | 0.8968 (4) | 0.0498 (16) | |
H7A | 0.3746 | 0.0370 | 0.9229 | 0.060* | |
H7B | 0.2936 | 0.1545 | 0.9410 | 0.060* | |
C8 | 0.5658 (10) | 0.1426 (5) | 0.8851 (4) | 0.0517 (17) | |
H8A | 0.6076 | 0.1470 | 0.9472 | 0.062* | |
H8B | 0.6500 | 0.0879 | 0.8549 | 0.062* | |
C9 | 0.7401 (8) | 0.2440 (5) | 0.7592 (5) | 0.0453 (14) | |
H9A | 0.8525 | 0.2132 | 0.7895 | 0.054* | |
H9B | 0.7575 | 0.3166 | 0.7336 | 0.054* | |
C10 | 0.7111 (8) | 0.1803 (4) | 0.6812 (4) | 0.0370 (11) | |
H10A | 0.7991 | 0.1960 | 0.6267 | 0.044* | |
H10B | 0.7336 | 0.1047 | 0.7019 | 0.044* | |
C11 | 0.4227 (8) | 0.1152 (4) | 0.6444 (3) | 0.0352 (11) | |
H11A | 0.5010 | 0.0691 | 0.6026 | 0.042* | |
H11B | 0.3057 | 0.1392 | 0.6156 | 0.042* | |
C12 | 0.3811 (9) | 0.0538 (4) | 0.7381 (4) | 0.0401 (12) | |
H12A | 0.2999 | 0.0001 | 0.7308 | 0.048* | |
H12B | 0.4977 | 0.0176 | 0.7610 | 0.048* | |
N10A | −0.4042 (17) | −0.3695 (7) | 0.6499 (7) | 0.029 (2) | 0.494 (10) |
H10C | −0.3897 | −0.3761 | 0.5863 | 0.035* | 0.494 (10) |
N10B | −0.5063 (17) | −0.3778 (6) | 0.6657 (6) | 0.027 (2) | 0.506 (10) |
H10D | −0.4980 | −0.3921 | 0.6039 | 0.033* | 0.506 (10) |
N11A | −0.6968 (14) | −0.2722 (8) | 0.7589 (8) | 0.036 (2) | 0.494 (10) |
H11C | −0.8056 | −0.2271 | 0.7556 | 0.043* | 0.494 (10) |
N11B | −0.6590 (13) | −0.2332 (7) | 0.7934 (6) | 0.028 (2) | 0.506 (10) |
H11D | −0.7586 | −0.1812 | 0.7905 | 0.033* | 0.506 (10) |
N12A | −0.3481 (16) | −0.2365 (10) | 0.7837 (7) | 0.030 (2) | 0.494 (10) |
H12C | −0.2684 | −0.1856 | 0.7823 | 0.036* | 0.494 (10) |
N12B | −0.2904 (16) | −0.2799 (11) | 0.7717 (7) | 0.025 (2) | 0.506 (10) |
H12D | −0.1974 | −0.2365 | 0.7690 | 0.030* | 0.506 (10) |
C13A | −0.488 (2) | −0.2301 (17) | 0.8680 (14) | 0.031 (4) | 0.494 (10) |
H13A | −0.4279 | −0.2588 | 0.9250 | 0.037* | 0.494 (10) |
H13B | −0.5366 | −0.1562 | 0.8745 | 0.037* | 0.494 (10) |
C13B | −0.3753 (17) | −0.2915 (8) | 0.8677 (7) | 0.033 (2) | 0.506 (10) |
H13C | −0.2917 | −0.2713 | 0.9106 | 0.040* | 0.506 (10) |
H13D | −0.3957 | −0.3654 | 0.8858 | 0.040* | 0.506 (10) |
C14A | −0.6427 (18) | −0.2907 (8) | 0.8569 (8) | 0.040 (3) | 0.494 (10) |
H14A | −0.7502 | −0.2694 | 0.9003 | 0.048* | 0.494 (10) |
H14B | −0.6044 | −0.3662 | 0.8724 | 0.048* | 0.494 (10) |
C15A | −0.5421 (16) | −0.4335 (10) | 0.6969 (8) | 0.036 (3)* | 0.494 (10) |
H15A | −0.5543 | −0.4908 | 0.6588 | 0.043* | 0.494 (10) |
H15B | −0.4997 | −0.4655 | 0.7574 | 0.043* | 0.494 (10) |
C14B | −0.561 (2) | −0.2215 (17) | 0.8750 (15) | 0.029 (3) | 0.506 (10) |
H14C | −0.6350 | −0.2429 | 0.9331 | 0.035* | 0.506 (10) |
H14D | −0.5393 | −0.1476 | 0.8758 | 0.035* | 0.506 (10) |
C15B | −0.7330 (15) | −0.3385 (7) | 0.8004 (7) | 0.031 (2) | 0.506 (10) |
H15C | −0.6648 | −0.3887 | 0.8449 | 0.038* | 0.506 (10) |
H15D | −0.8652 | −0.3310 | 0.8236 | 0.038* | 0.506 (10) |
C16 | −0.7121 (9) | −0.3767 (4) | 0.7120 (4) | 0.0434 (13) | |
H16A | −0.7949 | −0.4202 | 0.7529 | 0.052* | 0.494 (10) |
H16B | −0.7673 | −0.3579 | 0.6520 | 0.052* | 0.494 (10) |
H16C | −0.7968 | −0.3328 | 0.6706 | 0.052* | 0.506 (10) |
H16D | −0.7475 | −0.4486 | 0.7195 | 0.052* | 0.506 (10) |
C17A | −0.224 (2) | −0.3828 (11) | 0.6899 (12) | 0.036 (3) | 0.494 (10) |
H17A | −0.1336 | −0.3458 | 0.6472 | 0.044* | 0.494 (10) |
H17B | −0.1763 | −0.4579 | 0.6975 | 0.044* | 0.494 (10) |
C17B | −0.3657 (15) | −0.4449 (7) | 0.7178 (7) | 0.034 (2) | 0.506 (10) |
H17C | −0.3151 | −0.5048 | 0.6826 | 0.041* | 0.506 (10) |
H17D | −0.4234 | −0.4728 | 0.7785 | 0.041* | 0.506 (10) |
C18A | −0.2443 (19) | −0.3391 (15) | 0.7836 (9) | 0.038 (3) | 0.494 (10) |
H18A | −0.3065 | −0.3880 | 0.8301 | 0.045* | 0.494 (10) |
H18B | −0.1197 | −0.3352 | 0.8033 | 0.045* | 0.494 (10) |
C18B | −0.2086 (19) | −0.3823 (10) | 0.7338 (12) | 0.034 (3) | 0.506 (10) |
H18C | −0.1276 | −0.4234 | 0.7786 | 0.041* | 0.506 (10) |
H18D | −0.1331 | −0.3677 | 0.6745 | 0.041* | 0.506 (10) |
O1A | −0.0494 (19) | 0.1069 (11) | 0.9660 (11) | 0.0353 (19) | 0.25 |
O1B | 0.0000 | 0.0000 | 1.0000 | 0.0353 (19) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0304 (3) | 0.0251 (2) | 0.0303 (3) | 0.0029 (2) | −0.0037 (2) | −0.00509 (18) |
Pd2 | 0.0301 (3) | 0.0228 (2) | 0.0299 (3) | 0.00031 (19) | 0.0000 (2) | −0.00717 (18) |
Pd3 | 0.0304 (3) | 0.0279 (2) | 0.0317 (3) | −0.0078 (2) | 0.0052 (2) | −0.00439 (19) |
Br1 | 0.0460 (4) | 0.0434 (3) | 0.0697 (4) | 0.0030 (3) | −0.0053 (3) | −0.0240 (3) |
Cu1 | 0.0304 (3) | 0.0244 (3) | 0.0296 (3) | 0.0039 (2) | −0.0024 (2) | −0.0077 (2) |
Cu2 | 0.0345 (4) | 0.0260 (3) | 0.0323 (3) | −0.0074 (2) | 0.0066 (3) | −0.0052 (2) |
N1 | 0.032 (2) | 0.032 (2) | 0.028 (2) | 0.0039 (17) | 0.0007 (17) | −0.0070 (17) |
N2 | 0.043 (3) | 0.037 (2) | 0.039 (2) | −0.004 (2) | −0.001 (2) | −0.0018 (18) |
N3 | 0.044 (3) | 0.055 (3) | 0.046 (3) | −0.011 (2) | −0.003 (2) | −0.019 (2) |
N4 | 0.042 (3) | 0.028 (2) | 0.038 (2) | 0.0013 (19) | −0.005 (2) | −0.0075 (17) |
N5 | 0.036 (2) | 0.041 (2) | 0.033 (2) | −0.011 (2) | −0.0009 (19) | 0.0000 (18) |
N6 | 0.035 (3) | 0.032 (2) | 0.041 (2) | −0.0062 (19) | 0.008 (2) | −0.0033 (18) |
N7 | 0.046 (3) | 0.029 (2) | 0.037 (2) | 0.0029 (19) | 0.009 (2) | −0.0030 (17) |
N8 | 0.044 (3) | 0.038 (2) | 0.044 (3) | 0.012 (2) | −0.016 (2) | −0.019 (2) |
N9 | 0.030 (2) | 0.030 (2) | 0.033 (2) | 0.0050 (17) | 0.0034 (17) | −0.0040 (16) |
C1 | 0.033 (3) | 0.025 (2) | 0.031 (2) | −0.0003 (19) | 0.000 (2) | −0.0057 (18) |
C2 | 0.040 (3) | 0.029 (2) | 0.032 (2) | 0.002 (2) | 0.000 (2) | −0.0037 (19) |
C3 | 0.034 (3) | 0.033 (2) | 0.034 (2) | 0.001 (2) | 0.003 (2) | −0.010 (2) |
C4 | 0.030 (3) | 0.030 (2) | 0.034 (2) | 0.004 (2) | 0.001 (2) | −0.0043 (19) |
C5 | 0.038 (3) | 0.033 (2) | 0.033 (2) | −0.008 (2) | 0.002 (2) | −0.0054 (19) |
C6 | 0.032 (3) | 0.030 (2) | 0.036 (3) | −0.012 (2) | 0.005 (2) | −0.008 (2) |
C7 | 0.073 (5) | 0.034 (3) | 0.034 (3) | 0.012 (3) | 0.010 (3) | 0.002 (2) |
C8 | 0.067 (4) | 0.052 (3) | 0.032 (3) | 0.023 (3) | −0.012 (3) | −0.013 (2) |
C9 | 0.029 (3) | 0.047 (3) | 0.061 (4) | 0.007 (2) | −0.012 (3) | −0.015 (3) |
C10 | 0.031 (3) | 0.036 (3) | 0.041 (3) | 0.007 (2) | 0.000 (2) | −0.008 (2) |
C11 | 0.043 (3) | 0.031 (2) | 0.031 (2) | 0.001 (2) | 0.002 (2) | −0.0116 (19) |
C12 | 0.053 (4) | 0.026 (2) | 0.039 (3) | 0.001 (2) | 0.001 (3) | −0.007 (2) |
N10A | 0.025 (5) | 0.026 (4) | 0.036 (5) | 0.003 (4) | −0.002 (4) | −0.010 (3) |
N10B | 0.029 (5) | 0.023 (4) | 0.029 (4) | −0.005 (4) | 0.005 (4) | −0.001 (3) |
N11A | 0.030 (5) | 0.033 (5) | 0.043 (6) | 0.001 (4) | 0.007 (4) | −0.004 (5) |
N11B | 0.033 (5) | 0.019 (4) | 0.030 (4) | −0.003 (3) | 0.004 (4) | 0.000 (3) |
N12A | 0.030 (6) | 0.021 (5) | 0.040 (6) | −0.004 (4) | −0.005 (4) | −0.002 (4) |
N12B | 0.024 (5) | 0.018 (6) | 0.033 (5) | −0.002 (4) | −0.007 (4) | 0.003 (5) |
C13A | 0.037 (10) | 0.036 (8) | 0.019 (5) | −0.002 (10) | 0.007 (8) | −0.006 (4) |
C13B | 0.043 (6) | 0.031 (5) | 0.026 (5) | −0.006 (5) | −0.005 (4) | −0.003 (4) |
C14A | 0.047 (7) | 0.033 (5) | 0.035 (6) | 0.001 (5) | 0.013 (5) | −0.002 (4) |
C14B | 0.029 (8) | 0.028 (6) | 0.029 (7) | −0.003 (8) | 0.000 (7) | −0.005 (5) |
C15B | 0.041 (6) | 0.021 (4) | 0.031 (5) | −0.012 (4) | 0.011 (4) | −0.002 (4) |
C16 | 0.049 (4) | 0.038 (3) | 0.045 (3) | −0.021 (3) | −0.006 (3) | 0.007 (2) |
C17A | 0.035 (7) | 0.030 (6) | 0.042 (8) | 0.002 (5) | 0.001 (7) | −0.003 (6) |
C17B | 0.038 (6) | 0.022 (4) | 0.041 (5) | 0.004 (4) | 0.002 (4) | −0.006 (4) |
C18A | 0.027 (6) | 0.040 (8) | 0.044 (8) | −0.001 (6) | −0.002 (5) | 0.003 (7) |
C18B | 0.033 (6) | 0.028 (6) | 0.038 (7) | 0.010 (4) | 0.001 (7) | −0.005 (7) |
O1A | 0.017 (4) | 0.036 (4) | 0.047 (5) | 0.001 (3) | −0.001 (3) | 0.016 (4) |
O1B | 0.017 (4) | 0.036 (4) | 0.047 (5) | 0.001 (3) | −0.001 (3) | 0.016 (4) |
Pd1—C2i | 2.002 (6) | C11—H11A | 0.9900 |
Pd1—C1 | 2.010 (5) | C11—H11B | 0.9900 |
Pd1—C2 | 2.002 (6) | C12—H12A | 0.9900 |
Pd1—C1i | 2.010 (5) | C12—H12B | 0.9900 |
Pd2—C3ii | 2.003 (6) | N10A—C15A | 1.457 (16) |
Pd2—C3 | 2.003 (6) | N10A—C17A | 1.479 (19) |
Pd2—C4ii | 2.003 (5) | N10A—H10C | 0.9300 |
Pd2—C4 | 2.003 (5) | N10B—C17B | 1.475 (14) |
Pd3—C5iii | 2.000 (5) | N10B—C16 | 1.588 (13) |
Pd3—C5 | 2.000 (5) | N10B—H10D | 0.9300 |
Pd3—C6iii | 2.007 (6) | N11A—C14A | 1.500 (16) |
Pd3—C6 | 2.007 (6) | N11A—C16 | 1.600 (13) |
Cu1—N1 | 1.998 (4) | N11A—H11C | 0.9300 |
Cu1—N4 | 1.976 (4) | N11B—C14B | 1.48 (2) |
Cu1—N7 | 2.216 (4) | N11B—C15B | 1.518 (12) |
Cu1—N8 | 2.024 (5) | N11B—H11D | 0.9300 |
Cu1—N9 | 2.033 (4) | N12A—C18A | 1.446 (19) |
Cu2—N5 | 1.983 (5) | N12A—C13A | 1.52 (2) |
N6—Cu2iv | 1.980 (5) | N12A—H12C | 0.9300 |
Cu2—N10A | 2.125 (8) | N12B—C13B | 1.470 (14) |
Cu2—N11A | 2.029 (10) | N12B—C18B | 1.522 (18) |
Cu2—N12A | 1.917 (11) | N12B—H12D | 0.9300 |
Cu2—N10B | 2.195 (8) | C13A—C14A | 1.48 (2) |
Cu2—N6v | 1.980 (5) | C13A—H13A | 0.9900 |
Cu2—N11B | 2.022 (8) | C13A—H13B | 0.9900 |
Cu2—N12B | 2.137 (11) | C13B—C14B | 1.537 (18) |
N1—C1 | 1.130 (7) | C13B—H13C | 0.9900 |
N2—C2 | 1.151 (7) | C13B—H13D | 0.9900 |
N3—C3 | 1.143 (8) | C14A—H14A | 0.9900 |
N4—C4 | 1.126 (7) | C14A—H14B | 0.9900 |
N5—C5 | 1.130 (7) | C15A—C16 | 1.376 (13) |
N6—C6 | 1.134 (7) | C15A—H15A | 0.9900 |
N7—C7 | 1.475 (8) | C15A—H15B | 0.9900 |
N7—C12 | 1.483 (6) | C14B—H14C | 0.9900 |
N7—H7 | 0.9300 | C14B—H14D | 0.9900 |
N8—C9 | 1.479 (8) | C15B—C16 | 1.413 (11) |
N8—C8 | 1.486 (8) | C15B—H15C | 0.9900 |
N8—H8 | 0.9300 | C15B—H15D | 0.9900 |
N9—C11 | 1.479 (7) | C16—H16A | 0.9900 |
N9—C10 | 1.484 (7) | C16—H16B | 0.9900 |
N9—H9 | 0.9300 | C16—H16C | 0.9900 |
C7—C8 | 1.519 (11) | C16—H16D | 0.9901 |
C7—H7A | 0.9900 | C17A—C18A | 1.517 (19) |
C7—H7B | 0.9900 | C17A—H17A | 0.9900 |
C8—H8A | 0.9900 | C17A—H17B | 0.9900 |
C8—H8B | 0.9900 | C17B—C18B | 1.536 (19) |
C9—C10 | 1.518 (8) | C17B—H17C | 0.9900 |
C9—H9A | 0.9900 | C17B—H17D | 0.9900 |
C9—H9B | 0.9900 | C18A—H18A | 0.9900 |
C10—H10A | 0.9900 | C18A—H18B | 0.9900 |
C10—H10B | 0.9900 | C18B—H18C | 0.9900 |
C11—C12 | 1.522 (7) | C18B—H18D | 0.9900 |
C2i—Pd1—C2 | 180.000 (1) | N7—C12—H12A | 109.5 |
C2i—Pd1—C1i | 89.0 (2) | C11—C12—H12A | 109.5 |
C2—Pd1—C1i | 91.0 (2) | N7—C12—H12B | 109.5 |
C2i—Pd1—C1 | 91.0 (2) | C11—C12—H12B | 109.5 |
C2—Pd1—C1 | 89.0 (2) | H12A—C12—H12B | 108.1 |
C1i—Pd1—C1 | 180.0 (2) | C15A—N10A—C17A | 116.0 (10) |
C3ii—Pd2—C3 | 180.000 (1) | C15A—N10A—Cu2 | 108.2 (7) |
C3ii—Pd2—C4ii | 93.4 (2) | C17A—N10A—Cu2 | 98.1 (8) |
C3—Pd2—C4ii | 86.6 (2) | C15A—N10A—H10C | 111.3 |
C3ii—Pd2—C4 | 86.6 (2) | C17A—N10A—H10C | 111.3 |
C3—Pd2—C4 | 93.4 (2) | C17B—N10B—C16 | 115.2 (7) |
C4ii—Pd2—C4 | 180.000 (1) | C17B—N10B—Cu2 | 110.9 (7) |
C5iii—Pd3—C5 | 180.0 (2) | C16—N10B—Cu2 | 95.3 (5) |
C5iii—Pd3—C6iii | 90.2 (2) | C17B—N10B—H10D | 111.5 |
C5—Pd3—C6iii | 89.8 (2) | C16—N10B—H10D | 111.5 |
C5iii—Pd3—C6 | 89.8 (2) | Cu2—N10B—H10D | 111.5 |
C5—Pd3—C6 | 90.2 (2) | C14A—N11A—C16 | 114.3 (8) |
C6iii—Pd3—C6 | 180.0 (3) | C14A—N11A—Cu2 | 108.5 (8) |
N1—Cu1—N4 | 92.42 (18) | C16—N11A—Cu2 | 101.7 (5) |
N4—Cu1—N8 | 91.79 (19) | C14B—N11B—C15B | 112.0 (11) |
N1—Cu1—N8 | 162.4 (2) | C14B—N11B—Cu2 | 109.1 (9) |
N4—Cu1—N9 | 172.0 (2) | C15B—N11B—Cu2 | 111.0 (7) |
N1—Cu1—N9 | 90.27 (17) | C14B—N11B—H11D | 108.2 |
N8—Cu1—N9 | 83.47 (18) | C15B—N11B—H11D | 108.2 |
N4—Cu1—N7 | 102.54 (18) | Cu2—N11B—H11D | 108.2 |
N1—Cu1—N7 | 111.97 (19) | C18A—N12A—C13A | 111.3 (12) |
N7—Cu1—N8 | 83.7 (2) | C18A—N12A—Cu2 | 108.8 (8) |
N7—Cu1—N9 | 83.38 (17) | C13A—N12A—Cu2 | 106.3 (10) |
N12A—Cu2—N6v | 157.1 (4) | C13B—N12B—C18B | 114.5 (11) |
N5—Cu2—N12A | 93.0 (3) | C13B—N12B—Cu2 | 111.5 (8) |
N6v—Cu2—N5 | 91.86 (19) | C18B—N12B—Cu2 | 104.7 (8) |
N6v—Cu2—N11B | 96.5 (3) | C13B—N12B—H12D | 108.6 |
N5—Cu2—N11B | 153.1 (3) | C18B—N12B—H12D | 108.6 |
N11A—Cu2—N12A | 86.9 (5) | Cu2—N12B—H12D | 108.6 |
N6v—Cu2—N11A | 86.7 (3) | C14A—C13A—N12A | 109.7 (14) |
N5—Cu2—N11A | 176.0 (3) | C14A—C13A—H13A | 109.7 |
N10A—Cu2—N12A | 88.5 (5) | N12A—C13A—H13A | 109.7 |
N6v—Cu2—N10A | 112.7 (3) | C14A—C13A—H13B | 109.7 |
N5—Cu2—N10A | 99.7 (4) | N12A—C13A—H13B | 109.7 |
N10A—Cu2—N11A | 84.4 (4) | H13A—C13A—H13B | 108.2 |
N6v—Cu2—N12B | 175.6 (4) | N12B—C13B—C14B | 109.6 (11) |
N5—Cu2—N12B | 89.5 (3) | N12B—C13B—H13C | 109.8 |
N11B—Cu2—N12B | 80.4 (4) | C14B—C13B—H13C | 109.8 |
N6v—Cu2—N10B | 102.2 (3) | N12B—C13B—H13D | 109.8 |
N5—Cu2—N10B | 118.8 (3) | C14B—C13B—H13D | 109.8 |
N10B—Cu2—N11B | 84.3 (4) | H13C—C13B—H13D | 108.2 |
N10B—Cu2—N12B | 80.7 (4) | C13A—C14A—N11A | 110.4 (11) |
C1—N1—Cu1 | 167.1 (4) | C13A—C14A—H14A | 109.6 |
C4—N4—Cu1 | 177.6 (5) | N11A—C14A—H14A | 109.6 |
C5—N5—Cu2 | 170.7 (4) | C13A—C14A—H14B | 109.6 |
C6—N6—Cu2iv | 169.8 (4) | N11A—C14A—H14B | 109.6 |
C7—N7—C12 | 114.5 (5) | H14A—C14A—H14B | 108.1 |
C7—N7—Cu1 | 100.8 (4) | C16—C15A—N10A | 112.3 (9) |
C12—N7—Cu1 | 106.2 (3) | C16—C15A—H15A | 109.1 |
C7—N7—H7 | 111.6 | N10A—C15A—H15A | 109.1 |
C12—N7—H7 | 111.6 | C16—C15A—H15B | 109.1 |
Cu1—N7—H7 | 111.6 | N10A—C15A—H15B | 109.1 |
C9—N8—C8 | 113.1 (5) | H15A—C15A—H15B | 107.9 |
C9—N8—Cu1 | 105.3 (3) | N11B—C14B—C13B | 107.7 (13) |
C8—N8—Cu1 | 111.1 (4) | N11B—C14B—H14C | 110.2 |
C9—N8—H8 | 109.1 | C13B—C14B—H14C | 110.2 |
C8—N8—H8 | 109.1 | N11B—C14B—H14D | 110.2 |
Cu1—N8—H8 | 109.1 | C13B—C14B—H14D | 110.2 |
C11—N9—C10 | 114.6 (4) | H14C—C14B—H14D | 108.5 |
C11—N9—Cu1 | 104.6 (3) | C16—C15B—N11B | 109.7 (7) |
C10—N9—Cu1 | 111.6 (3) | C16—C15B—H15C | 109.7 |
C11—N9—H9 | 108.6 | N11B—C15B—H15C | 109.7 |
C10—N9—H9 | 108.6 | C16—C15B—H15D | 109.7 |
Cu1—N9—H9 | 108.6 | N11B—C15B—H15D | 109.7 |
N1—C1—Pd1 | 176.8 (5) | H15C—C15B—H15D | 108.2 |
N2—C2—Pd1 | 179.2 (5) | C15B—C16—N10B | 112.2 (7) |
N3—C3—Pd2 | 177.0 (5) | C15A—C16—N11A | 111.7 (7) |
N4—C4—Pd2 | 177.4 (5) | C15A—C16—H16A | 109.3 |
N5—C5—Pd3 | 177.4 (5) | N11A—C16—H16A | 109.3 |
N6—C6—Pd3 | 177.9 (5) | C15A—C16—H16B | 109.3 |
N7—C7—C8 | 110.8 (5) | N11A—C16—H16B | 109.3 |
N7—C7—H7A | 109.5 | H16A—C16—H16B | 107.9 |
C8—C7—H7A | 109.5 | C15B—C16—H16C | 109.5 |
N7—C7—H7B | 109.5 | N10B—C16—H16C | 109.3 |
C8—C7—H7B | 109.5 | C15B—C16—H16D | 108.3 |
H7A—C7—H7B | 108.1 | N10B—C16—H16D | 109.4 |
N8—C8—C7 | 112.5 (5) | H16C—C16—H16D | 108.1 |
N8—C8—H8A | 109.1 | N10A—C17A—C18A | 110.0 (11) |
C7—C8—H8A | 109.1 | N10A—C17A—H17A | 109.7 |
N8—C8—H8B | 109.1 | C18A—C17A—H17A | 109.7 |
C7—C8—H8B | 109.1 | N10A—C17A—H17B | 109.7 |
H8A—C8—H8B | 107.8 | C18A—C17A—H17B | 109.7 |
N8—C9—C10 | 109.5 (5) | H17A—C17A—H17B | 108.2 |
N8—C9—H9A | 109.8 | N10B—C17B—C18B | 110.4 (9) |
C10—C9—H9A | 109.8 | N10B—C17B—H17C | 109.6 |
N8—C9—H9B | 109.8 | C18B—C17B—H17C | 109.6 |
C10—C9—H9B | 109.8 | N10B—C17B—H17D | 109.6 |
H9A—C9—H9B | 108.2 | C18B—C17B—H17D | 109.6 |
N9—C10—C9 | 109.1 (4) | H17C—C17B—H17D | 108.1 |
N9—C10—H10A | 109.9 | N12A—C18A—C17A | 113.8 (11) |
C9—C10—H10A | 109.9 | N12A—C18A—H18A | 108.8 |
N9—C10—H10B | 109.9 | C17A—C18A—H18A | 108.8 |
C9—C10—H10B | 109.9 | N12A—C18A—H18B | 108.8 |
H10A—C10—H10B | 108.3 | C17A—C18A—H18B | 108.8 |
N9—C11—C12 | 111.0 (4) | H18A—C18A—H18B | 107.7 |
N9—C11—H11A | 109.4 | N12B—C18B—C17B | 109.3 (10) |
C12—C11—H11A | 109.4 | N12B—C18B—H18C | 109.8 |
N9—C11—H11B | 109.4 | C17B—C18B—H18C | 109.8 |
C12—C11—H11B | 109.4 | N12B—C18B—H18D | 109.8 |
H11A—C11—H11B | 108.0 | C17B—C18B—H18D | 109.8 |
N7—C12—C11 | 110.6 (4) | H18C—C18B—H18D | 108.3 |
N4—Cu1—N1—C1 | 85.7 (18) | N6v—Cu2—N11B—C14B | −144.6 (10) |
N8—Cu1—N1—C1 | −18 (2) | N5—Cu2—N11B—C14B | −37.2 (12) |
N9—Cu1—N1—C1 | −86.8 (18) | N11A—Cu2—N11B—C14B | 149.1 (14) |
N7—Cu1—N1—C1 | −169.8 (17) | N10A—Cu2—N11B—C14B | 100.8 (10) |
N4—Cu1—N7—C7 | −60.6 (4) | N12B—Cu2—N11B—C14B | 32.2 (10) |
N1—Cu1—N7—C7 | −158.5 (3) | N10B—Cu2—N11B—C14B | 113.7 (10) |
N8—Cu1—N7—C7 | 29.8 (4) | N12A—Cu2—N11B—C15B | −107.7 (8) |
N9—Cu1—N7—C7 | 113.9 (4) | N6v—Cu2—N11B—C15B | 91.4 (7) |
N4—Cu1—N7—C12 | 179.7 (4) | N5—Cu2—N11B—C15B | −161.2 (6) |
N1—Cu1—N7—C12 | 81.9 (4) | N11A—Cu2—N11B—C15B | 25.1 (9) |
N8—Cu1—N7—C12 | −89.8 (4) | N10A—Cu2—N11B—C15B | −23.2 (7) |
N9—Cu1—N7—C12 | −5.7 (4) | N12B—Cu2—N11B—C15B | −91.8 (7) |
N4—Cu1—N8—C9 | −141.6 (4) | N10B—Cu2—N11B—C15B | −10.3 (7) |
N1—Cu1—N8—C9 | −37.9 (7) | N6v—Cu2—N12A—C18A | 165.7 (7) |
N9—Cu1—N8—C9 | 31.9 (3) | N5—Cu2—N12A—C18A | −92.3 (8) |
N7—Cu1—N8—C9 | 115.9 (4) | N11B—Cu2—N12A—C18A | 109.0 (8) |
N4—Cu1—N8—C8 | 95.6 (4) | N11A—Cu2—N12A—C18A | 91.7 (8) |
N1—Cu1—N8—C8 | −160.6 (5) | N10A—Cu2—N12A—C18A | 7.3 (8) |
N9—Cu1—N8—C8 | −90.9 (4) | N12B—Cu2—N12A—C18A | −12.8 (10) |
N7—Cu1—N8—C8 | −6.9 (4) | N10B—Cu2—N12A—C18A | 26.9 (8) |
N1—Cu1—N9—C11 | −81.3 (3) | N6v—Cu2—N12A—C13A | 45.8 (15) |
N8—Cu1—N9—C11 | 115.2 (3) | N5—Cu2—N12A—C13A | 147.7 (11) |
N7—Cu1—N9—C11 | 30.8 (3) | N11B—Cu2—N12A—C13A | −10.9 (10) |
N1—Cu1—N9—C10 | 154.3 (4) | N11A—Cu2—N12A—C13A | −28.2 (11) |
N8—Cu1—N9—C10 | −9.3 (4) | N10A—Cu2—N12A—C13A | −112.7 (11) |
N7—Cu1—N9—C10 | −93.6 (4) | N12B—Cu2—N12A—C13A | −132.8 (19) |
C12—N7—C7—C8 | 66.0 (6) | N10B—Cu2—N12A—C13A | −93.1 (11) |
Cu1—N7—C7—C8 | −47.4 (5) | N12A—Cu2—N12B—C13B | 46.5 (14) |
C9—N8—C8—C7 | −136.3 (5) | N5—Cu2—N12B—C13B | 147.4 (8) |
Cu1—N8—C8—C7 | −18.1 (5) | N11B—Cu2—N12B—C13B | −7.6 (8) |
N7—C7—C8—N8 | 47.1 (6) | N11A—Cu2—N12B—C13B | −28.7 (8) |
C8—N8—C9—C10 | 72.2 (6) | N10A—Cu2—N12B—C13B | −112.2 (8) |
Cu1—N8—C9—C10 | −49.3 (5) | N10B—Cu2—N12B—C13B | −93.4 (8) |
C11—N9—C10—C9 | −134.1 (5) | N12A—Cu2—N12B—C18B | 170.9 (17) |
Cu1—N9—C10—C9 | −15.4 (6) | N5—Cu2—N12B—C18B | −88.3 (7) |
N8—C9—C10—N9 | 43.0 (6) | N11B—Cu2—N12B—C18B | 116.8 (8) |
C10—N9—C11—C12 | 69.8 (6) | N11A—Cu2—N12B—C18B | 95.6 (8) |
Cu1—N9—C11—C12 | −52.7 (5) | N10A—Cu2—N12B—C18B | 12.1 (7) |
C7—N7—C12—C11 | −131.0 (5) | N10B—Cu2—N12B—C18B | 31.0 (7) |
Cu1—N7—C12—C11 | −20.7 (6) | C18A—N12A—C13A—C14A | −72.4 (16) |
N9—C11—C12—N7 | 50.2 (7) | Cu2—N12A—C13A—C14A | 45.8 (16) |
N12A—Cu2—N10A—C15A | 90.9 (7) | C18B—N12B—C13B—C14B | −136.2 (12) |
N6v—Cu2—N10A—C15A | −80.2 (7) | Cu2—N12B—C13B—C14B | −17.5 (12) |
N5—Cu2—N10A—C15A | −176.3 (7) | N12A—C13A—C14A—N11A | −41.7 (17) |
N11B—Cu2—N10A—C15A | 21.5 (8) | C16—N11A—C14A—C13A | 130.5 (11) |
N11A—Cu2—N10A—C15A | 3.9 (7) | Cu2—N11A—C14A—C13A | 17.8 (12) |
N12B—Cu2—N10A—C15A | 97.5 (7) | C17A—N10A—C15A—C16 | 133.2 (10) |
N10B—Cu2—N10A—C15A | −17.5 (9) | Cu2—N10A—C15A—C16 | 24.2 (10) |
N12A—Cu2—N10A—C17A | −29.9 (8) | C15B—N11B—C14B—C13B | 72.7 (14) |
N6v—Cu2—N10A—C17A | 159.0 (7) | Cu2—N11B—C14B—C13B | −50.7 (14) |
N5—Cu2—N10A—C17A | 62.9 (8) | N12B—C13B—C14B—N11B | 43.8 (16) |
N11B—Cu2—N10A—C17A | −99.3 (8) | C14B—N11B—C15B—C16 | −141.3 (10) |
N11A—Cu2—N10A—C17A | −116.9 (9) | Cu2—N11B—C15B—C16 | −19.0 (10) |
N12B—Cu2—N10A—C17A | −23.3 (8) | N10A—C15A—C16—C15B | −92.5 (9) |
N10B—Cu2—N10A—C17A | −138.4 (15) | N10A—C15A—C16—N10B | 6.0 (8) |
N12A—Cu2—N10B—C17B | −18.2 (8) | N10A—C15A—C16—N11A | −49.7 (11) |
N6v—Cu2—N10B—C17B | 177.0 (7) | N11B—C15B—C16—C15A | 88.2 (10) |
N5—Cu2—N10B—C17B | 78.0 (7) | N11B—C15B—C16—N10B | 52.6 (10) |
N11B—Cu2—N10B—C17B | −87.5 (7) | N11B—C15B—C16—N11A | −10.8 (7) |
N11A—Cu2—N10B—C17B | −102.4 (8) | C17B—N10B—C16—C15A | −33.6 (10) |
N10A—Cu2—N10B—C17B | 54.0 (12) | Cu2—N10B—C16—C15A | −149.7 (12) |
N12B—Cu2—N10B—C17B | −6.3 (7) | C17B—N10B—C16—C15B | 61.4 (9) |
N12A—Cu2—N10B—C16 | 101.4 (5) | Cu2—N10B—C16—C15B | −54.7 (7) |
N6v—Cu2—N10B—C16 | −63.5 (5) | C17B—N10B—C16—N11A | 96.3 (8) |
N5—Cu2—N10B—C16 | −162.5 (4) | Cu2—N10B—C16—N11A | −19.8 (5) |
N11B—Cu2—N10B—C16 | 32.0 (5) | C14A—N11A—C16—C15A | −68.0 (11) |
N11A—Cu2—N10B—C16 | 17.1 (5) | Cu2—N11A—C16—C15A | 48.6 (8) |
N10A—Cu2—N10B—C16 | 173.5 (13) | C14A—N11A—C16—C15B | 29.4 (10) |
N12B—Cu2—N10B—C16 | 113.2 (5) | Cu2—N11A—C16—C15B | 146.0 (11) |
N12A—Cu2—N11A—C14A | 6.6 (7) | C14A—N11A—C16—N10B | −94.7 (9) |
N6v—Cu2—N11A—C14A | −151.5 (7) | Cu2—N11A—C16—N10B | 21.9 (6) |
N11B—Cu2—N11A—C14A | −37.1 (9) | C15A—N10A—C17A—C18A | −69.2 (13) |
N10A—Cu2—N11A—C14A | 95.4 (7) | Cu2—N10A—C17A—C18A | 45.6 (12) |
N12B—Cu2—N11A—C14A | 24.5 (8) | C16—N10B—C17B—C18B | −127.2 (10) |
N10B—Cu2—N11A—C14A | 103.5 (7) | Cu2—N10B—C17B—C18B | −20.4 (11) |
N12A—Cu2—N11A—C16 | −114.2 (6) | C13A—N12A—C18A—C17A | 134.9 (13) |
N6v—Cu2—N11A—C16 | 87.7 (5) | Cu2—N12A—C18A—C17A | 18.2 (13) |
N11B—Cu2—N11A—C16 | −158.0 (13) | N10A—C17A—C18A—N12A | −47.0 (15) |
N10A—Cu2—N11A—C16 | −25.4 (5) | C13B—N12B—C18B—C17B | 70.6 (14) |
N12B—Cu2—N11A—C16 | −96.3 (6) | Cu2—N12B—C18B—C17B | −51.9 (12) |
N10B—Cu2—N11A—C16 | −17.3 (5) | N10B—C17B—C18B—N12B | 48.8 (14) |
N12A—Cu2—N11B—C14B | 16.3 (10) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z+2; (iii) −x, −y, −z+1; (iv) x+1, y, z; (v) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O1A | 0.93 | 2.57 | 3.233 (15) | 129 |
N8—H8···N3vi | 0.93 | 2.05 | 2.960 (6) | 165 |
N9—H9···N2vii | 0.93 | 2.15 | 2.942 (6) | 142 |
N10A—H10C···N2viii | 0.93 | 2.62 | 3.282 (11) | 129 |
N10B—H10D···N2viii | 0.93 | 2.26 | 3.076 (10) | 146 |
N11A—H11C···Br1 | 0.93 | 2.66 | 3.513 (10) | 153 |
N11B—H11D···Br1 | 0.93 | 2.42 | 3.327 (9) | 163 |
N12A—H12C···Br1iv | 0.93 | 2.35 | 3.254 (10) | 165 |
N12B—H12D···Br1iv | 0.93 | 2.61 | 3.461 (10) | 153 |
Symmetry codes: (iv) x+1, y, z; (vi) −x+1, −y+1, −z+2; (vii) −x+1, −y+1, −z+1; (viii) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2Pd(CN)4(C6H15N3)2]Br2·[Cu2Pd2(CN)8(C6H15N3)2]·H2O |
Mr | 1580.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 193 |
a, b, c (Å) | 7.3214 (8), 12.9466 (14), 14.5178 (16) |
α, β, γ (°) | 83.699 (9), 84.378 (9), 82.878 (9) |
V (Å3) | 1352.3 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 4.05 |
Crystal size (mm) | 0.40 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Stoe IPDS-II |
Absorption correction | Multi-scan (WinGX; Farrugia, 1999) |
Tmin, Tmax | 0.410, 0.667 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22649, 5903, 4826 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.115, 1.03 |
No. of reflections | 5903 |
No. of parameters | 394 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.18, −1.36 |
Computer programs: X-AREA (Stoe & Cie, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Crystal Impact, 2002).
Pd1—C1 | 2.010 (5) | Cu1—N9 | 2.033 (4) |
Pd1—C2 | 2.002 (6) | Cu2—N5 | 1.983 (5) |
Pd2—C3 | 2.003 (6) | N6—Cu2i | 1.980 (5) |
Pd2—C4 | 2.003 (5) | Cu2—N10A | 2.125 (8) |
Pd3—C5 | 2.000 (5) | Cu2—N11A | 2.029 (10) |
Pd3—C6 | 2.007 (6) | Cu2—N12A | 1.917 (11) |
Cu1—N1 | 1.998 (4) | Cu2—N10B | 2.195 (8) |
Cu1—N4 | 1.976 (4) | Cu2—N11B | 2.022 (8) |
Cu1—N7 | 2.216 (4) | Cu2—N12B | 2.137 (11) |
Cu1—N8 | 2.024 (5) | ||
C2—Pd1—C1ii | 91.0 (2) | N7—Cu1—N9 | 83.38 (17) |
C2—Pd1—C1 | 89.0 (2) | N5—Cu2—N12A | 93.0 (3) |
C3iii—Pd2—C4 | 86.6 (2) | N11A—Cu2—N12A | 86.9 (5) |
C3—Pd2—C4 | 93.4 (2) | N10A—Cu2—N12A | 88.5 (5) |
C5iv—Pd3—C6 | 89.8 (2) | N5—Cu2—N10A | 99.7 (4) |
C5—Pd3—C6 | 90.2 (2) | N10A—Cu2—N11A | 84.4 (4) |
N1—Cu1—N4 | 92.42 (18) | N5—Cu2—N12B | 89.5 (3) |
N4—Cu1—N8 | 91.79 (19) | N11B—Cu2—N12B | 80.4 (4) |
N1—Cu1—N9 | 90.27 (17) | N10B—Cu2—N11B | 84.3 (4) |
N8—Cu1—N9 | 83.47 (18) | N10B—Cu2—N12B | 80.7 (4) |
N7—Cu1—N8 | 83.7 (2) |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) −x, −y+1, −z+2; (iv) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O1A | 0.93 | 2.57 | 3.233 (15) | 128.9 |
N8—H8···N3v | 0.93 | 2.05 | 2.960 (6) | 164.8 |
N9—H9···N2vi | 0.93 | 2.15 | 2.942 (6) | 142.1 |
N10A—H10C···N2vii | 0.93 | 2.62 | 3.282 (11) | 128.5 |
N10B—H10D···N2vii | 0.93 | 2.26 | 3.076 (10) | 146.2 |
N11A—H11C···Br1 | 0.93 | 2.66 | 3.513 (10) | 152.6 |
N11B—H11D···Br1 | 0.93 | 2.42 | 3.327 (9) | 163.4 |
N12A—H12C···Br1i | 0.93 | 2.35 | 3.254 (10) | 164.5 |
N12B—H12D···Br1i | 0.93 | 2.61 | 3.461 (10) | 152.6 |
Symmetry codes: (i) x+1, y, z; (v) −x+1, −y+1, −z+2; (vi) −x+1, −y+1, −z+1; (vii) x−1, y−1, z. |
Cyano complexes exhibit great structural variability due to the bridging ability of the cyano ligand. This structural variability allied with the presence of paramagnetic central atoms makes cyanocomplexes popular among chemists and physicists as materials exhibiting various interesting magnetic properties (Lescouezec et al., 2005; Ohba & Okawa, 2000; Garde et al., 2008; Bernhardt et al., 2005; Klokishner et al., 2007; Herrera et al., 2008).
In construction of low-dimensional cyano complexes, the so-called `brick and mortar' method can be applied (Willet et al., 1993), in which a metallic central atom coordinated by suitable blocking ligand(s) acts as the `brick' and the cyanide complex anion is used as the `mortar'. Previously, following these ideas we have prepared, structurally characterized and studied the magnetic properties of several low-dimensional cyanide complexes in which various bidentate ligands were used (Hanko et al., 2007; Kuchár et al., 2004, 2003). These complexes are also interesting as models for studies of the role of hydrogen bonds in mediating magnetic exchange interactions.
As a continuation of our effort to prepare one-dimensional cyano complexes, we have decided to use a cyclic triaza ligand, 1,4,7-triazacyclononane (tacn). This tridentate ligand, connected to a CuII central atom, affords mainly five-coordination (Han et al., 2004; Wang et al., 2004), thus leaving two coordination sites free for the polymerization process during crystallization. As a result of our synthetic procedure using tacn.3HBr, prepared according to the literature (White et al., 1979), we have isolated the title compound, (I).
The crystal structure of (I) is essentially ionic (Figs. 1–3). It is built up of positively charged 2,4-ribbons exhibiting composition [Cu(tacn)(NC)2—Pd(CN)2—Cu(tacn)]n2n+ and running along the (100) direction, bromide anions, electroneutral 2,2-CT chains [Cu(tacn)(NC)—Pd(CN)2—(CN)–] running along the (001) direction and one water molecule of crystallization. An alternative view of the structure is that it is formed of the abovementioned chains, with ribbons running perpendicularly between the chains, and with bromide anions and water molecules of crystallization placed in the free space between the chains and ribbons.
This type of 2,4-ribbon incorporating cyanide ligands and CuII central atoms has not been described previously, but a similar ribbon structural motif was found in [Mn6(tptz)6(MeOH)4(DMF)2W4(CN)32]8.2H2O.2.3MeOH [tptz is 2,4,6-tris(2-pyridyl)-1,3,5-triazine and DMF is N,N-dimethylformamide; Zhao et al., 2007). On the other hand, chains built up of cyano complex anions and CuII ions are not uncommon; as examples, Cu(en)2Ni(CN)4 or Cu(dmen)2Pd(CN)4 can be mentioned (en and dmen are ??; Seitz et al., 2001; Kuchár et al., 2004). The presence of both one-dimensional structural motifs within the same structure is, however, a unique feature of this structure.
Both the ribbon and the chain parts of the structure contain five-coordinated CuII ions. As expected, three coordination sites are occupied by the blocking tacn ligand, with Cu—N bonds within the range 1.917 (11)–2.216 (4) Å and with intrachelate N—Cu—N angles of 83.38 (17), 83.47 (18) and 83.7 (2)° (Table 1). The remaining two coordination sites around the CuII central ions are occupied by N atoms from bridging cyanide ligands with Cu—N distances in the range 1.976 (4)–1.998 (4) Å. As calculated following the suggestion of Addison et al. (1984), the τ parameters of atoms Cu1 (chain) and Cu2 are 0.98 and 1/3, respectively, indicating that the polyhedron around atom Cu1 is close to ideal trigonal bipyramidal while that around atom Cu2 is closer to square pyramidal. The geometric parameters within the tacn ligands are as expected (Schwindinger et al., 1980).
There are three crystallographically independent PdII ions in the structure. Each of them occupies a special position (centre of symmetry). All PdII ions exhibit square-planar coordination by four cyano ligands with a mean Pd—C bond length of 2.004 (3) Å; this value is close to that of 1.994 (1) found in [Cu(tn)Pd(CN)4] (tn is 1,3-diaminopropane; Legendre et al., 2008). All of the cyanide ligands within the ribbon exhibit bridging character, while amongst those in the [Pd(CN)4]2- anion within the chain, two are terminal and two link Cu and Pd ions. The C≡N bonds are from the range 1.126 (7)–1.151 (7) Å, which are normal values (Legendre et al., 2008). The Cu—N≡C angles formed by bridging cyanide ligands exhibit values in the range 167.1 (4)—177.6 (5)°. The presence of both bridging and terminal cyanide ligands in the structure was also detected by IR spectroscopy; in the spectrum there are absorption bands at 2183 and 2145 cm-1, which were attributed to the stretching vibrations of the bridging (higher wavenumbers) and terminal cyanide ligands. The absorption band at higher wavenumbers exhibits greater intensity, in line with the larger number of bridging cyanide ligands in the structure.
There is one non-coordinated bromide anion that occupies a general position, which hydrogen bonds to NH groups of the tacn ligands (Table 2). Two unique crystallographic positions are occupied by the O atom of the water molecule, one on a centre of symmetry, which is half occupied, and the other in a general position, 1.432 (2) Å away, with one-quarter occupancy. The water molecule, N atoms from the tacn ligands and terminal n atoms from the cyanide groups are involved in N—H···O and N—H···N(≡C) hydrogen bonds, respectively (Table 2 and Fig. 3).
N—H···N(≡C) hydrogen bonds connect the electroneutral chains to one another as well as to the chains of negatively charged ribbons, with N···N distances in the range 2.942 (6)–3.282 (11) Å. The water molecule interacts via an N—H···O hydrogen-bond interaction with H atoms from the electroneutral chain. At the same time, the O1B···Br1 (2.992 Å) and O1A···Br1 distances (3.249 and 3.384 Å), respectively, suggest the presence of further hydrogen-bonding interactions. The bromide anions form further weak hydrogen-bonding interactions of the N—H···Br type, with H···Br distances in the range 2.35–2.66 Å.