Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111054102/fn3092sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111054102/fn3092Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111054102/fn3092IIsup3.hkl |
CCDC references: 866745; 866746
meso-Tetraphenylporphyrin [H2(TPP), from now on] was synthesized according to the extensively used method devised by Adler et al. (1967). Chloroform was dried over molecular sieves while methanol was dried over metallic Mg. Both solvents were distilled prior to use.
H2(TPP) (120 mg, ~0.2 mmol) was dissolved in chloroform (8 ml). Then, a 2 M solution of HCl (0.5 ml) was added to methanol (2.5 ml) and poured into the porphyrin solution. The resulting green solution was stirred for 10 min and then left to slowly crystallize at 263 K. After a few days, a small quantity of [H4(TPP)]Cl2.8CHCl3 single crystals, suitable for X-ray analysis, appeared on the bottom of the flask. This deep-blue product was extremely unstable at room temperature, redissolving after some minutes if left in the solution and becoming very brittle while turning completely opaque when dried, at which point no reflections could be taken with the diffractometer (we suspect this was caused by the loss of the most volatile chloroform moieties). Therefore, extreme caution had to be observed in order to pick a fresh and appropriate crystal.
(5,10,15,20-Tetraphenylporphyrinato)copper(II) (CuTPP for short), (II), was synthesized by refluxing CuCl2.2H2O (234 mg) in dimethylformamide (50 ml) in the presence of H2(TPP) (425 mg) over a period of 2.5 h. The product was completely dried, washed twice with water and purified by chromatography on an alumina column, using chloroform as the eluent. The resulting red phase containing CuTPP was left open to the atmosphere at room temperature. After a few days, the chloroform had evaporated, leaving well formed crystals of CuTPP, (II).
All C- and N-bound H atoms were refined in isotropic approximation as riding on their parent atoms, with aromatic C—H = 0.95 Å, methine C—H = 1.00 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N). The disorder in four of the eight chloroform molecules in (I) required a rather complex model. The solvent molecule containing atom C46 was ordered, but refined using isotropic Cl atoms. The three chloroform molecules containing atoms C47, C48 and C49, respectively, were fully ordered and were refined with anisotropic displacement parameters for the non-H atoms. The chloroform molecule containing atom C45 was refined as being disordered over three positions. The anisotropic displacement parameters of each disordered position for atom C45 were constrained to be equal, while isotropic displacement parameters were refined for the Cl atoms in all three orientations and constrained to be equal in one orientation. A SUMP restraint (Sheldrick, 2008) in the form of sof(1) + sof(2) + sof(3) = 1.000 (1) was applied and gave a final distribution of the parts as 0.734 (6)/0.191 (5)/0.077 (4). Notably, the omission of the third orientation of this chloroform molecule results in a substantial increase of the R1 index by ca 0.7%. The three solvent molecules containing atoms C50, C51 and C52, were found to be disordered and were refined as being split over two orientations with final occupation-factor ratios of 0.529 (19):0.471 (19), 0.904 (4):0.096 (4) and 0.587 (14):0.413 (14), respectively. Isotropic displacement parameters were refined for all non-H atoms of these solvent molecules, except for those of the Cl atoms of the minor orientation of the molecule containing atom C51, which were kept fixed at 0.04 Å2. In addition the isotropic displacement parameters of the two disordered C atom positions of each of these solvent molecules were constrained to be equal. The C—Cl and Cl···Cl distances in all of the disordered chloroform molecules were restrained to 1.737 (2) and 2.848 (2) Å, respectively, as described in the Comment. Despite the complex disorder model, the residual electron density (located in the disordered solvent region) is still high, indicating that the real structure is perhaps even more complex. This may be the main reason for the relatively large value of R1.
For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999), publCIF (Westrip, 2010) and PLATON (Spek, 2009).
C44H32N42+·2Cl−·8CHCl3 | Z = 2 |
Mr = 1642.58 | F(000) = 1644 |
Triclinic, P1 | Dx = 1.58 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6031 (3) Å | Cell parameters from 11928 reflections |
b = 12.6132 (3) Å | θ = 2.3–28.7° |
c = 24.5118 (6) Å | µ = 1.06 mm−1 |
α = 87.706 (2)° | T = 120 K |
β = 82.025 (2)° | Prism, blue |
γ = 76.356 (2)° | 0.49 × 0.40 × 0.22 mm |
V = 3452.31 (15) Å3 |
Oxford Diffraction Xcalibur Sapphire2 (large Be window) diffractometer | 12824 independent reflections |
Radiation source: Mo Ka radiation | 9236 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 8.1883 pixels mm-1 | θmax = 25.5°, θmin = 2.3° |
ω scans | h = −12→14 |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2006), a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | k = −15→15 |
Tmin = 0.705, Tmax = 0.823 | l = −29→26 |
22549 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.095 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.261 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.1268P)2 + 26.0222P] where P = (Fo2 + 2Fc2)/3 |
12824 reflections | (Δ/σ)max = 0.035 |
720 parameters | Δρmax = 3.32 e Å−3 |
55 restraints | Δρmin = −2.09 e Å−3 |
C44H32N42+·2Cl−·8CHCl3 | γ = 76.356 (2)° |
Mr = 1642.58 | V = 3452.31 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.6031 (3) Å | Mo Kα radiation |
b = 12.6132 (3) Å | µ = 1.06 mm−1 |
c = 24.5118 (6) Å | T = 120 K |
α = 87.706 (2)° | 0.49 × 0.40 × 0.22 mm |
β = 82.025 (2)° |
Oxford Diffraction Xcalibur Sapphire2 (large Be window) diffractometer | 12824 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2006), a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | 9236 reflections with I > 2σ(I) |
Tmin = 0.705, Tmax = 0.823 | Rint = 0.030 |
22549 measured reflections |
R[F2 > 2σ(F2)] = 0.095 | 55 restraints |
wR(F2) = 0.261 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.1268P)2 + 26.0222P] where P = (Fo2 + 2Fc2)/3 |
12824 reflections | Δρmax = 3.32 e Å−3 |
720 parameters | Δρmin = −2.09 e Å−3 |
Experimental. CrysAlisPro (Oxford Diffraction, 2006), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (Clark & Reid, 1995) |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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) | |
C1 | 0.3898 (6) | 0.7809 (5) | 0.1483 (3) | 0.0195 (13) | |
C2 | 0.4636 (6) | 0.7226 (5) | 0.1020 (3) | 0.0213 (14) | |
H2 | 0.4898 | 0.7537 | 0.0679 | 0.026* | |
C3 | 0.4892 (6) | 0.6149 (5) | 0.1157 (3) | 0.0202 (13) | |
H3 | 0.536 | 0.5574 | 0.0927 | 0.024* | |
C4 | 0.4339 (6) | 0.6030 (5) | 0.1704 (3) | 0.0194 (13) | |
C5 | 0.4387 (6) | 0.5052 (5) | 0.2010 (3) | 0.0195 (13) | |
C6 | 0.5358 (6) | 0.4088 (5) | 0.1822 (3) | 0.0208 (13) | |
C7 | 0.6507 (6) | 0.4207 (6) | 0.1650 (3) | 0.0253 (15) | |
H7 | 0.6689 | 0.4899 | 0.1674 | 0.03* | |
C8 | 0.7402 (7) | 0.3316 (7) | 0.1441 (3) | 0.0370 (19) | |
H8 | 0.8188 | 0.3402 | 0.1317 | 0.044* | |
C9 | 0.7138 (8) | 0.2316 (7) | 0.1415 (3) | 0.040 (2) | |
H9 | 0.7745 | 0.1712 | 0.1268 | 0.048* | |
C10 | 0.6007 (9) | 0.2176 (6) | 0.1598 (3) | 0.040 (2) | |
H10 | 0.5841 | 0.1476 | 0.1583 | 0.049* | |
C11 | 0.5111 (7) | 0.3055 (5) | 0.1804 (3) | 0.0267 (15) | |
H11 | 0.4331 | 0.2958 | 0.1932 | 0.032* | |
C12 | 0.3558 (6) | 0.4931 (5) | 0.2472 (3) | 0.0187 (13) | |
C13 | 0.3704 (6) | 0.4106 (5) | 0.2893 (3) | 0.0235 (14) | |
H13 | 0.4409 | 0.3557 | 0.2925 | 0.028* | |
C14 | 0.2667 (6) | 0.4246 (6) | 0.3235 (3) | 0.0250 (15) | |
H14 | 0.2515 | 0.3809 | 0.3549 | 0.03* | |
C15 | 0.1834 (6) | 0.5164 (5) | 0.3045 (3) | 0.0213 (14) | |
C16 | 0.0635 (6) | 0.5578 (6) | 0.3267 (3) | 0.0233 (14) | |
C17 | 0.0007 (6) | 0.4843 (6) | 0.3623 (3) | 0.0260 (15) | |
C18 | −0.0001 (7) | 0.3814 (6) | 0.3438 (3) | 0.0316 (17) | |
H18 | 0.0429 | 0.3568 | 0.309 | 0.038* | |
C19 | −0.0626 (7) | 0.3144 (7) | 0.3754 (4) | 0.0390 (19) | |
H19 | −0.0625 | 0.2445 | 0.3623 | 0.047* | |
C20 | −0.1251 (7) | 0.3501 (7) | 0.4262 (4) | 0.042 (2) | |
H20 | −0.1684 | 0.3047 | 0.448 | 0.05* | |
C21 | −0.1246 (8) | 0.4519 (7) | 0.4451 (3) | 0.044 (2) | |
H21 | −0.1668 | 0.4756 | 0.4802 | 0.053* | |
C22 | −0.0631 (7) | 0.5192 (6) | 0.4135 (3) | 0.0346 (18) | |
H22 | −0.0643 | 0.5893 | 0.4266 | 0.042* | |
C23 | −0.0028 (6) | 0.6644 (6) | 0.3173 (3) | 0.0222 (14) | |
C24 | −0.1291 (6) | 0.7035 (6) | 0.3255 (3) | 0.0269 (15) | |
H24 | −0.1857 | 0.6614 | 0.3378 | 0.032* | |
C25 | −0.1552 (6) | 0.8116 (6) | 0.3126 (3) | 0.0244 (14) | |
H25 | −0.2331 | 0.858 | 0.3143 | 0.029* | |
C26 | −0.0445 (6) | 0.8431 (5) | 0.2959 (3) | 0.0205 (13) | |
C27 | −0.0292 (6) | 0.9477 (5) | 0.2809 (3) | 0.0223 (14) | |
C28 | −0.1286 (6) | 1.0417 (6) | 0.3007 (3) | 0.0241 (14) | |
C29 | −0.1843 (6) | 1.0444 (6) | 0.3550 (3) | 0.0236 (14) | |
H29 | −0.1568 | 0.9868 | 0.3796 | 0.028* | |
C30 | −0.2790 (7) | 1.1295 (6) | 0.3737 (3) | 0.0298 (16) | |
H30 | −0.317 | 1.1292 | 0.4106 | 0.036* | |
C31 | −0.3184 (6) | 1.2151 (6) | 0.3386 (3) | 0.0284 (16) | |
H31 | −0.3833 | 1.2738 | 0.3513 | 0.034* | |
C32 | −0.2621 (7) | 1.2144 (6) | 0.2846 (3) | 0.0325 (17) | |
H32 | −0.2881 | 1.2735 | 0.2605 | 0.039* | |
C33 | −0.1693 (7) | 1.1291 (6) | 0.2658 (3) | 0.0288 (16) | |
H33 | −0.1323 | 1.1294 | 0.2287 | 0.035* | |
C34 | 0.0729 (6) | 0.9683 (5) | 0.2493 (3) | 0.0218 (14) | |
C35 | 0.1117 (6) | 1.0682 (5) | 0.2450 (3) | 0.0238 (14) | |
H35 | 0.0727 | 1.1339 | 0.2639 | 0.029* | |
C36 | 0.2142 (7) | 1.0529 (6) | 0.2089 (3) | 0.0253 (15) | |
H36 | 0.2588 | 1.1062 | 0.198 | 0.03* | |
C37 | 0.2431 (6) | 0.9433 (5) | 0.1902 (3) | 0.0208 (14) | |
C38 | 0.3416 (6) | 0.8949 (5) | 0.1516 (3) | 0.0195 (13) | |
C39 | 0.3982 (6) | 0.9664 (5) | 0.1134 (3) | 0.0211 (14) | |
C40 | 0.3253 (7) | 1.0549 (5) | 0.0875 (3) | 0.0284 (16) | |
H40 | 0.2407 | 1.0653 | 0.0938 | 0.034* | |
C41 | 0.3756 (8) | 1.1260 (6) | 0.0532 (3) | 0.0353 (18) | |
H41 | 0.326 | 1.1848 | 0.0359 | 0.042* | |
C42 | 0.4981 (8) | 1.1113 (6) | 0.0443 (3) | 0.0331 (18) | |
H42 | 0.5328 | 1.1612 | 0.0214 | 0.04* | |
C43 | 0.5707 (7) | 1.0251 (6) | 0.0682 (3) | 0.0318 (17) | |
H43 | 0.6551 | 1.0152 | 0.0612 | 0.038* | |
C44 | 0.5212 (6) | 0.9520 (6) | 0.1028 (3) | 0.0242 (14) | |
H44 | 0.572 | 0.8924 | 0.119 | 0.029* | |
N1 | 0.3737 (5) | 0.7053 (4) | 0.1884 (2) | 0.0174 (11) | |
H1 | 0.3311 | 0.72 | 0.2209 | 0.021* | |
N2 | 0.2419 (5) | 0.5558 (4) | 0.2586 (2) | 0.0173 (11) | |
H2A | 0.2108 | 0.613 | 0.2393 | 0.021* | |
N3 | 0.0456 (5) | 0.7509 (4) | 0.2987 (2) | 0.0189 (11) | |
H3A | 0.1225 | 0.7477 | 0.29 | 0.023* | |
N4 | 0.1567 (5) | 0.8948 (4) | 0.2160 (2) | 0.0191 (11) | |
H4 | 0.155 | 0.8262 | 0.2119 | 0.023* | |
Cl1 | 0.30940 (15) | 0.76859 (13) | 0.31206 (6) | 0.0231 (4) | |
Cl2 | 0.10941 (14) | 0.68414 (13) | 0.16279 (7) | 0.0242 (4) | |
C45 | −0.1730 (9) | 0.6478 (8) | 0.1828 (4) | 0.031 (2)* | 0.734 (6) |
H45 | −0.1218 | 0.6986 | 0.189 | 0.038* | 0.734 (6) |
Cl3 | −0.3208 (3) | 0.7083 (3) | 0.21054 (16) | 0.0321 (10)* | 0.734 (6) |
Cl4 | −0.1675 (3) | 0.6305 (4) | 0.11151 (13) | 0.0391 (9)* | 0.734 (6) |
Cl5 | −0.1208 (2) | 0.5219 (2) | 0.21636 (11) | 0.0347 (8)* | 0.734 (6) |
C45A | −0.128 (3) | 0.570 (3) | 0.1860 (10) | 0.031 (2)* | 0.077 (4) |
H45A | −0.0678 | 0.6112 | 0.1934 | 0.038* | 0.077 (4) |
Cl3A | −0.2618 (15) | 0.6348 (14) | 0.2249 (7) | 0.017 (4)* | 0.077 (4) |
Cl4A | −0.1435 (18) | 0.5924 (18) | 0.1166 (6) | 0.017 (4)* | 0.077 (4) |
Cl5A | −0.0727 (15) | 0.4374 (13) | 0.2060 (7) | 0.017 (4)* | 0.077 (4) |
C45B | −0.202 (2) | 0.7166 (18) | 0.1783 (8) | 0.031 (2)* | 0.191 (5) |
H45B | −0.1278 | 0.6771 | 0.1935 | 0.038* | 0.191 (5) |
Cl3B | −0.3256 (8) | 0.6935 (8) | 0.2219 (4) | 0.012 (3)* | 0.191 (5) |
Cl4B | −0.1951 (12) | 0.6719 (11) | 0.1108 (4) | 0.038 (3)* | 0.191 (5) |
Cl5B | −0.2041 (7) | 0.8556 (6) | 0.1744 (3) | 0.021 (2)* | 0.191 (5) |
C46 | 0.5163 (8) | 0.5804 (7) | 0.3777 (4) | 0.043 (2) | |
H46 | 0.4485 | 0.6244 | 0.3594 | 0.052* | |
Cl6 | 0.5736 (3) | 0.6682 (3) | 0.41431 (13) | 0.0693 (7)* | |
Cl7 | 0.6284 (2) | 0.5122 (2) | 0.32691 (10) | 0.0544 (6)* | |
Cl8 | 0.4635 (3) | 0.4836 (2) | 0.42229 (11) | 0.0625 (7)* | |
C47 | 0.2978 (7) | 0.1794 (7) | 0.4729 (3) | 0.0349 (18) | |
H47 | 0.2985 | 0.1151 | 0.4502 | 0.042* | |
Cl9 | 0.4284 (2) | 0.2243 (2) | 0.45121 (10) | 0.0591 (7) | |
Cl10 | 0.2918 (2) | 0.1384 (2) | 0.54240 (9) | 0.0552 (6) | |
Cl11 | 0.1719 (2) | 0.2815 (2) | 0.46321 (9) | 0.0515 (6) | |
C48 | 0.1570 (7) | 0.8937 (7) | 0.4277 (3) | 0.0354 (18) | |
H48 | 0.2163 | 0.8529 | 0.3978 | 0.043* | |
Cl12 | 0.2284 (3) | 0.8918 (3) | 0.48634 (11) | 0.0700 (8) | |
Cl13 | 0.1083 (2) | 1.0289 (2) | 0.40557 (12) | 0.0595 (7) | |
Cl14 | 0.0374 (2) | 0.8291 (2) | 0.44134 (10) | 0.0518 (6) | |
C49 | 0.4190 (7) | 1.0040 (6) | 0.3108 (3) | 0.0316 (17) | |
H49 | 0.3581 | 0.9621 | 0.3058 | 0.038* | |
Cl15 | 0.3467 (2) | 1.14431 (16) | 0.31629 (9) | 0.0436 (5) | |
Cl16 | 0.4794 (2) | 0.95855 (19) | 0.37185 (10) | 0.0517 (6) | |
Cl17 | 0.5289 (2) | 0.9820 (2) | 0.25393 (11) | 0.0647 (7) | |
C50 | 0.2417 (13) | 0.6847 (13) | 0.0267 (10) | 0.044 (2)* | 0.529 (19) |
H50 | 0.2451 | 0.6599 | 0.0658 | 0.052* | 0.529 (19) |
Cl18 | 0.2011 (8) | 0.8325 (7) | 0.0277 (5) | 0.081 (3)* | 0.529 (19) |
Cl19 | 0.1258 (3) | 0.6338 (5) | 0.00320 (16) | 0.0278 (16)* | 0.529 (19) |
Cl20 | 0.3702 (6) | 0.6075 (5) | −0.0120 (2) | 0.0337 (18)* | 0.529 (19) |
C50A | 0.2432 (14) | 0.6698 (13) | 0.0220 (11) | 0.044 (2)* | 0.471 (19) |
H50A | 0.2516 | 0.6539 | 0.0618 | 0.052* | 0.471 (19) |
Cl1D | 0.2185 (4) | 0.8172 (4) | 0.0141 (2) | 0.0214 (17)* | 0.471 (19) |
Cl2D | 0.1357 (9) | 0.5966 (12) | 0.0055 (4) | 0.086 (3)* | 0.471 (19) |
Cl3D | 0.3877 (5) | 0.6204 (5) | −0.0149 (2) | 0.0217 (16)* | 0.471 (19) |
C51 | −0.0601 (9) | 0.9125 (8) | 0.1040 (4) | 0.045 (2)* | 0.904 (4) |
H51 | 0.0005 | 0.844 | 0.1106 | 0.054* | 0.904 (4) |
Cl21 | 0.0059 (2) | 1.0208 (2) | 0.10610 (10) | 0.0393 (6)* | 0.904 (4) |
Cl22 | −0.1815 (2) | 0.9244 (2) | 0.15746 (10) | 0.0464 (7)* | 0.904 (4) |
Cl23 | −0.1045 (3) | 0.9033 (2) | 0.03786 (12) | 0.0491 (7)* | 0.904 (4) |
C51A | −0.070 (3) | 0.880 (3) | 0.0899 (11) | 0.045 (2)* | 0.096 (4) |
H51A | −0.016 | 0.8141 | 0.1043 | 0.054* | 0.096 (4) |
Cl1E | −0.0145 (19) | 0.9938 (19) | 0.0991 (9) | 0.04* | 0.096 (4) |
Cl2E | −0.2132 (17) | 0.8943 (17) | 0.1256 (8) | 0.04* | 0.096 (4) |
Cl3E | −0.069 (2) | 0.8634 (19) | 0.0200 (7) | 0.04* | 0.096 (4) |
C52 | 0.1672 (15) | 0.4057 (17) | 0.1222 (6) | 0.050 (3)* | 0.587 (14) |
H52 | 0.1178 | 0.4817 | 0.1284 | 0.06* | 0.587 (14) |
Cl24 | 0.3081 (5) | 0.4220 (5) | 0.0767 (4) | 0.0664 (18)* | 0.587 (14) |
Cl25 | 0.1775 (5) | 0.3459 (4) | 0.1919 (2) | 0.0315 (15)* | 0.587 (14) |
Cl26 | 0.0694 (5) | 0.3325 (5) | 0.0963 (4) | 0.0650 (16)* | 0.587 (14) |
C52A | 0.1483 (18) | 0.418 (2) | 0.1231 (7) | 0.050 (3)* | 0.413 (14) |
H52A | 0.1009 | 0.4944 | 0.1306 | 0.06* | 0.413 (14) |
Cl1C | 0.2977 (4) | 0.4144 (4) | 0.0929 (2) | 0.0175 (16)* | 0.413 (14) |
Cl2C | 0.1657 (8) | 0.3424 (7) | 0.1835 (4) | 0.047 (3)* | 0.413 (14) |
Cl3C | 0.0861 (4) | 0.3516 (4) | 0.0772 (3) | 0.0228 (17)* | 0.413 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.019 (3) | 0.019 (3) | 0.021 (3) | −0.006 (3) | −0.004 (3) | 0.001 (3) |
C2 | 0.024 (3) | 0.018 (3) | 0.021 (3) | −0.005 (3) | 0.001 (3) | −0.002 (3) |
C3 | 0.021 (3) | 0.015 (3) | 0.023 (3) | −0.001 (3) | −0.004 (3) | −0.002 (3) |
C4 | 0.015 (3) | 0.015 (3) | 0.028 (3) | −0.003 (2) | −0.005 (3) | 0.000 (3) |
C5 | 0.021 (3) | 0.018 (3) | 0.023 (3) | −0.008 (3) | −0.007 (3) | −0.001 (3) |
C6 | 0.023 (3) | 0.020 (3) | 0.018 (3) | 0.002 (3) | −0.008 (3) | 0.000 (3) |
C7 | 0.025 (4) | 0.023 (3) | 0.023 (3) | 0.002 (3) | −0.003 (3) | 0.005 (3) |
C8 | 0.031 (4) | 0.042 (5) | 0.028 (4) | 0.010 (4) | 0.000 (3) | 0.006 (3) |
C9 | 0.044 (5) | 0.037 (5) | 0.024 (4) | 0.020 (4) | −0.004 (3) | 0.000 (3) |
C10 | 0.064 (6) | 0.020 (4) | 0.033 (4) | 0.007 (4) | −0.022 (4) | −0.006 (3) |
C11 | 0.030 (4) | 0.017 (3) | 0.031 (4) | 0.001 (3) | −0.011 (3) | 0.000 (3) |
C12 | 0.019 (3) | 0.014 (3) | 0.023 (3) | −0.003 (3) | −0.005 (3) | 0.000 (2) |
C13 | 0.026 (4) | 0.017 (3) | 0.028 (4) | −0.005 (3) | −0.007 (3) | 0.007 (3) |
C14 | 0.025 (4) | 0.022 (3) | 0.028 (4) | −0.007 (3) | −0.003 (3) | 0.007 (3) |
C15 | 0.026 (4) | 0.013 (3) | 0.025 (3) | −0.005 (3) | −0.004 (3) | 0.000 (3) |
C16 | 0.024 (4) | 0.024 (3) | 0.023 (3) | −0.008 (3) | 0.000 (3) | −0.003 (3) |
C17 | 0.025 (4) | 0.026 (4) | 0.029 (4) | −0.013 (3) | 0.001 (3) | 0.005 (3) |
C18 | 0.027 (4) | 0.031 (4) | 0.037 (4) | −0.008 (3) | −0.001 (3) | 0.002 (3) |
C19 | 0.037 (5) | 0.029 (4) | 0.054 (5) | −0.015 (4) | −0.008 (4) | 0.012 (4) |
C20 | 0.035 (4) | 0.042 (5) | 0.051 (5) | −0.019 (4) | −0.005 (4) | 0.023 (4) |
C21 | 0.046 (5) | 0.049 (5) | 0.033 (4) | −0.013 (4) | 0.010 (4) | 0.010 (4) |
C22 | 0.042 (5) | 0.025 (4) | 0.034 (4) | −0.010 (3) | 0.009 (3) | 0.001 (3) |
C23 | 0.026 (4) | 0.023 (3) | 0.018 (3) | −0.009 (3) | 0.001 (3) | −0.001 (3) |
C24 | 0.023 (4) | 0.029 (4) | 0.027 (4) | −0.008 (3) | 0.002 (3) | −0.001 (3) |
C25 | 0.018 (3) | 0.030 (4) | 0.024 (3) | −0.002 (3) | −0.003 (3) | −0.002 (3) |
C26 | 0.018 (3) | 0.024 (3) | 0.016 (3) | 0.001 (3) | −0.001 (2) | 0.000 (3) |
C27 | 0.029 (4) | 0.022 (3) | 0.016 (3) | −0.004 (3) | −0.007 (3) | −0.001 (3) |
C28 | 0.022 (3) | 0.026 (4) | 0.022 (3) | −0.003 (3) | −0.001 (3) | −0.001 (3) |
C29 | 0.023 (3) | 0.025 (4) | 0.019 (3) | 0.000 (3) | −0.002 (3) | 0.001 (3) |
C30 | 0.026 (4) | 0.033 (4) | 0.026 (4) | 0.001 (3) | 0.002 (3) | −0.003 (3) |
C31 | 0.021 (4) | 0.026 (4) | 0.032 (4) | 0.005 (3) | −0.001 (3) | −0.004 (3) |
C32 | 0.041 (4) | 0.025 (4) | 0.026 (4) | 0.002 (3) | −0.006 (3) | 0.004 (3) |
C33 | 0.032 (4) | 0.030 (4) | 0.022 (3) | −0.004 (3) | −0.003 (3) | 0.002 (3) |
C34 | 0.025 (4) | 0.018 (3) | 0.017 (3) | 0.005 (3) | −0.001 (3) | −0.002 (3) |
C35 | 0.030 (4) | 0.016 (3) | 0.021 (3) | 0.001 (3) | −0.001 (3) | 0.000 (3) |
C36 | 0.030 (4) | 0.018 (3) | 0.025 (3) | −0.004 (3) | 0.001 (3) | 0.003 (3) |
C37 | 0.021 (3) | 0.019 (3) | 0.019 (3) | 0.001 (3) | −0.003 (3) | 0.004 (3) |
C38 | 0.021 (3) | 0.019 (3) | 0.019 (3) | −0.005 (3) | −0.005 (3) | 0.000 (3) |
C39 | 0.024 (3) | 0.019 (3) | 0.018 (3) | −0.003 (3) | 0.000 (3) | 0.002 (3) |
C40 | 0.034 (4) | 0.017 (3) | 0.030 (4) | −0.001 (3) | 0.001 (3) | 0.002 (3) |
C41 | 0.053 (5) | 0.026 (4) | 0.027 (4) | −0.011 (4) | −0.006 (3) | 0.006 (3) |
C42 | 0.057 (5) | 0.029 (4) | 0.022 (3) | −0.027 (4) | −0.006 (3) | 0.004 (3) |
C43 | 0.035 (4) | 0.039 (4) | 0.026 (4) | −0.020 (4) | 0.001 (3) | −0.001 (3) |
C44 | 0.031 (4) | 0.022 (3) | 0.021 (3) | −0.009 (3) | −0.003 (3) | 0.000 (3) |
N1 | 0.016 (3) | 0.016 (3) | 0.018 (3) | −0.002 (2) | 0.000 (2) | 0.001 (2) |
N2 | 0.019 (3) | 0.014 (3) | 0.019 (3) | −0.003 (2) | −0.002 (2) | 0.002 (2) |
N3 | 0.016 (3) | 0.019 (3) | 0.019 (3) | −0.003 (2) | 0.003 (2) | 0.000 (2) |
N4 | 0.022 (3) | 0.012 (3) | 0.020 (3) | 0.000 (2) | 0.000 (2) | 0.002 (2) |
Cl1 | 0.0243 (8) | 0.0225 (8) | 0.0220 (8) | −0.0042 (6) | −0.0033 (6) | −0.0018 (6) |
Cl2 | 0.0215 (8) | 0.0254 (8) | 0.0244 (8) | −0.0008 (6) | −0.0056 (6) | −0.0014 (6) |
C46 | 0.044 (5) | 0.037 (5) | 0.051 (5) | −0.008 (4) | −0.017 (4) | 0.000 (4) |
C47 | 0.036 (4) | 0.043 (5) | 0.029 (4) | −0.017 (4) | −0.002 (3) | −0.002 (3) |
Cl9 | 0.0474 (13) | 0.0858 (19) | 0.0497 (13) | −0.0359 (13) | 0.0124 (10) | −0.0109 (12) |
Cl10 | 0.0698 (16) | 0.0734 (16) | 0.0369 (11) | −0.0422 (14) | −0.0189 (11) | 0.0205 (11) |
Cl11 | 0.0483 (13) | 0.0555 (14) | 0.0441 (12) | −0.0036 (11) | −0.0007 (10) | 0.0076 (10) |
C48 | 0.041 (5) | 0.044 (5) | 0.024 (4) | −0.018 (4) | 0.003 (3) | −0.003 (3) |
Cl12 | 0.091 (2) | 0.0820 (19) | 0.0587 (15) | −0.0491 (17) | −0.0434 (15) | 0.0284 (14) |
Cl13 | 0.0626 (16) | 0.0467 (13) | 0.0759 (17) | −0.0191 (12) | −0.0258 (13) | 0.0159 (12) |
Cl14 | 0.0542 (14) | 0.0619 (15) | 0.0488 (12) | −0.0336 (12) | −0.0065 (10) | 0.0067 (11) |
C49 | 0.040 (4) | 0.024 (4) | 0.031 (4) | −0.009 (3) | −0.002 (3) | 0.000 (3) |
Cl15 | 0.0518 (13) | 0.0266 (10) | 0.0506 (12) | −0.0008 (9) | −0.0137 (10) | −0.0065 (9) |
Cl16 | 0.0687 (16) | 0.0411 (12) | 0.0484 (13) | −0.0106 (11) | −0.0247 (11) | 0.0091 (10) |
Cl17 | 0.0527 (15) | 0.0761 (18) | 0.0526 (14) | −0.0016 (13) | 0.0158 (11) | −0.0079 (13) |
C1—N1 | 1.367 (8) | C37—C38 | 1.411 (9) |
C1—C38 | 1.417 (9) | C38—C39 | 1.470 (9) |
C1—C2 | 1.436 (9) | C39—C44 | 1.384 (10) |
C2—C3 | 1.359 (9) | C39—C40 | 1.419 (10) |
C2—H2 | 0.95 | C40—C41 | 1.378 (10) |
C3—C4 | 1.423 (9) | C40—H40 | 0.95 |
C3—H3 | 0.95 | C41—C42 | 1.377 (12) |
C4—N1 | 1.371 (8) | C41—H41 | 0.95 |
C4—C5 | 1.411 (9) | C42—C43 | 1.375 (11) |
C5—C12 | 1.409 (9) | C42—H42 | 0.95 |
C5—C6 | 1.488 (9) | C43—C44 | 1.396 (10) |
C6—C7 | 1.383 (10) | C43—H43 | 0.95 |
C6—C11 | 1.402 (10) | C44—H44 | 0.95 |
C7—C8 | 1.398 (10) | N1—H1 | 0.88 |
C7—H7 | 0.95 | N2—H2A | 0.88 |
C8—C9 | 1.373 (13) | N3—H3A | 0.88 |
C8—H8 | 0.95 | N4—H4 | 0.88 |
C9—C10 | 1.376 (13) | C45—Cl3 | 1.756 (10) |
C9—H9 | 0.95 | C45—Cl4 | 1.761 (9) |
C10—C11 | 1.386 (11) | C45—Cl5 | 1.773 (10) |
C10—H10 | 0.95 | C45—H45 | 1 |
C11—H11 | 0.95 | C45A—Cl5A | 1.72 (2) |
C12—N2 | 1.368 (8) | C45A—Cl4A | 1.74 (2) |
C12—C13 | 1.432 (9) | C45A—Cl3A | 1.74 (2) |
C13—C14 | 1.346 (10) | C45A—H45A | 1 |
C13—H13 | 0.95 | C45B—Cl3B | 1.741 (19) |
C14—C15 | 1.430 (9) | C45B—Cl5B | 1.747 (19) |
C14—H14 | 0.95 | C45B—Cl4B | 1.754 (19) |
C15—N2 | 1.369 (8) | C45B—H45 | 0.9755 |
C15—C16 | 1.406 (10) | C45B—H45B | 1 |
C16—C23 | 1.411 (10) | C46—Cl6 | 1.751 (9) |
C16—C17 | 1.492 (9) | C46—Cl7 | 1.758 (10) |
C17—C18 | 1.394 (11) | C46—Cl8 | 1.767 (9) |
C17—C22 | 1.397 (10) | C46—H46 | 1 |
C18—C19 | 1.386 (11) | C47—Cl11 | 1.742 (9) |
C18—H18 | 0.95 | C47—Cl9 | 1.748 (8) |
C19—C20 | 1.387 (13) | C47—Cl10 | 1.756 (8) |
C19—H19 | 0.95 | C47—H47 | 1 |
C20—C21 | 1.384 (13) | C48—Cl12 | 1.752 (8) |
C20—H20 | 0.95 | C48—Cl13 | 1.755 (9) |
C21—C22 | 1.382 (11) | C48—Cl14 | 1.756 (8) |
C21—H21 | 0.95 | C48—H48 | 1 |
C22—H22 | 0.95 | C49—Cl17 | 1.737 (8) |
C23—N3 | 1.375 (8) | C49—Cl16 | 1.759 (8) |
C23—C24 | 1.420 (10) | C49—Cl15 | 1.772 (8) |
C24—C25 | 1.359 (10) | C49—H49 | 1 |
C24—H24 | 0.95 | C50—Cl20 | 1.752 (15) |
C25—C26 | 1.434 (10) | C50—Cl19 | 1.790 (16) |
C25—H25 | 0.95 | C50—Cl18 | 1.811 (15) |
C26—N3 | 1.375 (8) | C50—H50 | 1 |
C26—C27 | 1.401 (9) | C50A—Cl3D | 1.774 (16) |
C27—C34 | 1.394 (10) | C50A—Cl2D | 1.813 (16) |
C27—C28 | 1.489 (10) | C50A—Cl1D | 1.820 (16) |
C28—C29 | 1.396 (9) | C50A—H50A | 1 |
C28—C33 | 1.400 (10) | C51—Cl21 | 1.722 (9) |
C29—C30 | 1.382 (10) | C51—Cl22 | 1.768 (9) |
C29—H29 | 0.95 | C51—Cl23 | 1.784 (9) |
C30—C31 | 1.383 (10) | C51—H51 | 1 |
C30—H30 | 0.95 | C51A—Cl3E | 1.73 (2) |
C31—C32 | 1.393 (10) | C51A—Cl2E | 1.74 (2) |
C31—H31 | 0.95 | C51A—Cl1E | 1.74 (2) |
C32—C33 | 1.373 (10) | C51A—H51A | 1 |
C32—H32 | 0.95 | C52—Cl26 | 1.812 (15) |
C33—H33 | 0.95 | C52—Cl25 | 1.847 (14) |
C34—N4 | 1.374 (8) | C52—Cl24 | 1.896 (14) |
C34—C35 | 1.431 (10) | C52—H52 | 1 |
C35—C36 | 1.359 (10) | C52A—Cl2C | 1.738 (18) |
C35—H35 | 0.95 | C52A—Cl3C | 1.754 (18) |
C36—C37 | 1.421 (10) | C52A—Cl1C | 1.779 (18) |
C36—H36 | 0.95 | C52A—H52A | 1 |
C37—N4 | 1.364 (9) | ||
N1—C1—C38 | 126.4 (6) | C1—C38—C39 | 118.3 (6) |
N1—C1—C2 | 107.0 (5) | C44—C39—C40 | 118.4 (6) |
C38—C1—C2 | 126.6 (6) | C44—C39—C38 | 122.1 (6) |
C3—C2—C1 | 107.6 (6) | C40—C39—C38 | 119.5 (6) |
C3—C2—H2 | 126.2 | C41—C40—C39 | 120.8 (7) |
C1—C2—H2 | 126.2 | C41—C40—H40 | 119.6 |
C2—C3—C4 | 108.4 (6) | C39—C40—H40 | 119.6 |
C2—C3—H3 | 125.8 | C42—C41—C40 | 119.6 (7) |
C4—C3—H3 | 125.8 | C42—C41—H41 | 120.2 |
N1—C4—C5 | 125.8 (6) | C40—C41—H41 | 120.2 |
N1—C4—C3 | 107.0 (5) | C43—C42—C41 | 120.6 (7) |
C5—C4—C3 | 127.2 (6) | C43—C42—H42 | 119.7 |
C12—C5—C4 | 123.9 (6) | C41—C42—H42 | 119.7 |
C12—C5—C6 | 118.4 (6) | C42—C43—C44 | 120.5 (7) |
C4—C5—C6 | 117.6 (6) | C42—C43—H43 | 119.8 |
C7—C6—C11 | 119.3 (6) | C44—C43—H43 | 119.8 |
C7—C6—C5 | 120.2 (6) | C39—C44—C43 | 120.0 (7) |
C11—C6—C5 | 120.4 (6) | C39—C44—H44 | 120 |
C6—C7—C8 | 120.3 (7) | C43—C44—H44 | 120 |
C6—C7—H7 | 119.8 | C1—N1—C4 | 109.9 (5) |
C8—C7—H7 | 119.8 | C1—N1—H1 | 125 |
C9—C8—C7 | 119.6 (8) | C4—N1—H1 | 125 |
C9—C8—H8 | 120.2 | C12—N2—C15 | 110.1 (5) |
C7—C8—H8 | 120.2 | C12—N2—H2A | 124.9 |
C8—C9—C10 | 120.9 (7) | C15—N2—H2A | 124.9 |
C8—C9—H9 | 119.6 | C23—N3—C26 | 109.5 (5) |
C10—C9—H9 | 119.6 | C23—N3—H3A | 125.2 |
C9—C10—C11 | 120.1 (8) | C26—N3—H3A | 125.2 |
C9—C10—H10 | 120 | C37—N4—C34 | 110.3 (5) |
C11—C10—H10 | 120 | C37—N4—H4 | 124.9 |
C10—C11—C6 | 119.8 (7) | C34—N4—H4 | 124.9 |
C10—C11—H11 | 120.1 | Cl3—C45—Cl4 | 108.9 (5) |
C6—C11—H11 | 120.1 | Cl3—C45—Cl5 | 110.7 (5) |
N2—C12—C5 | 125.7 (6) | Cl4—C45—Cl5 | 111.5 (5) |
N2—C12—C13 | 106.7 (5) | Cl3—C45—H45 | 107.8 |
C5—C12—C13 | 127.5 (6) | Cl4—C45—H45 | 109.1 |
C14—C13—C12 | 108.1 (6) | Cl5—C45—H45 | 108.8 |
C14—C13—H13 | 126 | Cl5A—C45A—Cl4A | 116.7 (19) |
C12—C13—H13 | 126 | Cl5A—C45A—Cl3A | 114.1 (18) |
C13—C14—C15 | 108.5 (6) | Cl4A—C45A—Cl3A | 108.4 (16) |
C13—C14—H14 | 125.8 | Cl5A—C45A—H45A | 105.6 |
C15—C14—H14 | 125.8 | Cl4A—C45A—H45A | 105.6 |
N2—C15—C16 | 125.7 (6) | Cl3A—C45A—H45A | 105.6 |
N2—C15—C14 | 106.6 (6) | Cl3B—C45B—Cl5B | 110.8 (13) |
C16—C15—C14 | 127.7 (6) | Cl3B—C45B—Cl4B | 113.1 (13) |
C15—C16—C23 | 124.4 (6) | Cl5B—C45B—Cl4B | 107.2 (12) |
C15—C16—C17 | 118.3 (6) | Cl3B—C45B—H45 | 122 |
C23—C16—C17 | 117.3 (6) | Cl5B—C45B—H45 | 91.8 |
C18—C17—C22 | 118.7 (6) | Cl4B—C45B—H45 | 109.2 |
C18—C17—C16 | 120.5 (6) | Cl3B—C45B—H45B | 108.5 |
C22—C17—C16 | 120.7 (6) | Cl5B—C45B—H45B | 108.5 |
C19—C18—C17 | 121.1 (7) | Cl4B—C45B—H45B | 108.5 |
C19—C18—H18 | 119.4 | H45—C45B—H45B | 17.9 |
C17—C18—H18 | 119.4 | Cl6—C46—Cl7 | 109.7 (5) |
C18—C19—C20 | 119.5 (8) | Cl6—C46—Cl8 | 110.8 (5) |
C18—C19—H19 | 120.3 | Cl7—C46—Cl8 | 109.4 (5) |
C20—C19—H19 | 120.3 | Cl6—C46—H46 | 108.9 |
C21—C20—C19 | 120.0 (7) | Cl7—C46—H46 | 108.9 |
C21—C20—H20 | 120 | Cl8—C46—H46 | 108.9 |
C19—C20—H20 | 120 | Cl11—C47—Cl9 | 110.5 (5) |
C22—C21—C20 | 120.6 (8) | Cl11—C47—Cl10 | 110.3 (4) |
C22—C21—H21 | 119.7 | Cl9—C47—Cl10 | 110.7 (4) |
C20—C21—H21 | 119.7 | Cl11—C47—H47 | 108.4 |
C21—C22—C17 | 120.2 (8) | Cl9—C47—H47 | 108.4 |
C21—C22—H22 | 119.9 | Cl10—C47—H47 | 108.4 |
C17—C22—H22 | 119.9 | Cl12—C48—Cl13 | 109.6 (5) |
N3—C23—C16 | 125.1 (6) | Cl12—C48—Cl14 | 110.7 (4) |
N3—C23—C24 | 107.3 (6) | Cl13—C48—Cl14 | 111.3 (5) |
C16—C23—C24 | 127.6 (6) | Cl12—C48—H48 | 108.4 |
C25—C24—C23 | 108.4 (6) | Cl13—C48—H48 | 108.4 |
C25—C24—H24 | 125.8 | Cl14—C48—H48 | 108.4 |
C23—C24—H24 | 125.8 | Cl17—C49—Cl16 | 111.2 (5) |
C24—C25—C26 | 107.9 (6) | Cl17—C49—Cl15 | 110.5 (4) |
C24—C25—H25 | 126.1 | Cl16—C49—Cl15 | 109.7 (4) |
C26—C25—H25 | 126.1 | Cl17—C49—H49 | 108.5 |
N3—C26—C27 | 125.8 (6) | Cl16—C49—H49 | 108.5 |
N3—C26—C25 | 106.9 (6) | Cl15—C49—H49 | 108.5 |
C27—C26—C25 | 127.3 (6) | Cl20—C50—Cl19 | 101.9 (9) |
C34—C27—C26 | 124.1 (6) | Cl20—C50—Cl18 | 124.2 (12) |
C34—C27—C28 | 118.8 (6) | Cl19—C50—Cl18 | 110.0 (10) |
C26—C27—C28 | 117.1 (6) | Cl20—C50—H50 | 106.5 |
C29—C28—C33 | 118.1 (6) | Cl19—C50—H50 | 106.5 |
C29—C28—C27 | 120.3 (6) | Cl18—C50—H50 | 106.5 |
C33—C28—C27 | 121.6 (6) | Cl3D—C50A—Cl2D | 112.4 (10) |
C30—C29—C28 | 121.1 (6) | Cl3D—C50A—Cl1D | 103.5 (10) |
C30—C29—H29 | 119.5 | Cl2D—C50A—Cl1D | 121.8 (13) |
C28—C29—H29 | 119.5 | Cl3D—C50A—H50A | 106 |
C29—C30—C31 | 120.1 (7) | Cl2D—C50A—H50A | 106 |
C29—C30—H30 | 120 | Cl1D—C50A—H50A | 106 |
C31—C30—H30 | 120 | Cl21—C51—Cl22 | 109.8 (5) |
C30—C31—C32 | 119.4 (7) | Cl21—C51—Cl23 | 110.7 (5) |
C30—C31—H31 | 120.3 | Cl22—C51—Cl23 | 112.1 (5) |
C32—C31—H31 | 120.3 | Cl21—C51—H51 | 108 |
C33—C32—C31 | 120.5 (7) | Cl22—C51—H51 | 108 |
C33—C32—H32 | 119.7 | Cl23—C51—H51 | 108 |
C31—C32—H32 | 119.7 | Cl3E—C51A—Cl2E | 111.3 (17) |
C32—C33—C28 | 120.8 (7) | Cl3E—C51A—Cl1E | 108.6 (17) |
C32—C33—H33 | 119.6 | Cl2E—C51A—Cl1E | 110.6 (17) |
C28—C33—H33 | 119.6 | Cl3E—C51A—H51A | 108.7 |
N4—C34—C27 | 126.0 (6) | Cl2E—C51A—H51A | 108.8 |
N4—C34—C35 | 106.3 (6) | Cl1E—C51A—H51A | 108.7 |
C27—C34—C35 | 127.7 (6) | Cl26—C52—Cl25 | 101.6 (8) |
C36—C35—C34 | 108.1 (6) | Cl26—C52—Cl24 | 119.3 (9) |
C36—C35—H35 | 126 | Cl25—C52—Cl24 | 119.7 (9) |
C34—C35—H35 | 126 | Cl26—C52—H52 | 104.9 |
C35—C36—C37 | 108.2 (6) | Cl25—C52—H52 | 104.9 |
C35—C36—H36 | 125.9 | Cl24—C52—H52 | 104.9 |
C37—C36—H36 | 125.9 | Cl2C—C52A—Cl3C | 110.7 (12) |
N4—C37—C38 | 126.7 (6) | Cl2C—C52A—Cl1C | 103.7 (11) |
N4—C37—C36 | 107.0 (6) | Cl3C—C52A—Cl1C | 106.5 (11) |
C38—C37—C36 | 126.2 (6) | Cl2C—C52A—H52A | 111.8 |
C37—C38—C1 | 123.3 (6) | Cl3C—C52A—H52A | 111.8 |
C37—C38—C39 | 118.5 (6) | Cl1C—C52A—H52A | 111.8 |
N1—C1—C2—C3 | 0.0 (8) | C25—C26—C27—C28 | 21.5 (10) |
C38—C1—C2—C3 | −179.3 (6) | C34—C27—C28—C29 | −135.1 (7) |
C1—C2—C3—C4 | −0.6 (8) | C26—C27—C28—C29 | 44.4 (9) |
C2—C3—C4—N1 | 0.9 (8) | C34—C27—C28—C33 | 45.1 (10) |
C2—C3—C4—C5 | −179.2 (6) | C26—C27—C28—C33 | −135.4 (7) |
N1—C4—C5—C12 | 19.8 (10) | C33—C28—C29—C30 | 1.6 (11) |
C3—C4—C5—C12 | −160.1 (7) | C27—C28—C29—C30 | −178.2 (7) |
N1—C4—C5—C6 | −161.8 (6) | C28—C29—C30—C31 | −1.4 (12) |
C3—C4—C5—C6 | 18.3 (10) | C29—C30—C31—C32 | 0.2 (12) |
C12—C5—C6—C7 | −139.4 (6) | C30—C31—C32—C33 | 0.8 (12) |
C4—C5—C6—C7 | 42.1 (9) | C31—C32—C33—C28 | −0.6 (12) |
C12—C5—C6—C11 | 42.4 (9) | C29—C28—C33—C32 | −0.6 (11) |
C4—C5—C6—C11 | −136.1 (7) | C27—C28—C33—C32 | 179.2 (7) |
C11—C6—C7—C8 | 2.3 (10) | C26—C27—C34—N4 | 19.2 (11) |
C5—C6—C7—C8 | −175.9 (6) | C28—C27—C34—N4 | −161.3 (6) |
C6—C7—C8—C9 | −1.0 (11) | C26—C27—C34—C35 | −160.7 (7) |
C7—C8—C9—C10 | −0.7 (11) | C28—C27—C34—C35 | 18.8 (10) |
C8—C9—C10—C11 | 1.1 (12) | N4—C34—C35—C36 | 1.4 (8) |
C9—C10—C11—C6 | 0.3 (11) | C27—C34—C35—C36 | −178.7 (7) |
C7—C6—C11—C10 | −2.0 (10) | C34—C35—C36—C37 | −0.7 (8) |
C5—C6—C11—C10 | 176.3 (6) | C35—C36—C37—N4 | −0.3 (8) |
C4—C5—C12—N2 | 22.8 (10) | C35—C36—C37—C38 | 178.7 (7) |
C6—C5—C12—N2 | −155.6 (6) | N4—C37—C38—C1 | −23.6 (11) |
C4—C5—C12—C13 | −161.1 (7) | C36—C37—C38—C1 | 157.6 (7) |
C6—C5—C12—C13 | 20.5 (10) | N4—C37—C38—C39 | 157.4 (6) |
N2—C12—C13—C14 | 0.9 (8) | C36—C37—C38—C39 | −21.4 (10) |
C5—C12—C13—C14 | −175.7 (7) | N1—C1—C38—C37 | −18.9 (11) |
C12—C13—C14—C15 | −0.3 (8) | C2—C1—C38—C37 | 160.3 (7) |
C13—C14—C15—N2 | −0.4 (8) | N1—C1—C38—C39 | 160.1 (6) |
C13—C14—C15—C16 | 177.7 (7) | C2—C1—C38—C39 | −20.7 (10) |
N2—C15—C16—C23 | −22.0 (11) | C37—C38—C39—C44 | 134.7 (7) |
C14—C15—C16—C23 | 160.3 (7) | C1—C38—C39—C44 | −44.4 (9) |
N2—C15—C16—C17 | 157.3 (6) | C37—C38—C39—C40 | −43.7 (9) |
C14—C15—C16—C17 | −20.4 (11) | C1—C38—C39—C40 | 137.2 (7) |
C15—C16—C17—C18 | −52.3 (10) | C44—C39—C40—C41 | −1.1 (11) |
C23—C16—C17—C18 | 127.0 (8) | C38—C39—C40—C41 | 177.4 (7) |
C15—C16—C17—C22 | 130.8 (8) | C39—C40—C41—C42 | −0.3 (11) |
C23—C16—C17—C22 | −49.9 (10) | C40—C41—C42—C43 | 1.4 (11) |
C22—C17—C18—C19 | −0.1 (12) | C41—C42—C43—C44 | −1.1 (11) |
C16—C17—C18—C19 | −177.0 (7) | C40—C39—C44—C43 | 1.5 (10) |
C17—C18—C19—C20 | −0.2 (12) | C38—C39—C44—C43 | −177.0 (6) |
C18—C19—C20—C21 | −0.2 (13) | C42—C43—C44—C39 | −0.4 (11) |
C19—C20—C21—C22 | 0.7 (14) | C38—C1—N1—C4 | 179.9 (6) |
C20—C21—C22—C17 | −1.0 (14) | C2—C1—N1—C4 | 0.6 (7) |
C18—C17—C22—C21 | 0.6 (12) | C5—C4—N1—C1 | 179.1 (6) |
C16—C17—C22—C21 | 177.6 (8) | C3—C4—N1—C1 | −1.0 (7) |
C15—C16—C23—N3 | −18.9 (11) | C5—C12—N2—C15 | 175.5 (6) |
C17—C16—C23—N3 | 161.8 (6) | C13—C12—N2—C15 | −1.2 (7) |
C15—C16—C23—C24 | 162.1 (7) | C16—C15—N2—C12 | −177.1 (6) |
C17—C16—C23—C24 | −17.2 (11) | C14—C15—N2—C12 | 1.0 (7) |
N3—C23—C24—C25 | −0.6 (8) | C16—C23—N3—C26 | −178.0 (6) |
C16—C23—C24—C25 | 178.5 (7) | C24—C23—N3—C26 | 1.2 (7) |
C23—C24—C25—C26 | −0.1 (8) | C27—C26—N3—C23 | 177.3 (6) |
C24—C25—C26—N3 | 0.8 (8) | C25—C26—N3—C23 | −1.3 (7) |
C24—C25—C26—C27 | −177.7 (7) | C38—C37—N4—C34 | −177.8 (6) |
N3—C26—C27—C34 | 22.8 (11) | C36—C37—N4—C34 | 1.2 (7) |
C25—C26—C27—C34 | −158.9 (7) | C27—C34—N4—C37 | 178.5 (6) |
N3—C26—C27—C28 | −156.7 (6) | C35—C34—N4—C37 | −1.6 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.88 | 2.30 | 3.110 (5) | 152 |
N3—H3A···Cl1 | 0.88 | 2.38 | 3.183 (6) | 152 |
N2—H2A···Cl2 | 0.88 | 2.38 | 3.167 (5) | 148 |
N4—H4···Cl2 | 0.88 | 2.40 | 3.198 (6) | 152 |
C45—H45···Cl2 | 1.00 | 2.64 | 3.382 (10) | 132 |
C46—H46···Cl1 | 1.00 | 2.50 | 3.474 (9) | 166 |
C48—H48···Cl1 | 1.00 | 2.39 | 3.362 (8) | 164 |
C49—H49···Cl1 | 1.00 | 2.63 | 3.492 (8) | 145 |
C50—H50···Cl2 | 1.00 | 2.65 | 3.47 (2) | 140 |
C51—H51···Cl2 | 1.00 | 2.52 | 3.467 (10) | 158 |
C52—H52···Cl2 | 1.00 | 2.70 | 3.57 (2) | 146 |
[Cu(C44H28N4)] | F(000) = 698 |
Mr = 676.24 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 11910 reflections |
a = 14.5813 (12) Å | θ = 2.3–26.0° |
b = 8.6068 (5) Å | µ = 0.72 mm−1 |
c = 14.6191 (11) Å | T = 120 K |
β = 118.56 (1)° | Plate, blue |
V = 1611.4 (2) Å3 | 0.53 × 0.23 × 0.02 mm |
Z = 2 |
KM-4-CCD Sapphire2 (large Be window) diffractometer | 3167 independent reflections |
Graphite monochromator | 2288 reflections with I > 2σ(I) |
Detector resolution: 8.1883 pixels mm-1 | Rint = 0.052 |
ω scans | θmax = 26.0°, θmin = 2.7° |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2006), a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | h = −17→16 |
Tmin = 0.777, Tmax = 0.992 | k = −10→10 |
11911 measured reflections | l = −17→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.1054P)2] where P = (Fo2 + 2Fc2)/3 |
3167 reflections | (Δ/σ)max < 0.001 |
223 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[Cu(C44H28N4)] | V = 1611.4 (2) Å3 |
Mr = 676.24 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.5813 (12) Å | µ = 0.72 mm−1 |
b = 8.6068 (5) Å | T = 120 K |
c = 14.6191 (11) Å | 0.53 × 0.23 × 0.02 mm |
β = 118.56 (1)° |
KM-4-CCD Sapphire2 (large Be window) diffractometer | 3167 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2006), a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | 2288 reflections with I > 2σ(I) |
Tmin = 0.777, Tmax = 0.992 | Rint = 0.052 |
11911 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.63 e Å−3 |
3167 reflections | Δρmin = −0.48 e Å−3 |
223 parameters |
Experimental. CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | 0 | 0 | 0.02046 (19) | |
N1 | −0.13381 (19) | 0.0220 (3) | 0.00558 (19) | 0.0185 (5) | |
N2 | 0.08109 (19) | 0.0314 (3) | 0.15490 (19) | 0.0189 (6) | |
C1 | −0.2336 (2) | 0.0143 (3) | −0.0767 (2) | 0.0181 (6) | |
C2 | −0.3075 (3) | 0.0505 (4) | −0.0407 (2) | 0.0243 (7) | |
H2 | −0.3813 | 0.0535 | −0.0821 | 0.029* | |
C3 | −0.2532 (2) | 0.0792 (4) | 0.0618 (2) | 0.0244 (7) | |
H3 | −0.2811 | 0.1079 | 0.1063 | 0.029* | |
C4 | −0.1448 (2) | 0.0583 (4) | 0.0913 (2) | 0.0198 (6) | |
C5 | −0.0640 (2) | 0.0744 (4) | 0.1933 (2) | 0.0204 (6) | |
C6 | −0.0919 (2) | 0.1097 (4) | 0.2774 (2) | 0.0239 (7) | |
C7 | −0.0763 (3) | 0.2575 (4) | 0.3195 (3) | 0.0319 (8) | |
H7 | −0.0496 | 0.3375 | 0.2941 | 0.038* | |
C8 | −0.1001 (3) | 0.2881 (5) | 0.3995 (3) | 0.0403 (9) | |
H8 | −0.0886 | 0.3894 | 0.4287 | 0.048* | |
C9 | −0.1392 (3) | 0.1763 (5) | 0.4365 (3) | 0.0443 (10) | |
H9 | −0.1529 | 0.1987 | 0.4924 | 0.053* | |
C10 | −0.1593 (4) | 0.0289 (5) | 0.3923 (3) | 0.0504 (11) | |
H10 | −0.1892 | −0.0491 | 0.4158 | 0.06* | |
C11 | −0.1347 (3) | −0.0027 (4) | 0.3130 (3) | 0.0381 (9) | |
H11 | −0.1477 | −0.1035 | 0.2829 | 0.046* | |
C12 | 0.0413 (2) | 0.0612 (4) | 0.2208 (2) | 0.0198 (6) | |
C13 | 0.1251 (2) | 0.0847 (4) | 0.3255 (2) | 0.0245 (7) | |
H13 | 0.1182 | 0.105 | 0.3859 | 0.029* | |
C14 | 0.2145 (3) | 0.0721 (4) | 0.3208 (2) | 0.0239 (7) | |
H14 | 0.2831 | 0.0838 | 0.3774 | 0.029* | |
C15 | 0.1879 (2) | 0.0378 (3) | 0.2149 (2) | 0.0194 (7) | |
C16 | 0.2610 (2) | 0.0169 (3) | 0.1798 (2) | 0.0177 (6) | |
C17 | 0.3745 (2) | 0.0278 (3) | 0.2577 (2) | 0.0200 (6) | |
C18 | 0.4207 (2) | −0.0821 (3) | 0.3356 (2) | 0.0208 (7) | |
H18 | 0.3798 | −0.1647 | 0.3399 | 0.025* | |
C19 | 0.5257 (2) | −0.0737 (4) | 0.4074 (2) | 0.0248 (7) | |
H19 | 0.5565 | −0.151 | 0.4598 | 0.03* | |
C20 | 0.5855 (3) | 0.0466 (4) | 0.4029 (3) | 0.0271 (7) | |
H20 | 0.6575 | 0.0531 | 0.4523 | 0.033* | |
C21 | 0.5403 (3) | 0.1570 (4) | 0.3265 (3) | 0.0327 (8) | |
H21 | 0.5816 | 0.2402 | 0.3235 | 0.039* | |
C22 | 0.4354 (3) | 0.1493 (4) | 0.2535 (3) | 0.0276 (7) | |
H22 | 0.4053 | 0.2264 | 0.2009 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0218 (3) | 0.0221 (3) | 0.0147 (3) | 0.0007 (2) | 0.0064 (2) | −0.0008 (2) |
N1 | 0.0177 (13) | 0.0233 (14) | 0.0128 (12) | 0.0015 (10) | 0.0060 (11) | −0.0011 (10) |
N2 | 0.0178 (13) | 0.0229 (14) | 0.0134 (12) | −0.0012 (10) | 0.0053 (11) | −0.0008 (10) |
C1 | 0.0196 (15) | 0.0178 (14) | 0.0142 (14) | 0.0017 (11) | 0.0060 (12) | 0.0015 (11) |
C2 | 0.0194 (17) | 0.0292 (16) | 0.0209 (16) | 0.0001 (12) | 0.0069 (14) | −0.0005 (14) |
C3 | 0.0240 (17) | 0.0287 (17) | 0.0221 (16) | 0.0013 (13) | 0.0125 (14) | 0.0008 (14) |
C4 | 0.0211 (16) | 0.0204 (14) | 0.0164 (14) | −0.0006 (12) | 0.0079 (13) | −0.0012 (12) |
C5 | 0.0251 (17) | 0.0201 (15) | 0.0155 (14) | 0.0005 (12) | 0.0092 (13) | −0.0003 (12) |
C6 | 0.0202 (16) | 0.0339 (17) | 0.0152 (14) | 0.0016 (13) | 0.0066 (13) | −0.0026 (13) |
C7 | 0.0284 (19) | 0.0383 (19) | 0.0302 (18) | −0.0034 (15) | 0.0151 (16) | −0.0078 (16) |
C8 | 0.035 (2) | 0.049 (2) | 0.039 (2) | −0.0018 (17) | 0.0190 (19) | −0.0199 (18) |
C9 | 0.047 (2) | 0.069 (3) | 0.0242 (18) | 0.001 (2) | 0.0232 (19) | −0.0110 (19) |
C10 | 0.066 (3) | 0.062 (3) | 0.041 (2) | −0.007 (2) | 0.040 (2) | −0.003 (2) |
C11 | 0.054 (2) | 0.039 (2) | 0.034 (2) | −0.0051 (17) | 0.031 (2) | −0.0081 (17) |
C12 | 0.0218 (17) | 0.0192 (14) | 0.0147 (14) | 0.0002 (12) | 0.0059 (13) | −0.0004 (12) |
C13 | 0.0282 (18) | 0.0299 (18) | 0.0117 (14) | 0.0011 (13) | 0.0066 (14) | −0.0024 (13) |
C14 | 0.0242 (18) | 0.0260 (16) | 0.0133 (14) | 0.0040 (13) | 0.0025 (13) | −0.0008 (13) |
C15 | 0.0243 (17) | 0.0177 (15) | 0.0119 (14) | 0.0008 (11) | 0.0052 (13) | −0.0003 (11) |
C16 | 0.0176 (15) | 0.0157 (14) | 0.0132 (13) | 0.0012 (11) | 0.0020 (12) | 0.0018 (11) |
C17 | 0.0193 (16) | 0.0242 (16) | 0.0143 (14) | 0.0013 (11) | 0.0062 (13) | −0.0036 (12) |
C18 | 0.0220 (17) | 0.0182 (15) | 0.0182 (15) | −0.0013 (12) | 0.0063 (14) | −0.0025 (12) |
C19 | 0.0236 (18) | 0.0258 (16) | 0.0188 (16) | 0.0046 (13) | 0.0051 (14) | −0.0006 (14) |
C20 | 0.0184 (17) | 0.0360 (18) | 0.0202 (16) | −0.0016 (13) | 0.0038 (14) | −0.0031 (14) |
C21 | 0.0298 (19) | 0.0315 (18) | 0.0309 (18) | −0.0094 (14) | 0.0097 (16) | 0.0013 (15) |
C22 | 0.0284 (19) | 0.0235 (16) | 0.0243 (17) | 0.0003 (13) | 0.0073 (15) | 0.0033 (14) |
Cu1—N1i | 2.000 (2) | C9—H9 | 0.95 |
Cu1—N1 | 2.000 (2) | C10—C11 | 1.394 (5) |
Cu1—N2 | 2.010 (2) | C10—H10 | 0.95 |
Cu1—N2i | 2.010 (2) | C11—H11 | 0.95 |
N1—C4 | 1.373 (4) | C12—C13 | 1.445 (4) |
N1—C1 | 1.377 (4) | C13—C14 | 1.344 (5) |
N2—C12 | 1.366 (4) | C13—H13 | 0.95 |
N2—C15 | 1.376 (4) | C14—C15 | 1.436 (4) |
C1—C16i | 1.390 (4) | C14—H14 | 0.95 |
C1—C2 | 1.440 (4) | C15—C16 | 1.396 (4) |
C2—C3 | 1.341 (4) | C16—C1i | 1.390 (4) |
C2—H2 | 0.95 | C16—C17 | 1.498 (4) |
C3—C4 | 1.438 (4) | C17—C18 | 1.383 (4) |
C3—H3 | 0.95 | C17—C22 | 1.392 (4) |
C4—C5 | 1.397 (4) | C18—C19 | 1.383 (4) |
C5—C12 | 1.393 (4) | C18—H18 | 0.95 |
C5—C6 | 1.499 (4) | C19—C20 | 1.375 (5) |
C6—C11 | 1.381 (5) | C19—H19 | 0.95 |
C6—C7 | 1.384 (5) | C20—C21 | 1.372 (5) |
C7—C8 | 1.395 (5) | C20—H20 | 0.95 |
C7—H7 | 0.95 | C21—C22 | 1.386 (5) |
C8—C9 | 1.356 (6) | C21—H21 | 0.95 |
C8—H8 | 0.95 | C22—H22 | 0.95 |
C9—C10 | 1.389 (6) | ||
N1i—Cu1—N1 | 180.00 (14) | C9—C10—C11 | 118.9 (4) |
N1i—Cu1—N2 | 89.94 (10) | C9—C10—H10 | 120.5 |
N1—Cu1—N2 | 90.06 (10) | C11—C10—H10 | 120.5 |
N1i—Cu1—N2i | 90.06 (10) | C6—C11—C10 | 121.3 (3) |
N1—Cu1—N2i | 89.94 (10) | C6—C11—H11 | 119.4 |
N2—Cu1—N2i | 180.00 (14) | C10—C11—H11 | 119.4 |
C4—N1—C1 | 105.8 (2) | N2—C12—C5 | 126.4 (3) |
C4—N1—Cu1 | 126.9 (2) | N2—C12—C13 | 110.2 (3) |
C1—N1—Cu1 | 127.2 (2) | C5—C12—C13 | 123.4 (3) |
C12—N2—C15 | 106.1 (2) | C14—C13—C12 | 106.5 (3) |
C12—N2—Cu1 | 126.9 (2) | C14—C13—H13 | 126.7 |
C15—N2—Cu1 | 126.9 (2) | C12—C13—H13 | 126.7 |
N1—C1—C16i | 126.3 (3) | C13—C14—C15 | 107.7 (3) |
N1—C1—C2 | 109.5 (3) | C13—C14—H14 | 126.2 |
C16i—C1—C2 | 124.2 (3) | C15—C14—H14 | 126.2 |
C3—C2—C1 | 107.7 (3) | N2—C15—C16 | 126.2 (3) |
C3—C2—H2 | 126.2 | N2—C15—C14 | 109.6 (3) |
C1—C2—H2 | 126.2 | C16—C15—C14 | 124.2 (3) |
C2—C3—C4 | 106.8 (3) | C1i—C16—C15 | 123.3 (3) |
C2—C3—H3 | 126.6 | C1i—C16—C17 | 118.4 (3) |
C4—C3—H3 | 126.6 | C15—C16—C17 | 118.2 (3) |
N1—C4—C5 | 126.2 (3) | C18—C17—C22 | 118.7 (3) |
N1—C4—C3 | 110.2 (3) | C18—C17—C16 | 120.6 (3) |
C5—C4—C3 | 123.6 (3) | C22—C17—C16 | 120.7 (3) |
C12—C5—C4 | 123.4 (3) | C19—C18—C17 | 121.1 (3) |
C12—C5—C6 | 118.3 (3) | C19—C18—H18 | 119.5 |
C4—C5—C6 | 118.3 (3) | C17—C18—H18 | 119.5 |
C11—C6—C7 | 119.0 (3) | C20—C19—C18 | 120.0 (3) |
C11—C6—C5 | 121.1 (3) | C20—C19—H19 | 120 |
C7—C6—C5 | 120.0 (3) | C18—C19—H19 | 120 |
C6—C7—C8 | 119.5 (3) | C21—C20—C19 | 119.5 (3) |
C6—C7—H7 | 120.2 | C21—C20—H20 | 120.3 |
C8—C7—H7 | 120.2 | C19—C20—H20 | 120.3 |
C9—C8—C7 | 121.4 (4) | C20—C21—C22 | 121.1 (3) |
C9—C8—H8 | 119.3 | C20—C21—H21 | 119.4 |
C7—C8—H8 | 119.3 | C22—C21—H21 | 119.4 |
C8—C9—C10 | 119.9 (3) | C21—C22—C17 | 119.6 (3) |
C8—C9—H9 | 120.1 | C21—C22—H22 | 120.2 |
C10—C9—H9 | 120.1 | C17—C22—H22 | 120.2 |
N2—Cu1—N1—C4 | 4.6 (2) | C5—C6—C11—C10 | 179.0 (4) |
N2i—Cu1—N1—C4 | −175.4 (2) | C9—C10—C11—C6 | −0.5 (7) |
N2—Cu1—N1—C1 | 179.9 (2) | C15—N2—C12—C5 | 176.6 (3) |
N2i—Cu1—N1—C1 | −0.1 (2) | Cu1—N2—C12—C5 | 0.6 (5) |
N1i—Cu1—N2—C12 | 177.7 (3) | C15—N2—C12—C13 | −0.9 (3) |
N1—Cu1—N2—C12 | −2.3 (3) | Cu1—N2—C12—C13 | −176.94 (19) |
N1i—Cu1—N2—C15 | 2.5 (2) | C4—C5—C12—N2 | −0.1 (5) |
N1—Cu1—N2—C15 | −177.5 (2) | C6—C5—C12—N2 | −179.3 (3) |
C4—N1—C1—C16i | 178.9 (3) | C4—C5—C12—C13 | 177.2 (3) |
Cu1—N1—C1—C16i | 2.9 (4) | C6—C5—C12—C13 | −2.0 (5) |
C4—N1—C1—C2 | 1.4 (3) | N2—C12—C13—C14 | 1.4 (4) |
Cu1—N1—C1—C2 | −174.7 (2) | C5—C12—C13—C14 | −176.2 (3) |
N1—C1—C2—C3 | −0.2 (3) | C12—C13—C14—C15 | −1.2 (3) |
C16i—C1—C2—C3 | −177.8 (3) | C12—N2—C15—C16 | −178.9 (3) |
C1—C2—C3—C4 | −1.1 (4) | Cu1—N2—C15—C16 | −3.0 (4) |
C1—N1—C4—C5 | 178.3 (3) | C12—N2—C15—C14 | 0.2 (3) |
Cu1—N1—C4—C5 | −5.6 (4) | Cu1—N2—C15—C14 | 176.19 (19) |
C1—N1—C4—C3 | −2.1 (3) | C13—C14—C15—N2 | 0.7 (4) |
Cu1—N1—C4—C3 | 174.00 (19) | C13—C14—C15—C16 | 179.8 (3) |
C2—C3—C4—N1 | 2.0 (4) | N2—C15—C16—C1i | −0.2 (5) |
C2—C3—C4—C5 | −178.3 (3) | C14—C15—C16—C1i | −179.2 (3) |
N1—C4—C5—C12 | 2.7 (5) | N2—C15—C16—C17 | −179.8 (3) |
C3—C4—C5—C12 | −176.9 (3) | C14—C15—C16—C17 | 1.2 (4) |
N1—C4—C5—C6 | −178.1 (3) | C1i—C16—C17—C18 | −112.7 (3) |
C3—C4—C5—C6 | 2.3 (5) | C15—C16—C17—C18 | 66.9 (4) |
C12—C5—C6—C11 | −107.3 (4) | C1i—C16—C17—C22 | 67.6 (4) |
C4—C5—C6—C11 | 73.4 (4) | C15—C16—C17—C22 | −112.8 (3) |
C12—C5—C6—C7 | 73.7 (4) | C22—C17—C18—C19 | −0.9 (5) |
C4—C5—C6—C7 | −105.5 (4) | C16—C17—C18—C19 | 179.5 (3) |
C11—C6—C7—C8 | 2.6 (5) | C17—C18—C19—C20 | 0.9 (5) |
C5—C6—C7—C8 | −178.4 (3) | C18—C19—C20—C21 | −0.4 (5) |
C6—C7—C8—C9 | −0.6 (6) | C19—C20—C21—C22 | −0.2 (5) |
C7—C8—C9—C10 | −1.9 (6) | C20—C21—C22—C17 | 0.2 (5) |
C8—C9—C10—C11 | 2.5 (7) | C18—C17—C22—C21 | 0.3 (5) |
C7—C6—C11—C10 | −2.0 (6) | C16—C17—C22—C21 | 179.9 (3) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C44H32N42+·2Cl−·8CHCl3 | [Cu(C44H28N4)] |
Mr | 1642.58 | 676.24 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 11.6031 (3), 12.6132 (3), 24.5118 (6) | 14.5813 (12), 8.6068 (5), 14.6191 (11) |
α, β, γ (°) | 87.706 (2), 82.025 (2), 76.356 (2) | 90, 118.56 (1), 90 |
V (Å3) | 3452.31 (15) | 1611.4 (2) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.06 | 0.72 |
Crystal size (mm) | 0.49 × 0.40 × 0.22 | 0.53 × 0.23 × 0.02 |
Data collection | ||
Diffractometer | Oxford Diffraction Xcalibur Sapphire2 (large Be window) diffractometer | KM-4-CCD Sapphire2 (large Be window) diffractometer |
Absorption correction | Analytical [CrysAlis PRO (Oxford Diffraction, 2006), a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | Analytical [CrysAlis PRO (Oxford Diffraction, 2006), a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] |
Tmin, Tmax | 0.705, 0.823 | 0.777, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22549, 12824, 9236 | 11911, 3167, 2288 |
Rint | 0.030 | 0.052 |
(sin θ/λ)max (Å−1) | 0.606 | 0.617 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.095, 0.261, 1.05 | 0.052, 0.147, 0.96 |
No. of reflections | 12824 | 3167 |
No. of parameters | 720 | 223 |
No. of restraints | 55 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.1268P)2 + 26.0222P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.1054P)2] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 3.32, −2.09 | 0.63, −0.48 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999), publCIF (Westrip, 2010) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.88 | 2.30 | 3.110 (5) | 152.1 |
N3—H3A···Cl1 | 0.88 | 2.38 | 3.183 (6) | 151.6 |
N2—H2A···Cl2 | 0.88 | 2.38 | 3.167 (5) | 148.3 |
N4—H4···Cl2 | 0.88 | 2.40 | 3.198 (6) | 151.9 |
C45—H45···Cl2 | 1.00 | 2.64 | 3.382 (10) | 131.5 |
C46—H46···Cl1 | 1.00 | 2.50 | 3.474 (9) | 165.8 |
C48—H48···Cl1 | 1.00 | 2.39 | 3.362 (8) | 163.5 |
C49—H49···Cl1 | 1.00 | 2.63 | 3.492 (8) | 145.0 |
C50—H50···Cl2 | 1.00 | 2.65 | 3.47 (2) | 140.0 |
C51—H51···Cl2 | 1.00 | 2.52 | 3.467 (10) | 158.3 |
C52—H52···Cl2 | 1.00 | 2.70 | 3.57 (2) | 146.3 |
Anion | Solvent | py1–py3 | py2–py4 | Δ24 | Substitution | local symmetry | Reference | |
meso β | ||||||||
Cl | CHCl3 | 125.5 (4) | 126.3 (4) | 0.390 | Ph | H | 1 | This work |
Cl | CHCl3 | 120.32 | 121.88 | 0.429 | 4-MePh | H | 1 | Grubisha et al. (2008) |
Cl | H2O/MeCN | 126.4 | 111.6 | 0.446 | Ph | H | 1 | Larsen et al. (2004) |
Cl | MeCN/hydroquinone | 90.69 | 90.69 | 0.64 | Ph | Ph | 2 | Harada & Kojima (2005) |
Cl | CH2Cl2 | 98.93 | 98.23 | 0.605 | Ph | Et | 1 | Senge & Kalisch (1999) |
Cl | Toluene | 103.5 | 103.5 | 0.556 | Ph | Et | -4 | Hu et al. (2007) |
Cl | CHCl3/MeOH | 131.34 | 134.29 | 0.376 | Ph | Et,H* | 1 | Jaquinod et al.(1998) |
Cl | TTF/MeCN, H2O | 94.13 | 94.13 | 0.617 | Ph | Ph | 2 | Nakanishi et al. (2008) |
Cl | MeCN | 90.35 | 90.35 | 0.647 | Ph | Ph | 2 | Kojima et al. (2007) |
Cl | MeCN/CHCl3, H2O | 90.6 | 90.6 | 0.639 | Ph | Ph | 2 | Kojima et al. (2007) |
Cl | p-xylene/MeCN | 90.05 | 90.05 | 0.644 | Ph | Ph | 2 | Kojima et al. (2007) |
Cl, FeCl4 | none | 113.91 | 113.91 | 0.524 | Ph | H | -4 | Stone & Fleischer (1968) |
Cl | H2O | 126.91 | 126.1 | 0.394 | 4-Py | H | 1 | Stone & Fleischer (1968) |
Cl | tBu-O-Me | 115.86 | 115.86 | 0.496 | 4-MeOCOPh | c-Hexane | -4 | Finikova et al. (2002) |
BF4 | CHCl3/H2O | 131.48 | 135.06 | 0.340 | Ph | H | 1 | Rayati et al. (2008) |
ClO4 | MeOH | 118.56 | 117.26 | 0.464 | H | Me,Et | 1 | Senge et al. (1994) |
Note: (*) this structure presents a special feature: it contains three fused porphyrin rings. Note that usually programs calculate acute dihedral angles, so the values cited here are those of the corresponding supplementary ones. |
Porphyrins and metalloporphyrins have been studied for many years because of their biochemical relevance as well as their applications. In biology, these tetrapyrrolic macrocycles fulfill such diverse roles as molecular binding, light harvesting, catalysis, and energy and/or electron transfer (Burrell et al., 2001). From the technological point of view, porphyrins have been useful in a range of applications, from molecular sensing to the development of dye-sensitized solar cells (Hagfeldt et al., 2010). Also, these compounds have been found to possess a rich macromolecular chemistry, i.a. promoting DNA cleavage (Börjesson et al., 2010), serving as the core for metallodendrimers (Newkome et al., 1999) or as the building blocks for other self-organized nanostructures (Harada & Kojima, 2005).
Much work has been devoted to 5,10,15,20-tetraphenylporphyrin and its derived metal complexes, which is understandable given the facile and rapid synthesis of this porphyrin. On some occasions, protonated porphyrins may be obtained in parallel with metal complexes. While they do not share the popularity of their free-base or coordinated relatives, porphyrin dications have been found very useful in elucidating the nature of the structural distortions of porphyrin derivatives.
The study of the geometrical distortion of porphyrins may give rise to interesting nanostructured materials. For instance, it has recently been demonstrated that the puckering of saddle-distorted porphyrins results in nanochannel materials in which photochemically induced electron transfer to guest molecules can be recorded (Kojima et al., 2007; Nakanishi et al., 2008).
Porphyrin molecules upon protonation become nonplanar largely because of the strain caused by the four H-atom interaction at the ring core (Stone & Fleischer, 1968). This behaviour is observed in several structures of protonated porphyrins, where the ring is forced to adopt a distorted geometry described as saddled, ruffled, domed, propellered [spelling correct?] or waved. Saddled is the most common (Senge & Kalisch, 1999). Data on selected structures of protonated porphyrins are presented in Table 1. The symmetry of the porphyrin macrocycle deformation was analysed by Stone & Fleischer (1968) in terms of irreducible representations of the point group D4h. The distortions can be classified as: sad B1u, ruf B2u, dom A2u, pro A1u and wav(1) or wav(2) Eg, respectively. From the symbols one can infer that local symmetry of the porphyrin molecule can be 2 or 4 for the first two conformations. Local symmetry 4 is allowed only for dom and pro, whereas 1 is allowed only for the wav forms. Obviously, this is true only for porphrins with full D4h symmetry. For an analysis of deformation in a less symmetric molecule, see Sun et al. (2012).
Generally, the presence of substituents on the β positions causes the porphyrins to deviate more from planarity than meso (i.e. 5,10,15,20-) substituents. Cheng et al. (1997) compared meso (Ph, mesityl and H) and β (Et, H) substitution in several diacid porphyrins. Their octaethyl β-substituted porphyrins were less distorted than Ph- or mesityl-substituted molecules in meso positions. They concluded that the stiffness of the substituent must also be taken into account as a factor influencing the distortion. Among the compounds in Table 1, the β substitution by stiff Ph groups inevitably leads to a strongly distorted conformation (Δ24 > 0.6 and dihedral angles between the opposite pyrrole rings close to 90°).
A general view of 5,10,15,20-tetraphenylporphyrin-21,23-diium dichloride chloroform octasolvate, (I), and the definition of the atom-labelling scheme are shown in Fig. 1. Two N—H bonds (from N1 and N3) are directed above the mean plane of the molecule and form hydrogen bonds with chloride ion Cl1 and the remaining N—H bonds point down to the second chloride ion (Cl2).
Three chloroform molecules bound by a C—H···Cl hydrogen bond to the Cl1 atom, as well as the stand-alone molecule are well ordered. However, the remaining four chloroform molecules, all linked to the Cl2 atom, display strong disorder (see Fig. 2). As the disordered chloroform molecules have a severe impact on R indices, building an appropriate disorder model was crucial. In our attempt, all the chloroform molecules were restrained to the geometry of a `regular' molecule. In order to define this, the Cambridge Structural Database (CSD; Allen, 2002) was queried for data on the mean chloroform geometry observed in crystals. A total of 4707 examples were found. These provided a statistically relevant estimation of the mean C—Cl bond length value (1.737 Å, with a sample standard uncertainty of 0.06 Å) and the mean 1,3 Cl···Cl distance (2.838 Å, with a sample standard uncertainty of 0.08 Å). All the disordered molecules were restrained to the above-mentioned values, while their standard uncertainties were shrunk to 0.002 Å. One molecule (C45—Cl3—Cl4—Cl5) had to be split over three positions, and the other three were disordered over two positions. It appears all four molecules have some degree of `orbiting rotational freedom' over the acceptor atom and may interchange, while still being linked to chloride atom Cl2.
Many similarities can be found in the structure of 5,10,15,20-tetrakis(4-methylphenyl)porphyrin-21,23-diium dichloride chloroform heptasolvate (Grubisha et al., 2008). Again, the porphyrin ring is distorted, which manifests in dihedral angles between opposite pyrrole rings of ca 120°. More interestingly, the chloroform molecules are bound to the chloride ions by C—H···Cl hydrogen bonds, four from one side of the porphyrin ring plane and three from the other (Fig. 2b), forming a similar pattern to that of the new structure.
meso-Tetraphenylporphyrindiium dichloride is known to form `binary' solvates with acetonitrile and water (Larsen et al., 2004). It forms a similar core with a saddledistorted porphyrin and Cl- anions as acceptors for the N—H bonds from both sides of the porphyrin plane. The similarity ends there as the structure is further stabilized by O—H···Cl hydrogen bonds with water molecules and the remaining acetonitrile seems to play a space-filling role only.
Other structures with 22,24-dihydro-5,10,15,20-tetraphenylporphyrindiium dications contain a number of combinations of anions and solvents: porphyrin bis(hydrogen sulfate) methanol solvate (Senge & Kalisch, 1999), porphyrin diperchlorate benzene solvate (Cheng et al., 1997), porphyrin bis(tetrafluoroborate) chloroform solvate dihydrate (Rayati et al., 2008) and porphyrin diperchlorate methanol solvate (Senge et al., 1994; Senge & Kalisch, 1999).
In the case of 22,24-dihydro-5,10,15,20-tetraphenylporphyrin chloride ferrichloride, no solvent is trapped in the structure (Stone & Fleischer, 1968).
Two X-ray crystal structures for (5,10,15,20-tetraphenylporphyrinato)copper(II), (II), have been determined so far, viz. a tetragonal form crystallizing in I42d, determined twice [by Fleischer et al. (1964) at 295 K, d = 1.421 Mg m-1, then by Zeller et al. (2004) at 100 K, d = 1.461 Mg m-1], and another tetragonal form with symmetry I4/m [He (2007), d = 1.290 Mg m-1 at 290 K]. Other structures of CuTPP contained additional guest molecules, such as benzene and C78 fullerene (Epple et al., 2009), 4-picoline (Byrn et al., 1993) or m-xylene (Byrn et al., 1991), fullerene C60 either alone or accompanied by toluene and C2HCl3 (Konarev et al., 2001). While the conformation of the 24-membered macrocycle is saddled (local 4) for TPPCu crystallizing in I42d, a flat core (local 4/m) is observed in the case of the I4/m space group. The present monoclinic structure (P21/n) has local symmetry 1 which only allows for the wave conformation (Eg-type representation). The deviation of the macrocycle from flatness is not strong (Δ24 = 0.0428 Å), but clearly no fourfold symmetry is present (see Fig. 3). The same type of conformation with a local centre of symmetry is present in all the solvated structures mentioned above (excluding Konarev et al., 2001). Comparing the densities of known polymorphs with 1.394 Mg m-1, we see that when CuTPP crystallizes from chloroform it does not present the most dense packing and probably it is not the most thermodynamically stable. It follows the Ostwald's rule of stages (Ostwald, 1897; Threlfall, 2003), which states that crystallization often favours the least stable polymorphs. Although the validity of this rule is questionable, the balance between kinetics and thermodynamics allows us to obtain the less dense monoclinic form of CuTPP. Chloroform is generally disregarded as a solvent, because of its tendency to form disordered structures. However, it is worth keeping in mind that chloroform may be helpful when trying to obtain less stable polymorphs as in the current case.