Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105010760/gg1253sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105010760/gg1253Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105010760/gg1253IIsup3.hkl |
CCDC references: 278537; 278538
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.
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.
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.
[Cu(C14H12N2)2]2(PF6)2(C12H10N4)0.5·C2H3N | Z = 2 |
Mr = 1396.24 | F(000) = 1426 |
Triclinic, P1 | Dx = 1.568 Mg m−3 |
Hall symbol: -P1 | Melting point: not measured K |
a = 13.6775 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.0221 (5) Å | Cell parameters from 22175 reflections |
c = 17.2879 (6) Å | θ = 4.9–56.1° |
α = 111.776 (1)° | µ = 0.86 mm−1 |
β = 91.679 (1)° | T = 90 K |
γ = 104.212 (1)° | Cubic, red |
V = 2957.96 (18) Å3 | 0.20 × 0.20 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 14342 independent reflections |
Radiation source: rotating anode | 12664 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω scans | θmax = 28.1°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→18 |
Tmin = 0.782, Tmax = 0.919 | k = −18→18 |
45314 measured reflections | l = −22→22 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | H-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 reflections | Δρmax = 1.03 e Å−3 |
849 parameters | Δρmin = −0.69 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0133 (4) |
[Cu(C14H12N2)2]2(PF6)2(C12H10N4)0.5·C2H3N | γ = 104.212 (1)° |
Mr = 1396.24 | V = 2957.96 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 13.6775 (5) Å | Mo Kα radiation |
b = 14.0221 (5) Å | µ = 0.86 mm−1 |
c = 17.2879 (6) Å | T = 90 K |
α = 111.776 (1)° | 0.20 × 0.20 × 0.20 mm |
β = 91.679 (1)° |
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 = 0.919 | Rint = 0.023 |
45314 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.03 e Å−3 |
14342 reflections | Δρmin = −0.69 e Å−3 |
849 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.040605 (13) | 0.253855 (14) | 0.263530 (10) | 0.01441 (5) | |
Cu2 | 0.672579 (13) | 0.806172 (14) | 0.246437 (11) | 0.01431 (5) | |
N1 | −0.06378 (9) | 0.24801 (10) | 0.34476 (7) | 0.0136 (2) | |
N10 | 0.47393 (9) | 0.53999 (9) | 0.01087 (8) | 0.0153 (2) | |
N1S | 0.81905 (15) | 0.76658 (14) | 0.46545 (10) | 0.0358 (4) | |
N2 | 0.12510 (9) | 0.37670 (10) | 0.36760 (7) | 0.0135 (2) | |
N3 | 0.01559 (9) | 0.24898 (10) | 0.14632 (8) | 0.0141 (2) | |
N4 | 0.11593 (9) | 0.14164 (9) | 0.20480 (8) | 0.0137 (2) | |
N5 | 0.57553 (9) | 0.79546 (10) | 0.33107 (8) | 0.0139 (2) | |
N6 | 0.76802 (9) | 0.91613 (10) | 0.35299 (8) | 0.0142 (2) | |
N7 | 0.62281 (9) | 0.83739 (10) | 0.14703 (8) | 0.0137 (2) | |
N8 | 0.72591 (9) | 0.70006 (10) | 0.15487 (7) | 0.0133 (2) | |
N9 | 0.30178 (10) | 0.80067 (11) | −0.03212 (9) | 0.0214 (3) | |
P1 | 0.14600 (3) | 0.69708 (3) | 0.21966 (2) | 0.01714 (8) | |
P2 | 0.50268 (3) | 0.28465 (3) | 0.31493 (3) | 0.02073 (9) | |
C1 | −0.16077 (11) | 0.19075 (12) | 0.33093 (9) | 0.0157 (3) | |
C10 | 0.21810 (11) | 0.44096 (12) | 0.37644 (9) | 0.0158 (3) | |
C11 | 0.07941 (11) | 0.38281 (11) | 0.43757 (9) | 0.0129 (3) | |
C12 | −0.02217 (11) | 0.31474 (11) | 0.42539 (9) | 0.0134 (3) | |
C13 | −0.20631 (12) | 0.11992 (13) | 0.24186 (10) | 0.0212 (3) | |
C14 | 0.26407 (12) | 0.43455 (13) | 0.29755 (10) | 0.0205 (3) | |
C15 | −0.03477 (11) | 0.30332 (12) | 0.11908 (9) | 0.0175 (3) | |
C16 | −0.04474 (12) | 0.29005 (13) | 0.03426 (10) | 0.0214 (3) | |
C17 | −0.00286 (12) | 0.21939 (13) | −0.02308 (10) | 0.0214 (3) | |
C18 | 0.05071 (11) | 0.16093 (12) | 0.00388 (9) | 0.0175 (3) | |
C19 | 0.09740 (12) | 0.08522 (13) | −0.05104 (9) | 0.0217 (3) | |
C1S | 0.63604 (17) | 0.64642 (17) | 0.45241 (14) | 0.0386 (5) | |
C2 | −0.21953 (12) | 0.19578 (12) | 0.39738 (10) | 0.0188 (3) | |
C20 | 0.15000 (12) | 0.03341 (13) | −0.02122 (10) | 0.0221 (3) | |
C21 | 0.16009 (11) | 0.05131 (11) | 0.06611 (9) | 0.0171 (3) | |
C22 | 0.21480 (12) | 0.00004 (12) | 0.10049 (11) | 0.0223 (3) | |
C23 | 0.21922 (12) | 0.02092 (13) | 0.18451 (11) | 0.0228 (3) | |
C24 | 0.16881 (11) | 0.09288 (12) | 0.23615 (10) | 0.0172 (3) | |
C25 | 0.11273 (10) | 0.12267 (11) | 0.12128 (9) | 0.0137 (3) | |
C26 | 0.05823 (11) | 0.17894 (11) | 0.08979 (9) | 0.0142 (3) | |
C27 | −0.07941 (13) | 0.37991 (13) | 0.18357 (10) | 0.0239 (3) | |
C28 | 0.17500 (12) | 0.11756 (13) | 0.32837 (10) | 0.0215 (3) | |
C29 | 0.48094 (11) | 0.73270 (12) | 0.31818 (9) | 0.0156 (3) | |
C2S | 0.73890 (17) | 0.71369 (15) | 0.45964 (11) | 0.0301 (4) | |
C3 | −0.17666 (12) | 0.25851 (12) | 0.47867 (10) | 0.0185 (3) | |
C30 | 0.41959 (12) | 0.74442 (13) | 0.38379 (10) | 0.0197 (3) | |
C31 | 0.45818 (12) | 0.81936 (13) | 0.46308 (10) | 0.0207 (3) | |
C32 | 0.55868 (12) | 0.88548 (12) | 0.47866 (9) | 0.0173 (3) | |
C33 | 0.60658 (13) | 0.96354 (13) | 0.55986 (10) | 0.0211 (3) | |
C34 | 0.70476 (13) | 1.02150 (12) | 0.57177 (9) | 0.0202 (3) | |
C35 | 0.76390 (12) | 1.00678 (12) | 0.50304 (9) | 0.0167 (3) | |
C36 | 0.86818 (12) | 1.06060 (12) | 0.51247 (10) | 0.0196 (3) | |
C37 | 0.91908 (12) | 1.03938 (12) | 0.44358 (10) | 0.0197 (3) | |
C38 | 0.86685 (11) | 0.96654 (12) | 0.36375 (10) | 0.0170 (3) | |
C39 | 0.71787 (11) | 0.93400 (11) | 0.42207 (9) | 0.0141 (3) | |
C4 | −0.07471 (12) | 0.32137 (12) | 0.49521 (9) | 0.0159 (3) | |
C40 | 0.61406 (11) | 0.87087 (11) | 0.40982 (9) | 0.0140 (3) | |
C41 | 0.44300 (12) | 0.64627 (13) | 0.23280 (10) | 0.0209 (3) | |
C42 | 0.92144 (12) | 0.94280 (13) | 0.28771 (10) | 0.0213 (3) | |
C43 | 0.57007 (11) | 0.90498 (12) | 0.14463 (10) | 0.0171 (3) | |
C44 | 0.55138 (12) | 0.92158 (12) | 0.07061 (10) | 0.0205 (3) | |
C45 | 0.58302 (11) | 0.86402 (13) | −0.00244 (10) | 0.0194 (3) | |
C46 | 0.63400 (11) | 0.78789 (12) | −0.00256 (9) | 0.0156 (3) | |
C47 | 0.66669 (11) | 0.72132 (13) | −0.07656 (9) | 0.0189 (3) | |
C48 | 0.71859 (11) | 0.65206 (12) | −0.07242 (9) | 0.0183 (3) | |
C49 | 0.74262 (11) | 0.64366 (11) | 0.00575 (9) | 0.0149 (3) | |
C5 | −0.02428 (13) | 0.39214 (12) | 0.57785 (9) | 0.0191 (3) | |
C50 | 0.80055 (11) | 0.57673 (12) | 0.01424 (9) | 0.0177 (3) | |
C51 | 0.81996 (12) | 0.57407 (12) | 0.09145 (10) | 0.0188 (3) | |
C52 | 0.78010 (11) | 0.63548 (12) | 0.16128 (9) | 0.0156 (3) | |
C53 | 0.70873 (10) | 0.70556 (11) | 0.07859 (9) | 0.0128 (3) | |
C54 | 0.65335 (10) | 0.77895 (11) | 0.07434 (9) | 0.0131 (3) | |
C55 | 0.52859 (13) | 0.96034 (13) | 0.22321 (10) | 0.0232 (3) | |
C56 | 0.79633 (13) | 0.62968 (14) | 0.24541 (10) | 0.0232 (3) | |
C57 | 0.30835 (12) | 0.76635 (13) | 0.03050 (10) | 0.0197 (3) | |
C58 | 0.35327 (11) | 0.68677 (12) | 0.02729 (9) | 0.0167 (3) | |
C59 | 0.39316 (11) | 0.63723 (11) | −0.04593 (9) | 0.0146 (3) | |
C6 | 0.07193 (13) | 0.45518 (12) | 0.58913 (9) | 0.0188 (3) | |
C60 | 0.38425 (11) | 0.66947 (12) | −0.11216 (9) | 0.0171 (3) | |
C61 | 0.33947 (12) | 0.75172 (13) | −0.10185 (10) | 0.0205 (3) | |
C62 | 0.44654 (11) | 0.55590 (11) | −0.05365 (9) | 0.0151 (3) | |
C7 | 0.12588 (12) | 0.45358 (11) | 0.51905 (9) | 0.0154 (3) | |
C8 | 0.22439 (12) | 0.51994 (12) | 0.52706 (9) | 0.0182 (3) | |
C9 | 0.26995 (12) | 0.51343 (12) | 0.45611 (10) | 0.0185 (3) | |
F1 | 0.11599 (11) | 0.67094 (12) | 0.12319 (7) | 0.0497 (3) | |
F10 | 0.46927 (10) | 0.20364 (10) | 0.21930 (7) | 0.0434 (3) | |
F11 | 0.38836 (9) | 0.28045 (13) | 0.32952 (9) | 0.0525 (4) | |
F12A | 0.5011 (5) | 0.3794 (3) | 0.2814 (4) | 0.0366 (9) | 0.75 (2) |
F12B | 0.5445 (19) | 0.3864 (6) | 0.3063 (9) | 0.049 (4) | 0.25 (2) |
F2 | 0.18105 (10) | 0.58991 (9) | 0.19443 (9) | 0.0434 (3) | |
F3 | 0.03416 (8) | 0.63257 (10) | 0.22346 (8) | 0.0383 (3) | |
F4 | 0.17798 (9) | 0.72217 (10) | 0.31647 (7) | 0.0387 (3) | |
F5 | 0.11236 (10) | 0.80434 (10) | 0.24575 (11) | 0.0530 (4) | |
F6 | 0.25889 (8) | 0.76293 (10) | 0.21720 (7) | 0.0339 (2) | |
F7A | 0.5081 (8) | 0.1951 (4) | 0.34637 (19) | 0.0539 (16) | 0.75 (2) |
F7B | 0.4533 (15) | 0.1703 (9) | 0.3293 (9) | 0.039 (3) | 0.25 (2) |
F8 | 0.53765 (10) | 0.36878 (12) | 0.40928 (8) | 0.0515 (4) | |
F9 | 0.61847 (10) | 0.29397 (16) | 0.29918 (8) | 0.0684 (5) | |
H13A | −0.1579 | 0.1328 | 0.2037 | 0.032* | |
H13B | −0.2692 | 0.1357 | 0.2287 | 0.032* | |
H13C | −0.2216 | 0.0450 | 0.2350 | 0.032* | |
H14A | 0.2478 | 0.3597 | 0.2582 | 0.031* | |
H14B | 0.3381 | 0.4642 | 0.3112 | 0.031* | |
H14C | 0.2363 | 0.4755 | 0.2717 | 0.031* | |
H16 | −0.0806 | 0.3302 | 0.0167 | 0.026* | |
H17 | −0.0099 | 0.2099 | −0.0805 | 0.026* | |
H19 | 0.0912 | 0.0713 | −0.1094 | 0.026* | |
H1S1 | 0.6210 | 0.6489 | 0.5081 | 0.058* | |
H1S2 | 0.6311 | 0.5726 | 0.4150 | 0.058* | |
H1S3 | 0.5870 | 0.6726 | 0.4293 | 0.058* | |
H2 | −0.2890 | 0.1555 | 0.3857 | 0.023* | |
H20 | 0.1809 | −0.0158 | −0.0588 | 0.027* | |
H22 | 0.2483 | −0.0486 | 0.0656 | 0.027* | |
H23 | 0.2563 | −0.0130 | 0.2083 | 0.027* | |
H27A | −0.1033 | 0.3505 | 0.2251 | 0.036* | |
H27B | −0.1367 | 0.3912 | 0.1560 | 0.036* | |
H27C | −0.0274 | 0.4482 | 0.2118 | 0.036* | |
H28A | 0.2443 | 0.1594 | 0.3556 | 0.032* | |
H28B | 0.1577 | 0.0507 | 0.3374 | 0.032* | |
H28C | 0.1271 | 0.1587 | 0.3525 | 0.032* | |
H3 | −0.2153 | 0.2597 | 0.5236 | 0.022* | |
H30 | 0.3517 | 0.7003 | 0.3729 | 0.024* | |
H31 | 0.4174 | 0.8267 | 0.5074 | 0.025* | |
H33 | 0.5688 | 0.9748 | 0.6061 | 0.025* | |
H34 | 0.7350 | 1.0726 | 0.6263 | 0.024* | |
H36 | 0.9026 | 1.1109 | 0.5660 | 0.023* | |
H37 | 0.9896 | 1.0737 | 0.4495 | 0.024* | |
H41A | 0.4798 | 0.6666 | 0.1910 | 0.031* | |
H41B | 0.3701 | 0.6360 | 0.2194 | 0.031* | |
H41C | 0.4543 | 0.5796 | 0.2320 | 0.031* | |
H42A | 0.8728 | 0.8941 | 0.2378 | 0.032* | |
H42B | 0.9742 | 0.9094 | 0.2948 | 0.032* | |
H42C | 0.9529 | 1.0095 | 0.2809 | 0.032* | |
H44 | 0.5167 | 0.9728 | 0.0713 | 0.025* | |
H45 | 0.5708 | 0.8753 | −0.0523 | 0.023* | |
H47 | 0.6518 | 0.7258 | −0.1289 | 0.023* | |
H48 | 0.7394 | 0.6084 | −0.1221 | 0.022* | |
H5 | −0.0587 | 0.3949 | 0.6252 | 0.023* | |
H50 | 0.8258 | 0.5340 | −0.0331 | 0.021* | |
H51 | 0.8604 | 0.5307 | 0.0981 | 0.023* | |
H55A | 0.4632 | 0.9139 | 0.2256 | 0.035* | |
H55B | 0.5187 | 1.0272 | 0.2230 | 0.035* | |
H55C | 0.5767 | 0.9761 | 0.2724 | 0.035* | |
H56A | 0.7840 | 0.6924 | 0.2891 | 0.035* | |
H56B | 0.8665 | 0.6282 | 0.2565 | 0.035* | |
H56C | 0.7491 | 0.5647 | 0.2455 | 0.035* | |
H57 | 0.2804 | 0.7988 | 0.0800 | 0.024* | |
H58 | 0.3569 | 0.6663 | 0.0737 | 0.020* | |
H6 | 0.1041 | 0.5012 | 0.6444 | 0.023* | |
H60 | 0.4083 | 0.6359 | −0.1636 | 0.021* | |
H61 | 0.3355 | 0.7744 | −0.1470 | 0.025* | |
H62 | 0.4609 | 0.5145 | −0.1073 | 0.018* | |
H8 | 0.2591 | 0.5687 | 0.5809 | 0.022* | |
H9 | 0.3365 | 0.5579 | 0.4609 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01688 (9) | 0.01713 (9) | 0.00910 (8) | 0.00648 (7) | 0.00428 (6) | 0.00368 (7) |
Cu2 | 0.01462 (9) | 0.01850 (9) | 0.01005 (9) | 0.00674 (7) | 0.00388 (6) | 0.00430 (7) |
P1 | 0.01722 (18) | 0.02216 (19) | 0.01451 (17) | 0.00739 (15) | 0.00397 (14) | 0.00854 (15) |
P2 | 0.02061 (19) | 0.0224 (2) | 0.01578 (18) | 0.00520 (15) | 0.00000 (14) | 0.00431 (15) |
F1 | 0.0495 (8) | 0.0757 (10) | 0.0240 (6) | 0.0053 (7) | −0.0058 (5) | 0.0280 (6) |
F2 | 0.0403 (7) | 0.0274 (6) | 0.0558 (8) | 0.0175 (5) | −0.0049 (6) | 0.0046 (5) |
F3 | 0.0192 (5) | 0.0476 (7) | 0.0425 (7) | −0.0026 (5) | 0.0028 (5) | 0.0192 (6) |
F4 | 0.0393 (6) | 0.0494 (7) | 0.0169 (5) | −0.0075 (5) | −0.0002 (4) | 0.0141 (5) |
F5 | 0.0420 (7) | 0.0344 (7) | 0.0864 (11) | 0.0236 (6) | 0.0085 (7) | 0.0195 (7) |
F6 | 0.0234 (5) | 0.0464 (7) | 0.0352 (6) | 0.0034 (5) | 0.0101 (4) | 0.0229 (5) |
F7A | 0.108 (5) | 0.0401 (15) | 0.0277 (11) | 0.035 (2) | 0.0120 (17) | 0.0201 (10) |
F7B | 0.066 (7) | 0.028 (3) | 0.035 (4) | 0.020 (4) | 0.022 (4) | 0.021 (3) |
F8 | 0.0328 (6) | 0.0671 (9) | 0.0241 (6) | 0.0060 (6) | 0.0034 (5) | −0.0111 (6) |
F9 | 0.0322 (7) | 0.1269 (15) | 0.0295 (7) | 0.0413 (8) | 0.0034 (5) | 0.0000 (8) |
F10 | 0.0500 (7) | 0.0441 (7) | 0.0173 (5) | −0.0086 (6) | −0.0035 (5) | 0.0053 (5) |
F11 | 0.0235 (6) | 0.0868 (11) | 0.0443 (7) | 0.0044 (6) | 0.0087 (5) | 0.0287 (7) |
F12A | 0.0495 (19) | 0.0369 (11) | 0.0416 (17) | 0.0243 (12) | 0.0245 (14) | 0.0264 (12) |
F12B | 0.074 (9) | 0.023 (3) | 0.043 (5) | −0.004 (4) | 0.023 (6) | 0.014 (3) |
N1 | 0.0154 (6) | 0.0147 (5) | 0.0123 (5) | 0.0063 (4) | 0.0039 (4) | 0.0056 (5) |
N2 | 0.0151 (6) | 0.0152 (5) | 0.0123 (5) | 0.0072 (4) | 0.0035 (4) | 0.0057 (4) |
N3 | 0.0140 (5) | 0.0150 (5) | 0.0127 (5) | 0.0030 (4) | 0.0028 (4) | 0.0055 (5) |
N4 | 0.0133 (5) | 0.0134 (5) | 0.0135 (6) | 0.0030 (4) | 0.0037 (4) | 0.0045 (4) |
N5 | 0.0147 (6) | 0.0164 (6) | 0.0130 (5) | 0.0076 (5) | 0.0037 (4) | 0.0063 (5) |
N6 | 0.0155 (6) | 0.0151 (6) | 0.0136 (5) | 0.0067 (5) | 0.0026 (4) | 0.0059 (5) |
N7 | 0.0121 (5) | 0.0139 (5) | 0.0145 (6) | 0.0033 (4) | 0.0017 (4) | 0.0052 (5) |
N8 | 0.0121 (5) | 0.0157 (6) | 0.0118 (5) | 0.0040 (4) | 0.0031 (4) | 0.0046 (4) |
N9 | 0.0196 (6) | 0.0253 (7) | 0.0256 (7) | 0.0122 (5) | 0.0063 (5) | 0.0129 (6) |
N10 | 0.0150 (6) | 0.0130 (5) | 0.0195 (6) | 0.0072 (5) | 0.0054 (5) | 0.0058 (5) |
C1 | 0.0170 (7) | 0.0156 (6) | 0.0164 (7) | 0.0064 (5) | 0.0044 (5) | 0.0068 (5) |
C2 | 0.0160 (7) | 0.0208 (7) | 0.0231 (7) | 0.0072 (6) | 0.0077 (6) | 0.0108 (6) |
C3 | 0.0222 (7) | 0.0216 (7) | 0.0191 (7) | 0.0121 (6) | 0.0118 (6) | 0.0117 (6) |
C4 | 0.0214 (7) | 0.0169 (7) | 0.0153 (7) | 0.0113 (6) | 0.0080 (5) | 0.0087 (5) |
C5 | 0.0293 (8) | 0.0211 (7) | 0.0128 (7) | 0.0144 (6) | 0.0092 (6) | 0.0080 (6) |
C6 | 0.0291 (8) | 0.0190 (7) | 0.0098 (6) | 0.0117 (6) | 0.0033 (6) | 0.0041 (5) |
C7 | 0.0214 (7) | 0.0149 (6) | 0.0123 (6) | 0.0097 (5) | 0.0024 (5) | 0.0052 (5) |
C8 | 0.0225 (7) | 0.0163 (7) | 0.0140 (7) | 0.0070 (6) | −0.0016 (5) | 0.0030 (5) |
C9 | 0.0173 (7) | 0.0178 (7) | 0.0203 (7) | 0.0050 (5) | 0.0009 (6) | 0.0072 (6) |
C10 | 0.0172 (7) | 0.0167 (7) | 0.0161 (7) | 0.0078 (5) | 0.0042 (5) | 0.0073 (5) |
C11 | 0.0165 (6) | 0.0139 (6) | 0.0115 (6) | 0.0084 (5) | 0.0033 (5) | 0.0057 (5) |
C12 | 0.0179 (7) | 0.0141 (6) | 0.0117 (6) | 0.0091 (5) | 0.0043 (5) | 0.0057 (5) |
C13 | 0.0182 (7) | 0.0225 (7) | 0.0185 (7) | 0.0018 (6) | 0.0014 (6) | 0.0056 (6) |
C14 | 0.0178 (7) | 0.0244 (8) | 0.0182 (7) | 0.0036 (6) | 0.0058 (6) | 0.0082 (6) |
C15 | 0.0169 (7) | 0.0179 (7) | 0.0175 (7) | 0.0030 (5) | 0.0010 (5) | 0.0077 (6) |
C16 | 0.0194 (7) | 0.0258 (8) | 0.0200 (7) | 0.0019 (6) | −0.0011 (6) | 0.0131 (6) |
C17 | 0.0188 (7) | 0.0288 (8) | 0.0137 (7) | −0.0022 (6) | −0.0004 (5) | 0.0107 (6) |
C18 | 0.0150 (7) | 0.0202 (7) | 0.0116 (6) | −0.0028 (5) | 0.0019 (5) | 0.0049 (5) |
C19 | 0.0198 (7) | 0.0243 (8) | 0.0105 (6) | −0.0036 (6) | 0.0052 (5) | 0.0011 (6) |
C20 | 0.0198 (7) | 0.0197 (7) | 0.0162 (7) | −0.0006 (6) | 0.0089 (6) | −0.0014 (6) |
C21 | 0.0151 (7) | 0.0130 (6) | 0.0174 (7) | 0.0009 (5) | 0.0064 (5) | 0.0010 (5) |
C22 | 0.0206 (7) | 0.0158 (7) | 0.0281 (8) | 0.0069 (6) | 0.0104 (6) | 0.0043 (6) |
C23 | 0.0212 (7) | 0.0200 (7) | 0.0304 (8) | 0.0098 (6) | 0.0069 (6) | 0.0105 (7) |
C24 | 0.0149 (7) | 0.0166 (7) | 0.0202 (7) | 0.0035 (5) | 0.0032 (5) | 0.0076 (6) |
C25 | 0.0126 (6) | 0.0127 (6) | 0.0124 (6) | 0.0003 (5) | 0.0040 (5) | 0.0030 (5) |
C26 | 0.0126 (6) | 0.0144 (6) | 0.0116 (6) | −0.0008 (5) | 0.0024 (5) | 0.0034 (5) |
C27 | 0.0296 (8) | 0.0230 (8) | 0.0225 (8) | 0.0139 (7) | 0.0024 (6) | 0.0083 (6) |
C28 | 0.0202 (7) | 0.0276 (8) | 0.0209 (7) | 0.0088 (6) | 0.0030 (6) | 0.0129 (6) |
C29 | 0.0151 (6) | 0.0194 (7) | 0.0154 (6) | 0.0083 (5) | 0.0044 (5) | 0.0077 (5) |
C30 | 0.0164 (7) | 0.0241 (7) | 0.0220 (7) | 0.0086 (6) | 0.0083 (6) | 0.0104 (6) |
C31 | 0.0236 (8) | 0.0255 (8) | 0.0183 (7) | 0.0131 (6) | 0.0120 (6) | 0.0097 (6) |
C32 | 0.0231 (7) | 0.0193 (7) | 0.0151 (7) | 0.0127 (6) | 0.0078 (6) | 0.0082 (6) |
C33 | 0.0317 (8) | 0.0224 (7) | 0.0134 (7) | 0.0151 (6) | 0.0087 (6) | 0.0064 (6) |
C34 | 0.0322 (8) | 0.0177 (7) | 0.0116 (6) | 0.0126 (6) | 0.0021 (6) | 0.0032 (5) |
C35 | 0.0235 (7) | 0.0146 (6) | 0.0140 (6) | 0.0095 (6) | 0.0010 (5) | 0.0052 (5) |
C36 | 0.0239 (8) | 0.0163 (7) | 0.0167 (7) | 0.0064 (6) | −0.0044 (6) | 0.0044 (6) |
C37 | 0.0170 (7) | 0.0182 (7) | 0.0235 (8) | 0.0051 (6) | −0.0027 (6) | 0.0080 (6) |
C38 | 0.0172 (7) | 0.0174 (7) | 0.0190 (7) | 0.0078 (5) | 0.0023 (5) | 0.0082 (6) |
C39 | 0.0183 (7) | 0.0140 (6) | 0.0132 (6) | 0.0089 (5) | 0.0029 (5) | 0.0061 (5) |
C40 | 0.0180 (7) | 0.0157 (6) | 0.0124 (6) | 0.0099 (5) | 0.0039 (5) | 0.0066 (5) |
C41 | 0.0164 (7) | 0.0256 (8) | 0.0171 (7) | 0.0041 (6) | 0.0034 (5) | 0.0052 (6) |
C42 | 0.0161 (7) | 0.0240 (8) | 0.0218 (7) | 0.0043 (6) | 0.0046 (6) | 0.0074 (6) |
C43 | 0.0146 (6) | 0.0153 (6) | 0.0205 (7) | 0.0038 (5) | 0.0017 (5) | 0.0063 (6) |
C44 | 0.0176 (7) | 0.0193 (7) | 0.0271 (8) | 0.0048 (6) | 0.0002 (6) | 0.0122 (6) |
C45 | 0.0166 (7) | 0.0231 (7) | 0.0207 (7) | 0.0009 (6) | −0.0015 (6) | 0.0141 (6) |
C46 | 0.0124 (6) | 0.0175 (7) | 0.0154 (7) | −0.0004 (5) | 0.0007 (5) | 0.0076 (5) |
C47 | 0.0165 (7) | 0.0251 (7) | 0.0129 (6) | −0.0001 (6) | 0.0014 (5) | 0.0089 (6) |
C48 | 0.0175 (7) | 0.0211 (7) | 0.0117 (6) | 0.0008 (6) | 0.0045 (5) | 0.0040 (5) |
C49 | 0.0125 (6) | 0.0159 (6) | 0.0134 (6) | 0.0008 (5) | 0.0040 (5) | 0.0042 (5) |
C50 | 0.0161 (7) | 0.0165 (7) | 0.0175 (7) | 0.0046 (5) | 0.0070 (5) | 0.0031 (5) |
C51 | 0.0175 (7) | 0.0187 (7) | 0.0219 (7) | 0.0087 (6) | 0.0066 (6) | 0.0074 (6) |
C52 | 0.0146 (6) | 0.0175 (7) | 0.0161 (7) | 0.0060 (5) | 0.0038 (5) | 0.0068 (5) |
C53 | 0.0106 (6) | 0.0133 (6) | 0.0130 (6) | 0.0012 (5) | 0.0024 (5) | 0.0046 (5) |
C54 | 0.0102 (6) | 0.0140 (6) | 0.0139 (6) | 0.0013 (5) | 0.0017 (5) | 0.0054 (5) |
C55 | 0.0253 (8) | 0.0229 (8) | 0.0238 (8) | 0.0142 (6) | 0.0060 (6) | 0.0067 (6) |
C56 | 0.0290 (8) | 0.0306 (8) | 0.0181 (7) | 0.0175 (7) | 0.0061 (6) | 0.0124 (6) |
C57 | 0.0186 (7) | 0.0217 (7) | 0.0220 (7) | 0.0101 (6) | 0.0080 (6) | 0.0089 (6) |
C58 | 0.0166 (7) | 0.0176 (7) | 0.0185 (7) | 0.0059 (5) | 0.0054 (5) | 0.0089 (6) |
C59 | 0.0118 (6) | 0.0145 (6) | 0.0184 (7) | 0.0045 (5) | 0.0031 (5) | 0.0068 (5) |
C60 | 0.0154 (7) | 0.0209 (7) | 0.0168 (7) | 0.0072 (6) | 0.0041 (5) | 0.0078 (6) |
C61 | 0.0188 (7) | 0.0271 (8) | 0.0215 (7) | 0.0101 (6) | 0.0037 (6) | 0.0137 (6) |
C62 | 0.0141 (6) | 0.0139 (6) | 0.0173 (7) | 0.0050 (5) | 0.0048 (5) | 0.0052 (5) |
N1S | 0.0539 (11) | 0.0338 (9) | 0.0251 (8) | 0.0236 (8) | 0.0044 (7) | 0.0103 (7) |
C1S | 0.0518 (13) | 0.0373 (11) | 0.0402 (11) | 0.0254 (10) | 0.0103 (9) | 0.0215 (9) |
C2S | 0.0539 (12) | 0.0284 (9) | 0.0170 (8) | 0.0271 (9) | 0.0060 (7) | 0.0086 (7) |
Cu1—N1 | 2.0402 (12) | C21—C22 | 1.409 (2) |
Cu1—N2 | 2.0350 (12) | C22—C23 | 1.367 (2) |
Cu1—N3 | 2.0182 (12) | C22—H22 | 0.9500 |
Cu1—N4 | 2.0591 (12) | C23—C24 | 1.414 (2) |
Cu2—N5 | 2.0259 (12) | C23—H23 | 0.9500 |
Cu2—N6 | 2.0587 (12) | C24—C28 | 1.496 (2) |
Cu2—N7 | 2.0602 (12) | C25—C26 | 1.435 (2) |
Cu2—N8 | 2.0261 (12) | C27—H27A | 0.9800 |
P1—F1 | 1.5865 (12) | C27—H27B | 0.9800 |
P1—F5 | 1.5893 (12) | C27—H27C | 0.9800 |
P1—F3 | 1.5916 (11) | C28—H28A | 0.9800 |
P1—F2 | 1.5993 (12) | C28—H28B | 0.9800 |
P1—F4 | 1.6002 (11) | C28—H28C | 0.9800 |
P1—F6 | 1.6035 (11) | C29—C30 | 1.415 (2) |
P2—F12B | 1.465 (9) | C29—C41 | 1.495 (2) |
P2—F7A | 1.558 (3) | C30—C31 | 1.371 (2) |
P2—F11 | 1.5814 (13) | C30—H30 | 0.9500 |
P2—F8 | 1.5908 (12) | C31—C32 | 1.410 (2) |
P2—F10 | 1.5937 (11) | C31—H31 | 0.9500 |
P2—F9 | 1.5966 (13) | C32—C40 | 1.4073 (19) |
P2—F12A | 1.639 (3) | C32—C33 | 1.432 (2) |
P2—F7B | 1.692 (8) | C33—C34 | 1.353 (2) |
N1—C1 | 1.3332 (19) | C33—H33 | 0.9500 |
N1—C12 | 1.3664 (18) | C34—C35 | 1.437 (2) |
N2—C10 | 1.3330 (19) | C34—H34 | 0.9500 |
N2—C11 | 1.3618 (18) | C35—C39 | 1.404 (2) |
N3—C15 | 1.3347 (19) | C35—C36 | 1.413 (2) |
N3—C26 | 1.3647 (18) | C36—C37 | 1.371 (2) |
N4—C24 | 1.3338 (19) | C36—H36 | 0.9500 |
N4—C25 | 1.3649 (18) | C37—C38 | 1.413 (2) |
N5—C29 | 1.3328 (19) | C37—H37 | 0.9500 |
N5—C40 | 1.3658 (18) | C38—C42 | 1.500 (2) |
N6—C38 | 1.3342 (19) | C39—C40 | 1.439 (2) |
N6—C39 | 1.3674 (18) | C41—H41A | 0.9800 |
N7—C43 | 1.3354 (19) | C41—H41B | 0.9800 |
N7—C54 | 1.3638 (18) | C41—H41C | 0.9800 |
N8—C52 | 1.3346 (18) | C42—H42A | 0.9800 |
N8—C53 | 1.3661 (18) | C42—H42B | 0.9800 |
N9—C61 | 1.337 (2) | C42—H42C | 0.9800 |
N9—C57 | 1.347 (2) | C43—C44 | 1.410 (2) |
N10—C62 | 1.279 (2) | C43—C55 | 1.500 (2) |
N10—N10i | 1.415 (2) | C44—C45 | 1.371 (2) |
C1—C2 | 1.412 (2) | C44—H44 | 0.9500 |
C1—C13 | 1.500 (2) | C45—C46 | 1.411 (2) |
C2—C3 | 1.369 (2) | C45—H45 | 0.9500 |
C2—H2 | 0.9500 | C46—C54 | 1.4044 (19) |
C3—C4 | 1.410 (2) | C46—C47 | 1.435 (2) |
C3—H3 | 0.9500 | C47—C48 | 1.356 (2) |
C4—C12 | 1.4079 (19) | C47—H47 | 0.9500 |
C4—C5 | 1.434 (2) | C48—C49 | 1.435 (2) |
C5—C6 | 1.355 (2) | C48—H48 | 0.9500 |
C5—H5 | 0.9500 | C49—C53 | 1.4052 (19) |
C6—C7 | 1.433 (2) | C49—C50 | 1.411 (2) |
C6—H6 | 0.9500 | C50—C51 | 1.369 (2) |
C7—C11 | 1.4049 (19) | C50—H50 | 0.9500 |
C7—C8 | 1.406 (2) | C51—C52 | 1.412 (2) |
C8—C9 | 1.375 (2) | C51—H51 | 0.9500 |
C8—H8 | 0.9500 | C52—C56 | 1.500 (2) |
C9—C10 | 1.408 (2) | C53—C54 | 1.4401 (19) |
C9—H9 | 0.9500 | C55—H55A | 0.9800 |
C10—C14 | 1.500 (2) | C55—H55B | 0.9800 |
C11—C12 | 1.438 (2) | C55—H55C | 0.9800 |
C13—H13A | 0.9800 | C56—H56A | 0.9800 |
C13—H13B | 0.9800 | C56—H56B | 0.9800 |
C13—H13C | 0.9800 | C56—H56C | 0.9800 |
C14—H14A | 0.9800 | C57—C58 | 1.385 (2) |
C14—H14B | 0.9800 | C57—H57 | 0.9500 |
C14—H14C | 0.9800 | C58—C59 | 1.399 (2) |
C15—C16 | 1.406 (2) | C58—H58 | 0.9500 |
C15—C27 | 1.498 (2) | C59—C60 | 1.390 (2) |
C16—C17 | 1.370 (2) | C59—C62 | 1.4673 (19) |
C16—H16 | 0.9500 | C60—C61 | 1.392 (2) |
C17—C18 | 1.409 (2) | C60—H60 | 0.9500 |
C17—H17 | 0.9500 | C61—H61 | 0.9500 |
C18—C26 | 1.4072 (19) | C62—H62 | 0.9500 |
C18—C19 | 1.434 (2) | N1S—C2S | 1.141 (3) |
C19—C20 | 1.351 (3) | C1S—C2S | 1.461 (3) |
C19—H19 | 0.9500 | C1S—H1S1 | 0.9800 |
C20—C21 | 1.432 (2) | C1S—H1S2 | 0.9800 |
C20—H20 | 0.9500 | C1S—H1S3 | 0.9800 |
C21—C25 | 1.4060 (19) | ||
N1—Cu1—N2 | 82.42 (5) | C23—C22—C21 | 119.37 (14) |
N1—Cu1—N3 | 127.02 (5) | C23—C22—H22 | 120.3 |
N1—Cu1—N4 | 128.14 (5) | C21—C22—H22 | 120.3 |
N2—Cu1—N3 | 128.70 (5) | C22—C23—C24 | 120.18 (15) |
N2—Cu1—N4 | 113.29 (5) | C22—C23—H23 | 119.9 |
N3—Cu1—N4 | 82.54 (5) | C24—C23—H23 | 119.9 |
N5—Cu2—N6 | 82.24 (5) | N4—C24—C23 | 121.45 (14) |
N5—Cu2—N7 | 117.54 (5) | N4—C24—C28 | 118.14 (13) |
N5—Cu2—N8 | 134.81 (5) | C23—C24—C28 | 120.40 (14) |
N6—Cu2—N7 | 125.71 (5) | N4—C25—C21 | 122.92 (14) |
N6—Cu2—N8 | 120.45 (5) | N4—C25—C26 | 117.53 (12) |
N7—Cu2—N8 | 82.30 (5) | C21—C25—C26 | 119.55 (13) |
F1—P1—F5 | 90.67 (9) | N3—C26—C18 | 122.81 (14) |
F1—P1—F3 | 90.08 (7) | N3—C26—C25 | 117.20 (12) |
F5—P1—F3 | 90.64 (7) | C18—C26—C25 | 120.00 (13) |
F1—P1—F2 | 89.95 (8) | C15—C27—H27A | 109.5 |
F5—P1—F2 | 179.24 (8) | C15—C27—H27B | 109.5 |
F3—P1—F2 | 89.80 (7) | H27A—C27—H27B | 109.5 |
F1—P1—F4 | 178.84 (8) | C15—C27—H27C | 109.5 |
F5—P1—F4 | 90.34 (8) | H27A—C27—H27C | 109.5 |
F3—P1—F4 | 90.47 (6) | H27B—C27—H27C | 109.5 |
F2—P1—F4 | 89.04 (7) | C24—C28—H28A | 109.5 |
F1—P1—F6 | 90.65 (7) | C24—C28—H28B | 109.5 |
F5—P1—F6 | 89.07 (7) | H28A—C28—H28B | 109.5 |
F3—P1—F6 | 179.22 (7) | C24—C28—H28C | 109.5 |
F2—P1—F6 | 90.49 (7) | H28A—C28—H28C | 109.5 |
F4—P1—F6 | 88.81 (6) | H28B—C28—H28C | 109.5 |
F12B—P2—F7A | 153.7 (8) | N5—C29—C30 | 121.32 (14) |
F12B—P2—F11 | 105.2 (10) | N5—C29—C41 | 117.76 (13) |
F7A—P2—F11 | 95.4 (4) | C30—C29—C41 | 120.87 (14) |
F12B—P2—F8 | 76.2 (6) | C31—C30—C29 | 120.01 (14) |
F7A—P2—F8 | 88.21 (19) | C31—C30—H30 | 120.0 |
F11—P2—F8 | 88.85 (7) | C29—C30—H30 | 120.0 |
F12B—P2—F10 | 101.8 (6) | C30—C31—C32 | 119.73 (14) |
F7A—P2—F10 | 93.62 (18) | C30—C31—H31 | 120.1 |
F11—P2—F10 | 91.82 (7) | C32—C31—H31 | 120.1 |
F8—P2—F10 | 177.99 (8) | C40—C32—C31 | 116.94 (14) |
F12B—P2—F9 | 72.0 (10) | C40—C32—C33 | 119.33 (14) |
F7A—P2—F9 | 87.4 (4) | C31—C32—C33 | 123.71 (14) |
F11—P2—F9 | 177.18 (10) | C34—C33—C32 | 121.10 (14) |
F8—P2—F9 | 90.87 (7) | C34—C33—H33 | 119.5 |
F10—P2—F9 | 88.36 (7) | C32—C33—H33 | 119.5 |
F7A—P2—F12A | 178.0 (3) | C33—C34—C35 | 120.84 (14) |
F11—P2—F12A | 86.56 (17) | C33—C34—H34 | 119.6 |
F8—P2—F12A | 91.7 (2) | C35—C34—H34 | 119.6 |
F10—P2—F12A | 86.4 (2) | C39—C35—C36 | 117.21 (14) |
F9—P2—F12A | 90.64 (18) | C39—C35—C34 | 119.38 (14) |
F12B—P2—F7B | 177.4 (4) | C36—C35—C34 | 123.39 (14) |
F11—P2—F7B | 73.5 (5) | C37—C36—C35 | 119.28 (14) |
F8—P2—F7B | 101.5 (5) | C37—C36—H36 | 120.4 |
F10—P2—F7B | 80.5 (5) | C35—C36—H36 | 120.4 |
F9—P2—F7B | 109.3 (5) | C36—C37—C38 | 120.13 (15) |
F12A—P2—F7B | 155.7 (5) | C36—C37—H37 | 119.9 |
C1—N1—C12 | 118.40 (12) | C38—C37—H37 | 119.9 |
C1—N1—Cu1 | 130.64 (10) | N6—C38—C37 | 121.70 (14) |
C12—N1—Cu1 | 110.96 (9) | N6—C38—C42 | 117.55 (13) |
C10—N2—C11 | 118.74 (12) | C37—C38—C42 | 120.75 (14) |
C10—N2—Cu1 | 129.68 (10) | N6—C39—C35 | 123.26 (14) |
C11—N2—Cu1 | 111.23 (9) | N6—C39—C40 | 117.05 (13) |
C15—N3—C26 | 118.61 (13) | C35—C39—C40 | 119.65 (13) |
C15—N3—Cu1 | 129.28 (10) | N5—C40—C32 | 123.09 (14) |
C26—N3—Cu1 | 112.11 (9) | N5—C40—C39 | 117.23 (12) |
C24—N4—C25 | 118.68 (12) | C32—C40—C39 | 119.62 (13) |
C24—N4—Cu1 | 130.60 (10) | C29—C41—H41A | 109.5 |
C25—N4—Cu1 | 110.60 (9) | C29—C41—H41B | 109.5 |
C29—N5—C40 | 118.88 (12) | H41A—C41—H41B | 109.5 |
C29—N5—Cu2 | 129.05 (10) | C29—C41—H41C | 109.5 |
C40—N5—Cu2 | 111.85 (10) | H41A—C41—H41C | 109.5 |
C38—N6—C39 | 118.34 (13) | H41B—C41—H41C | 109.5 |
C38—N6—Cu2 | 130.65 (10) | C38—C42—H42A | 109.5 |
C39—N6—Cu2 | 110.96 (10) | C38—C42—H42B | 109.5 |
C43—N7—C54 | 118.36 (13) | H42A—C42—H42B | 109.5 |
C43—N7—Cu2 | 130.50 (10) | C38—C42—H42C | 109.5 |
C54—N7—Cu2 | 111.12 (9) | H42A—C42—H42C | 109.5 |
C52—N8—C53 | 118.62 (12) | H42B—C42—H42C | 109.5 |
C52—N8—Cu2 | 129.14 (10) | N7—C43—C44 | 121.54 (14) |
C53—N8—Cu2 | 111.99 (9) | N7—C43—C55 | 117.37 (13) |
C61—N9—C57 | 116.57 (13) | C44—C43—C55 | 121.07 (14) |
C62—N10—N10i | 111.19 (15) | C45—C44—C43 | 120.28 (14) |
N1—C1—C2 | 121.62 (14) | C45—C44—H44 | 119.9 |
N1—C1—C13 | 117.86 (13) | C43—C44—H44 | 119.9 |
C2—C1—C13 | 120.52 (14) | C44—C45—C46 | 119.16 (14) |
C3—C2—C1 | 120.15 (14) | C44—C45—H45 | 120.4 |
C3—C2—H2 | 119.9 | C46—C45—H45 | 120.4 |
C1—C2—H2 | 119.9 | C54—C46—C45 | 117.20 (14) |
C2—C3—C4 | 119.53 (13) | C54—C46—C47 | 119.66 (14) |
C2—C3—H3 | 120.2 | C45—C46—C47 | 123.14 (14) |
C4—C3—H3 | 120.2 | C48—C47—C46 | 120.61 (14) |
C12—C4—C3 | 116.93 (14) | C48—C47—H47 | 119.7 |
C12—C4—C5 | 119.45 (14) | C46—C47—H47 | 119.7 |
C3—C4—C5 | 123.61 (13) | C47—C48—C49 | 121.08 (14) |
C6—C5—C4 | 120.75 (14) | C47—C48—H48 | 119.5 |
C6—C5—H5 | 119.6 | C49—C48—H48 | 119.5 |
C4—C5—H5 | 119.6 | C53—C49—C50 | 117.28 (13) |
C5—C6—C7 | 121.12 (14) | C53—C49—C48 | 119.39 (13) |
C5—C6—H6 | 119.4 | C50—C49—C48 | 123.32 (13) |
C7—C6—H6 | 119.4 | C51—C50—C49 | 119.27 (13) |
C11—C7—C8 | 117.29 (13) | C51—C50—H50 | 120.4 |
C11—C7—C6 | 119.34 (14) | C49—C50—H50 | 120.4 |
C8—C7—C6 | 123.38 (14) | C50—C51—C52 | 120.31 (14) |
C9—C8—C7 | 119.31 (14) | C50—C51—H51 | 119.8 |
C9—C8—H8 | 120.3 | C52—C51—H51 | 119.8 |
C7—C8—H8 | 120.3 | N8—C52—C51 | 121.41 (13) |
C8—C9—C10 | 120.08 (14) | N8—C52—C56 | 117.47 (13) |
C8—C9—H9 | 120.0 | C51—C52—C56 | 121.12 (13) |
C10—C9—H9 | 120.0 | N8—C53—C49 | 123.03 (13) |
N2—C10—C9 | 121.52 (13) | N8—C53—C54 | 117.35 (12) |
N2—C10—C14 | 117.02 (13) | C49—C53—C54 | 119.62 (13) |
C9—C10—C14 | 121.44 (14) | N7—C54—C46 | 123.32 (13) |
N2—C11—C7 | 123.06 (13) | N7—C54—C53 | 117.10 (12) |
N2—C11—C12 | 117.20 (12) | C46—C54—C53 | 119.58 (13) |
C7—C11—C12 | 119.72 (13) | C43—C55—H55A | 109.5 |
N1—C12—C4 | 123.25 (14) | C43—C55—H55B | 109.5 |
N1—C12—C11 | 117.19 (12) | H55A—C55—H55B | 109.5 |
C4—C12—C11 | 119.54 (13) | C43—C55—H55C | 109.5 |
C1—C13—H13A | 109.5 | H55A—C55—H55C | 109.5 |
C1—C13—H13B | 109.5 | H55B—C55—H55C | 109.5 |
H13A—C13—H13B | 109.5 | C52—C56—H56A | 109.5 |
C1—C13—H13C | 109.5 | C52—C56—H56B | 109.5 |
H13A—C13—H13C | 109.5 | H56A—C56—H56B | 109.5 |
H13B—C13—H13C | 109.5 | C52—C56—H56C | 109.5 |
C10—C14—H14A | 109.5 | H56A—C56—H56C | 109.5 |
C10—C14—H14B | 109.5 | H56B—C56—H56C | 109.5 |
H14A—C14—H14B | 109.5 | N9—C57—C58 | 124.20 (14) |
C10—C14—H14C | 109.5 | N9—C57—H57 | 117.9 |
H14A—C14—H14C | 109.5 | C58—C57—H57 | 117.9 |
H14B—C14—H14C | 109.5 | C57—C58—C59 | 118.35 (14) |
N3—C15—C16 | 121.74 (14) | C57—C58—H58 | 120.8 |
N3—C15—C27 | 116.65 (13) | C59—C58—H58 | 120.8 |
C16—C15—C27 | 121.61 (14) | C60—C59—C58 | 118.18 (13) |
C17—C16—C15 | 120.11 (15) | C60—C59—C62 | 119.51 (13) |
C17—C16—H16 | 119.9 | C58—C59—C62 | 122.27 (13) |
C15—C16—H16 | 119.9 | C59—C60—C61 | 118.88 (14) |
C16—C17—C18 | 119.39 (14) | C59—C60—H60 | 120.6 |
C16—C17—H17 | 120.3 | C61—C60—H60 | 120.6 |
C18—C17—H17 | 120.3 | N9—C61—C60 | 123.77 (14) |
C26—C18—C17 | 117.35 (14) | N9—C61—H61 | 118.1 |
C26—C18—C19 | 118.94 (14) | C60—C61—H61 | 118.1 |
C17—C18—C19 | 123.72 (14) | N10—C62—C59 | 120.86 (13) |
C20—C19—C18 | 121.08 (14) | N10—C62—H62 | 119.6 |
C20—C19—H19 | 119.5 | C59—C62—H62 | 119.6 |
C18—C19—H19 | 119.5 | C2S—C1S—H1S1 | 109.5 |
C19—C20—C21 | 121.15 (14) | C2S—C1S—H1S2 | 109.5 |
C19—C20—H20 | 119.4 | H1S1—C1S—H1S2 | 109.5 |
C21—C20—H20 | 119.4 | C2S—C1S—H1S3 | 109.5 |
C25—C21—C22 | 117.37 (14) | H1S1—C1S—H1S3 | 109.5 |
C25—C21—C20 | 119.24 (14) | H1S2—C1S—H1S3 | 109.5 |
C22—C21—C20 | 123.38 (14) | N1S—C2S—C1S | 179.7 (2) |
N3—Cu1—N1—C1 | 38.97 (15) | C24—N4—C25—C26 | −177.92 (13) |
N2—Cu1—N1—C1 | 172.56 (13) | Cu1—N4—C25—C26 | −1.48 (15) |
N4—Cu1—N1—C1 | −73.69 (14) | C22—C21—C25—N4 | −1.5 (2) |
N3—Cu1—N1—C12 | −141.76 (9) | C20—C21—C25—N4 | 177.88 (13) |
N2—Cu1—N1—C12 | −8.16 (9) | C22—C21—C25—C26 | 178.46 (13) |
N4—Cu1—N1—C12 | 105.59 (10) | C20—C21—C25—C26 | −2.1 (2) |
N3—Cu1—N2—C10 | −45.98 (14) | C15—N3—C26—C18 | −0.5 (2) |
N1—Cu1—N2—C10 | −178.17 (13) | Cu1—N3—C26—C18 | 179.62 (11) |
N4—Cu1—N2—C10 | 53.44 (13) | C15—N3—C26—C25 | 179.35 (13) |
N3—Cu1—N2—C11 | 141.01 (9) | Cu1—N3—C26—C25 | −0.52 (15) |
N1—Cu1—N2—C11 | 8.82 (9) | C17—C18—C26—N3 | 0.5 (2) |
N4—Cu1—N2—C11 | −119.57 (9) | C19—C18—C26—N3 | −179.58 (13) |
N2—Cu1—N3—C15 | −66.13 (14) | C17—C18—C26—C25 | −179.35 (13) |
N1—Cu1—N3—C15 | 46.98 (15) | C19—C18—C26—C25 | 0.6 (2) |
N4—Cu1—N3—C15 | 179.92 (13) | N4—C25—C26—N3 | 1.40 (19) |
N2—Cu1—N3—C26 | 113.73 (10) | C21—C25—C26—N3 | −178.59 (12) |
N1—Cu1—N3—C26 | −133.16 (9) | N4—C25—C26—C18 | −178.74 (12) |
N4—Cu1—N3—C26 | −0.22 (9) | C21—C25—C26—C18 | 1.3 (2) |
N3—Cu1—N4—C24 | 176.80 (13) | C40—N5—C29—C30 | 1.4 (2) |
N2—Cu1—N4—C24 | 47.74 (14) | Cu2—N5—C29—C30 | −172.65 (11) |
N1—Cu1—N4—C24 | −51.20 (15) | C40—N5—C29—C41 | −176.17 (13) |
N3—Cu1—N4—C25 | 0.92 (9) | Cu2—N5—C29—C41 | 9.80 (19) |
N2—Cu1—N4—C25 | −128.14 (9) | N5—C29—C30—C31 | −1.9 (2) |
N1—Cu1—N4—C25 | 132.92 (9) | C41—C29—C30—C31 | 175.53 (15) |
N8—Cu2—N5—C29 | −52.44 (15) | C29—C30—C31—C32 | 0.8 (2) |
N6—Cu2—N5—C29 | −178.28 (13) | C30—C31—C32—C40 | 0.8 (2) |
N7—Cu2—N5—C29 | 55.32 (13) | C30—C31—C32—C33 | −177.92 (15) |
N8—Cu2—N5—C40 | 133.19 (9) | C40—C32—C33—C34 | −1.6 (2) |
N6—Cu2—N5—C40 | 7.35 (9) | C31—C32—C33—C34 | 177.07 (15) |
N7—Cu2—N5—C40 | −119.05 (9) | C32—C33—C34—C35 | 0.3 (2) |
N5—Cu2—N6—C38 | 171.54 (13) | C33—C34—C35—C39 | 2.3 (2) |
N8—Cu2—N6—C38 | 33.39 (14) | C33—C34—C35—C36 | −176.38 (14) |
N7—Cu2—N6—C38 | −69.98 (14) | C39—C35—C36—C37 | −0.4 (2) |
N5—Cu2—N6—C39 | −6.00 (9) | C34—C35—C36—C37 | 178.32 (14) |
N8—Cu2—N6—C39 | −144.15 (9) | C35—C36—C37—C38 | 1.7 (2) |
N7—Cu2—N6—C39 | 112.48 (10) | C39—N6—C38—C37 | −1.9 (2) |
N5—Cu2—N7—C43 | 41.70 (14) | Cu2—N6—C38—C37 | −179.33 (10) |
N8—Cu2—N7—C43 | 178.71 (13) | C39—N6—C38—C42 | 177.79 (13) |
N6—Cu2—N7—C43 | −59.11 (14) | Cu2—N6—C38—C42 | 0.4 (2) |
N5—Cu2—N7—C54 | −140.11 (9) | C36—C37—C38—N6 | −0.5 (2) |
N8—Cu2—N7—C54 | −3.10 (9) | C36—C37—C38—C42 | 179.77 (14) |
N6—Cu2—N7—C54 | 119.09 (9) | C38—N6—C39—C35 | 3.3 (2) |
N5—Cu2—N8—C52 | −61.07 (15) | Cu2—N6—C39—C35 | −178.78 (11) |
N6—Cu2—N8—C52 | 50.22 (14) | C38—N6—C39—C40 | −174.15 (12) |
N7—Cu2—N8—C52 | 177.36 (13) | Cu2—N6—C39—C40 | 3.74 (15) |
N5—Cu2—N8—C53 | 124.79 (10) | C36—C35—C39—N6 | −2.2 (2) |
N6—Cu2—N8—C53 | −123.92 (9) | C34—C35—C39—N6 | 179.08 (13) |
N7—Cu2—N8—C53 | 3.22 (9) | C36—C35—C39—C40 | 175.24 (13) |
C12—N1—C1—C2 | −1.6 (2) | C34—C35—C39—C40 | −3.5 (2) |
Cu1—N1—C1—C2 | 177.63 (11) | C29—N5—C40—C32 | 0.3 (2) |
C12—N1—C1—C13 | 178.46 (13) | Cu2—N5—C40—C32 | 175.29 (11) |
Cu1—N1—C1—C13 | −2.3 (2) | C29—N5—C40—C39 | 177.42 (12) |
N1—C1—C2—C3 | −1.6 (2) | Cu2—N5—C40—C39 | −7.57 (15) |
C13—C1—C2—C3 | 178.33 (14) | C31—C32—C40—N5 | −1.4 (2) |
C1—C2—C3—C4 | 2.6 (2) | C33—C32—C40—N5 | 177.40 (13) |
C2—C3—C4—C12 | −0.5 (2) | C31—C32—C40—C39 | −178.43 (13) |
C2—C3—C4—C5 | 177.89 (14) | C33—C32—C40—C39 | 0.3 (2) |
C12—C4—C5—C6 | 2.3 (2) | N6—C39—C40—N5 | 2.56 (18) |
C3—C4—C5—C6 | −176.05 (14) | C35—C39—C40—N5 | −175.02 (12) |
C4—C5—C6—C7 | 0.4 (2) | N6—C39—C40—C32 | 179.80 (12) |
C5—C6—C7—C11 | −2.2 (2) | C35—C39—C40—C32 | 2.2 (2) |
C5—C6—C7—C8 | 177.75 (14) | C54—N7—C43—C44 | −4.0 (2) |
C11—C7—C8—C9 | 0.4 (2) | Cu2—N7—C43—C44 | 174.06 (11) |
C6—C7—C8—C9 | −179.49 (14) | C54—N7—C43—C55 | 174.17 (13) |
C7—C8—C9—C10 | 0.0 (2) | Cu2—N7—C43—C55 | −7.7 (2) |
C11—N2—C10—C9 | 0.8 (2) | N7—C43—C44—C45 | 3.3 (2) |
Cu1—N2—C10—C9 | −171.80 (11) | C55—C43—C44—C45 | −174.85 (15) |
C11—N2—C10—C14 | −177.78 (13) | C43—C44—C45—C46 | 0.3 (2) |
Cu1—N2—C10—C14 | 9.65 (19) | C44—C45—C46—C54 | −2.7 (2) |
C8—C9—C10—N2 | −0.7 (2) | C44—C45—C46—C47 | 177.73 (14) |
C8—C9—C10—C14 | 177.81 (14) | C54—C46—C47—C48 | −1.9 (2) |
C10—N2—C11—C7 | −0.3 (2) | C45—C46—C47—C48 | 177.67 (14) |
Cu1—N2—C11—C7 | 173.61 (11) | C46—C47—C48—C49 | −0.3 (2) |
C10—N2—C11—C12 | 178.05 (12) | C47—C48—C49—C53 | 2.2 (2) |
Cu1—N2—C11—C12 | −8.08 (15) | C47—C48—C49—C50 | −176.86 (14) |
C8—C7—C11—N2 | −0.3 (2) | C53—C49—C50—C51 | 0.7 (2) |
C6—C7—C11—N2 | 179.58 (13) | C48—C49—C50—C51 | 179.83 (14) |
C8—C7—C11—C12 | −178.61 (12) | C49—C50—C51—C52 | 1.7 (2) |
C6—C7—C11—C12 | 1.3 (2) | C53—N8—C52—C51 | 0.4 (2) |
C1—N1—C12—C4 | 3.9 (2) | Cu2—N8—C52—C51 | −173.41 (11) |
Cu1—N1—C12—C4 | −175.49 (11) | C53—N8—C52—C56 | −179.02 (13) |
C1—N1—C12—C11 | −174.36 (12) | Cu2—N8—C52—C56 | 7.2 (2) |
Cu1—N1—C12—C11 | 6.26 (15) | C50—C51—C52—N8 | −2.3 (2) |
C3—C4—C12—N1 | −2.8 (2) | C50—C51—C52—C56 | 177.06 (15) |
C5—C4—C12—N1 | 178.73 (13) | C52—N8—C53—C49 | 2.2 (2) |
C3—C4—C12—C11 | 175.36 (12) | Cu2—N8—C53—C49 | 177.00 (11) |
C5—C4—C12—C11 | −3.1 (2) | C52—N8—C53—C54 | −177.69 (12) |
N2—C11—C12—N1 | 1.24 (18) | Cu2—N8—C53—C54 | −2.87 (15) |
C7—C11—C12—N1 | 179.60 (12) | C50—C49—C53—N8 | −2.7 (2) |
N2—C11—C12—C4 | −177.08 (12) | C48—C49—C53—N8 | 178.12 (13) |
C7—C11—C12—C4 | 1.3 (2) | C50—C49—C53—C54 | 177.13 (13) |
C26—N3—C15—C16 | 0.0 (2) | C48—C49—C53—C54 | −2.0 (2) |
Cu1—N3—C15—C16 | 179.86 (11) | C43—N7—C54—C46 | 1.4 (2) |
C26—N3—C15—C27 | −179.48 (13) | Cu2—N7—C54—C46 | −177.05 (11) |
Cu1—N3—C15—C27 | 0.4 (2) | C43—N7—C54—C53 | −179.08 (12) |
N3—C15—C16—C17 | 0.5 (2) | Cu2—N7—C54—C53 | 2.49 (15) |
C27—C15—C16—C17 | 179.92 (15) | C45—C46—C54—N7 | 2.0 (2) |
C15—C16—C17—C18 | −0.4 (2) | C47—C46—C54—N7 | −178.44 (13) |
C16—C17—C18—C26 | 0.0 (2) | C45—C46—C54—C53 | −177.54 (13) |
C16—C17—C18—C19 | −179.93 (14) | C47—C46—C54—C53 | 2.0 (2) |
C26—C18—C19—C20 | −1.6 (2) | N8—C53—C54—N7 | 0.22 (19) |
C17—C18—C19—C20 | 178.34 (15) | C49—C53—C54—N7 | −179.65 (12) |
C18—C19—C20—C21 | 0.7 (2) | N8—C53—C54—C46 | 179.78 (12) |
C19—C20—C21—C25 | 1.2 (2) | C49—C53—C54—C46 | −0.1 (2) |
C19—C20—C21—C22 | −179.46 (15) | C61—N9—C57—C58 | 1.6 (2) |
C25—C21—C22—C23 | 0.3 (2) | N9—C57—C58—C59 | −1.1 (2) |
C20—C21—C22—C23 | −179.09 (15) | C57—C58—C59—C60 | −0.9 (2) |
C21—C22—C23—C24 | 0.3 (2) | C57—C58—C59—C62 | 176.94 (14) |
C25—N4—C24—C23 | −1.4 (2) | C58—C59—C60—C61 | 2.2 (2) |
Cu1—N4—C24—C23 | −176.96 (11) | C62—C59—C60—C61 | −175.74 (14) |
C25—N4—C24—C28 | 177.70 (13) | C57—N9—C61—C60 | −0.2 (2) |
Cu1—N4—C24—C28 | 2.1 (2) | C59—C60—C61—N9 | −1.7 (2) |
C22—C23—C24—N4 | 0.2 (2) | N10i—N10—C62—C59 | −178.60 (14) |
C22—C23—C24—C28 | −178.86 (15) | C60—C59—C62—N10 | 165.82 (14) |
C24—N4—C25—C21 | 2.1 (2) | C58—C59—C62—N10 | −12.0 (2) |
Cu1—N4—C25—C21 | 178.50 (11) |
Symmetry code: (i) −x+1, −y+1, −z. |
[Cu(C14H12N2)2](C2N3) | F(000) = 1128 |
Mr = 546.12 | Dx = 1.412 Mg m−3 |
Monoclinic, P21/n | Melting point: not measured K |
Hall symbol: -P2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 15.0055 (5) Å | Cell parameters from 19294 reflections |
b = 10.3286 (3) Å | θ = 4.7–56.5° |
c = 16.8878 (5) Å | µ = 0.88 mm−1 |
β = 101.138 (1)° | T = 90 K |
V = 2568.1 (1) Å3 | Parallelepiped, orange |
Z = 4 | 0.3 × 0.2 × 0.1 mm |
Bruker SMART CCD area-detector diffractometer | 7446 independent reflections |
Radiation source: rotating anode | 6422 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 30.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −21→21 |
Tmin = 0.719, Tmax = 0.941 | k = −14→14 |
44252 measured reflections | l = −23→23 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | H-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 reflections | Δρmax = 0.45 e Å−3 |
348 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0108 (6) |
[Cu(C14H12N2)2](C2N3) | V = 2568.1 (1) Å3 |
Mr = 546.12 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 15.0055 (5) Å | µ = 0.88 mm−1 |
b = 10.3286 (3) Å | T = 90 K |
c = 16.8878 (5) Å | 0.3 × 0.2 × 0.1 mm |
β = 101.138 (1)° |
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 = 0.941 | Rint = 0.033 |
44252 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.45 e Å−3 |
7446 reflections | Δρmin = −0.39 e Å−3 |
348 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.775418 (10) | 0.295452 (15) | 0.054163 (9) | 0.01750 (6) | |
N1 | 0.78925 (7) | 0.10113 (10) | 0.05254 (6) | 0.01492 (19) | |
N3 | 0.71650 (7) | 0.40778 (10) | −0.04079 (6) | 0.0159 (2) | |
N2 | 0.91389 (7) | 0.28856 (10) | 0.08982 (6) | 0.0162 (2) | |
N4 | 0.69177 (7) | 0.39728 (10) | 0.11180 (6) | 0.0166 (2) | |
C26 | 0.66039 (8) | 0.49860 (11) | −0.01785 (7) | 0.0146 (2) | |
N6 | 0.45912 (9) | 0.08346 (13) | 0.19782 (9) | 0.0337 (3) | |
C18 | 0.61373 (8) | 0.59160 (12) | −0.07100 (8) | 0.0168 (2) | |
C21 | 0.59059 (8) | 0.58410 (12) | 0.09139 (8) | 0.0181 (2) | |
C12 | 0.87787 (8) | 0.06378 (11) | 0.07237 (7) | 0.0140 (2) | |
C3 | 0.83686 (9) | −0.16001 (13) | 0.05273 (8) | 0.0209 (2) | |
H3 | 0.8521 | −0.2492 | 0.0519 | 0.025* | |
C7 | 1.03710 (8) | 0.13094 (12) | 0.11500 (7) | 0.0167 (2) | |
C25 | 0.64792 (8) | 0.49387 (11) | 0.06440 (7) | 0.0153 (2) | |
C9 | 1.06786 (9) | 0.35842 (13) | 0.13225 (9) | 0.0234 (3) | |
H9 | 1.1092 | 0.4282 | 0.1462 | 0.028* | |
C23 | 0.62178 (10) | 0.47432 (15) | 0.21863 (9) | 0.0253 (3) | |
H23 | 0.6135 | 0.4651 | 0.2727 | 0.030* | |
C27 | 0.78719 (11) | 0.30235 (14) | −0.14058 (9) | 0.0257 (3) | |
H27A | 0.8384 | 0.2868 | −0.0960 | 0.039* | |
H27B | 0.8101 | 0.3295 | −0.1885 | 0.039* | |
H27C | 0.7518 | 0.2226 | −0.1525 | 0.039* | |
C16 | 0.68493 (9) | 0.49894 (13) | −0.17373 (8) | 0.0213 (2) | |
H16 | 0.6952 | 0.4976 | −0.2275 | 0.026* | |
C19 | 0.55435 (9) | 0.68147 (12) | −0.04193 (9) | 0.0198 (2) | |
H19 | 0.5220 | 0.7438 | −0.0777 | 0.024* | |
C17 | 0.62828 (9) | 0.59055 (13) | −0.15105 (8) | 0.0208 (2) | |
H17 | 0.5992 | 0.6526 | −0.1890 | 0.025* | |
C22 | 0.57983 (10) | 0.57342 (14) | 0.17223 (9) | 0.0236 (3) | |
H22 | 0.5438 | 0.6344 | 0.1942 | 0.028* | |
C14 | 0.93809 (10) | 0.51921 (13) | 0.10180 (10) | 0.0260 (3) | |
H14A | 0.9282 | 0.5469 | 0.0453 | 0.039* | |
H14B | 0.9820 | 0.5772 | 0.1347 | 0.039* | |
H14C | 0.8805 | 0.5222 | 0.1209 | 0.039* | |
C24 | 0.67736 (9) | 0.38536 (13) | 0.18694 (8) | 0.0205 (2) | |
C8 | 1.09975 (9) | 0.23319 (14) | 0.13516 (9) | 0.0221 (3) | |
H8 | 1.1629 | 0.2159 | 0.1505 | 0.026* | |
C11 | 0.94461 (8) | 0.16388 (12) | 0.09319 (7) | 0.0148 (2) | |
C6 | 1.06375 (9) | −0.00253 (13) | 0.11465 (8) | 0.0193 (2) | |
H6 | 1.1262 | −0.0251 | 0.1285 | 0.023* | |
C4 | 0.90559 (8) | −0.06626 (12) | 0.07322 (7) | 0.0161 (2) | |
C15 | 0.72777 (9) | 0.40696 (12) | −0.11717 (8) | 0.0183 (2) | |
N7 | 0.29411 (10) | 0.04206 (16) | 0.16951 (9) | 0.0358 (3) | |
C1 | 0.72529 (8) | 0.01055 (13) | 0.03414 (8) | 0.0184 (2) | |
C10 | 0.97425 (9) | 0.38352 (13) | 0.10870 (8) | 0.0196 (2) | |
C5 | 1.00031 (9) | −0.09668 (12) | 0.09469 (8) | 0.0193 (2) | |
H5 | 1.0191 | −0.1845 | 0.0950 | 0.023* | |
C28 | 0.72234 (11) | 0.27445 (15) | 0.23640 (9) | 0.0267 (3) | |
H28A | 0.7229 | 0.1985 | 0.2017 | 0.040* | |
H28B | 0.6887 | 0.2541 | 0.2791 | 0.040* | |
H28C | 0.7849 | 0.2982 | 0.2607 | 0.040* | |
C20 | 0.54403 (9) | 0.67816 (13) | 0.03594 (9) | 0.0207 (2) | |
H20 | 0.5052 | 0.7393 | 0.0542 | 0.025* | |
C30 | 0.37201 (10) | 0.05583 (14) | 0.18202 (9) | 0.0253 (3) | |
C13 | 0.62866 (9) | 0.05463 (14) | 0.01348 (10) | 0.0260 (3) | |
H13A | 0.6125 | 0.0987 | 0.0601 | 0.039* | |
H13B | 0.5889 | −0.0205 | −0.0009 | 0.039* | |
H13C | 0.6213 | 0.1146 | −0.0323 | 0.039* | |
C2 | 0.74786 (9) | −0.12181 (13) | 0.03393 (9) | 0.0227 (3) | |
H2 | 0.7012 | −0.1848 | 0.0207 | 0.027* | |
C29 | 0.51677 (11) | −0.01107 (17) | 0.19272 (10) | 0.0309 (3) | |
N5 | 0.57204 (12) | −0.0879 (2) | 0.19002 (11) | 0.0506 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01722 (9) | 0.01421 (8) | 0.02046 (9) | 0.00531 (5) | 0.00212 (6) | 0.00099 (5) |
N1 | 0.0151 (5) | 0.0143 (5) | 0.0152 (4) | 0.0020 (4) | 0.0024 (4) | 0.0003 (3) |
N3 | 0.0148 (4) | 0.0142 (5) | 0.0183 (5) | 0.0019 (4) | 0.0025 (4) | −0.0003 (4) |
N2 | 0.0182 (5) | 0.0129 (5) | 0.0168 (5) | 0.0018 (4) | 0.0017 (4) | 0.0000 (4) |
N4 | 0.0164 (5) | 0.0142 (5) | 0.0189 (5) | 0.0002 (4) | 0.0025 (4) | −0.0008 (4) |
C26 | 0.0119 (5) | 0.0122 (5) | 0.0191 (5) | 0.0000 (4) | 0.0018 (4) | −0.0009 (4) |
N6 | 0.0280 (6) | 0.0240 (6) | 0.0456 (8) | 0.0016 (5) | −0.0012 (6) | 0.0014 (6) |
C18 | 0.0133 (5) | 0.0131 (5) | 0.0227 (6) | 0.0003 (4) | 0.0001 (4) | 0.0002 (4) |
C21 | 0.0152 (5) | 0.0146 (5) | 0.0252 (6) | −0.0013 (4) | 0.0051 (4) | −0.0046 (4) |
C12 | 0.0159 (5) | 0.0129 (5) | 0.0133 (5) | 0.0021 (4) | 0.0027 (4) | 0.0004 (4) |
C3 | 0.0240 (6) | 0.0124 (5) | 0.0260 (6) | 0.0017 (5) | 0.0043 (5) | −0.0002 (5) |
C7 | 0.0158 (5) | 0.0167 (5) | 0.0168 (5) | 0.0030 (4) | 0.0016 (4) | −0.0002 (4) |
C25 | 0.0132 (5) | 0.0128 (5) | 0.0195 (5) | −0.0016 (4) | 0.0024 (4) | −0.0021 (4) |
C9 | 0.0202 (6) | 0.0187 (6) | 0.0294 (7) | −0.0033 (5) | 0.0004 (5) | −0.0020 (5) |
C23 | 0.0309 (7) | 0.0254 (7) | 0.0217 (6) | −0.0013 (5) | 0.0100 (5) | −0.0042 (5) |
C27 | 0.0308 (7) | 0.0248 (7) | 0.0237 (6) | 0.0109 (5) | 0.0107 (5) | 0.0019 (5) |
C16 | 0.0231 (6) | 0.0219 (6) | 0.0185 (6) | 0.0027 (5) | 0.0032 (5) | 0.0030 (5) |
C19 | 0.0148 (5) | 0.0134 (5) | 0.0298 (7) | 0.0020 (4) | 0.0006 (5) | 0.0002 (5) |
C17 | 0.0197 (6) | 0.0182 (6) | 0.0228 (6) | 0.0022 (5) | 0.0000 (5) | 0.0044 (5) |
C22 | 0.0245 (6) | 0.0207 (6) | 0.0276 (7) | 0.0002 (5) | 0.0100 (5) | −0.0073 (5) |
C14 | 0.0270 (7) | 0.0138 (6) | 0.0347 (7) | 0.0006 (5) | −0.0002 (6) | −0.0013 (5) |
C24 | 0.0228 (6) | 0.0199 (6) | 0.0189 (6) | −0.0020 (5) | 0.0039 (5) | −0.0017 (5) |
C8 | 0.0164 (6) | 0.0219 (6) | 0.0263 (6) | 0.0002 (5) | 0.0003 (5) | −0.0010 (5) |
C11 | 0.0161 (5) | 0.0132 (5) | 0.0148 (5) | 0.0020 (4) | 0.0022 (4) | −0.0002 (4) |
C6 | 0.0176 (5) | 0.0191 (6) | 0.0204 (6) | 0.0066 (4) | 0.0017 (4) | 0.0003 (5) |
C4 | 0.0193 (6) | 0.0131 (5) | 0.0160 (5) | 0.0026 (4) | 0.0036 (4) | 0.0004 (4) |
C15 | 0.0183 (6) | 0.0170 (6) | 0.0197 (6) | 0.0027 (4) | 0.0039 (4) | 0.0005 (4) |
N7 | 0.0278 (7) | 0.0489 (9) | 0.0325 (7) | 0.0066 (6) | 0.0102 (5) | 0.0011 (6) |
C1 | 0.0161 (5) | 0.0175 (6) | 0.0214 (6) | 0.0007 (4) | 0.0032 (4) | −0.0002 (4) |
C10 | 0.0217 (6) | 0.0147 (5) | 0.0216 (6) | 0.0006 (4) | 0.0022 (5) | −0.0003 (4) |
C5 | 0.0211 (6) | 0.0154 (5) | 0.0210 (6) | 0.0070 (4) | 0.0031 (5) | 0.0009 (4) |
C28 | 0.0338 (8) | 0.0262 (7) | 0.0202 (6) | 0.0027 (6) | 0.0050 (5) | 0.0040 (5) |
C20 | 0.0160 (5) | 0.0137 (5) | 0.0325 (7) | 0.0020 (4) | 0.0050 (5) | −0.0037 (5) |
C30 | 0.0313 (7) | 0.0241 (7) | 0.0207 (6) | 0.0058 (5) | 0.0054 (5) | 0.0021 (5) |
C13 | 0.0147 (6) | 0.0237 (7) | 0.0383 (8) | 0.0008 (5) | 0.0015 (5) | −0.0036 (6) |
C2 | 0.0214 (6) | 0.0164 (6) | 0.0297 (7) | −0.0030 (5) | 0.0031 (5) | −0.0012 (5) |
C29 | 0.0265 (7) | 0.0365 (8) | 0.0279 (7) | 0.0031 (6) | 0.0007 (6) | 0.0013 (6) |
N5 | 0.0385 (8) | 0.0611 (11) | 0.0497 (10) | 0.0199 (8) | 0.0020 (7) | −0.0073 (8) |
Cu1—N1 | 2.0185 (11) | C23—H23 | 0.9500 |
Cu1—N4 | 2.0251 (11) | C27—C15 | 1.5016 (18) |
Cu1—N3 | 2.0374 (11) | C27—H27A | 0.9800 |
Cu1—N2 | 2.0498 (11) | C27—H27B | 0.9800 |
N1—C1 | 1.3333 (16) | C27—H27C | 0.9800 |
N1—C12 | 1.3628 (15) | C16—C17 | 1.3749 (19) |
N3—C15 | 1.3330 (16) | C16—C15 | 1.4110 (18) |
N3—C26 | 1.3656 (15) | C16—H16 | 0.9500 |
N2—C10 | 1.3314 (16) | C19—C20 | 1.354 (2) |
N2—C11 | 1.3653 (15) | C19—H19 | 0.9500 |
N4—C24 | 1.3336 (17) | C17—H17 | 0.9500 |
N4—C25 | 1.3657 (16) | C22—H22 | 0.9500 |
C26—C18 | 1.4056 (16) | C14—C10 | 1.4992 (19) |
C26—C25 | 1.4378 (17) | C14—H14A | 0.9800 |
N6—C30 | 1.314 (2) | C14—H14B | 0.9800 |
N6—C29 | 1.318 (2) | C14—H14C | 0.9800 |
C18—C17 | 1.4105 (19) | C24—C28 | 1.499 (2) |
C18—C19 | 1.4371 (17) | C8—H8 | 0.9500 |
C21—C25 | 1.4028 (17) | C6—C5 | 1.3570 (19) |
C21—C22 | 1.4098 (19) | C6—H6 | 0.9500 |
C21—C20 | 1.4339 (19) | C4—C5 | 1.4323 (17) |
C12—C4 | 1.4053 (16) | N7—C30 | 1.156 (2) |
C12—C11 | 1.4351 (17) | C1—C2 | 1.4085 (19) |
C3—C2 | 1.3698 (19) | C1—C13 | 1.4954 (18) |
C3—C4 | 1.4082 (18) | C5—H5 | 0.9500 |
C3—H3 | 0.9500 | C28—H28A | 0.9800 |
C7—C11 | 1.4070 (17) | C28—H28B | 0.9800 |
C7—C8 | 1.4113 (18) | C28—H28C | 0.9800 |
C7—C6 | 1.4357 (17) | C20—H20 | 0.9500 |
C9—C8 | 1.377 (2) | C13—H13A | 0.9800 |
C9—C10 | 1.4081 (19) | C13—H13B | 0.9800 |
C9—H9 | 0.9500 | C13—H13C | 0.9800 |
C23—C22 | 1.367 (2) | C2—H2 | 0.9500 |
C23—C24 | 1.4136 (19) | C29—N5 | 1.155 (2) |
N1—Cu1—N4 | 126.72 (4) | C16—C17—H17 | 120.3 |
N1—Cu1—N3 | 125.85 (4) | C18—C17—H17 | 120.3 |
N4—Cu1—N3 | 82.39 (4) | C23—C22—C21 | 119.18 (12) |
N1—Cu1—N2 | 82.44 (4) | C23—C22—H22 | 120.4 |
N4—Cu1—N2 | 124.34 (4) | C21—C22—H22 | 120.4 |
N3—Cu1—N2 | 120.80 (4) | C10—C14—H14A | 109.5 |
C1—N1—C12 | 118.87 (11) | C10—C14—H14B | 109.5 |
C1—N1—Cu1 | 129.02 (9) | H14A—C14—H14B | 109.5 |
C12—N1—Cu1 | 112.10 (8) | C10—C14—H14C | 109.5 |
C15—N3—C26 | 118.64 (11) | H14A—C14—H14C | 109.5 |
C15—N3—Cu1 | 129.88 (9) | H14B—C14—H14C | 109.5 |
C26—N3—Cu1 | 111.44 (8) | N4—C24—C23 | 121.07 (13) |
C10—N2—C11 | 118.44 (11) | N4—C24—C28 | 117.54 (12) |
C10—N2—Cu1 | 130.46 (9) | C23—C24—C28 | 121.39 (12) |
C11—N2—Cu1 | 111.10 (8) | C9—C8—C7 | 118.92 (12) |
C24—N4—C25 | 118.48 (11) | C9—C8—H8 | 120.5 |
C24—N4—Cu1 | 129.71 (9) | C7—C8—H8 | 120.5 |
C25—N4—Cu1 | 111.77 (8) | N2—C11—C7 | 123.16 (11) |
N3—C26—C18 | 123.14 (11) | N2—C11—C12 | 117.08 (11) |
N3—C26—C25 | 116.94 (11) | C7—C11—C12 | 119.76 (11) |
C18—C26—C25 | 119.89 (11) | C5—C6—C7 | 120.43 (12) |
C30—N6—C29 | 117.74 (14) | C5—C6—H6 | 119.8 |
C26—C18—C17 | 117.16 (11) | C7—C6—H6 | 119.8 |
C26—C18—C19 | 119.24 (12) | C12—C4—C3 | 116.97 (11) |
C17—C18—C19 | 123.59 (12) | C12—C4—C5 | 119.31 (11) |
C25—C21—C22 | 117.05 (12) | C3—C4—C5 | 123.72 (11) |
C25—C21—C20 | 119.34 (12) | N3—C15—C16 | 121.63 (12) |
C22—C21—C20 | 123.56 (12) | N3—C15—C27 | 116.88 (11) |
N1—C12—C4 | 123.09 (11) | C16—C15—C27 | 121.49 (12) |
N1—C12—C11 | 117.26 (10) | N1—C1—C2 | 121.27 (12) |
C4—C12—C11 | 119.66 (11) | N1—C1—C13 | 117.56 (12) |
C2—C3—C4 | 119.59 (12) | C2—C1—C13 | 121.18 (12) |
C2—C3—H3 | 120.2 | N2—C10—C9 | 121.83 (12) |
C4—C3—H3 | 120.2 | N2—C10—C14 | 116.80 (12) |
C11—C7—C8 | 117.36 (11) | C9—C10—C14 | 121.36 (12) |
C11—C7—C6 | 119.51 (12) | C6—C5—C4 | 121.32 (11) |
C8—C7—C6 | 123.12 (12) | C6—C5—H5 | 119.3 |
N4—C25—C21 | 123.44 (12) | C4—C5—H5 | 119.3 |
N4—C25—C26 | 116.95 (11) | C24—C28—H28A | 109.5 |
C21—C25—C26 | 119.58 (11) | C24—C28—H28B | 109.5 |
C8—C9—C10 | 120.27 (12) | H28A—C28—H28B | 109.5 |
C8—C9—H9 | 119.9 | C24—C28—H28C | 109.5 |
C10—C9—H9 | 119.9 | H28A—C28—H28C | 109.5 |
C22—C23—C24 | 120.66 (13) | H28B—C28—H28C | 109.5 |
C22—C23—H23 | 119.7 | C19—C20—C21 | 121.24 (12) |
C24—C23—H23 | 119.7 | C19—C20—H20 | 119.4 |
C15—C27—H27A | 109.5 | C21—C20—H20 | 119.4 |
C15—C27—H27B | 109.5 | N7—C30—N6 | 174.36 (17) |
H27A—C27—H27B | 109.5 | C1—C13—H13A | 109.5 |
C15—C27—H27C | 109.5 | C1—C13—H13B | 109.5 |
H27A—C27—H27C | 109.5 | H13A—C13—H13B | 109.5 |
H27B—C27—H27C | 109.5 | C1—C13—H13C | 109.5 |
C17—C16—C15 | 120.01 (12) | H13A—C13—H13C | 109.5 |
C17—C16—H16 | 120.0 | H13B—C13—H13C | 109.5 |
C15—C16—H16 | 120.0 | C3—C2—C1 | 120.21 (12) |
C20—C19—C18 | 120.68 (12) | C3—C2—H2 | 119.9 |
C20—C19—H19 | 119.7 | C1—C2—H2 | 119.9 |
C18—C19—H19 | 119.7 | N5—C29—N6 | 175.3 (2) |
C16—C17—C18 | 119.39 (12) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu(C14H12N2)2]2(PF6)2(C12H10N4)0.5·C2H3N | [Cu(C14H12N2)2](C2N3) |
Mr | 1396.24 | 546.12 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 90 | 90 |
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 |
V (Å3) | 2957.96 (18) | 2568.1 (1) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.86 | 0.88 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 | 0.3 × 0.2 × 0.1 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.782, 0.919 | 0.719, 0.941 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 45314, 14342, 12664 | 44252, 7446, 6422 |
Rint | 0.023 | 0.033 |
(sin θ/λ)max (Å−1) | 0.662 | 0.703 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.082, 1.04 | 0.029, 0.085, 1.06 |
No. of reflections | 14342 | 7446 |
No. of parameters | 849 | 348 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.03, −0.69 | 0.45, −0.39 |
Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Cu1—N1 | 2.0402 (12) | Cu2—N5 | 2.0259 (12) |
Cu1—N2 | 2.0350 (12) | Cu2—N6 | 2.0587 (12) |
Cu1—N3 | 2.0182 (12) | Cu2—N7 | 2.0602 (12) |
Cu1—N4 | 2.0591 (12) | Cu2—N8 | 2.0261 (12) |
N1—Cu1—N2 | 82.42 (5) | N5—Cu2—N6 | 82.24 (5) |
N1—Cu1—N3 | 127.02 (5) | N5—Cu2—N7 | 117.54 (5) |
N1—Cu1—N4 | 128.14 (5) | N5—Cu2—N8 | 134.81 (5) |
N2—Cu1—N3 | 128.70 (5) | N6—Cu2—N7 | 125.71 (5) |
N2—Cu1—N4 | 113.29 (5) | N6—Cu2—N8 | 120.45 (5) |
N3—Cu1—N4 | 82.54 (5) | N7—Cu2—N8 | 82.30 (5) |
Cu1—N1 | 2.0185 (11) | Cu1—N3 | 2.0374 (11) |
Cu1—N4 | 2.0251 (11) | Cu1—N2 | 2.0498 (11) |
N1—Cu1—N4 | 126.72 (4) | N3—Cu1—N2 | 120.80 (4) |
N1—Cu1—N3 | 125.85 (4) | C30—N6—C29 | 117.74 (14) |
N4—Cu1—N3 | 82.39 (4) | N7—C30—N6 | 174.36 (17) |
N1—Cu1—N2 | 82.44 (4) | N5—C29—N6 | 175.3 (2) |
N4—Cu1—N2 | 124.34 (4) |
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 π–π 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 π–π 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)°.