Download citation
Download citation
link to html
Two new salts of the cation [CuI(dmp)2]+ (dmp is 2,9-dimeth­yl-1,10-phenanthroline, C14H12N2), namely bis­[bis­(2,9-dimeth­yl-1,10-phenanthroline-κ2N,N′)copper(I)] bis­(hexa­fluorophos­phate) hemi[bis­(4-pyridylmethyl­idene)hydrazine] acetonitrile solvate, [Cu(C14H12N2)2]2(PF6)2·0.5C12H10N4·C2H3N or [Cu(dmp)2]2(PF6)2·0.5(bpmh)·CH3CN [bpmh is bis­(4-pyridylmethyl­idene)hydrazine, C12H10N4], (I), and bis­(2,9-dimeth­yl-1,10-phenanthroline-κ2N,N′)copper(I) dicyanamide, [Cu(C14H12N2)2](C2N3) or [Cu(dmp)2][N(CN)2], (II), are reported. The Cu—N bond lengths and the distortion from idealized tetra­hedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is π–π stacked with a dmp ligand at a distance of 3.4 Å, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide mol­ecule is present as an uncoordinated counter-ion.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105010760/gg1253sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105010760/gg1253Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105010760/gg1253IIsup3.hkl
Contains datablock II

CCDC references: 278537; 278538

Comment top

Complexes of copper chelated with 2,9-dimethyl-1,10-phenanthroline (dmp) have attracted attention due to their long-lived excited states and potential use in solar energy conversion (Blake et al., 1998; Kuang et al., 2002; Chen et al., 2002; Morpurgo et al., 1984; Cuttell et al., 2002). Such compounds absorb light in the visible range to undergo a metal-to-ligand charge-transfer (MLCT). Upon excitation, the molecules are known to undergo a geometry change, and this change has been observed in one such compound through time-resolved X-ray diffraction (Coppens et al., 2004). Kovalevsky et al. (2003, 2004) have recently reported on a series of [CuI(dmp)2]+ salts with varying counterions, in an attempt to correlate the ground-state structure and spectroscopic properties. Much attention has been focused on the distortion of the [CuI(dmp)2]+ cation from its idealized tetrahedral geometry. Understanding the effects of packing forces on the geometry of the cation is a necessary preliminary step for understanding the geometry changes associated with photoexcitation. Here, we report the crystal structures of two new [CuI(dmp)2]+ compounds.

Crystals of [Cu(dmp)2]2[PF6]2.0.5 b pm h·CH3CN, (I), contain two [CuI(dmp)2]+ cations, two [PF6] anions, one acetonitrile solvent molecule, and one half-molecule of bpmh (residing on an inversion center) in the asymmetric unit. All bond lengths and angles are within their expected ranges. Two F atoms of one of the [PF6] anions are disordered. The pyridyl ring of the bpmh ligand is almost coplanar with a dmp ligand, with an interplanar distance of 3.545 (1) Å, and stabilized by ππ stacking; two dmp ligands related by inversion symmetry have an interplanar separation of 3.378 (1) Å.

Crystals of (I) were prepared in an attempt to link the two Cu atoms through a bpmh linkage. While the bpmh molecule has often been utilized as a linker in the construction of supramolecular frameworks (Ma & Coppens, 2003) and in metal polymers (Ag, Co, Mn, Ni, Pb, Zn), to date no examples of a Cu complex with a bridging bpmh are known. Several examples of Cu compounds with similar bridging ligands, but containing a heterocyclic five-membered ring rather than the dimethylhydrazine group, are known (Du et al., 2002, 2004; Dong et al., 2003; Huang et al., 2004). Even though an excess of the ligand was used during the synthesis of (I), the bpmh was incorporated into the crystal in an uncoordinated arrangement. Goodgame et al. (2001) reported another crystal in which a molecule which usually acts as a linker, 1-(4'-pyridyl)pyridin-4-one, co-crystallizes in a Cu complex instead. Kovalevsky et al. (2003) reported an example in which an uncoordinated dmp molecule is ππ stacked with a coordinated dmp ligand.

The rocking, wagging, and flattening distortions of the cations were calculated using a method described previously by Dobson et al. (1984). For cation A, the flattening distortion is rather large at θz = 79.6°, whereas the rocking and wagging distortions are θx = 87.8° and θy = 84.7°, respectively. Cation B has slightly larger rocking and wagging distortions of θx = 84.6° and θy = 84.2°, respectively, and a smaller flattening of θz = 81.3°. Kovalevsky et al. have reported two other PF6 salts of this cation, one of which crystallizes with a 0.5-occupancy CH2Cl2 solvent molecule. The cations in the crystals of both these compounds are considerably more distorted than cations A or B in (I). The overall distortion of the cations in (I) is nearly the same and in the middle of the range of all previously reported salts of this cation (Kovalevsky et al., 2003). In cation A, the Cu—N distances range from 2.026 (1) to 2.060 (1) Å; cation B has a similar Cu—N distance range of 2.018 (1)–2.059 (1) Å.

Compound (II), [Cu(dmp)2][N(CN)2], crystallizes with one [CuI(dmp)2]+ cation and one [N(CN)2] anion in the asymmetric unit. All bond lengths and angles lie within their expected ranges. The Cu—N bond length range is 2.019 (1)–2.050 (1) Å. The rocking and wagging distortions in the cation are θx = 88.2° and θy = 86.9°, with a flattening of θz = 88.6°. The overall distortion of the cation is quite small and comparable with that of the least distorted salt reported to date, with a p-tosylate counterion (Kovalevsky et al., 2003).

The [N(CN)2] ion (dca) is a much-used ligand in Cu coordination chemistry. It has attracted recent attention because of its multiple coordination modes and interesting magnetic properties (Vangdal et al., 2002). However, it is rarely found as an uncoordinated counterion. Two cases have been reported. In the first case, the dca anion is semicoordinated in [Cu2(tppz)(dca)3(H2O)].(dca)·H2O, with N—Cu 2.939 Å (Carranza et al., 2003). However, in (II) the dca anion is completely uncoordinated, the shortest Cu···N distance being 4.641 Å. In the second case, dca is linked to a cation via an N—H···N hydrogen bond in the salt [Cu(C2N3)(trien)][C2N3] (Luo et al., 2003). In (II), only weaker C—H···N interactions exist, the shortest being 0.2 Å longer than the N—H···N bond linking the cation and anion in the compound prepared by Luo et al. The previously reported compounds also contain at least one coordinated dca anion. In (II), all dca atoms are coplanar, whereas the central C—N—C bond angle is 117.74 (14)°. The two terminal C—N bonds are bent slightly outwards, with NC—N angles of 174.36 (17) and 175.3 (2)°.

Experimental top

In attempting to synthesize polymeric CuI dmp complexes, we found that [Cu(dmp)2] will often form even when it is not favored by the stoichiometry. Compound (I) was synthesized by dissolving [CuI(CH3CN)4][PF6] (1.0 mmol), dmp (0.9 mmol), and bpmh (1.3 mmol) in CH2Cl2 (30 ml) and CH3CN (20 ml). The bright-red solution was heated to 343 K and stirred for 3 h. The solid remaining after the reaction was filtered off. Dark-red crystals were obtained by gas-phase ether diffusion into the solution. Compound (II) was synthesized by dissolving CuICl (1.0 mmol), dmp (0.9 mmol), and NaN(CN)2 (1.3 mmol) in ethanol (15 ml) and water (15 ml). The orange solution was stirred and heated to 343 K for 3 h. Orange crystals were grown by slow evaporation of the solution.

Refinement top

H atoms were located in difference maps and treated as riding atoms for the aromatic and methylene H atoms, with C—H distances of 0.95 Å [Please check added text] and with Uiso(H) = 1.2Ueq(C), and in idealized positions for CH3, with C—H distances of 0.98 Å [Please check added text] and with Uiso(H) = 1.?Ueq(C) [Please provide missing information]. Free isotropic refinement of H atoms did not lead to a significant improvment in the R factor.

Computing details top

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The two cations of (I) with the bpmh molecule. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The stacking involving the bpmh molecule and a dmp of cation A in (I). Displacement ellipsoids are drawn at the 50% probability level. The full bpmh molecule is depicted for clarity.
[Figure 3] Fig. 3. Compound (II), with H atoms omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.
(I) Bis[bis(2,9-dimethyl-1,10-phenanthroline-κ2N,N')copper(I)] bis(hexafluorophosphate) hemi[bis(4-pyridylmethylidyne)hydrazine] acetonitrile solvate top
Crystal data top
[Cu(C14H12N2)2]2(PF6)2(C12H10N4)0.5·C2H3NZ = 2
Mr = 1396.24F(000) = 1426
Triclinic, P1Dx = 1.568 Mg m3
Hall symbol: -P1Melting point: not measured K
a = 13.6775 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 14.0221 (5) ÅCell parameters from 22175 reflections
c = 17.2879 (6) Åθ = 4.9–56.1°
α = 111.776 (1)°µ = 0.86 mm1
β = 91.679 (1)°T = 90 K
γ = 104.212 (1)°Cubic, red
V = 2957.96 (18) Å30.20 × 0.20 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
14342 independent reflections
Radiation source: rotating anode12664 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ϕ and ω scansθmax = 28.1°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1818
Tmin = 0.782, Tmax = 0.919k = 1818
45314 measured reflectionsl = 2222
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.082 w = 1/[σ2(Fo2) + (0.0399P)2 + 2.1375P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.002
14342 reflectionsΔρmax = 1.03 e Å3
849 parametersΔρmin = 0.69 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0133 (4)
Crystal data top
[Cu(C14H12N2)2]2(PF6)2(C12H10N4)0.5·C2H3Nγ = 104.212 (1)°
Mr = 1396.24V = 2957.96 (18) Å3
Triclinic, P1Z = 2
a = 13.6775 (5) ÅMo Kα radiation
b = 14.0221 (5) ŵ = 0.86 mm1
c = 17.2879 (6) ÅT = 90 K
α = 111.776 (1)°0.20 × 0.20 × 0.20 mm
β = 91.679 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
14342 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
12664 reflections with I > 2σ(I)
Tmin = 0.782, Tmax = 0.919Rint = 0.023
45314 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.082H-atom parameters constrained
S = 1.04Δρmax = 1.03 e Å3
14342 reflectionsΔρmin = 0.69 e Å3
849 parameters
Special details top

Experimental. 'Blessing, R. (1995) Acta Crystallogr., A51, 33–38'

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.040605 (13)0.253855 (14)0.263530 (10)0.01441 (5)
Cu20.672579 (13)0.806172 (14)0.246437 (11)0.01431 (5)
N10.06378 (9)0.24801 (10)0.34476 (7)0.0136 (2)
N100.47393 (9)0.53999 (9)0.01087 (8)0.0153 (2)
N1S0.81905 (15)0.76658 (14)0.46545 (10)0.0358 (4)
N20.12510 (9)0.37670 (10)0.36760 (7)0.0135 (2)
N30.01559 (9)0.24898 (10)0.14632 (8)0.0141 (2)
N40.11593 (9)0.14164 (9)0.20480 (8)0.0137 (2)
N50.57553 (9)0.79546 (10)0.33107 (8)0.0139 (2)
N60.76802 (9)0.91613 (10)0.35299 (8)0.0142 (2)
N70.62281 (9)0.83739 (10)0.14703 (8)0.0137 (2)
N80.72591 (9)0.70006 (10)0.15487 (7)0.0133 (2)
N90.30178 (10)0.80067 (11)0.03212 (9)0.0214 (3)
P10.14600 (3)0.69708 (3)0.21966 (2)0.01714 (8)
P20.50268 (3)0.28465 (3)0.31493 (3)0.02073 (9)
C10.16077 (11)0.19075 (12)0.33093 (9)0.0157 (3)
C100.21810 (11)0.44096 (12)0.37644 (9)0.0158 (3)
C110.07941 (11)0.38281 (11)0.43757 (9)0.0129 (3)
C120.02217 (11)0.31474 (11)0.42539 (9)0.0134 (3)
C130.20631 (12)0.11992 (13)0.24186 (10)0.0212 (3)
C140.26407 (12)0.43455 (13)0.29755 (10)0.0205 (3)
C150.03477 (11)0.30332 (12)0.11908 (9)0.0175 (3)
C160.04474 (12)0.29005 (13)0.03426 (10)0.0214 (3)
C170.00286 (12)0.21939 (13)0.02308 (10)0.0214 (3)
C180.05071 (11)0.16093 (12)0.00388 (9)0.0175 (3)
C190.09740 (12)0.08522 (13)0.05104 (9)0.0217 (3)
C1S0.63604 (17)0.64642 (17)0.45241 (14)0.0386 (5)
C20.21953 (12)0.19578 (12)0.39738 (10)0.0188 (3)
C200.15000 (12)0.03341 (13)0.02122 (10)0.0221 (3)
C210.16009 (11)0.05131 (11)0.06611 (9)0.0171 (3)
C220.21480 (12)0.00004 (12)0.10049 (11)0.0223 (3)
C230.21922 (12)0.02092 (13)0.18451 (11)0.0228 (3)
C240.16881 (11)0.09288 (12)0.23615 (10)0.0172 (3)
C250.11273 (10)0.12267 (11)0.12128 (9)0.0137 (3)
C260.05823 (11)0.17894 (11)0.08979 (9)0.0142 (3)
C270.07941 (13)0.37991 (13)0.18357 (10)0.0239 (3)
C280.17500 (12)0.11756 (13)0.32837 (10)0.0215 (3)
C290.48094 (11)0.73270 (12)0.31818 (9)0.0156 (3)
C2S0.73890 (17)0.71369 (15)0.45964 (11)0.0301 (4)
C30.17666 (12)0.25851 (12)0.47867 (10)0.0185 (3)
C300.41959 (12)0.74442 (13)0.38379 (10)0.0197 (3)
C310.45818 (12)0.81936 (13)0.46308 (10)0.0207 (3)
C320.55868 (12)0.88548 (12)0.47866 (9)0.0173 (3)
C330.60658 (13)0.96354 (13)0.55986 (10)0.0211 (3)
C340.70476 (13)1.02150 (12)0.57177 (9)0.0202 (3)
C350.76390 (12)1.00678 (12)0.50304 (9)0.0167 (3)
C360.86818 (12)1.06060 (12)0.51247 (10)0.0196 (3)
C370.91908 (12)1.03938 (12)0.44358 (10)0.0197 (3)
C380.86685 (11)0.96654 (12)0.36375 (10)0.0170 (3)
C390.71787 (11)0.93400 (11)0.42207 (9)0.0141 (3)
C40.07471 (12)0.32137 (12)0.49521 (9)0.0159 (3)
C400.61406 (11)0.87087 (11)0.40982 (9)0.0140 (3)
C410.44300 (12)0.64627 (13)0.23280 (10)0.0209 (3)
C420.92144 (12)0.94280 (13)0.28771 (10)0.0213 (3)
C430.57007 (11)0.90498 (12)0.14463 (10)0.0171 (3)
C440.55138 (12)0.92158 (12)0.07061 (10)0.0205 (3)
C450.58302 (11)0.86402 (13)0.00244 (10)0.0194 (3)
C460.63400 (11)0.78789 (12)0.00256 (9)0.0156 (3)
C470.66669 (11)0.72132 (13)0.07656 (9)0.0189 (3)
C480.71859 (11)0.65206 (12)0.07242 (9)0.0183 (3)
C490.74262 (11)0.64366 (11)0.00575 (9)0.0149 (3)
C50.02428 (13)0.39214 (12)0.57785 (9)0.0191 (3)
C500.80055 (11)0.57673 (12)0.01424 (9)0.0177 (3)
C510.81996 (12)0.57407 (12)0.09145 (10)0.0188 (3)
C520.78010 (11)0.63548 (12)0.16128 (9)0.0156 (3)
C530.70873 (10)0.70556 (11)0.07859 (9)0.0128 (3)
C540.65335 (10)0.77895 (11)0.07434 (9)0.0131 (3)
C550.52859 (13)0.96034 (13)0.22321 (10)0.0232 (3)
C560.79633 (13)0.62968 (14)0.24541 (10)0.0232 (3)
C570.30835 (12)0.76635 (13)0.03050 (10)0.0197 (3)
C580.35327 (11)0.68677 (12)0.02729 (9)0.0167 (3)
C590.39316 (11)0.63723 (11)0.04593 (9)0.0146 (3)
C60.07193 (13)0.45518 (12)0.58913 (9)0.0188 (3)
C600.38425 (11)0.66947 (12)0.11216 (9)0.0171 (3)
C610.33947 (12)0.75172 (13)0.10185 (10)0.0205 (3)
C620.44654 (11)0.55590 (11)0.05365 (9)0.0151 (3)
C70.12588 (12)0.45358 (11)0.51905 (9)0.0154 (3)
C80.22439 (12)0.51994 (12)0.52706 (9)0.0182 (3)
C90.26995 (12)0.51343 (12)0.45611 (10)0.0185 (3)
F10.11599 (11)0.67094 (12)0.12319 (7)0.0497 (3)
F100.46927 (10)0.20364 (10)0.21930 (7)0.0434 (3)
F110.38836 (9)0.28045 (13)0.32952 (9)0.0525 (4)
F12A0.5011 (5)0.3794 (3)0.2814 (4)0.0366 (9)0.75 (2)
F12B0.5445 (19)0.3864 (6)0.3063 (9)0.049 (4)0.25 (2)
F20.18105 (10)0.58991 (9)0.19443 (9)0.0434 (3)
F30.03416 (8)0.63257 (10)0.22346 (8)0.0383 (3)
F40.17798 (9)0.72217 (10)0.31647 (7)0.0387 (3)
F50.11236 (10)0.80434 (10)0.24575 (11)0.0530 (4)
F60.25889 (8)0.76293 (10)0.21720 (7)0.0339 (2)
F7A0.5081 (8)0.1951 (4)0.34637 (19)0.0539 (16)0.75 (2)
F7B0.4533 (15)0.1703 (9)0.3293 (9)0.039 (3)0.25 (2)
F80.53765 (10)0.36878 (12)0.40928 (8)0.0515 (4)
F90.61847 (10)0.29397 (16)0.29918 (8)0.0684 (5)
H13A0.15790.13280.20370.032*
H13B0.26920.13570.22870.032*
H13C0.22160.04500.23500.032*
H14A0.24780.35970.25820.031*
H14B0.33810.46420.31120.031*
H14C0.23630.47550.27170.031*
H160.08060.33020.01670.026*
H170.00990.20990.08050.026*
H190.09120.07130.10940.026*
H1S10.62100.64890.50810.058*
H1S20.63110.57260.41500.058*
H1S30.58700.67260.42930.058*
H20.28900.15550.38570.023*
H200.18090.01580.05880.027*
H220.24830.04860.06560.027*
H230.25630.01300.20830.027*
H27A0.10330.35050.22510.036*
H27B0.13670.39120.15600.036*
H27C0.02740.44820.21180.036*
H28A0.24430.15940.35560.032*
H28B0.15770.05070.33740.032*
H28C0.12710.15870.35250.032*
H30.21530.25970.52360.022*
H300.35170.70030.37290.024*
H310.41740.82670.50740.025*
H330.56880.97480.60610.025*
H340.73501.07260.62630.024*
H360.90261.11090.56600.023*
H370.98961.07370.44950.024*
H41A0.47980.66660.19100.031*
H41B0.37010.63600.21940.031*
H41C0.45430.57960.23200.031*
H42A0.87280.89410.23780.032*
H42B0.97420.90940.29480.032*
H42C0.95291.00950.28090.032*
H440.51670.97280.07130.025*
H450.57080.87530.05230.023*
H470.65180.72580.12890.023*
H480.73940.60840.12210.022*
H50.05870.39490.62520.023*
H500.82580.53400.03310.021*
H510.86040.53070.09810.023*
H55A0.46320.91390.22560.035*
H55B0.51871.02720.22300.035*
H55C0.57670.97610.27240.035*
H56A0.78400.69240.28910.035*
H56B0.86650.62820.25650.035*
H56C0.74910.56470.24550.035*
H570.28040.79880.08000.024*
H580.35690.66630.07370.020*
H60.10410.50120.64440.023*
H600.40830.63590.16360.021*
H610.33550.77440.14700.025*
H620.46090.51450.10730.018*
H80.25910.56870.58090.022*
H90.33650.55790.46090.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01688 (9)0.01713 (9)0.00910 (8)0.00648 (7)0.00428 (6)0.00368 (7)
Cu20.01462 (9)0.01850 (9)0.01005 (9)0.00674 (7)0.00388 (6)0.00430 (7)
P10.01722 (18)0.02216 (19)0.01451 (17)0.00739 (15)0.00397 (14)0.00854 (15)
P20.02061 (19)0.0224 (2)0.01578 (18)0.00520 (15)0.00000 (14)0.00431 (15)
F10.0495 (8)0.0757 (10)0.0240 (6)0.0053 (7)0.0058 (5)0.0280 (6)
F20.0403 (7)0.0274 (6)0.0558 (8)0.0175 (5)0.0049 (6)0.0046 (5)
F30.0192 (5)0.0476 (7)0.0425 (7)0.0026 (5)0.0028 (5)0.0192 (6)
F40.0393 (6)0.0494 (7)0.0169 (5)0.0075 (5)0.0002 (4)0.0141 (5)
F50.0420 (7)0.0344 (7)0.0864 (11)0.0236 (6)0.0085 (7)0.0195 (7)
F60.0234 (5)0.0464 (7)0.0352 (6)0.0034 (5)0.0101 (4)0.0229 (5)
F7A0.108 (5)0.0401 (15)0.0277 (11)0.035 (2)0.0120 (17)0.0201 (10)
F7B0.066 (7)0.028 (3)0.035 (4)0.020 (4)0.022 (4)0.021 (3)
F80.0328 (6)0.0671 (9)0.0241 (6)0.0060 (6)0.0034 (5)0.0111 (6)
F90.0322 (7)0.1269 (15)0.0295 (7)0.0413 (8)0.0034 (5)0.0000 (8)
F100.0500 (7)0.0441 (7)0.0173 (5)0.0086 (6)0.0035 (5)0.0053 (5)
F110.0235 (6)0.0868 (11)0.0443 (7)0.0044 (6)0.0087 (5)0.0287 (7)
F12A0.0495 (19)0.0369 (11)0.0416 (17)0.0243 (12)0.0245 (14)0.0264 (12)
F12B0.074 (9)0.023 (3)0.043 (5)0.004 (4)0.023 (6)0.014 (3)
N10.0154 (6)0.0147 (5)0.0123 (5)0.0063 (4)0.0039 (4)0.0056 (5)
N20.0151 (6)0.0152 (5)0.0123 (5)0.0072 (4)0.0035 (4)0.0057 (4)
N30.0140 (5)0.0150 (5)0.0127 (5)0.0030 (4)0.0028 (4)0.0055 (5)
N40.0133 (5)0.0134 (5)0.0135 (6)0.0030 (4)0.0037 (4)0.0045 (4)
N50.0147 (6)0.0164 (6)0.0130 (5)0.0076 (5)0.0037 (4)0.0063 (5)
N60.0155 (6)0.0151 (6)0.0136 (5)0.0067 (5)0.0026 (4)0.0059 (5)
N70.0121 (5)0.0139 (5)0.0145 (6)0.0033 (4)0.0017 (4)0.0052 (5)
N80.0121 (5)0.0157 (6)0.0118 (5)0.0040 (4)0.0031 (4)0.0046 (4)
N90.0196 (6)0.0253 (7)0.0256 (7)0.0122 (5)0.0063 (5)0.0129 (6)
N100.0150 (6)0.0130 (5)0.0195 (6)0.0072 (5)0.0054 (5)0.0058 (5)
C10.0170 (7)0.0156 (6)0.0164 (7)0.0064 (5)0.0044 (5)0.0068 (5)
C20.0160 (7)0.0208 (7)0.0231 (7)0.0072 (6)0.0077 (6)0.0108 (6)
C30.0222 (7)0.0216 (7)0.0191 (7)0.0121 (6)0.0118 (6)0.0117 (6)
C40.0214 (7)0.0169 (7)0.0153 (7)0.0113 (6)0.0080 (5)0.0087 (5)
C50.0293 (8)0.0211 (7)0.0128 (7)0.0144 (6)0.0092 (6)0.0080 (6)
C60.0291 (8)0.0190 (7)0.0098 (6)0.0117 (6)0.0033 (6)0.0041 (5)
C70.0214 (7)0.0149 (6)0.0123 (6)0.0097 (5)0.0024 (5)0.0052 (5)
C80.0225 (7)0.0163 (7)0.0140 (7)0.0070 (6)0.0016 (5)0.0030 (5)
C90.0173 (7)0.0178 (7)0.0203 (7)0.0050 (5)0.0009 (6)0.0072 (6)
C100.0172 (7)0.0167 (7)0.0161 (7)0.0078 (5)0.0042 (5)0.0073 (5)
C110.0165 (6)0.0139 (6)0.0115 (6)0.0084 (5)0.0033 (5)0.0057 (5)
C120.0179 (7)0.0141 (6)0.0117 (6)0.0091 (5)0.0043 (5)0.0057 (5)
C130.0182 (7)0.0225 (7)0.0185 (7)0.0018 (6)0.0014 (6)0.0056 (6)
C140.0178 (7)0.0244 (8)0.0182 (7)0.0036 (6)0.0058 (6)0.0082 (6)
C150.0169 (7)0.0179 (7)0.0175 (7)0.0030 (5)0.0010 (5)0.0077 (6)
C160.0194 (7)0.0258 (8)0.0200 (7)0.0019 (6)0.0011 (6)0.0131 (6)
C170.0188 (7)0.0288 (8)0.0137 (7)0.0022 (6)0.0004 (5)0.0107 (6)
C180.0150 (7)0.0202 (7)0.0116 (6)0.0028 (5)0.0019 (5)0.0049 (5)
C190.0198 (7)0.0243 (8)0.0105 (6)0.0036 (6)0.0052 (5)0.0011 (6)
C200.0198 (7)0.0197 (7)0.0162 (7)0.0006 (6)0.0089 (6)0.0014 (6)
C210.0151 (7)0.0130 (6)0.0174 (7)0.0009 (5)0.0064 (5)0.0010 (5)
C220.0206 (7)0.0158 (7)0.0281 (8)0.0069 (6)0.0104 (6)0.0043 (6)
C230.0212 (7)0.0200 (7)0.0304 (8)0.0098 (6)0.0069 (6)0.0105 (7)
C240.0149 (7)0.0166 (7)0.0202 (7)0.0035 (5)0.0032 (5)0.0076 (6)
C250.0126 (6)0.0127 (6)0.0124 (6)0.0003 (5)0.0040 (5)0.0030 (5)
C260.0126 (6)0.0144 (6)0.0116 (6)0.0008 (5)0.0024 (5)0.0034 (5)
C270.0296 (8)0.0230 (8)0.0225 (8)0.0139 (7)0.0024 (6)0.0083 (6)
C280.0202 (7)0.0276 (8)0.0209 (7)0.0088 (6)0.0030 (6)0.0129 (6)
C290.0151 (6)0.0194 (7)0.0154 (6)0.0083 (5)0.0044 (5)0.0077 (5)
C300.0164 (7)0.0241 (7)0.0220 (7)0.0086 (6)0.0083 (6)0.0104 (6)
C310.0236 (8)0.0255 (8)0.0183 (7)0.0131 (6)0.0120 (6)0.0097 (6)
C320.0231 (7)0.0193 (7)0.0151 (7)0.0127 (6)0.0078 (6)0.0082 (6)
C330.0317 (8)0.0224 (7)0.0134 (7)0.0151 (6)0.0087 (6)0.0064 (6)
C340.0322 (8)0.0177 (7)0.0116 (6)0.0126 (6)0.0021 (6)0.0032 (5)
C350.0235 (7)0.0146 (6)0.0140 (6)0.0095 (6)0.0010 (5)0.0052 (5)
C360.0239 (8)0.0163 (7)0.0167 (7)0.0064 (6)0.0044 (6)0.0044 (6)
C370.0170 (7)0.0182 (7)0.0235 (8)0.0051 (6)0.0027 (6)0.0080 (6)
C380.0172 (7)0.0174 (7)0.0190 (7)0.0078 (5)0.0023 (5)0.0082 (6)
C390.0183 (7)0.0140 (6)0.0132 (6)0.0089 (5)0.0029 (5)0.0061 (5)
C400.0180 (7)0.0157 (6)0.0124 (6)0.0099 (5)0.0039 (5)0.0066 (5)
C410.0164 (7)0.0256 (8)0.0171 (7)0.0041 (6)0.0034 (5)0.0052 (6)
C420.0161 (7)0.0240 (8)0.0218 (7)0.0043 (6)0.0046 (6)0.0074 (6)
C430.0146 (6)0.0153 (6)0.0205 (7)0.0038 (5)0.0017 (5)0.0063 (6)
C440.0176 (7)0.0193 (7)0.0271 (8)0.0048 (6)0.0002 (6)0.0122 (6)
C450.0166 (7)0.0231 (7)0.0207 (7)0.0009 (6)0.0015 (6)0.0141 (6)
C460.0124 (6)0.0175 (7)0.0154 (7)0.0004 (5)0.0007 (5)0.0076 (5)
C470.0165 (7)0.0251 (7)0.0129 (6)0.0001 (6)0.0014 (5)0.0089 (6)
C480.0175 (7)0.0211 (7)0.0117 (6)0.0008 (6)0.0045 (5)0.0040 (5)
C490.0125 (6)0.0159 (6)0.0134 (6)0.0008 (5)0.0040 (5)0.0042 (5)
C500.0161 (7)0.0165 (7)0.0175 (7)0.0046 (5)0.0070 (5)0.0031 (5)
C510.0175 (7)0.0187 (7)0.0219 (7)0.0087 (6)0.0066 (6)0.0074 (6)
C520.0146 (6)0.0175 (7)0.0161 (7)0.0060 (5)0.0038 (5)0.0068 (5)
C530.0106 (6)0.0133 (6)0.0130 (6)0.0012 (5)0.0024 (5)0.0046 (5)
C540.0102 (6)0.0140 (6)0.0139 (6)0.0013 (5)0.0017 (5)0.0054 (5)
C550.0253 (8)0.0229 (8)0.0238 (8)0.0142 (6)0.0060 (6)0.0067 (6)
C560.0290 (8)0.0306 (8)0.0181 (7)0.0175 (7)0.0061 (6)0.0124 (6)
C570.0186 (7)0.0217 (7)0.0220 (7)0.0101 (6)0.0080 (6)0.0089 (6)
C580.0166 (7)0.0176 (7)0.0185 (7)0.0059 (5)0.0054 (5)0.0089 (6)
C590.0118 (6)0.0145 (6)0.0184 (7)0.0045 (5)0.0031 (5)0.0068 (5)
C600.0154 (7)0.0209 (7)0.0168 (7)0.0072 (6)0.0041 (5)0.0078 (6)
C610.0188 (7)0.0271 (8)0.0215 (7)0.0101 (6)0.0037 (6)0.0137 (6)
C620.0141 (6)0.0139 (6)0.0173 (7)0.0050 (5)0.0048 (5)0.0052 (5)
N1S0.0539 (11)0.0338 (9)0.0251 (8)0.0236 (8)0.0044 (7)0.0103 (7)
C1S0.0518 (13)0.0373 (11)0.0402 (11)0.0254 (10)0.0103 (9)0.0215 (9)
C2S0.0539 (12)0.0284 (9)0.0170 (8)0.0271 (9)0.0060 (7)0.0086 (7)
Geometric parameters (Å, º) top
Cu1—N12.0402 (12)C21—C221.409 (2)
Cu1—N22.0350 (12)C22—C231.367 (2)
Cu1—N32.0182 (12)C22—H220.9500
Cu1—N42.0591 (12)C23—C241.414 (2)
Cu2—N52.0259 (12)C23—H230.9500
Cu2—N62.0587 (12)C24—C281.496 (2)
Cu2—N72.0602 (12)C25—C261.435 (2)
Cu2—N82.0261 (12)C27—H27A0.9800
P1—F11.5865 (12)C27—H27B0.9800
P1—F51.5893 (12)C27—H27C0.9800
P1—F31.5916 (11)C28—H28A0.9800
P1—F21.5993 (12)C28—H28B0.9800
P1—F41.6002 (11)C28—H28C0.9800
P1—F61.6035 (11)C29—C301.415 (2)
P2—F12B1.465 (9)C29—C411.495 (2)
P2—F7A1.558 (3)C30—C311.371 (2)
P2—F111.5814 (13)C30—H300.9500
P2—F81.5908 (12)C31—C321.410 (2)
P2—F101.5937 (11)C31—H310.9500
P2—F91.5966 (13)C32—C401.4073 (19)
P2—F12A1.639 (3)C32—C331.432 (2)
P2—F7B1.692 (8)C33—C341.353 (2)
N1—C11.3332 (19)C33—H330.9500
N1—C121.3664 (18)C34—C351.437 (2)
N2—C101.3330 (19)C34—H340.9500
N2—C111.3618 (18)C35—C391.404 (2)
N3—C151.3347 (19)C35—C361.413 (2)
N3—C261.3647 (18)C36—C371.371 (2)
N4—C241.3338 (19)C36—H360.9500
N4—C251.3649 (18)C37—C381.413 (2)
N5—C291.3328 (19)C37—H370.9500
N5—C401.3658 (18)C38—C421.500 (2)
N6—C381.3342 (19)C39—C401.439 (2)
N6—C391.3674 (18)C41—H41A0.9800
N7—C431.3354 (19)C41—H41B0.9800
N7—C541.3638 (18)C41—H41C0.9800
N8—C521.3346 (18)C42—H42A0.9800
N8—C531.3661 (18)C42—H42B0.9800
N9—C611.337 (2)C42—H42C0.9800
N9—C571.347 (2)C43—C441.410 (2)
N10—C621.279 (2)C43—C551.500 (2)
N10—N10i1.415 (2)C44—C451.371 (2)
C1—C21.412 (2)C44—H440.9500
C1—C131.500 (2)C45—C461.411 (2)
C2—C31.369 (2)C45—H450.9500
C2—H20.9500C46—C541.4044 (19)
C3—C41.410 (2)C46—C471.435 (2)
C3—H30.9500C47—C481.356 (2)
C4—C121.4079 (19)C47—H470.9500
C4—C51.434 (2)C48—C491.435 (2)
C5—C61.355 (2)C48—H480.9500
C5—H50.9500C49—C531.4052 (19)
C6—C71.433 (2)C49—C501.411 (2)
C6—H60.9500C50—C511.369 (2)
C7—C111.4049 (19)C50—H500.9500
C7—C81.406 (2)C51—C521.412 (2)
C8—C91.375 (2)C51—H510.9500
C8—H80.9500C52—C561.500 (2)
C9—C101.408 (2)C53—C541.4401 (19)
C9—H90.9500C55—H55A0.9800
C10—C141.500 (2)C55—H55B0.9800
C11—C121.438 (2)C55—H55C0.9800
C13—H13A0.9800C56—H56A0.9800
C13—H13B0.9800C56—H56B0.9800
C13—H13C0.9800C56—H56C0.9800
C14—H14A0.9800C57—C581.385 (2)
C14—H14B0.9800C57—H570.9500
C14—H14C0.9800C58—C591.399 (2)
C15—C161.406 (2)C58—H580.9500
C15—C271.498 (2)C59—C601.390 (2)
C16—C171.370 (2)C59—C621.4673 (19)
C16—H160.9500C60—C611.392 (2)
C17—C181.409 (2)C60—H600.9500
C17—H170.9500C61—H610.9500
C18—C261.4072 (19)C62—H620.9500
C18—C191.434 (2)N1S—C2S1.141 (3)
C19—C201.351 (3)C1S—C2S1.461 (3)
C19—H190.9500C1S—H1S10.9800
C20—C211.432 (2)C1S—H1S20.9800
C20—H200.9500C1S—H1S30.9800
C21—C251.4060 (19)
N1—Cu1—N282.42 (5)C23—C22—C21119.37 (14)
N1—Cu1—N3127.02 (5)C23—C22—H22120.3
N1—Cu1—N4128.14 (5)C21—C22—H22120.3
N2—Cu1—N3128.70 (5)C22—C23—C24120.18 (15)
N2—Cu1—N4113.29 (5)C22—C23—H23119.9
N3—Cu1—N482.54 (5)C24—C23—H23119.9
N5—Cu2—N682.24 (5)N4—C24—C23121.45 (14)
N5—Cu2—N7117.54 (5)N4—C24—C28118.14 (13)
N5—Cu2—N8134.81 (5)C23—C24—C28120.40 (14)
N6—Cu2—N7125.71 (5)N4—C25—C21122.92 (14)
N6—Cu2—N8120.45 (5)N4—C25—C26117.53 (12)
N7—Cu2—N882.30 (5)C21—C25—C26119.55 (13)
F1—P1—F590.67 (9)N3—C26—C18122.81 (14)
F1—P1—F390.08 (7)N3—C26—C25117.20 (12)
F5—P1—F390.64 (7)C18—C26—C25120.00 (13)
F1—P1—F289.95 (8)C15—C27—H27A109.5
F5—P1—F2179.24 (8)C15—C27—H27B109.5
F3—P1—F289.80 (7)H27A—C27—H27B109.5
F1—P1—F4178.84 (8)C15—C27—H27C109.5
F5—P1—F490.34 (8)H27A—C27—H27C109.5
F3—P1—F490.47 (6)H27B—C27—H27C109.5
F2—P1—F489.04 (7)C24—C28—H28A109.5
F1—P1—F690.65 (7)C24—C28—H28B109.5
F5—P1—F689.07 (7)H28A—C28—H28B109.5
F3—P1—F6179.22 (7)C24—C28—H28C109.5
F2—P1—F690.49 (7)H28A—C28—H28C109.5
F4—P1—F688.81 (6)H28B—C28—H28C109.5
F12B—P2—F7A153.7 (8)N5—C29—C30121.32 (14)
F12B—P2—F11105.2 (10)N5—C29—C41117.76 (13)
F7A—P2—F1195.4 (4)C30—C29—C41120.87 (14)
F12B—P2—F876.2 (6)C31—C30—C29120.01 (14)
F7A—P2—F888.21 (19)C31—C30—H30120.0
F11—P2—F888.85 (7)C29—C30—H30120.0
F12B—P2—F10101.8 (6)C30—C31—C32119.73 (14)
F7A—P2—F1093.62 (18)C30—C31—H31120.1
F11—P2—F1091.82 (7)C32—C31—H31120.1
F8—P2—F10177.99 (8)C40—C32—C31116.94 (14)
F12B—P2—F972.0 (10)C40—C32—C33119.33 (14)
F7A—P2—F987.4 (4)C31—C32—C33123.71 (14)
F11—P2—F9177.18 (10)C34—C33—C32121.10 (14)
F8—P2—F990.87 (7)C34—C33—H33119.5
F10—P2—F988.36 (7)C32—C33—H33119.5
F7A—P2—F12A178.0 (3)C33—C34—C35120.84 (14)
F11—P2—F12A86.56 (17)C33—C34—H34119.6
F8—P2—F12A91.7 (2)C35—C34—H34119.6
F10—P2—F12A86.4 (2)C39—C35—C36117.21 (14)
F9—P2—F12A90.64 (18)C39—C35—C34119.38 (14)
F12B—P2—F7B177.4 (4)C36—C35—C34123.39 (14)
F11—P2—F7B73.5 (5)C37—C36—C35119.28 (14)
F8—P2—F7B101.5 (5)C37—C36—H36120.4
F10—P2—F7B80.5 (5)C35—C36—H36120.4
F9—P2—F7B109.3 (5)C36—C37—C38120.13 (15)
F12A—P2—F7B155.7 (5)C36—C37—H37119.9
C1—N1—C12118.40 (12)C38—C37—H37119.9
C1—N1—Cu1130.64 (10)N6—C38—C37121.70 (14)
C12—N1—Cu1110.96 (9)N6—C38—C42117.55 (13)
C10—N2—C11118.74 (12)C37—C38—C42120.75 (14)
C10—N2—Cu1129.68 (10)N6—C39—C35123.26 (14)
C11—N2—Cu1111.23 (9)N6—C39—C40117.05 (13)
C15—N3—C26118.61 (13)C35—C39—C40119.65 (13)
C15—N3—Cu1129.28 (10)N5—C40—C32123.09 (14)
C26—N3—Cu1112.11 (9)N5—C40—C39117.23 (12)
C24—N4—C25118.68 (12)C32—C40—C39119.62 (13)
C24—N4—Cu1130.60 (10)C29—C41—H41A109.5
C25—N4—Cu1110.60 (9)C29—C41—H41B109.5
C29—N5—C40118.88 (12)H41A—C41—H41B109.5
C29—N5—Cu2129.05 (10)C29—C41—H41C109.5
C40—N5—Cu2111.85 (10)H41A—C41—H41C109.5
C38—N6—C39118.34 (13)H41B—C41—H41C109.5
C38—N6—Cu2130.65 (10)C38—C42—H42A109.5
C39—N6—Cu2110.96 (10)C38—C42—H42B109.5
C43—N7—C54118.36 (13)H42A—C42—H42B109.5
C43—N7—Cu2130.50 (10)C38—C42—H42C109.5
C54—N7—Cu2111.12 (9)H42A—C42—H42C109.5
C52—N8—C53118.62 (12)H42B—C42—H42C109.5
C52—N8—Cu2129.14 (10)N7—C43—C44121.54 (14)
C53—N8—Cu2111.99 (9)N7—C43—C55117.37 (13)
C61—N9—C57116.57 (13)C44—C43—C55121.07 (14)
C62—N10—N10i111.19 (15)C45—C44—C43120.28 (14)
N1—C1—C2121.62 (14)C45—C44—H44119.9
N1—C1—C13117.86 (13)C43—C44—H44119.9
C2—C1—C13120.52 (14)C44—C45—C46119.16 (14)
C3—C2—C1120.15 (14)C44—C45—H45120.4
C3—C2—H2119.9C46—C45—H45120.4
C1—C2—H2119.9C54—C46—C45117.20 (14)
C2—C3—C4119.53 (13)C54—C46—C47119.66 (14)
C2—C3—H3120.2C45—C46—C47123.14 (14)
C4—C3—H3120.2C48—C47—C46120.61 (14)
C12—C4—C3116.93 (14)C48—C47—H47119.7
C12—C4—C5119.45 (14)C46—C47—H47119.7
C3—C4—C5123.61 (13)C47—C48—C49121.08 (14)
C6—C5—C4120.75 (14)C47—C48—H48119.5
C6—C5—H5119.6C49—C48—H48119.5
C4—C5—H5119.6C53—C49—C50117.28 (13)
C5—C6—C7121.12 (14)C53—C49—C48119.39 (13)
C5—C6—H6119.4C50—C49—C48123.32 (13)
C7—C6—H6119.4C51—C50—C49119.27 (13)
C11—C7—C8117.29 (13)C51—C50—H50120.4
C11—C7—C6119.34 (14)C49—C50—H50120.4
C8—C7—C6123.38 (14)C50—C51—C52120.31 (14)
C9—C8—C7119.31 (14)C50—C51—H51119.8
C9—C8—H8120.3C52—C51—H51119.8
C7—C8—H8120.3N8—C52—C51121.41 (13)
C8—C9—C10120.08 (14)N8—C52—C56117.47 (13)
C8—C9—H9120.0C51—C52—C56121.12 (13)
C10—C9—H9120.0N8—C53—C49123.03 (13)
N2—C10—C9121.52 (13)N8—C53—C54117.35 (12)
N2—C10—C14117.02 (13)C49—C53—C54119.62 (13)
C9—C10—C14121.44 (14)N7—C54—C46123.32 (13)
N2—C11—C7123.06 (13)N7—C54—C53117.10 (12)
N2—C11—C12117.20 (12)C46—C54—C53119.58 (13)
C7—C11—C12119.72 (13)C43—C55—H55A109.5
N1—C12—C4123.25 (14)C43—C55—H55B109.5
N1—C12—C11117.19 (12)H55A—C55—H55B109.5
C4—C12—C11119.54 (13)C43—C55—H55C109.5
C1—C13—H13A109.5H55A—C55—H55C109.5
C1—C13—H13B109.5H55B—C55—H55C109.5
H13A—C13—H13B109.5C52—C56—H56A109.5
C1—C13—H13C109.5C52—C56—H56B109.5
H13A—C13—H13C109.5H56A—C56—H56B109.5
H13B—C13—H13C109.5C52—C56—H56C109.5
C10—C14—H14A109.5H56A—C56—H56C109.5
C10—C14—H14B109.5H56B—C56—H56C109.5
H14A—C14—H14B109.5N9—C57—C58124.20 (14)
C10—C14—H14C109.5N9—C57—H57117.9
H14A—C14—H14C109.5C58—C57—H57117.9
H14B—C14—H14C109.5C57—C58—C59118.35 (14)
N3—C15—C16121.74 (14)C57—C58—H58120.8
N3—C15—C27116.65 (13)C59—C58—H58120.8
C16—C15—C27121.61 (14)C60—C59—C58118.18 (13)
C17—C16—C15120.11 (15)C60—C59—C62119.51 (13)
C17—C16—H16119.9C58—C59—C62122.27 (13)
C15—C16—H16119.9C59—C60—C61118.88 (14)
C16—C17—C18119.39 (14)C59—C60—H60120.6
C16—C17—H17120.3C61—C60—H60120.6
C18—C17—H17120.3N9—C61—C60123.77 (14)
C26—C18—C17117.35 (14)N9—C61—H61118.1
C26—C18—C19118.94 (14)C60—C61—H61118.1
C17—C18—C19123.72 (14)N10—C62—C59120.86 (13)
C20—C19—C18121.08 (14)N10—C62—H62119.6
C20—C19—H19119.5C59—C62—H62119.6
C18—C19—H19119.5C2S—C1S—H1S1109.5
C19—C20—C21121.15 (14)C2S—C1S—H1S2109.5
C19—C20—H20119.4H1S1—C1S—H1S2109.5
C21—C20—H20119.4C2S—C1S—H1S3109.5
C25—C21—C22117.37 (14)H1S1—C1S—H1S3109.5
C25—C21—C20119.24 (14)H1S2—C1S—H1S3109.5
C22—C21—C20123.38 (14)N1S—C2S—C1S179.7 (2)
N3—Cu1—N1—C138.97 (15)C24—N4—C25—C26177.92 (13)
N2—Cu1—N1—C1172.56 (13)Cu1—N4—C25—C261.48 (15)
N4—Cu1—N1—C173.69 (14)C22—C21—C25—N41.5 (2)
N3—Cu1—N1—C12141.76 (9)C20—C21—C25—N4177.88 (13)
N2—Cu1—N1—C128.16 (9)C22—C21—C25—C26178.46 (13)
N4—Cu1—N1—C12105.59 (10)C20—C21—C25—C262.1 (2)
N3—Cu1—N2—C1045.98 (14)C15—N3—C26—C180.5 (2)
N1—Cu1—N2—C10178.17 (13)Cu1—N3—C26—C18179.62 (11)
N4—Cu1—N2—C1053.44 (13)C15—N3—C26—C25179.35 (13)
N3—Cu1—N2—C11141.01 (9)Cu1—N3—C26—C250.52 (15)
N1—Cu1—N2—C118.82 (9)C17—C18—C26—N30.5 (2)
N4—Cu1—N2—C11119.57 (9)C19—C18—C26—N3179.58 (13)
N2—Cu1—N3—C1566.13 (14)C17—C18—C26—C25179.35 (13)
N1—Cu1—N3—C1546.98 (15)C19—C18—C26—C250.6 (2)
N4—Cu1—N3—C15179.92 (13)N4—C25—C26—N31.40 (19)
N2—Cu1—N3—C26113.73 (10)C21—C25—C26—N3178.59 (12)
N1—Cu1—N3—C26133.16 (9)N4—C25—C26—C18178.74 (12)
N4—Cu1—N3—C260.22 (9)C21—C25—C26—C181.3 (2)
N3—Cu1—N4—C24176.80 (13)C40—N5—C29—C301.4 (2)
N2—Cu1—N4—C2447.74 (14)Cu2—N5—C29—C30172.65 (11)
N1—Cu1—N4—C2451.20 (15)C40—N5—C29—C41176.17 (13)
N3—Cu1—N4—C250.92 (9)Cu2—N5—C29—C419.80 (19)
N2—Cu1—N4—C25128.14 (9)N5—C29—C30—C311.9 (2)
N1—Cu1—N4—C25132.92 (9)C41—C29—C30—C31175.53 (15)
N8—Cu2—N5—C2952.44 (15)C29—C30—C31—C320.8 (2)
N6—Cu2—N5—C29178.28 (13)C30—C31—C32—C400.8 (2)
N7—Cu2—N5—C2955.32 (13)C30—C31—C32—C33177.92 (15)
N8—Cu2—N5—C40133.19 (9)C40—C32—C33—C341.6 (2)
N6—Cu2—N5—C407.35 (9)C31—C32—C33—C34177.07 (15)
N7—Cu2—N5—C40119.05 (9)C32—C33—C34—C350.3 (2)
N5—Cu2—N6—C38171.54 (13)C33—C34—C35—C392.3 (2)
N8—Cu2—N6—C3833.39 (14)C33—C34—C35—C36176.38 (14)
N7—Cu2—N6—C3869.98 (14)C39—C35—C36—C370.4 (2)
N5—Cu2—N6—C396.00 (9)C34—C35—C36—C37178.32 (14)
N8—Cu2—N6—C39144.15 (9)C35—C36—C37—C381.7 (2)
N7—Cu2—N6—C39112.48 (10)C39—N6—C38—C371.9 (2)
N5—Cu2—N7—C4341.70 (14)Cu2—N6—C38—C37179.33 (10)
N8—Cu2—N7—C43178.71 (13)C39—N6—C38—C42177.79 (13)
N6—Cu2—N7—C4359.11 (14)Cu2—N6—C38—C420.4 (2)
N5—Cu2—N7—C54140.11 (9)C36—C37—C38—N60.5 (2)
N8—Cu2—N7—C543.10 (9)C36—C37—C38—C42179.77 (14)
N6—Cu2—N7—C54119.09 (9)C38—N6—C39—C353.3 (2)
N5—Cu2—N8—C5261.07 (15)Cu2—N6—C39—C35178.78 (11)
N6—Cu2—N8—C5250.22 (14)C38—N6—C39—C40174.15 (12)
N7—Cu2—N8—C52177.36 (13)Cu2—N6—C39—C403.74 (15)
N5—Cu2—N8—C53124.79 (10)C36—C35—C39—N62.2 (2)
N6—Cu2—N8—C53123.92 (9)C34—C35—C39—N6179.08 (13)
N7—Cu2—N8—C533.22 (9)C36—C35—C39—C40175.24 (13)
C12—N1—C1—C21.6 (2)C34—C35—C39—C403.5 (2)
Cu1—N1—C1—C2177.63 (11)C29—N5—C40—C320.3 (2)
C12—N1—C1—C13178.46 (13)Cu2—N5—C40—C32175.29 (11)
Cu1—N1—C1—C132.3 (2)C29—N5—C40—C39177.42 (12)
N1—C1—C2—C31.6 (2)Cu2—N5—C40—C397.57 (15)
C13—C1—C2—C3178.33 (14)C31—C32—C40—N51.4 (2)
C1—C2—C3—C42.6 (2)C33—C32—C40—N5177.40 (13)
C2—C3—C4—C120.5 (2)C31—C32—C40—C39178.43 (13)
C2—C3—C4—C5177.89 (14)C33—C32—C40—C390.3 (2)
C12—C4—C5—C62.3 (2)N6—C39—C40—N52.56 (18)
C3—C4—C5—C6176.05 (14)C35—C39—C40—N5175.02 (12)
C4—C5—C6—C70.4 (2)N6—C39—C40—C32179.80 (12)
C5—C6—C7—C112.2 (2)C35—C39—C40—C322.2 (2)
C5—C6—C7—C8177.75 (14)C54—N7—C43—C444.0 (2)
C11—C7—C8—C90.4 (2)Cu2—N7—C43—C44174.06 (11)
C6—C7—C8—C9179.49 (14)C54—N7—C43—C55174.17 (13)
C7—C8—C9—C100.0 (2)Cu2—N7—C43—C557.7 (2)
C11—N2—C10—C90.8 (2)N7—C43—C44—C453.3 (2)
Cu1—N2—C10—C9171.80 (11)C55—C43—C44—C45174.85 (15)
C11—N2—C10—C14177.78 (13)C43—C44—C45—C460.3 (2)
Cu1—N2—C10—C149.65 (19)C44—C45—C46—C542.7 (2)
C8—C9—C10—N20.7 (2)C44—C45—C46—C47177.73 (14)
C8—C9—C10—C14177.81 (14)C54—C46—C47—C481.9 (2)
C10—N2—C11—C70.3 (2)C45—C46—C47—C48177.67 (14)
Cu1—N2—C11—C7173.61 (11)C46—C47—C48—C490.3 (2)
C10—N2—C11—C12178.05 (12)C47—C48—C49—C532.2 (2)
Cu1—N2—C11—C128.08 (15)C47—C48—C49—C50176.86 (14)
C8—C7—C11—N20.3 (2)C53—C49—C50—C510.7 (2)
C6—C7—C11—N2179.58 (13)C48—C49—C50—C51179.83 (14)
C8—C7—C11—C12178.61 (12)C49—C50—C51—C521.7 (2)
C6—C7—C11—C121.3 (2)C53—N8—C52—C510.4 (2)
C1—N1—C12—C43.9 (2)Cu2—N8—C52—C51173.41 (11)
Cu1—N1—C12—C4175.49 (11)C53—N8—C52—C56179.02 (13)
C1—N1—C12—C11174.36 (12)Cu2—N8—C52—C567.2 (2)
Cu1—N1—C12—C116.26 (15)C50—C51—C52—N82.3 (2)
C3—C4—C12—N12.8 (2)C50—C51—C52—C56177.06 (15)
C5—C4—C12—N1178.73 (13)C52—N8—C53—C492.2 (2)
C3—C4—C12—C11175.36 (12)Cu2—N8—C53—C49177.00 (11)
C5—C4—C12—C113.1 (2)C52—N8—C53—C54177.69 (12)
N2—C11—C12—N11.24 (18)Cu2—N8—C53—C542.87 (15)
C7—C11—C12—N1179.60 (12)C50—C49—C53—N82.7 (2)
N2—C11—C12—C4177.08 (12)C48—C49—C53—N8178.12 (13)
C7—C11—C12—C41.3 (2)C50—C49—C53—C54177.13 (13)
C26—N3—C15—C160.0 (2)C48—C49—C53—C542.0 (2)
Cu1—N3—C15—C16179.86 (11)C43—N7—C54—C461.4 (2)
C26—N3—C15—C27179.48 (13)Cu2—N7—C54—C46177.05 (11)
Cu1—N3—C15—C270.4 (2)C43—N7—C54—C53179.08 (12)
N3—C15—C16—C170.5 (2)Cu2—N7—C54—C532.49 (15)
C27—C15—C16—C17179.92 (15)C45—C46—C54—N72.0 (2)
C15—C16—C17—C180.4 (2)C47—C46—C54—N7178.44 (13)
C16—C17—C18—C260.0 (2)C45—C46—C54—C53177.54 (13)
C16—C17—C18—C19179.93 (14)C47—C46—C54—C532.0 (2)
C26—C18—C19—C201.6 (2)N8—C53—C54—N70.22 (19)
C17—C18—C19—C20178.34 (15)C49—C53—C54—N7179.65 (12)
C18—C19—C20—C210.7 (2)N8—C53—C54—C46179.78 (12)
C19—C20—C21—C251.2 (2)C49—C53—C54—C460.1 (2)
C19—C20—C21—C22179.46 (15)C61—N9—C57—C581.6 (2)
C25—C21—C22—C230.3 (2)N9—C57—C58—C591.1 (2)
C20—C21—C22—C23179.09 (15)C57—C58—C59—C600.9 (2)
C21—C22—C23—C240.3 (2)C57—C58—C59—C62176.94 (14)
C25—N4—C24—C231.4 (2)C58—C59—C60—C612.2 (2)
Cu1—N4—C24—C23176.96 (11)C62—C59—C60—C61175.74 (14)
C25—N4—C24—C28177.70 (13)C57—N9—C61—C600.2 (2)
Cu1—N4—C24—C282.1 (2)C59—C60—C61—N91.7 (2)
C22—C23—C24—N40.2 (2)N10i—N10—C62—C59178.60 (14)
C22—C23—C24—C28178.86 (15)C60—C59—C62—N10165.82 (14)
C24—N4—C25—C212.1 (2)C58—C59—C62—N1012.0 (2)
Cu1—N4—C25—C21178.50 (11)
Symmetry code: (i) x+1, y+1, z.
(II) Bis(2,9-dimethyl-1,10-phenanthroline-κ2N,N')copper(I) dicyanamide top
Crystal data top
[Cu(C14H12N2)2](C2N3)F(000) = 1128
Mr = 546.12Dx = 1.412 Mg m3
Monoclinic, P21/nMelting point: not measured K
Hall symbol: -P2ynMo Kα radiation, λ = 0.71073 Å
a = 15.0055 (5) ÅCell parameters from 19294 reflections
b = 10.3286 (3) Åθ = 4.7–56.5°
c = 16.8878 (5) ŵ = 0.88 mm1
β = 101.138 (1)°T = 90 K
V = 2568.1 (1) Å3Parallelepiped, orange
Z = 40.3 × 0.2 × 0.1 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
7446 independent reflections
Radiation source: rotating anode6422 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ϕ and ω scansθmax = 30.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2121
Tmin = 0.719, Tmax = 0.941k = 1414
44252 measured reflectionsl = 2323
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.085 w = 1/[σ2(Fo2) + (0.04P)2 + 1.4111P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
7446 reflectionsΔρmax = 0.45 e Å3
348 parametersΔρmin = 0.39 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0108 (6)
Crystal data top
[Cu(C14H12N2)2](C2N3)V = 2568.1 (1) Å3
Mr = 546.12Z = 4
Monoclinic, P21/nMo Kα radiation
a = 15.0055 (5) ŵ = 0.88 mm1
b = 10.3286 (3) ÅT = 90 K
c = 16.8878 (5) Å0.3 × 0.2 × 0.1 mm
β = 101.138 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
7446 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
6422 reflections with I > 2σ(I)
Tmin = 0.719, Tmax = 0.941Rint = 0.033
44252 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.085H-atom parameters constrained
S = 1.06Δρmax = 0.45 e Å3
7446 reflectionsΔρmin = 0.39 e Å3
348 parameters
Special details top

Experimental. 'Blessing, R. (1995) Acta Crystallogr., A51, 33–38'

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.775418 (10)0.295452 (15)0.054163 (9)0.01750 (6)
N10.78925 (7)0.10113 (10)0.05254 (6)0.01492 (19)
N30.71650 (7)0.40778 (10)0.04079 (6)0.0159 (2)
N20.91389 (7)0.28856 (10)0.08982 (6)0.0162 (2)
N40.69177 (7)0.39728 (10)0.11180 (6)0.0166 (2)
C260.66039 (8)0.49860 (11)0.01785 (7)0.0146 (2)
N60.45912 (9)0.08346 (13)0.19782 (9)0.0337 (3)
C180.61373 (8)0.59160 (12)0.07100 (8)0.0168 (2)
C210.59059 (8)0.58410 (12)0.09139 (8)0.0181 (2)
C120.87787 (8)0.06378 (11)0.07237 (7)0.0140 (2)
C30.83686 (9)0.16001 (13)0.05273 (8)0.0209 (2)
H30.85210.24920.05190.025*
C71.03710 (8)0.13094 (12)0.11500 (7)0.0167 (2)
C250.64792 (8)0.49387 (11)0.06440 (7)0.0153 (2)
C91.06786 (9)0.35842 (13)0.13225 (9)0.0234 (3)
H91.10920.42820.14620.028*
C230.62178 (10)0.47432 (15)0.21863 (9)0.0253 (3)
H230.61350.46510.27270.030*
C270.78719 (11)0.30235 (14)0.14058 (9)0.0257 (3)
H27A0.83840.28680.09600.039*
H27B0.81010.32950.18850.039*
H27C0.75180.22260.15250.039*
C160.68493 (9)0.49894 (13)0.17373 (8)0.0213 (2)
H160.69520.49760.22750.026*
C190.55435 (9)0.68147 (12)0.04193 (9)0.0198 (2)
H190.52200.74380.07770.024*
C170.62828 (9)0.59055 (13)0.15105 (8)0.0208 (2)
H170.59920.65260.18900.025*
C220.57983 (10)0.57342 (14)0.17223 (9)0.0236 (3)
H220.54380.63440.19420.028*
C140.93809 (10)0.51921 (13)0.10180 (10)0.0260 (3)
H14A0.92820.54690.04530.039*
H14B0.98200.57720.13470.039*
H14C0.88050.52220.12090.039*
C240.67736 (9)0.38536 (13)0.18694 (8)0.0205 (2)
C81.09975 (9)0.23319 (14)0.13516 (9)0.0221 (3)
H81.16290.21590.15050.026*
C110.94461 (8)0.16388 (12)0.09319 (7)0.0148 (2)
C61.06375 (9)0.00253 (13)0.11465 (8)0.0193 (2)
H61.12620.02510.12850.023*
C40.90559 (8)0.06626 (12)0.07322 (7)0.0161 (2)
C150.72777 (9)0.40696 (12)0.11717 (8)0.0183 (2)
N70.29411 (10)0.04206 (16)0.16951 (9)0.0358 (3)
C10.72529 (8)0.01055 (13)0.03414 (8)0.0184 (2)
C100.97425 (9)0.38352 (13)0.10870 (8)0.0196 (2)
C51.00031 (9)0.09668 (12)0.09469 (8)0.0193 (2)
H51.01910.18450.09500.023*
C280.72234 (11)0.27445 (15)0.23640 (9)0.0267 (3)
H28A0.72290.19850.20170.040*
H28B0.68870.25410.27910.040*
H28C0.78490.29820.26070.040*
C200.54403 (9)0.67816 (13)0.03594 (9)0.0207 (2)
H200.50520.73930.05420.025*
C300.37201 (10)0.05583 (14)0.18202 (9)0.0253 (3)
C130.62866 (9)0.05463 (14)0.01348 (10)0.0260 (3)
H13A0.61250.09870.06010.039*
H13B0.58890.02050.00090.039*
H13C0.62130.11460.03230.039*
C20.74786 (9)0.12181 (13)0.03393 (9)0.0227 (3)
H20.70120.18480.02070.027*
C290.51677 (11)0.01107 (17)0.19272 (10)0.0309 (3)
N50.57204 (12)0.0879 (2)0.19002 (11)0.0506 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01722 (9)0.01421 (8)0.02046 (9)0.00531 (5)0.00212 (6)0.00099 (5)
N10.0151 (5)0.0143 (5)0.0152 (4)0.0020 (4)0.0024 (4)0.0003 (3)
N30.0148 (4)0.0142 (5)0.0183 (5)0.0019 (4)0.0025 (4)0.0003 (4)
N20.0182 (5)0.0129 (5)0.0168 (5)0.0018 (4)0.0017 (4)0.0000 (4)
N40.0164 (5)0.0142 (5)0.0189 (5)0.0002 (4)0.0025 (4)0.0008 (4)
C260.0119 (5)0.0122 (5)0.0191 (5)0.0000 (4)0.0018 (4)0.0009 (4)
N60.0280 (6)0.0240 (6)0.0456 (8)0.0016 (5)0.0012 (6)0.0014 (6)
C180.0133 (5)0.0131 (5)0.0227 (6)0.0003 (4)0.0001 (4)0.0002 (4)
C210.0152 (5)0.0146 (5)0.0252 (6)0.0013 (4)0.0051 (4)0.0046 (4)
C120.0159 (5)0.0129 (5)0.0133 (5)0.0021 (4)0.0027 (4)0.0004 (4)
C30.0240 (6)0.0124 (5)0.0260 (6)0.0017 (5)0.0043 (5)0.0002 (5)
C70.0158 (5)0.0167 (5)0.0168 (5)0.0030 (4)0.0016 (4)0.0002 (4)
C250.0132 (5)0.0128 (5)0.0195 (5)0.0016 (4)0.0024 (4)0.0021 (4)
C90.0202 (6)0.0187 (6)0.0294 (7)0.0033 (5)0.0004 (5)0.0020 (5)
C230.0309 (7)0.0254 (7)0.0217 (6)0.0013 (5)0.0100 (5)0.0042 (5)
C270.0308 (7)0.0248 (7)0.0237 (6)0.0109 (5)0.0107 (5)0.0019 (5)
C160.0231 (6)0.0219 (6)0.0185 (6)0.0027 (5)0.0032 (5)0.0030 (5)
C190.0148 (5)0.0134 (5)0.0298 (7)0.0020 (4)0.0006 (5)0.0002 (5)
C170.0197 (6)0.0182 (6)0.0228 (6)0.0022 (5)0.0000 (5)0.0044 (5)
C220.0245 (6)0.0207 (6)0.0276 (7)0.0002 (5)0.0100 (5)0.0073 (5)
C140.0270 (7)0.0138 (6)0.0347 (7)0.0006 (5)0.0002 (6)0.0013 (5)
C240.0228 (6)0.0199 (6)0.0189 (6)0.0020 (5)0.0039 (5)0.0017 (5)
C80.0164 (6)0.0219 (6)0.0263 (6)0.0002 (5)0.0003 (5)0.0010 (5)
C110.0161 (5)0.0132 (5)0.0148 (5)0.0020 (4)0.0022 (4)0.0002 (4)
C60.0176 (5)0.0191 (6)0.0204 (6)0.0066 (4)0.0017 (4)0.0003 (5)
C40.0193 (6)0.0131 (5)0.0160 (5)0.0026 (4)0.0036 (4)0.0004 (4)
C150.0183 (6)0.0170 (6)0.0197 (6)0.0027 (4)0.0039 (4)0.0005 (4)
N70.0278 (7)0.0489 (9)0.0325 (7)0.0066 (6)0.0102 (5)0.0011 (6)
C10.0161 (5)0.0175 (6)0.0214 (6)0.0007 (4)0.0032 (4)0.0002 (4)
C100.0217 (6)0.0147 (5)0.0216 (6)0.0006 (4)0.0022 (5)0.0003 (4)
C50.0211 (6)0.0154 (5)0.0210 (6)0.0070 (4)0.0031 (5)0.0009 (4)
C280.0338 (8)0.0262 (7)0.0202 (6)0.0027 (6)0.0050 (5)0.0040 (5)
C200.0160 (5)0.0137 (5)0.0325 (7)0.0020 (4)0.0050 (5)0.0037 (5)
C300.0313 (7)0.0241 (7)0.0207 (6)0.0058 (5)0.0054 (5)0.0021 (5)
C130.0147 (6)0.0237 (7)0.0383 (8)0.0008 (5)0.0015 (5)0.0036 (6)
C20.0214 (6)0.0164 (6)0.0297 (7)0.0030 (5)0.0031 (5)0.0012 (5)
C290.0265 (7)0.0365 (8)0.0279 (7)0.0031 (6)0.0007 (6)0.0013 (6)
N50.0385 (8)0.0611 (11)0.0497 (10)0.0199 (8)0.0020 (7)0.0073 (8)
Geometric parameters (Å, º) top
Cu1—N12.0185 (11)C23—H230.9500
Cu1—N42.0251 (11)C27—C151.5016 (18)
Cu1—N32.0374 (11)C27—H27A0.9800
Cu1—N22.0498 (11)C27—H27B0.9800
N1—C11.3333 (16)C27—H27C0.9800
N1—C121.3628 (15)C16—C171.3749 (19)
N3—C151.3330 (16)C16—C151.4110 (18)
N3—C261.3656 (15)C16—H160.9500
N2—C101.3314 (16)C19—C201.354 (2)
N2—C111.3653 (15)C19—H190.9500
N4—C241.3336 (17)C17—H170.9500
N4—C251.3657 (16)C22—H220.9500
C26—C181.4056 (16)C14—C101.4992 (19)
C26—C251.4378 (17)C14—H14A0.9800
N6—C301.314 (2)C14—H14B0.9800
N6—C291.318 (2)C14—H14C0.9800
C18—C171.4105 (19)C24—C281.499 (2)
C18—C191.4371 (17)C8—H80.9500
C21—C251.4028 (17)C6—C51.3570 (19)
C21—C221.4098 (19)C6—H60.9500
C21—C201.4339 (19)C4—C51.4323 (17)
C12—C41.4053 (16)N7—C301.156 (2)
C12—C111.4351 (17)C1—C21.4085 (19)
C3—C21.3698 (19)C1—C131.4954 (18)
C3—C41.4082 (18)C5—H50.9500
C3—H30.9500C28—H28A0.9800
C7—C111.4070 (17)C28—H28B0.9800
C7—C81.4113 (18)C28—H28C0.9800
C7—C61.4357 (17)C20—H200.9500
C9—C81.377 (2)C13—H13A0.9800
C9—C101.4081 (19)C13—H13B0.9800
C9—H90.9500C13—H13C0.9800
C23—C221.367 (2)C2—H20.9500
C23—C241.4136 (19)C29—N51.155 (2)
N1—Cu1—N4126.72 (4)C16—C17—H17120.3
N1—Cu1—N3125.85 (4)C18—C17—H17120.3
N4—Cu1—N382.39 (4)C23—C22—C21119.18 (12)
N1—Cu1—N282.44 (4)C23—C22—H22120.4
N4—Cu1—N2124.34 (4)C21—C22—H22120.4
N3—Cu1—N2120.80 (4)C10—C14—H14A109.5
C1—N1—C12118.87 (11)C10—C14—H14B109.5
C1—N1—Cu1129.02 (9)H14A—C14—H14B109.5
C12—N1—Cu1112.10 (8)C10—C14—H14C109.5
C15—N3—C26118.64 (11)H14A—C14—H14C109.5
C15—N3—Cu1129.88 (9)H14B—C14—H14C109.5
C26—N3—Cu1111.44 (8)N4—C24—C23121.07 (13)
C10—N2—C11118.44 (11)N4—C24—C28117.54 (12)
C10—N2—Cu1130.46 (9)C23—C24—C28121.39 (12)
C11—N2—Cu1111.10 (8)C9—C8—C7118.92 (12)
C24—N4—C25118.48 (11)C9—C8—H8120.5
C24—N4—Cu1129.71 (9)C7—C8—H8120.5
C25—N4—Cu1111.77 (8)N2—C11—C7123.16 (11)
N3—C26—C18123.14 (11)N2—C11—C12117.08 (11)
N3—C26—C25116.94 (11)C7—C11—C12119.76 (11)
C18—C26—C25119.89 (11)C5—C6—C7120.43 (12)
C30—N6—C29117.74 (14)C5—C6—H6119.8
C26—C18—C17117.16 (11)C7—C6—H6119.8
C26—C18—C19119.24 (12)C12—C4—C3116.97 (11)
C17—C18—C19123.59 (12)C12—C4—C5119.31 (11)
C25—C21—C22117.05 (12)C3—C4—C5123.72 (11)
C25—C21—C20119.34 (12)N3—C15—C16121.63 (12)
C22—C21—C20123.56 (12)N3—C15—C27116.88 (11)
N1—C12—C4123.09 (11)C16—C15—C27121.49 (12)
N1—C12—C11117.26 (10)N1—C1—C2121.27 (12)
C4—C12—C11119.66 (11)N1—C1—C13117.56 (12)
C2—C3—C4119.59 (12)C2—C1—C13121.18 (12)
C2—C3—H3120.2N2—C10—C9121.83 (12)
C4—C3—H3120.2N2—C10—C14116.80 (12)
C11—C7—C8117.36 (11)C9—C10—C14121.36 (12)
C11—C7—C6119.51 (12)C6—C5—C4121.32 (11)
C8—C7—C6123.12 (12)C6—C5—H5119.3
N4—C25—C21123.44 (12)C4—C5—H5119.3
N4—C25—C26116.95 (11)C24—C28—H28A109.5
C21—C25—C26119.58 (11)C24—C28—H28B109.5
C8—C9—C10120.27 (12)H28A—C28—H28B109.5
C8—C9—H9119.9C24—C28—H28C109.5
C10—C9—H9119.9H28A—C28—H28C109.5
C22—C23—C24120.66 (13)H28B—C28—H28C109.5
C22—C23—H23119.7C19—C20—C21121.24 (12)
C24—C23—H23119.7C19—C20—H20119.4
C15—C27—H27A109.5C21—C20—H20119.4
C15—C27—H27B109.5N7—C30—N6174.36 (17)
H27A—C27—H27B109.5C1—C13—H13A109.5
C15—C27—H27C109.5C1—C13—H13B109.5
H27A—C27—H27C109.5H13A—C13—H13B109.5
H27B—C27—H27C109.5C1—C13—H13C109.5
C17—C16—C15120.01 (12)H13A—C13—H13C109.5
C17—C16—H16120.0H13B—C13—H13C109.5
C15—C16—H16120.0C3—C2—C1120.21 (12)
C20—C19—C18120.68 (12)C3—C2—H2119.9
C20—C19—H19119.7C1—C2—H2119.9
C18—C19—H19119.7N5—C29—N6175.3 (2)
C16—C17—C18119.39 (12)

Experimental details

(I)(II)
Crystal data
Chemical formula[Cu(C14H12N2)2]2(PF6)2(C12H10N4)0.5·C2H3N[Cu(C14H12N2)2](C2N3)
Mr1396.24546.12
Crystal system, space groupTriclinic, P1Monoclinic, P21/n
Temperature (K)9090
a, b, c (Å)13.6775 (5), 14.0221 (5), 17.2879 (6)15.0055 (5), 10.3286 (3), 16.8878 (5)
α, β, γ (°)111.776 (1), 91.679 (1), 104.212 (1)90, 101.138 (1), 90
V3)2957.96 (18)2568.1 (1)
Z24
Radiation typeMo KαMo Kα
µ (mm1)0.860.88
Crystal size (mm)0.20 × 0.20 × 0.200.3 × 0.2 × 0.1
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.782, 0.9190.719, 0.941
No. of measured, independent and
observed [I > 2σ(I)] reflections
45314, 14342, 12664 44252, 7446, 6422
Rint0.0230.033
(sin θ/λ)max1)0.6620.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.082, 1.04 0.029, 0.085, 1.06
No. of reflections143427446
No. of parameters849348
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.03, 0.690.45, 0.39

Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
Cu1—N12.0402 (12)Cu2—N52.0259 (12)
Cu1—N22.0350 (12)Cu2—N62.0587 (12)
Cu1—N32.0182 (12)Cu2—N72.0602 (12)
Cu1—N42.0591 (12)Cu2—N82.0261 (12)
N1—Cu1—N282.42 (5)N5—Cu2—N682.24 (5)
N1—Cu1—N3127.02 (5)N5—Cu2—N7117.54 (5)
N1—Cu1—N4128.14 (5)N5—Cu2—N8134.81 (5)
N2—Cu1—N3128.70 (5)N6—Cu2—N7125.71 (5)
N2—Cu1—N4113.29 (5)N6—Cu2—N8120.45 (5)
N3—Cu1—N482.54 (5)N7—Cu2—N882.30 (5)
Selected geometric parameters (Å, º) for (II) top
Cu1—N12.0185 (11)Cu1—N32.0374 (11)
Cu1—N42.0251 (11)Cu1—N22.0498 (11)
N1—Cu1—N4126.72 (4)N3—Cu1—N2120.80 (4)
N1—Cu1—N3125.85 (4)C30—N6—C29117.74 (14)
N4—Cu1—N382.39 (4)N7—C30—N6174.36 (17)
N1—Cu1—N282.44 (4)N5—C29—N6175.3 (2)
N4—Cu1—N2124.34 (4)
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds