Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051872/pk2051sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051872/pk2051Isup2.hkl |
CCDC reference: 612853
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.004 Å
- R factor = 0.048
- wR factor = 0.117
- Data-to-parameter ratio = 14.4
checkCIF/PLATON results
No syntax errors found
Alert level B ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.583 0.818 Tmin(prime) and Tmax expected: 0.814 0.818 RR(prime) = 0.717 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.71 PLAT231_ALERT_4_B Hirshfeld Test (Solvent) C93 - C94 .. 9.47 su PLAT231_ALERT_4_B Hirshfeld Test (Solvent) C94 - C95 .. 11.79 su
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.33 Ratio PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 30 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.23 Ratio PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.02 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.38 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.05 Ratio PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for C94 PLAT431_ALERT_2_C Short Inter HL..A Contact Cl1 .. O11 .. 3.25 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact C19 .. C37 .. 3.16 Ang.
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C58 H52 Cl2.67 N4 Ni1 O8 Atom count from _chemical_formula_moiety:C58.02 H52.02 Cl2.66 N4 Ni1 PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (2) 2.03 PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni2 (2) 2.16
0 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: Diane Conrad, Christopher Yeisley, and Jennifer DeCoskey are undergraduates who worked on synthesizing, purifying, and crystallizing the samples of the porphyrin. Edward Zovinka is the research advisor and Allen Hunter and Matthias Zeller are the crystallographers on the project. |
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
For details of the synthesis, see: Tsuchida, et al.(1990). For related examples of ortho-substituted porphyrins, see: Bhyrappa, et al. (1997). For related literature, see: Allen (2002); Arciero & Hooper (1997); Arciero et al. (1993); Igarashi et al. (1997); Kadish et al. (2002); Rothemund & Menotti (1948).
All of the starting materials were purchased from Aldrich and used without further purification. The ligand, 5,10,15,20-tetra-(2',6'-dimethoxyphenyl)porphyrin, [(H2T-2',6'-DMP)P] was synthesized following literature methods (Tsuchida et al., 1990). The porphyrin ligand, (H2T-2',6'-DMP)P, (17.0 mg, 2.0×10 -5 mol) was dissolved in glacial acetic acid (20 ml). Nickel acetate (0.50 mg, 2.0×10 -4 mol) was added after all of the ligand dissolved and then heated to reflux at 391 K (118 °C) for half an hour (Rothemund, 1948). Upon cooling, the solvent was removed through rotary evaporation. The resulting red crystals were dissolved in dichloromethane and the solution was chromatographed on a dry alumina column with dichloromethane as the eluent. (60% Yield); Rf (Alumina, DCM) 0.95; I·R·(KBr): 1587, 1471, 1431, 1348, 1250 [µas (C—O—C)], 1110, and 1002 [µ (C—H)] cm-1; λmax(DCM): 413, 526, and 557 nm; ε: 1.2×105, 7.8×103, and 2.2×103 cm-1M-1. 1HNMR (CDCl3): 3.5(–OMe), 6.9–7.5(aromatic), and 8.6(pyrrole) p.p.m..
Methyl and methylene chloride H atoms were placed in calculated positions with C—H = 0.98 and 0.99 Å, respectively. All other H atoms were located in difference density Fourier maps. H atoms were refined with Uiso(H) = 1.2 Ueq or 1.5 Ueq (CMe only) of the respective carrier atoms.
The chemistry of the enzyme hydroxylamine oxidoreductase (HAO) from nitrosomonas europaea has been of interest for a number of years (Arciero & Hooper, 1997). The X-ray crystal structure of HAO shows a complex trimer with each subunit containing seven c-type heme units in addition to a novel heme at the active site, heme P460 (Igarashi et al., 1997). The 5-coordinate heme P460 active site appears to have originated from a five-coordinate c-type heme from one subunit that has been modified with a covalent crosslink to a tyrosine residue from the adjacent subunit (Arciero & Hooper, 1997; Igarashi et al., 1997; Arciero et al., 1993). The C3 ring carbon of the tyrosine is linked to the 5 meso position of the heme, so that the oxygen of the tyrosine is "ortho" to the porphyrin meso carbon (Igarashi et al., 1997; Arciero et al., 1993). In order to explore the chemistry of synthetic models of heme P460, we have begun a systematic examination of ortho substituted porphyrins, beginning with tetra(2',6'-dimethoxyphenyl)porphyrin, (H2T-2',6'-DMP)P. The molecule has oxygen substituents in the ortho position and serves as the non reactive control to compare with the more redox active ligand, tetra(2',6'-dihydroxyphenyl)porphyrin. Future work will focus on synthesizing and studying the more reactive metal ligand complexes with the biologically important iron ion.
The characterized metalloporphyrin is stable to both air and moisture in both the solid and solution environments. Following purification, different solvent systems including toluene, were examined in order to determine the best system. X-ray quality crystals were obtained by layering a dichloromethane solution of the metalloporphyrin with pentane. The asymmetric unit consists of 1.5 nickel porphyrins, 2 dichloromethanes, and one toluene molecule. The toluene molecule was carried over from the test solutions. One of the Ni[T(2',6'-DMP)P] molecules is located on an inversion center and is planar in the solid state (Figure 1) while the other assumes a saddle-shaped geometry (Figure 2). In both cases the nickel ion are 1.9474 (19) Å and 1.9554 (19) Å while they range between 1.9198 (19) Å and 1.9319 (19) Å for the ruffled complex. Non-planar nickel porphyrins are commonly known to exist because the small nickel ion favors a short metal-nitrogen bond distance leading to porphyrin conformational flexibility (Kadish et al., 2002). The coordination geometry is unexceptional and similar to other nickel porphyrin systems, average Ni—N bond distance of 1.920 Å listed in the Cambridge Crystallographic Database (Allen, 2002).
For details of the synthesis, see: Tsuchida, et al.(1990). For related examples of ortho-substituted porphyrins, see: Bhyrappa, et al. (1997). For related literature, see: Allen (2002); Arciero & Hooper (1997); Arciero et al. (1993); Igarashi et al. (1997); Kadish et al. (2002); Rothemund & Menotti (1948).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
Fig. 1. Ellipsoid (50% probability) plot of planar Ni[T(2',6'-DMP)P] | |
Fig. 2. : Ellispoid (50% probability) plot of saddle-shaped Ni[T(2',6'-DMP)P] |
[Ni(C52H44N4O8)]·0.67C7H8·1.33CH2Cl2 | F(000) = 3392 |
Mr = 1086.26 | Dx = 1.395 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9043 reflections |
a = 16.8286 (10) Å | θ = 2.3–32.0° |
b = 26.1041 (15) Å | µ = 0.57 mm−1 |
c = 17.6845 (10) Å | T = 100 K |
β = 92.813 (1)° | Octagonal column, red |
V = 7759.4 (8) Å3 | 0.35 × 0.35 × 0.35 mm |
Z = 6 |
Bruker SMART APEX CCD diffractometer | 15859 independent reflections |
Radiation source: fine-focus sealed tube | 13340 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω scans | θmax = 26.4°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | h = −21→21 |
Tmin = 0.583, Tmax = 0.818 | k = 0→32 |
72528 measured reflections | l = 0→22 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0482P)2 + 10.5281P] where P = (Fo2 + 2Fc2)/3 |
15859 reflections | (Δ/σ)max = 0.001 |
1100 parameters | Δρmax = 1.07 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
[Ni(C52H44N4O8)]·0.67C7H8·1.33CH2Cl2 | V = 7759.4 (8) Å3 |
Mr = 1086.26 | Z = 6 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.8286 (10) Å | µ = 0.57 mm−1 |
b = 26.1041 (15) Å | T = 100 K |
c = 17.6845 (10) Å | 0.35 × 0.35 × 0.35 mm |
β = 92.813 (1)° |
Bruker SMART APEX CCD diffractometer | 15859 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | 13340 reflections with I > 2σ(I) |
Tmin = 0.583, Tmax = 0.818 | Rint = 0.036 |
72528 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0482P)2 + 10.5281P] where P = (Fo2 + 2Fc2)/3 |
15859 reflections | Δρmax = 1.07 e Å−3 |
1100 parameters | Δρmin = −0.59 e Å−3 |
Experimental. Hydrogen atoms of the solvent molecules and methyl hydrogen atoms were placed in calculated positions and were refined with an isotropic displacement parameter 1.2 (methylene, aromatic) or 1.5 (methyl) times that of the adjacent carbon atom. Methyl hydrogen atoms were allowed to rotate to best fit the experimental electron density. All other hydrogen atoms were located in the difference Fourier map and were refined with an isotropic displacement parameter 1.2 times that of the adjacent carbon atom. |
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 > 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 | ||
Ni2 | 0.596867 (17) | 0.241274 (11) | 0.612644 (16) | 0.01220 (8) | |
N4 | 0.68062 (11) | 0.28069 (8) | 0.57001 (11) | 0.0142 (4) | |
N3 | 0.53415 (11) | 0.24643 (7) | 0.51849 (11) | 0.0141 (4) | |
O7 | 0.89977 (10) | 0.18742 (7) | 0.63691 (10) | 0.0237 (4) | |
N6 | 0.50932 (11) | 0.20910 (7) | 0.65961 (11) | 0.0141 (4) | |
N5 | 0.66332 (11) | 0.22972 (7) | 0.70310 (11) | 0.0137 (4) | |
O8 | 0.84678 (11) | 0.35033 (7) | 0.72834 (11) | 0.0262 (4) | |
O11 | 0.40439 (10) | 0.09919 (7) | 0.48806 (11) | 0.0236 (4) | |
O6 | 0.69411 (11) | 0.25715 (7) | 0.33494 (10) | 0.0251 (4) | |
O10 | 0.49128 (11) | 0.27889 (7) | 0.86637 (10) | 0.0265 (4) | |
C19 | 0.75781 (14) | 0.28722 (9) | 0.59886 (13) | 0.0151 (5) | |
O12 | 0.27877 (11) | 0.25079 (7) | 0.55419 (12) | 0.0273 (4) | |
C61 | 0.87726 (14) | 0.26963 (10) | 0.68284 (13) | 0.0171 (5) | |
O9 | 0.60155 (12) | 0.11457 (7) | 0.87314 (10) | 0.0267 (4) | |
C21 | 0.74458 (14) | 0.23685 (9) | 0.71209 (13) | 0.0149 (5) | |
C16 | 0.67716 (14) | 0.30818 (9) | 0.50290 (13) | 0.0158 (5) | |
C20 | 0.79052 (13) | 0.26313 (9) | 0.66264 (13) | 0.0148 (5) | |
C11 | 0.46349 (14) | 0.22146 (9) | 0.49961 (13) | 0.0159 (5) | |
C81 | 0.33861 (14) | 0.17382 (10) | 0.52166 (13) | 0.0179 (5) | |
C76 | 0.50707 (15) | 0.23676 (10) | 0.90949 (14) | 0.0206 (5) | |
O5 | 0.56918 (13) | 0.40381 (7) | 0.42029 (12) | 0.0332 (5) | |
C51 | 0.62966 (14) | 0.33097 (10) | 0.37358 (14) | 0.0196 (5) | |
C63 | 1.01218 (15) | 0.23661 (11) | 0.69016 (14) | 0.0227 (5) | |
H63 | 1.0486 (18) | 0.2099 (12) | 0.6846 (17) | 0.027* | |
C14 | 0.55155 (14) | 0.27339 (9) | 0.45416 (13) | 0.0161 (5) | |
C25 | 0.56294 (14) | 0.20379 (9) | 0.79141 (13) | 0.0170 (5) | |
C71 | 0.54430 (14) | 0.19650 (10) | 0.87226 (13) | 0.0183 (5) | |
C26 | 0.50200 (14) | 0.20021 (9) | 0.73618 (13) | 0.0163 (5) | |
C24 | 0.64059 (14) | 0.21387 (9) | 0.77339 (13) | 0.0161 (5) | |
C66 | 0.90475 (15) | 0.31501 (10) | 0.71644 (14) | 0.0204 (5) | |
C27 | 0.42455 (15) | 0.18019 (10) | 0.74965 (15) | 0.0199 (5) | |
H27 | 0.4072 (17) | 0.1712 (11) | 0.7960 (17) | 0.024* | |
C29 | 0.43799 (14) | 0.19333 (9) | 0.62593 (14) | 0.0159 (5) | |
C18 | 0.80039 (15) | 0.32123 (10) | 0.55187 (14) | 0.0180 (5) | |
H18 | 0.8524 (18) | 0.3318 (11) | 0.5610 (16) | 0.022* | |
C13 | 0.49232 (15) | 0.26431 (10) | 0.39483 (14) | 0.0198 (5) | |
H13 | 0.4931 (17) | 0.2790 (11) | 0.3487 (17) | 0.024* | |
C82 | 0.26848 (15) | 0.20226 (10) | 0.52574 (15) | 0.0218 (5) | |
C12 | 0.43876 (15) | 0.23178 (10) | 0.42224 (14) | 0.0199 (5) | |
H12 | 0.3946 (18) | 0.2196 (11) | 0.3989 (17) | 0.024* | |
C15 | 0.61727 (14) | 0.30463 (9) | 0.44733 (13) | 0.0163 (5) | |
C86 | 0.33303 (15) | 0.12423 (10) | 0.49208 (14) | 0.0206 (5) | |
C30 | 0.41679 (14) | 0.19564 (9) | 0.54936 (13) | 0.0153 (5) | |
C28 | 0.38597 (15) | 0.17516 (9) | 0.68174 (14) | 0.0186 (5) | |
H28 | 0.3333 (18) | 0.1630 (11) | 0.6689 (16) | 0.022* | |
C23 | 0.70803 (15) | 0.20973 (10) | 0.82528 (14) | 0.0193 (5) | |
H23 | 0.7059 (17) | 0.2007 (11) | 0.8756 (17) | 0.023* | |
C64 | 1.03728 (16) | 0.28227 (12) | 0.72230 (15) | 0.0255 (6) | |
H64 | 1.0896 (19) | 0.2870 (12) | 0.7353 (17) | 0.031* | |
C17 | 0.75053 (15) | 0.33476 (10) | 0.49350 (14) | 0.0192 (5) | |
H17 | 0.7602 (17) | 0.3581 (11) | 0.4515 (17) | 0.023* | |
C88 | 0.40178 (17) | 0.04627 (10) | 0.46742 (16) | 0.0260 (6) | |
H88A | 0.3704 | 0.0273 | 0.5034 | 0.039* | |
H88B | 0.4560 | 0.0325 | 0.4684 | 0.039* | |
H88C | 0.3772 | 0.0427 | 0.4163 | 0.039* | |
C62 | 0.93145 (14) | 0.23035 (10) | 0.66991 (13) | 0.0178 (5) | |
C74 | 0.51001 (15) | 0.18744 (11) | 1.02360 (15) | 0.0241 (6) | |
H74 | 0.4990 (18) | 0.1845 (12) | 1.0741 (18) | 0.029* | |
C73 | 0.54676 (16) | 0.14733 (11) | 0.98899 (15) | 0.0242 (6) | |
H73 | 0.5597 (18) | 0.1172 (12) | 1.0135 (18) | 0.029* | |
C22 | 0.77252 (15) | 0.22230 (10) | 0.78716 (14) | 0.0179 (5) | |
H22 | 0.8257 (18) | 0.2238 (11) | 0.8041 (16) | 0.022* | |
C72 | 0.56433 (15) | 0.15206 (10) | 0.91275 (14) | 0.0210 (5) | |
C52 | 0.67073 (15) | 0.30599 (11) | 0.31744 (14) | 0.0221 (5) | |
C56 | 0.60523 (16) | 0.38164 (11) | 0.36116 (16) | 0.0259 (6) | |
C75 | 0.48903 (15) | 0.23228 (11) | 0.98583 (15) | 0.0238 (6) | |
H75 | 0.4628 (18) | 0.2612 (12) | 1.0097 (17) | 0.029* | |
C85 | 0.26012 (16) | 0.10302 (11) | 0.46886 (17) | 0.0272 (6) | |
H85 | 0.2583 (18) | 0.0686 (13) | 0.4495 (18) | 0.033* | |
C65 | 0.98518 (16) | 0.32191 (11) | 0.73549 (14) | 0.0241 (6) | |
H65 | 1.0034 (18) | 0.3505 (12) | 0.7589 (17) | 0.029* | |
C67 | 0.95131 (17) | 0.14461 (11) | 0.62543 (17) | 0.0291 (6) | |
H67A | 0.9947 | 0.1552 | 0.5938 | 0.044* | |
H67B | 0.9209 | 0.1169 | 0.6001 | 0.044* | |
H67C | 0.9735 | 0.1325 | 0.6745 | 0.044* | |
C78 | 0.4623 (2) | 0.32409 (12) | 0.90185 (17) | 0.0370 (7) | |
H78A | 0.4090 | 0.3176 | 0.9195 | 0.055* | |
H78B | 0.4600 | 0.3523 | 0.8653 | 0.055* | |
H78C | 0.4982 | 0.3333 | 0.9450 | 0.055* | |
C54 | 0.65872 (17) | 0.38009 (13) | 0.23798 (17) | 0.0339 (7) | |
H54 | 0.6695 (19) | 0.3962 (13) | 0.190 (2) | 0.041* | |
C87 | 0.20951 (17) | 0.28180 (11) | 0.55885 (17) | 0.0297 (6) | |
H87A | 0.1831 | 0.2851 | 0.5084 | 0.045* | |
H87B | 0.2248 | 0.3158 | 0.5780 | 0.045* | |
H87C | 0.1730 | 0.2658 | 0.5933 | 0.045* | |
C53 | 0.68507 (16) | 0.33037 (13) | 0.24927 (15) | 0.0293 (6) | |
H53 | 0.7141 (19) | 0.3126 (12) | 0.2121 (19) | 0.035* | |
C83 | 0.19512 (16) | 0.18168 (12) | 0.50232 (17) | 0.0283 (6) | |
H83 | 0.1481 (19) | 0.2020 (12) | 0.5056 (18) | 0.034* | |
C84 | 0.19222 (17) | 0.13226 (12) | 0.47404 (18) | 0.0315 (7) | |
H84 | 0.142 (2) | 0.1179 (13) | 0.4588 (18) | 0.038* | |
C57 | 0.75223 (17) | 0.23331 (12) | 0.28985 (17) | 0.0331 (7) | |
H57A | 0.7305 | 0.2296 | 0.2377 | 0.050* | |
H57B | 0.7657 | 0.1994 | 0.3107 | 0.050* | |
H57C | 0.8002 | 0.2546 | 0.2903 | 0.050* | |
C55 | 0.61919 (18) | 0.40616 (13) | 0.29261 (18) | 0.0340 (7) | |
H55 | 0.601 (2) | 0.4378 (14) | 0.2860 (19) | 0.041* | |
C77 | 0.6456 (2) | 0.07702 (13) | 0.91679 (19) | 0.0421 (8) | |
H77A | 0.6825 | 0.0942 | 0.9531 | 0.063* | |
H77B | 0.6757 | 0.0555 | 0.8830 | 0.063* | |
H77C | 0.6087 | 0.0556 | 0.9442 | 0.063* | |
C58 | 0.5607 (2) | 0.45806 (12) | 0.4196 (2) | 0.0420 (8) | |
H58A | 0.6127 | 0.4740 | 0.4131 | 0.063* | |
H58B | 0.5399 | 0.4694 | 0.4676 | 0.063* | |
H58C | 0.5238 | 0.4682 | 0.3777 | 0.063* | |
C68 | 0.8687 (2) | 0.39563 (13) | 0.7681 (2) | 0.0446 (9) | |
H68A | 0.8940 | 0.3866 | 0.8174 | 0.067* | |
H68B | 0.8212 | 0.4164 | 0.7756 | 0.067* | |
H68C | 0.9062 | 0.4153 | 0.7388 | 0.067* | |
Ni1 | 1.0000 | 0.0000 | 0.5000 | 0.01166 (9) | |
O1 | 0.77710 (10) | 0.14246 (7) | 0.45736 (10) | 0.0232 (4) | |
N2 | 0.95487 (11) | 0.02206 (7) | 0.40132 (11) | 0.0135 (4) | |
N1 | 0.89857 (11) | 0.01353 (7) | 0.54459 (11) | 0.0133 (4) | |
O3 | 1.11481 (11) | 0.10768 (7) | 0.28228 (10) | 0.0251 (4) | |
O4 | 1.09479 (11) | −0.06494 (7) | 0.22073 (10) | 0.0247 (4) | |
O2 | 0.70622 (11) | −0.01526 (7) | 0.35264 (12) | 0.0299 (4) | |
C4 | 0.82942 (14) | 0.03238 (9) | 0.50919 (13) | 0.0146 (5) | |
C31 | 0.73783 (14) | 0.06384 (9) | 0.40707 (13) | 0.0155 (5) | |
C5 | 0.81837 (14) | 0.04401 (9) | 0.43304 (13) | 0.0147 (5) | |
C6 | 0.87830 (14) | 0.03886 (9) | 0.38304 (13) | 0.0155 (5) | |
C2 | 0.79852 (14) | 0.02140 (9) | 0.62966 (14) | 0.0175 (5) | |
H2 | 0.7739 (16) | 0.0204 (11) | 0.6768 (16) | 0.021* | |
C9 | 0.99282 (14) | 0.02552 (9) | 0.33387 (13) | 0.0152 (5) | |
C41 | 1.10539 (14) | 0.02204 (9) | 0.24785 (13) | 0.0162 (5) | |
C10 | 1.07108 (14) | 0.01279 (9) | 0.32309 (13) | 0.0146 (5) | |
C1 | 0.87928 (14) | 0.00641 (9) | 0.61884 (13) | 0.0153 (5) | |
C3 | 0.76809 (15) | 0.03784 (9) | 0.56207 (14) | 0.0173 (5) | |
H3 | 0.7178 (17) | 0.0510 (11) | 0.5498 (16) | 0.021* | |
C7 | 0.86906 (15) | 0.05238 (10) | 0.30469 (14) | 0.0185 (5) | |
H7 | 0.8211 (18) | 0.0655 (11) | 0.2842 (16) | 0.022* | |
C32 | 0.71661 (15) | 0.11368 (10) | 0.42606 (14) | 0.0196 (5) | |
C8 | 0.93984 (15) | 0.04450 (9) | 0.27425 (14) | 0.0179 (5) | |
H8 | 0.9556 (16) | 0.0515 (11) | 0.2239 (17) | 0.022* | |
C46 | 1.11854 (15) | −0.01760 (10) | 0.19747 (14) | 0.0197 (5) | |
C36 | 0.68011 (15) | 0.03202 (10) | 0.37257 (15) | 0.0214 (5) | |
C34 | 0.58228 (16) | 0.09765 (11) | 0.38401 (15) | 0.0256 (6) | |
H34 | 0.5295 (19) | 0.1092 (12) | 0.3801 (17) | 0.031* | |
C33 | 0.63846 (16) | 0.13127 (11) | 0.41439 (15) | 0.0232 (6) | |
H33 | 0.6255 (18) | 0.1634 (12) | 0.4278 (17) | 0.028* | |
C42 | 1.12752 (15) | 0.07169 (10) | 0.22874 (14) | 0.0202 (5) | |
C35 | 0.60150 (16) | 0.04870 (11) | 0.36158 (16) | 0.0253 (6) | |
H35 | 0.5617 (19) | 0.0263 (12) | 0.3412 (17) | 0.030* | |
C37 | 0.75520 (18) | 0.18772 (11) | 0.49739 (16) | 0.0293 (6) | |
H37A | 0.7317 | 0.2127 | 0.4615 | 0.044* | |
H37B | 0.8026 | 0.2025 | 0.5233 | 0.044* | |
H37C | 0.7163 | 0.1788 | 0.5347 | 0.044* | |
C44 | 1.17342 (18) | 0.04142 (12) | 0.11123 (16) | 0.0307 (7) | |
H44 | 1.1991 (19) | 0.0461 (12) | 0.0677 (19) | 0.037* | |
C43 | 1.16141 (17) | 0.08176 (12) | 0.15954 (16) | 0.0279 (6) | |
H43 | 1.1753 (19) | 0.1135 (13) | 0.1495 (18) | 0.034* | |
C47 | 1.13464 (18) | 0.15975 (10) | 0.26538 (18) | 0.0309 (6) | |
H47A | 1.1915 | 0.1621 | 0.2562 | 0.046* | |
H47B | 1.1225 | 0.1817 | 0.3083 | 0.046* | |
H47C | 1.1035 | 0.1710 | 0.2201 | 0.046* | |
C45 | 1.15278 (17) | −0.00822 (12) | 0.12861 (15) | 0.0269 (6) | |
H45 | 1.1582 (18) | −0.0353 (12) | 0.0956 (18) | 0.032* | |
C48 | 1.1157 (2) | −0.10829 (11) | 0.17662 (18) | 0.0379 (7) | |
H48A | 1.0897 | −0.1057 | 0.1260 | 0.057* | |
H48B | 1.0983 | −0.1397 | 0.2012 | 0.057* | |
H48C | 1.1736 | −0.1092 | 0.1724 | 0.057* | |
C38 | 0.6501 (2) | −0.04850 (12) | 0.3142 (2) | 0.0472 (9) | |
H38A | 0.6095 | −0.0588 | 0.3489 | 0.071* | |
H38B | 0.6777 | −0.0790 | 0.2964 | 0.071* | |
H38C | 0.6248 | −0.0305 | 0.2708 | 0.071* | |
Cl1 | 0.56586 (5) | 0.08927 (3) | 0.59577 (5) | 0.03955 (19) | |
Cl2 | 0.60288 (5) | 0.02551 (3) | 0.72804 (5) | 0.0425 (2) | |
C98 | 0.6032 (3) | 0.08763 (13) | 0.6895 (2) | 0.0544 (10) | |
H98A | 0.5708 | 0.1104 | 0.7204 | 0.065* | |
H98B | 0.6584 | 0.1009 | 0.6920 | 0.065* | |
Cl3 | 0.91634 (7) | 0.16930 (4) | 0.17449 (6) | 0.0580 (3) | |
Cl4 | 0.87511 (8) | 0.10083 (4) | 0.04958 (6) | 0.0727 (4) | |
C99 | 0.9249 (2) | 0.15800 (14) | 0.0773 (2) | 0.0499 (9) | |
H99A | 0.9818 | 0.1553 | 0.0661 | 0.060* | |
H99B | 0.9017 | 0.1871 | 0.0480 | 0.060* | |
C94 | 0.4412 (4) | 1.0101 (3) | 0.8930 (3) | 0.106 (2) | |
H94 | 0.4951 | 1.0199 | 0.9028 | 0.127* | |
C91 | 0.3222 (2) | 0.89776 (14) | 0.8166 (2) | 0.0481 (9) | |
H91A | 0.2679 | 0.8882 | 0.8287 | 0.072* | |
H91B | 0.3595 | 0.8717 | 0.8366 | 0.072* | |
H91C | 0.3256 | 0.9001 | 0.7616 | 0.072* | |
C95 | 0.3817 (4) | 1.0449 (3) | 0.9115 (4) | 0.0999 (19) | |
H95 | 0.3947 | 1.0779 | 0.9312 | 0.120* | |
C92 | 0.3420 (2) | 0.94673 (17) | 0.8504 (2) | 0.0513 (9) | |
C97 | 0.2852 (3) | 0.98259 (17) | 0.8662 (3) | 0.0628 (11) | |
H97 | 0.2308 | 0.9753 | 0.8538 | 0.075* | |
C93 | 0.4256 (3) | 0.96124 (19) | 0.8604 (2) | 0.0669 (13) | |
H93 | 0.4672 | 0.9392 | 0.8459 | 0.080* | |
C96 | 0.3056 (3) | 1.0300 (2) | 0.9004 (3) | 0.0848 (17) | |
H96 | 0.2644 | 1.0519 | 0.9159 | 0.102* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni2 | 0.01087 (14) | 0.01424 (15) | 0.01158 (14) | −0.00010 (11) | 0.00142 (11) | −0.00092 (11) |
N4 | 0.0120 (9) | 0.0166 (10) | 0.0141 (9) | 0.0004 (8) | 0.0022 (7) | −0.0026 (8) |
N3 | 0.0135 (10) | 0.0170 (10) | 0.0118 (9) | 0.0001 (8) | 0.0018 (7) | −0.0009 (8) |
O7 | 0.0203 (9) | 0.0212 (9) | 0.0297 (10) | 0.0046 (7) | 0.0021 (8) | −0.0025 (8) |
N6 | 0.0130 (10) | 0.0151 (10) | 0.0143 (9) | 0.0000 (8) | 0.0024 (7) | −0.0007 (8) |
N5 | 0.0136 (10) | 0.0153 (10) | 0.0124 (9) | 0.0014 (8) | 0.0014 (7) | −0.0021 (8) |
O8 | 0.0208 (9) | 0.0256 (10) | 0.0322 (10) | −0.0015 (8) | −0.0008 (8) | −0.0126 (8) |
O11 | 0.0191 (9) | 0.0173 (9) | 0.0343 (10) | 0.0004 (7) | −0.0004 (8) | −0.0054 (8) |
O6 | 0.0246 (10) | 0.0296 (10) | 0.0218 (9) | −0.0030 (8) | 0.0085 (8) | −0.0020 (8) |
O10 | 0.0332 (11) | 0.0270 (10) | 0.0200 (9) | 0.0077 (8) | 0.0081 (8) | −0.0013 (8) |
C19 | 0.0133 (11) | 0.0165 (12) | 0.0157 (11) | 0.0008 (9) | 0.0025 (9) | −0.0046 (9) |
O12 | 0.0174 (9) | 0.0235 (10) | 0.0407 (11) | 0.0047 (7) | −0.0021 (8) | −0.0096 (8) |
C61 | 0.0148 (12) | 0.0239 (13) | 0.0126 (11) | −0.0034 (10) | 0.0006 (9) | 0.0011 (9) |
O9 | 0.0343 (11) | 0.0226 (10) | 0.0235 (10) | 0.0024 (8) | 0.0045 (8) | −0.0002 (8) |
C21 | 0.0146 (11) | 0.0131 (11) | 0.0172 (11) | 0.0024 (9) | 0.0008 (9) | −0.0024 (9) |
C16 | 0.0175 (12) | 0.0148 (11) | 0.0152 (11) | 0.0020 (9) | 0.0025 (9) | −0.0016 (9) |
C20 | 0.0124 (11) | 0.0168 (12) | 0.0153 (11) | 0.0003 (9) | 0.0018 (9) | −0.0071 (9) |
C11 | 0.0152 (12) | 0.0162 (11) | 0.0162 (11) | 0.0021 (9) | 0.0008 (9) | −0.0022 (9) |
C81 | 0.0180 (12) | 0.0202 (12) | 0.0156 (11) | −0.0020 (10) | 0.0002 (9) | 0.0015 (9) |
C76 | 0.0166 (12) | 0.0269 (14) | 0.0183 (12) | −0.0017 (10) | 0.0020 (9) | −0.0008 (10) |
O5 | 0.0423 (12) | 0.0232 (10) | 0.0338 (11) | 0.0084 (9) | 0.0006 (9) | 0.0043 (9) |
C51 | 0.0150 (12) | 0.0253 (13) | 0.0181 (12) | −0.0054 (10) | −0.0030 (9) | 0.0042 (10) |
C63 | 0.0172 (13) | 0.0335 (15) | 0.0176 (12) | 0.0049 (11) | 0.0025 (10) | 0.0067 (11) |
C14 | 0.0164 (12) | 0.0162 (12) | 0.0156 (11) | 0.0047 (9) | 0.0021 (9) | −0.0010 (9) |
C25 | 0.0192 (12) | 0.0161 (12) | 0.0162 (12) | −0.0006 (9) | 0.0043 (9) | −0.0011 (9) |
C71 | 0.0146 (12) | 0.0262 (13) | 0.0143 (11) | −0.0030 (10) | 0.0019 (9) | −0.0011 (10) |
C26 | 0.0170 (12) | 0.0171 (12) | 0.0153 (11) | 0.0021 (9) | 0.0059 (9) | −0.0027 (9) |
C24 | 0.0182 (12) | 0.0143 (11) | 0.0162 (11) | 0.0006 (9) | 0.0028 (9) | −0.0024 (9) |
C66 | 0.0181 (12) | 0.0269 (14) | 0.0162 (12) | −0.0009 (10) | 0.0020 (9) | −0.0004 (10) |
C27 | 0.0181 (12) | 0.0228 (13) | 0.0194 (12) | −0.0008 (10) | 0.0067 (10) | 0.0004 (10) |
C29 | 0.0135 (11) | 0.0134 (11) | 0.0209 (12) | 0.0017 (9) | 0.0017 (9) | −0.0020 (9) |
C18 | 0.0146 (12) | 0.0199 (12) | 0.0195 (12) | −0.0034 (10) | 0.0023 (9) | −0.0008 (10) |
C13 | 0.0187 (13) | 0.0261 (14) | 0.0147 (12) | 0.0003 (10) | 0.0002 (9) | 0.0011 (10) |
C82 | 0.0182 (13) | 0.0249 (13) | 0.0222 (13) | 0.0000 (10) | −0.0011 (10) | −0.0018 (11) |
C12 | 0.0168 (12) | 0.0239 (13) | 0.0188 (12) | −0.0017 (10) | −0.0017 (10) | −0.0029 (10) |
C15 | 0.0168 (12) | 0.0151 (12) | 0.0173 (11) | 0.0022 (9) | 0.0036 (9) | 0.0007 (9) |
C86 | 0.0173 (12) | 0.0220 (13) | 0.0225 (13) | 0.0003 (10) | 0.0013 (10) | −0.0002 (10) |
C30 | 0.0127 (11) | 0.0144 (11) | 0.0190 (12) | 0.0028 (9) | 0.0016 (9) | −0.0023 (9) |
C28 | 0.0139 (12) | 0.0183 (12) | 0.0239 (13) | −0.0020 (10) | 0.0034 (10) | −0.0013 (10) |
C23 | 0.0219 (13) | 0.0215 (13) | 0.0147 (12) | −0.0003 (10) | 0.0011 (10) | 0.0002 (10) |
C64 | 0.0132 (12) | 0.0460 (17) | 0.0170 (12) | −0.0039 (12) | −0.0016 (10) | 0.0052 (12) |
C17 | 0.0200 (13) | 0.0186 (12) | 0.0191 (12) | −0.0016 (10) | 0.0032 (10) | 0.0012 (10) |
C88 | 0.0296 (15) | 0.0183 (13) | 0.0302 (15) | 0.0010 (11) | 0.0010 (11) | −0.0022 (11) |
C62 | 0.0177 (12) | 0.0238 (13) | 0.0120 (11) | 0.0002 (10) | 0.0015 (9) | 0.0036 (9) |
C74 | 0.0193 (13) | 0.0395 (16) | 0.0138 (12) | −0.0079 (11) | 0.0044 (10) | −0.0003 (11) |
C73 | 0.0219 (13) | 0.0306 (15) | 0.0200 (13) | −0.0075 (11) | −0.0004 (10) | 0.0043 (11) |
C22 | 0.0158 (12) | 0.0213 (13) | 0.0164 (12) | −0.0002 (10) | −0.0020 (9) | −0.0018 (10) |
C72 | 0.0188 (12) | 0.0257 (13) | 0.0188 (12) | −0.0037 (10) | 0.0026 (10) | −0.0017 (10) |
C52 | 0.0152 (12) | 0.0321 (15) | 0.0189 (12) | −0.0079 (11) | −0.0009 (10) | 0.0012 (11) |
C56 | 0.0214 (13) | 0.0276 (14) | 0.0283 (14) | −0.0041 (11) | −0.0038 (11) | 0.0060 (11) |
C75 | 0.0186 (13) | 0.0345 (15) | 0.0186 (13) | −0.0022 (11) | 0.0052 (10) | −0.0039 (11) |
C85 | 0.0243 (14) | 0.0227 (14) | 0.0340 (15) | −0.0044 (11) | −0.0037 (11) | −0.0059 (12) |
C65 | 0.0213 (13) | 0.0351 (16) | 0.0157 (12) | −0.0094 (12) | 0.0004 (10) | −0.0030 (11) |
C67 | 0.0319 (15) | 0.0229 (14) | 0.0332 (15) | 0.0069 (12) | 0.0094 (12) | 0.0014 (12) |
C78 | 0.0453 (19) | 0.0361 (17) | 0.0300 (16) | 0.0179 (14) | 0.0072 (13) | −0.0049 (13) |
C54 | 0.0255 (15) | 0.052 (2) | 0.0240 (14) | −0.0140 (14) | −0.0038 (12) | 0.0179 (14) |
C87 | 0.0256 (15) | 0.0316 (15) | 0.0322 (15) | 0.0098 (12) | 0.0027 (12) | −0.0062 (12) |
C53 | 0.0199 (13) | 0.0488 (18) | 0.0192 (13) | −0.0125 (13) | 0.0020 (11) | 0.0027 (13) |
C83 | 0.0143 (13) | 0.0337 (16) | 0.0366 (16) | 0.0020 (11) | −0.0010 (11) | −0.0028 (13) |
C84 | 0.0183 (14) | 0.0358 (16) | 0.0396 (17) | −0.0065 (12) | −0.0060 (12) | −0.0048 (13) |
C57 | 0.0249 (15) | 0.0431 (18) | 0.0323 (16) | −0.0026 (13) | 0.0115 (12) | −0.0084 (13) |
C55 | 0.0299 (16) | 0.0340 (17) | 0.0369 (17) | −0.0071 (13) | −0.0091 (13) | 0.0173 (14) |
C77 | 0.054 (2) | 0.0326 (17) | 0.0401 (18) | 0.0138 (15) | 0.0014 (15) | 0.0043 (14) |
C58 | 0.0438 (19) | 0.0247 (16) | 0.057 (2) | 0.0080 (14) | −0.0073 (16) | 0.0017 (15) |
C68 | 0.0324 (17) | 0.0385 (19) | 0.063 (2) | −0.0021 (14) | 0.0007 (15) | −0.0281 (17) |
Ni1 | 0.0108 (2) | 0.0125 (2) | 0.0118 (2) | 0.00122 (15) | 0.00184 (15) | 0.00077 (16) |
O1 | 0.0208 (9) | 0.0195 (9) | 0.0291 (10) | 0.0050 (7) | −0.0023 (7) | −0.0079 (8) |
N2 | 0.0127 (9) | 0.0137 (10) | 0.0141 (9) | 0.0009 (7) | 0.0017 (7) | 0.0006 (8) |
N1 | 0.0124 (9) | 0.0140 (9) | 0.0136 (9) | 0.0000 (7) | 0.0013 (7) | 0.0001 (8) |
O3 | 0.0336 (11) | 0.0161 (9) | 0.0264 (10) | −0.0035 (8) | 0.0112 (8) | 0.0021 (7) |
O4 | 0.0330 (11) | 0.0187 (9) | 0.0231 (9) | 0.0005 (8) | 0.0099 (8) | −0.0028 (7) |
O2 | 0.0236 (10) | 0.0205 (10) | 0.0448 (12) | −0.0026 (8) | −0.0075 (9) | −0.0047 (9) |
C4 | 0.0132 (11) | 0.0110 (11) | 0.0195 (12) | −0.0014 (9) | 0.0009 (9) | −0.0002 (9) |
C31 | 0.0123 (11) | 0.0197 (12) | 0.0146 (11) | 0.0027 (9) | 0.0022 (9) | 0.0041 (9) |
C5 | 0.0131 (11) | 0.0132 (11) | 0.0177 (11) | −0.0006 (9) | −0.0017 (9) | −0.0023 (9) |
C6 | 0.0142 (11) | 0.0143 (11) | 0.0182 (12) | 0.0003 (9) | 0.0011 (9) | −0.0005 (9) |
C2 | 0.0156 (12) | 0.0188 (12) | 0.0184 (12) | 0.0006 (9) | 0.0043 (9) | −0.0001 (10) |
C9 | 0.0182 (12) | 0.0105 (11) | 0.0170 (11) | −0.0002 (9) | 0.0011 (9) | 0.0000 (9) |
C41 | 0.0130 (11) | 0.0212 (12) | 0.0145 (11) | 0.0010 (9) | 0.0019 (9) | 0.0034 (9) |
C10 | 0.0178 (12) | 0.0114 (11) | 0.0151 (11) | −0.0014 (9) | 0.0051 (9) | −0.0001 (9) |
C1 | 0.0150 (11) | 0.0127 (11) | 0.0184 (12) | −0.0011 (9) | 0.0026 (9) | −0.0001 (9) |
C3 | 0.0137 (12) | 0.0178 (12) | 0.0206 (12) | 0.0007 (9) | 0.0010 (9) | −0.0017 (10) |
C7 | 0.0192 (13) | 0.0204 (12) | 0.0158 (12) | 0.0032 (10) | −0.0001 (10) | 0.0014 (10) |
C32 | 0.0194 (13) | 0.0243 (13) | 0.0153 (12) | 0.0026 (10) | 0.0024 (9) | 0.0017 (10) |
C8 | 0.0201 (12) | 0.0193 (12) | 0.0145 (12) | 0.0016 (10) | 0.0016 (9) | 0.0018 (10) |
C46 | 0.0181 (12) | 0.0232 (13) | 0.0181 (12) | 0.0015 (10) | 0.0020 (10) | 0.0014 (10) |
C36 | 0.0185 (13) | 0.0224 (13) | 0.0233 (13) | −0.0005 (10) | 0.0015 (10) | 0.0048 (10) |
C34 | 0.0144 (13) | 0.0388 (16) | 0.0237 (13) | 0.0073 (11) | 0.0030 (10) | 0.0109 (12) |
C33 | 0.0202 (13) | 0.0274 (14) | 0.0221 (13) | 0.0092 (11) | 0.0037 (10) | 0.0026 (11) |
C42 | 0.0173 (12) | 0.0224 (13) | 0.0214 (13) | 0.0015 (10) | 0.0047 (10) | 0.0018 (10) |
C35 | 0.0164 (13) | 0.0325 (15) | 0.0265 (14) | −0.0054 (11) | −0.0038 (10) | 0.0063 (12) |
C37 | 0.0347 (16) | 0.0242 (14) | 0.0287 (15) | 0.0070 (12) | −0.0010 (12) | −0.0091 (12) |
C44 | 0.0314 (16) | 0.0424 (18) | 0.0194 (13) | −0.0033 (13) | 0.0125 (12) | 0.0044 (12) |
C43 | 0.0325 (15) | 0.0277 (15) | 0.0241 (14) | −0.0049 (12) | 0.0070 (11) | 0.0082 (12) |
C47 | 0.0353 (16) | 0.0157 (13) | 0.0425 (17) | −0.0041 (11) | 0.0096 (13) | 0.0025 (12) |
C45 | 0.0284 (15) | 0.0330 (16) | 0.0200 (13) | −0.0007 (12) | 0.0079 (11) | −0.0046 (12) |
C48 | 0.056 (2) | 0.0216 (15) | 0.0380 (17) | 0.0058 (14) | 0.0166 (15) | −0.0060 (13) |
C38 | 0.0360 (18) | 0.0269 (16) | 0.077 (3) | −0.0056 (14) | −0.0147 (17) | −0.0142 (17) |
Cl1 | 0.0371 (4) | 0.0414 (4) | 0.0392 (4) | 0.0162 (3) | −0.0074 (3) | −0.0107 (3) |
Cl2 | 0.0602 (5) | 0.0289 (4) | 0.0393 (4) | 0.0004 (4) | 0.0128 (4) | −0.0051 (3) |
C98 | 0.097 (3) | 0.0266 (17) | 0.0376 (19) | 0.0003 (18) | −0.0127 (19) | −0.0066 (14) |
Cl3 | 0.0790 (7) | 0.0395 (5) | 0.0535 (5) | −0.0142 (5) | −0.0165 (5) | 0.0081 (4) |
Cl4 | 0.1128 (10) | 0.0517 (6) | 0.0563 (6) | −0.0378 (6) | 0.0321 (6) | −0.0142 (5) |
C99 | 0.053 (2) | 0.0367 (19) | 0.061 (2) | −0.0149 (16) | 0.0108 (18) | 0.0124 (17) |
C94 | 0.075 (4) | 0.157 (6) | 0.082 (4) | −0.053 (4) | −0.017 (3) | 0.012 (4) |
C91 | 0.046 (2) | 0.057 (2) | 0.0427 (19) | 0.0159 (17) | 0.0148 (16) | 0.0271 (17) |
C95 | 0.082 (4) | 0.103 (5) | 0.114 (5) | −0.009 (4) | −0.002 (4) | −0.028 (4) |
C92 | 0.048 (2) | 0.067 (3) | 0.0395 (19) | 0.0072 (19) | 0.0044 (16) | 0.0194 (18) |
C97 | 0.050 (2) | 0.066 (3) | 0.073 (3) | −0.002 (2) | 0.008 (2) | −0.013 (2) |
C93 | 0.063 (3) | 0.084 (3) | 0.051 (2) | −0.023 (2) | −0.018 (2) | 0.018 (2) |
C96 | 0.058 (3) | 0.089 (4) | 0.107 (4) | 0.002 (3) | −0.006 (3) | −0.061 (3) |
Ni2—N6 | 1.9198 (19) | C53—H53 | 0.96 (3) |
Ni2—N4 | 1.928 (2) | C83—C84 | 1.383 (4) |
Ni2—N5 | 1.9300 (19) | C83—H83 | 0.96 (3) |
Ni2—N3 | 1.9319 (19) | C84—H84 | 0.95 (3) |
N4—C19 | 1.383 (3) | C57—H57A | 0.9800 |
N4—C16 | 1.386 (3) | C57—H57B | 0.9800 |
N3—C14 | 1.381 (3) | C57—H57C | 0.9800 |
N3—C11 | 1.383 (3) | C55—H55 | 0.89 (4) |
O7—C62 | 1.360 (3) | C77—H77A | 0.9800 |
O7—C67 | 1.435 (3) | C77—H77B | 0.9800 |
N6—C29 | 1.377 (3) | C77—H77C | 0.9800 |
N6—C26 | 1.385 (3) | C58—H58A | 0.9800 |
N5—C21 | 1.381 (3) | C58—H58B | 0.9800 |
N5—C24 | 1.382 (3) | C58—H58C | 0.9800 |
O8—C66 | 1.366 (3) | C68—H68A | 0.9800 |
O8—C68 | 1.415 (3) | C68—H68B | 0.9800 |
O11—C86 | 1.372 (3) | C68—H68C | 0.9800 |
O11—C88 | 1.429 (3) | Ni1—N1 | 1.9474 (19) |
O6—C52 | 1.365 (3) | Ni1—N1i | 1.9474 (19) |
O6—C57 | 1.434 (3) | Ni1—N2 | 1.9554 (19) |
O10—C76 | 1.357 (3) | Ni1—N2i | 1.9554 (19) |
O10—C78 | 1.433 (3) | O1—C32 | 1.361 (3) |
C19—C20 | 1.382 (3) | O1—C37 | 1.435 (3) |
C19—C18 | 1.432 (3) | N2—C9 | 1.383 (3) |
O12—C82 | 1.371 (3) | N2—C6 | 1.384 (3) |
O12—C87 | 1.425 (3) | N1—C1 | 1.381 (3) |
C61—C66 | 1.394 (4) | N1—C4 | 1.384 (3) |
C61—C62 | 1.399 (3) | O3—C42 | 1.358 (3) |
C61—C20 | 1.495 (3) | O3—C47 | 1.435 (3) |
O9—C72 | 1.373 (3) | O4—C46 | 1.368 (3) |
O9—C77 | 1.432 (4) | O4—C48 | 1.428 (3) |
C21—C20 | 1.378 (3) | O2—C36 | 1.362 (3) |
C21—C22 | 1.437 (3) | O2—C38 | 1.430 (3) |
C16—C15 | 1.376 (3) | C4—C5 | 1.384 (3) |
C16—C17 | 1.433 (3) | C4—C3 | 1.433 (3) |
C11—C30 | 1.383 (3) | C31—C32 | 1.395 (3) |
C11—C12 | 1.436 (3) | C31—C36 | 1.396 (4) |
C81—C86 | 1.398 (4) | C31—C5 | 1.502 (3) |
C81—C82 | 1.399 (4) | C5—C6 | 1.380 (3) |
C81—C30 | 1.494 (3) | C6—C7 | 1.431 (3) |
C76—C75 | 1.403 (3) | C2—C3 | 1.347 (3) |
C76—C71 | 1.404 (4) | C2—C1 | 1.436 (3) |
O5—C56 | 1.363 (3) | C2—H2 | 0.95 (3) |
O5—C58 | 1.423 (4) | C9—C10 | 1.381 (3) |
C51—C52 | 1.399 (4) | C9—C8 | 1.435 (3) |
C51—C56 | 1.399 (4) | C41—C46 | 1.390 (4) |
C51—C15 | 1.498 (3) | C41—C42 | 1.395 (3) |
C63—C64 | 1.378 (4) | C41—C10 | 1.496 (3) |
C63—C62 | 1.398 (4) | C10—C1i | 1.385 (3) |
C63—H63 | 0.94 (3) | C1—C10i | 1.385 (3) |
C14—C15 | 1.384 (3) | C3—H3 | 0.93 (3) |
C14—C13 | 1.431 (3) | C7—C8 | 1.347 (3) |
C25—C26 | 1.384 (3) | C7—H7 | 0.93 (3) |
C25—C24 | 1.385 (3) | C32—C33 | 1.399 (4) |
C25—C71 | 1.491 (3) | C8—H8 | 0.96 (3) |
C71—C72 | 1.396 (4) | C46—C45 | 1.394 (4) |
C26—C27 | 1.435 (3) | C36—C35 | 1.397 (4) |
C24—C23 | 1.428 (3) | C34—C33 | 1.379 (4) |
C66—C65 | 1.390 (4) | C34—C35 | 1.381 (4) |
C27—C28 | 1.343 (4) | C34—H34 | 0.94 (3) |
C27—H27 | 0.91 (3) | C33—H33 | 0.90 (3) |
C29—C30 | 1.385 (3) | C42—C43 | 1.400 (4) |
C29—C28 | 1.432 (3) | C35—H35 | 0.95 (3) |
C18—C17 | 1.345 (4) | C37—H37A | 0.9800 |
C18—H18 | 0.92 (3) | C37—H37B | 0.9800 |
C13—C12 | 1.346 (4) | C37—H37C | 0.9800 |
C13—H13 | 0.90 (3) | C44—C43 | 1.377 (4) |
C82—C83 | 1.391 (4) | C44—C45 | 1.380 (4) |
C12—H12 | 0.89 (3) | C44—H44 | 0.91 (3) |
C86—C85 | 1.390 (4) | C43—H43 | 0.88 (3) |
C28—H28 | 0.96 (3) | C47—H47A | 0.9800 |
C23—C22 | 1.346 (4) | C47—H47B | 0.9800 |
C23—H23 | 0.92 (3) | C47—H47C | 0.9800 |
C64—C65 | 1.384 (4) | C45—H45 | 0.92 (3) |
C64—H64 | 0.91 (3) | C48—H48A | 0.9800 |
C17—H17 | 0.98 (3) | C48—H48B | 0.9800 |
C88—H88A | 0.9800 | C48—H48C | 0.9800 |
C88—H88B | 0.9800 | C38—H38A | 0.9800 |
C88—H88C | 0.9800 | C38—H38B | 0.9800 |
C74—C73 | 1.375 (4) | C38—H38C | 0.9800 |
C74—C75 | 1.385 (4) | Cl1—C98 | 1.745 (4) |
C74—H74 | 0.92 (3) | Cl2—C98 | 1.759 (4) |
C73—C72 | 1.400 (4) | C98—H98A | 0.9900 |
C73—H73 | 0.92 (3) | C98—H98B | 0.9900 |
C22—H22 | 0.93 (3) | Cl3—C99 | 1.757 (4) |
C52—C53 | 1.395 (4) | Cl4—C99 | 1.769 (4) |
C56—C55 | 1.401 (4) | C99—H99A | 0.9900 |
C75—H75 | 0.98 (3) | C99—H99B | 0.9900 |
C85—C84 | 1.381 (4) | C94—C95 | 1.403 (9) |
C85—H85 | 0.96 (3) | C94—C93 | 1.420 (8) |
C65—H65 | 0.90 (3) | C94—H94 | 0.9500 |
C67—H67A | 0.9800 | C91—C92 | 1.444 (6) |
C67—H67B | 0.9800 | C91—H91A | 0.9800 |
C67—H67C | 0.9800 | C91—H91B | 0.9800 |
C78—H78A | 0.9800 | C91—H91C | 0.9800 |
C78—H78B | 0.9800 | C95—C96 | 1.343 (7) |
C78—H78C | 0.9800 | C95—H95 | 0.9500 |
C54—C55 | 1.379 (5) | C92—C97 | 1.377 (6) |
C54—C53 | 1.383 (5) | C92—C93 | 1.458 (6) |
C54—H54 | 0.97 (3) | C97—C96 | 1.412 (6) |
C87—H87A | 0.9800 | C97—H97 | 0.9500 |
C87—H87B | 0.9800 | C93—H93 | 0.9500 |
C87—H87C | 0.9800 | C96—H96 | 0.9500 |
N6—Ni2—N4 | 173.60 (8) | C84—C83—H83 | 121.6 (19) |
N6—Ni2—N5 | 89.93 (8) | C82—C83—H83 | 119.5 (19) |
N4—Ni2—N5 | 90.14 (8) | C85—C84—C83 | 121.7 (3) |
N6—Ni2—N3 | 90.28 (8) | C85—C84—H84 | 119 (2) |
N4—Ni2—N3 | 90.27 (8) | C83—C84—H84 | 119 (2) |
N5—Ni2—N3 | 174.32 (8) | O6—C57—H57A | 109.5 |
C19—N4—C16 | 104.56 (19) | O6—C57—H57B | 109.5 |
C19—N4—Ni2 | 127.81 (16) | H57A—C57—H57B | 109.5 |
C16—N4—Ni2 | 127.62 (16) | O6—C57—H57C | 109.5 |
C14—N3—C11 | 104.83 (19) | H57A—C57—H57C | 109.5 |
C14—N3—Ni2 | 128.06 (16) | H57B—C57—H57C | 109.5 |
C11—N3—Ni2 | 127.04 (16) | C54—C55—C56 | 119.2 (3) |
C62—O7—C67 | 118.4 (2) | C54—C55—H55 | 123 (2) |
C29—N6—C26 | 104.79 (19) | C56—C55—H55 | 118 (2) |
C29—N6—Ni2 | 127.95 (16) | O9—C77—H77A | 109.5 |
C26—N6—Ni2 | 127.10 (16) | O9—C77—H77B | 109.5 |
C21—N5—C24 | 104.65 (19) | H77A—C77—H77B | 109.5 |
C21—N5—Ni2 | 127.19 (16) | O9—C77—H77C | 109.5 |
C24—N5—Ni2 | 128.14 (16) | H77A—C77—H77C | 109.5 |
C66—O8—C68 | 118.0 (2) | H77B—C77—H77C | 109.5 |
C86—O11—C88 | 117.2 (2) | O5—C58—H58A | 109.5 |
C52—O6—C57 | 118.4 (2) | O5—C58—H58B | 109.5 |
C76—O10—C78 | 118.9 (2) | H58A—C58—H58B | 109.5 |
C20—C19—N4 | 125.1 (2) | O5—C58—H58C | 109.5 |
C20—C19—C18 | 124.4 (2) | H58A—C58—H58C | 109.5 |
N4—C19—C18 | 110.5 (2) | H58B—C58—H58C | 109.5 |
C82—O12—C87 | 117.2 (2) | O8—C68—H68A | 109.5 |
C66—C61—C62 | 119.2 (2) | O8—C68—H68B | 109.5 |
C66—C61—C20 | 119.9 (2) | H68A—C68—H68B | 109.5 |
C62—C61—C20 | 121.0 (2) | O8—C68—H68C | 109.5 |
C72—O9—C77 | 116.8 (2) | H68A—C68—H68C | 109.5 |
C20—C21—N5 | 125.2 (2) | H68B—C68—H68C | 109.5 |
C20—C21—C22 | 123.3 (2) | N1—Ni1—N1i | 180.0 |
N5—C21—C22 | 110.4 (2) | N1—Ni1—N2 | 89.90 (8) |
C15—C16—N4 | 125.1 (2) | N1i—Ni1—N2 | 90.10 (8) |
C15—C16—C17 | 123.7 (2) | N1—Ni1—N2i | 90.10 (8) |
N4—C16—C17 | 110.5 (2) | N1i—Ni1—N2i | 89.90 (8) |
C21—C20—C19 | 122.1 (2) | N2—Ni1—N2i | 180.00 (12) |
C21—C20—C61 | 118.4 (2) | C32—O1—C37 | 116.8 (2) |
C19—C20—C61 | 119.2 (2) | C9—N2—C6 | 104.00 (19) |
N3—C11—C30 | 125.8 (2) | C9—N2—Ni1 | 127.83 (16) |
N3—C11—C12 | 110.3 (2) | C6—N2—Ni1 | 128.16 (16) |
C30—C11—C12 | 123.4 (2) | C1—N1—C4 | 104.26 (19) |
C86—C81—C82 | 118.0 (2) | C1—N1—Ni1 | 127.76 (16) |
C86—C81—C30 | 121.2 (2) | C4—N1—Ni1 | 127.98 (16) |
C82—C81—C30 | 120.8 (2) | C42—O3—C47 | 117.6 (2) |
O10—C76—C75 | 124.2 (2) | C46—O4—C48 | 117.9 (2) |
O10—C76—C71 | 115.0 (2) | C36—O2—C38 | 117.3 (2) |
C75—C76—C71 | 120.8 (2) | C5—C4—N1 | 126.0 (2) |
C56—O5—C58 | 117.6 (2) | C5—C4—C3 | 123.1 (2) |
C52—C51—C56 | 118.7 (2) | N1—C4—C3 | 110.9 (2) |
C52—C51—C15 | 119.9 (2) | C32—C31—C36 | 118.7 (2) |
C56—C51—C15 | 121.2 (2) | C32—C31—C5 | 119.1 (2) |
C64—C63—C62 | 118.8 (3) | C36—C31—C5 | 121.8 (2) |
C64—C63—H63 | 119.8 (19) | C6—C5—C4 | 122.3 (2) |
C62—C63—H63 | 121.3 (19) | C6—C5—C31 | 121.0 (2) |
N3—C14—C15 | 125.1 (2) | C4—C5—C31 | 116.7 (2) |
N3—C14—C13 | 110.6 (2) | C5—C6—N2 | 125.6 (2) |
C15—C14—C13 | 124.4 (2) | C5—C6—C7 | 123.2 (2) |
C26—C25—C24 | 121.7 (2) | N2—C6—C7 | 111.1 (2) |
C26—C25—C71 | 119.0 (2) | C3—C2—C1 | 106.8 (2) |
C24—C25—C71 | 119.3 (2) | C3—C2—H2 | 128.7 (17) |
C72—C71—C76 | 118.9 (2) | C1—C2—H2 | 124.4 (17) |
C72—C71—C25 | 122.8 (2) | C10—C9—N2 | 126.0 (2) |
C76—C71—C25 | 118.3 (2) | C10—C9—C8 | 123.0 (2) |
C25—C26—N6 | 125.5 (2) | N2—C9—C8 | 111.1 (2) |
C25—C26—C27 | 123.7 (2) | C46—C41—C42 | 118.9 (2) |
N6—C26—C27 | 110.4 (2) | C46—C41—C10 | 122.0 (2) |
N5—C24—C25 | 124.7 (2) | C42—C41—C10 | 119.0 (2) |
N5—C24—C23 | 110.8 (2) | C9—C10—C1i | 122.0 (2) |
C25—C24—C23 | 124.5 (2) | C9—C10—C41 | 119.8 (2) |
O8—C66—C65 | 124.7 (2) | C1i—C10—C41 | 118.2 (2) |
O8—C66—C61 | 114.5 (2) | N1—C1—C10i | 126.3 (2) |
C65—C66—C61 | 120.8 (2) | N1—C1—C2 | 111.0 (2) |
C28—C27—C26 | 106.9 (2) | C10i—C1—C2 | 122.7 (2) |
C28—C27—H27 | 127.9 (18) | C2—C3—C4 | 107.0 (2) |
C26—C27—H27 | 125.2 (18) | C2—C3—H3 | 128.8 (17) |
N6—C29—C30 | 126.0 (2) | C4—C3—H3 | 124.1 (17) |
N6—C29—C28 | 110.5 (2) | C8—C7—C6 | 107.0 (2) |
C30—C29—C28 | 123.5 (2) | C8—C7—H7 | 131.7 (18) |
C17—C18—C19 | 107.3 (2) | C6—C7—H7 | 121.1 (18) |
C17—C18—H18 | 127.3 (18) | O1—C32—C31 | 114.7 (2) |
C19—C18—H18 | 125.4 (18) | O1—C32—C33 | 123.9 (2) |
C12—C13—C14 | 107.2 (2) | C31—C32—C33 | 121.4 (2) |
C12—C13—H13 | 129.3 (19) | C7—C8—C9 | 106.8 (2) |
C14—C13—H13 | 123.5 (19) | C7—C8—H8 | 129.3 (17) |
O12—C82—C83 | 124.1 (2) | C9—C8—H8 | 123.9 (17) |
O12—C82—C81 | 114.7 (2) | O4—C46—C41 | 114.9 (2) |
C83—C82—C81 | 121.2 (2) | O4—C46—C45 | 124.1 (2) |
C13—C12—C11 | 107.1 (2) | C41—C46—C45 | 121.0 (2) |
C13—C12—H12 | 128.1 (19) | O2—C36—C31 | 115.2 (2) |
C11—C12—H12 | 124.8 (19) | O2—C36—C35 | 124.2 (2) |
C16—C15—C14 | 122.5 (2) | C31—C36—C35 | 120.6 (2) |
C16—C15—C51 | 117.6 (2) | C33—C34—C35 | 122.3 (2) |
C14—C15—C51 | 119.5 (2) | C33—C34—H34 | 117.0 (19) |
O11—C86—C85 | 123.9 (2) | C35—C34—H34 | 120.6 (19) |
O11—C86—C81 | 114.7 (2) | C34—C33—C32 | 118.0 (3) |
C85—C86—C81 | 121.5 (2) | C34—C33—H33 | 121.6 (19) |
C11—C30—C29 | 121.1 (2) | C32—C33—H33 | 120 (2) |
C11—C30—C81 | 119.7 (2) | O3—C42—C41 | 114.9 (2) |
C29—C30—C81 | 119.0 (2) | O3—C42—C43 | 124.3 (2) |
C27—C28—C29 | 107.4 (2) | C41—C42—C43 | 120.8 (2) |
C27—C28—H28 | 130.2 (17) | C34—C35—C36 | 118.8 (3) |
C29—C28—H28 | 122.4 (17) | C34—C35—H35 | 120.6 (19) |
C22—C23—C24 | 107.1 (2) | C36—C35—H35 | 120.5 (19) |
C22—C23—H23 | 128.0 (18) | O1—C37—H37A | 109.5 |
C24—C23—H23 | 124.8 (18) | O1—C37—H37B | 109.5 |
C63—C64—C65 | 122.2 (2) | H37A—C37—H37B | 109.5 |
C63—C64—H64 | 120 (2) | O1—C37—H37C | 109.5 |
C65—C64—H64 | 118 (2) | H37A—C37—H37C | 109.5 |
C18—C17—C16 | 107.0 (2) | H37B—C37—H37C | 109.5 |
C18—C17—H17 | 128.6 (17) | C43—C44—C45 | 122.2 (3) |
C16—C17—H17 | 124.4 (17) | C43—C44—H44 | 121 (2) |
O11—C88—H88A | 109.5 | C45—C44—H44 | 117 (2) |
O11—C88—H88B | 109.5 | C44—C43—C42 | 118.5 (3) |
H88A—C88—H88B | 109.5 | C44—C43—H43 | 123 (2) |
O11—C88—H88C | 109.5 | C42—C43—H43 | 118 (2) |
H88A—C88—H88C | 109.5 | O3—C47—H47A | 109.5 |
H88B—C88—H88C | 109.5 | O3—C47—H47B | 109.5 |
O7—C62—C63 | 124.2 (2) | H47A—C47—H47B | 109.5 |
O7—C62—C61 | 115.4 (2) | O3—C47—H47C | 109.5 |
C63—C62—C61 | 120.4 (2) | H47A—C47—H47C | 109.5 |
C73—C74—C75 | 122.6 (2) | H47B—C47—H47C | 109.5 |
C73—C74—H74 | 118.9 (19) | C44—C45—C46 | 118.6 (3) |
C75—C74—H74 | 118.5 (19) | C44—C45—H45 | 123 (2) |
C74—C73—C72 | 118.8 (3) | C46—C45—H45 | 118 (2) |
C74—C73—H73 | 122.9 (19) | O4—C48—H48A | 109.5 |
C72—C73—H73 | 118 (2) | O4—C48—H48B | 109.5 |
C23—C22—C21 | 107.0 (2) | H48A—C48—H48B | 109.5 |
C23—C22—H22 | 129.5 (18) | O4—C48—H48C | 109.5 |
C21—C22—H22 | 123.5 (18) | H48A—C48—H48C | 109.5 |
O9—C72—C71 | 115.8 (2) | H48B—C48—H48C | 109.5 |
O9—C72—C73 | 123.5 (2) | O2—C38—H38A | 109.5 |
C71—C72—C73 | 120.7 (2) | O2—C38—H38B | 109.5 |
O6—C52—C53 | 124.2 (3) | H38A—C38—H38B | 109.5 |
O6—C52—C51 | 114.9 (2) | O2—C38—H38C | 109.5 |
C53—C52—C51 | 120.9 (3) | H38A—C38—H38C | 109.5 |
O5—C56—C51 | 114.8 (2) | H38B—C38—H38C | 109.5 |
O5—C56—C55 | 124.7 (3) | Cl1—C98—Cl2 | 112.50 (19) |
C51—C56—C55 | 120.5 (3) | Cl1—C98—H98A | 109.1 |
C74—C75—C76 | 118.2 (3) | Cl2—C98—H98A | 109.1 |
C74—C75—H75 | 123.5 (18) | Cl1—C98—H98B | 109.1 |
C76—C75—H75 | 118.3 (18) | Cl2—C98—H98B | 109.1 |
C84—C85—C86 | 118.8 (3) | H98A—C98—H98B | 107.8 |
C84—C85—H85 | 121.9 (19) | Cl3—C99—Cl4 | 110.61 (18) |
C86—C85—H85 | 119.3 (19) | Cl3—C99—H99A | 109.5 |
C64—C65—C66 | 118.7 (3) | Cl4—C99—H99A | 109.5 |
C64—C65—H65 | 120 (2) | Cl3—C99—H99B | 109.5 |
C66—C65—H65 | 122 (2) | Cl4—C99—H99B | 109.5 |
O7—C67—H67A | 109.5 | H99A—C99—H99B | 108.1 |
O7—C67—H67B | 109.5 | C95—C94—C93 | 123.8 (5) |
H67A—C67—H67B | 109.5 | C95—C94—H94 | 118.1 |
O7—C67—H67C | 109.5 | C93—C94—H94 | 118.1 |
H67A—C67—H67C | 109.5 | C92—C91—H91A | 109.5 |
H67B—C67—H67C | 109.5 | C92—C91—H91B | 109.5 |
O10—C78—H78A | 109.5 | H91A—C91—H91B | 109.5 |
O10—C78—H78B | 109.5 | C92—C91—H91C | 109.5 |
H78A—C78—H78B | 109.5 | H91A—C91—H91C | 109.5 |
O10—C78—H78C | 109.5 | H91B—C91—H91C | 109.5 |
H78A—C78—H78C | 109.5 | C96—C95—C94 | 117.7 (6) |
H78B—C78—H78C | 109.5 | C96—C95—H95 | 121.2 |
C55—C54—C53 | 121.6 (3) | C94—C95—H95 | 121.2 |
C55—C54—H54 | 121 (2) | C97—C92—C91 | 122.4 (4) |
C53—C54—H54 | 117 (2) | C97—C92—C93 | 118.3 (4) |
O12—C87—H87A | 109.5 | C91—C92—C93 | 118.8 (4) |
O12—C87—H87B | 109.5 | C92—C97—C96 | 121.7 (4) |
H87A—C87—H87B | 109.5 | C92—C97—H97 | 119.2 |
O12—C87—H87C | 109.5 | C96—C97—H97 | 119.2 |
H87A—C87—H87C | 109.5 | C94—C93—C92 | 116.1 (5) |
H87B—C87—H87C | 109.5 | C94—C93—H93 | 121.9 |
C54—C53—C52 | 119.0 (3) | C92—C93—H93 | 121.9 |
C54—C53—H53 | 122 (2) | C95—C96—C97 | 121.8 (5) |
C52—C53—H53 | 119 (2) | C95—C96—H96 | 119.1 |
C84—C83—C82 | 118.9 (3) | C97—C96—H96 | 119.1 |
Symmetry code: (i) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C52H44N4O8)]·0.67C7H8·1.33CH2Cl2 |
Mr | 1086.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 16.8286 (10), 26.1041 (15), 17.6845 (10) |
β (°) | 92.813 (1) |
V (Å3) | 7759.4 (8) |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 0.57 |
Crystal size (mm) | 0.35 × 0.35 × 0.35 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS in SAINT-Plus; Bruker, 2003) |
Tmin, Tmax | 0.583, 0.818 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 72528, 15859, 13340 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.117, 1.07 |
No. of reflections | 15859 |
No. of parameters | 1100 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0482P)2 + 10.5281P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.07, −0.59 |
Computer programs: SMART (Bruker, 2002), SAINT-Plus (Bruker, 2003), SHELXTL (Bruker, 2000).
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The chemistry of the enzyme hydroxylamine oxidoreductase (HAO) from nitrosomonas europaea has been of interest for a number of years (Arciero & Hooper, 1997). The X-ray crystal structure of HAO shows a complex trimer with each subunit containing seven c-type heme units in addition to a novel heme at the active site, heme P460 (Igarashi et al., 1997). The 5-coordinate heme P460 active site appears to have originated from a five-coordinate c-type heme from one subunit that has been modified with a covalent crosslink to a tyrosine residue from the adjacent subunit (Arciero & Hooper, 1997; Igarashi et al., 1997; Arciero et al., 1993). The C3 ring carbon of the tyrosine is linked to the 5 meso position of the heme, so that the oxygen of the tyrosine is "ortho" to the porphyrin meso carbon (Igarashi et al., 1997; Arciero et al., 1993). In order to explore the chemistry of synthetic models of heme P460, we have begun a systematic examination of ortho substituted porphyrins, beginning with tetra(2',6'-dimethoxyphenyl)porphyrin, (H2T-2',6'-DMP)P. The molecule has oxygen substituents in the ortho position and serves as the non reactive control to compare with the more redox active ligand, tetra(2',6'-dihydroxyphenyl)porphyrin. Future work will focus on synthesizing and studying the more reactive metal ligand complexes with the biologically important iron ion.
The characterized metalloporphyrin is stable to both air and moisture in both the solid and solution environments. Following purification, different solvent systems including toluene, were examined in order to determine the best system. X-ray quality crystals were obtained by layering a dichloromethane solution of the metalloporphyrin with pentane. The asymmetric unit consists of 1.5 nickel porphyrins, 2 dichloromethanes, and one toluene molecule. The toluene molecule was carried over from the test solutions. One of the Ni[T(2',6'-DMP)P] molecules is located on an inversion center and is planar in the solid state (Figure 1) while the other assumes a saddle-shaped geometry (Figure 2). In both cases the nickel ion are 1.9474 (19) Å and 1.9554 (19) Å while they range between 1.9198 (19) Å and 1.9319 (19) Å for the ruffled complex. Non-planar nickel porphyrins are commonly known to exist because the small nickel ion favors a short metal-nitrogen bond distance leading to porphyrin conformational flexibility (Kadish et al., 2002). The coordination geometry is unexceptional and similar to other nickel porphyrin systems, average Ni—N bond distance of 1.920 Å listed in the Cambridge Crystallographic Database (Allen, 2002).