Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102018309/sk1578sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102018309/sk1578Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102018309/sk1578IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102018309/sk1578IIIsup4.hkl |
CCDC references: 201250; 201251; 201252
Complexes (I)-(III) were prepared using the standard literature methods of Belokon (1992a,b). The ligand (S)-2-[(N-1-(2-picolyl)prolyl)amino]-, (S)-2-[(N-1-(3-picolyl)prolyl)amino]- or (S)-2-[(N-1-(ethyl)prolyl)amino]benzophenone, racemic phenylalanine (5 equivalents) and nickel(II) nitrate hexahydrate (2 equivalents) were dissolved in anhydrous methanol, and a 1.3M solution of sodium methoxide (22 equivalents) in methanol was added. The resulting orange-coloured solution was heated for 2 h at 323 K, cooled in ice and then quenched with water. The resulting suspension was extracted with dichloromethane and the combined organic phases were dried over sodium sulfate, before being concentrated in vacuo to give a red-brown residue. The required complex was obtained after purification of this residue on silica gel (8:1 chloroform-acetone). All three complexes were dark red-brown and the crystals were grown in acetone with the addition of pentane and under cooling. Further optimization of the method of producing the complexes has appeared since we conducted our research (Nadvornik & Popkov, 2002; Belokon et al., 1998).
The C—H atoms in (I) and (II) were placed geometrically and refined riding on their parent atoms, at distances of 0.95–1.00 Å and with Uiso(H) = 1.2Ueq(C). The corresponding C—H range in (III) was 0.94–0.99 Å and methyl H atoms had Uiso(H) = 1.5Ueq(C). The water H atoms in (II) were not located.
For all compounds, data collection: STADI4 (Stoe & Cie, 1995); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Bruker, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).
[Ni(C33H30N4O3)] | F(000) = 2464 |
Mr = 589.32 | Dx = 1.423 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 35 reflections |
a = 11.722 (2) Å | θ = 13–15° |
b = 18.391 (14) Å | µ = 0.75 mm−1 |
c = 25.528 (6) Å | T = 150 K |
V = 5503 (4) Å3 | Block, red |
Z = 8 | 0.42 × 0.33 × 0.29 mm |
Stoe Stadi-4 four-circle diffractometer | 4490 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.136 |
Graphite monochromator | θmax = 25.1°, θmin = 2.6° |
ω/2θ scans | h = 0→13 |
Absorption correction: ψ scan (X-RED; Stoe & Cie, 1995) | k = 0→21 |
Tmin = 0.730, Tmax = 0.825 | l = 0→30 |
6352 measured reflections | 3 standard reflections every 60 min |
5359 independent reflections | intensity decay: variation +−15.5% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.054 | w = 1/[σ2(Fo2) + (0.0088P)2 + 15.94P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.115 | (Δ/σ)max = 0.002 |
S = 1.18 | Δρmax = 0.48 e Å−3 |
5355 reflections | Δρmin = −0.46 e Å−3 |
740 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
109 restraints | Extinction coefficient: 0.00049 (11) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) with x Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.03 (2) |
[Ni(C33H30N4O3)] | V = 5503 (4) Å3 |
Mr = 589.32 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.722 (2) Å | µ = 0.75 mm−1 |
b = 18.391 (14) Å | T = 150 K |
c = 25.528 (6) Å | 0.42 × 0.33 × 0.29 mm |
Stoe Stadi-4 four-circle diffractometer | 4490 reflections with I > 2σ(I) |
Absorption correction: ψ scan (X-RED; Stoe & Cie, 1995) | Rint = 0.136 |
Tmin = 0.730, Tmax = 0.825 | 3 standard reflections every 60 min |
6352 measured reflections | intensity decay: variation +−15.5% |
5359 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0088P)2 + 15.94P] where P = (Fo2 + 2Fc2)/3 |
S = 1.18 | Δρmax = 0.48 e Å−3 |
5355 reflections | Δρmin = −0.46 e Å−3 |
740 parameters | Absolute structure: Flack (1983) with x Friedel pairs |
109 restraints | Absolute structure parameter: −0.03 (2) |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.16886 (9) | 0.58688 (5) | 0.05129 (3) | 0.0212 (2) | |
N1 | −0.0099 (6) | 0.5467 (4) | −0.0188 (3) | 0.0307 (17) | |
C1 | −0.0164 (7) | 0.5536 (4) | −0.0717 (3) | 0.032 (2) | |
H1 | 0.0307 | 0.5231 | −0.0925 | 0.038* | |
C2 | −0.0870 (7) | 0.6018 (4) | −0.0969 (3) | 0.033 (2) | |
H2 | −0.0874 | 0.6052 | −0.1341 | 0.039* | |
C3 | −0.1570 (8) | 0.6449 (5) | −0.0671 (3) | 0.036 (2) | |
H3 | −0.2066 | 0.6789 | −0.0834 | 0.044* | |
C4 | −0.1550 (7) | 0.6388 (4) | −0.0136 (3) | 0.0322 (19) | |
H4 | −0.2048 | 0.6671 | 0.0076 | 0.039* | |
C5 | −0.0788 (6) | 0.5903 (4) | 0.0091 (3) | 0.0261 (17) | |
C6 | −0.0653 (6) | 0.5837 (5) | 0.0678 (3) | 0.0284 (18) | |
H6A | −0.1344 | 0.6034 | 0.0850 | 0.034* | |
H6B | −0.0596 | 0.5315 | 0.0771 | 0.034* | |
N2 | 0.0365 (5) | 0.6224 (3) | 0.0885 (2) | 0.0238 (14) | |
C7 | 0.0446 (8) | 0.6120 (4) | 0.1471 (3) | 0.033 (2) | |
H7A | 0.1180 | 0.5888 | 0.1565 | 0.040* | |
H7B | −0.0184 | 0.5808 | 0.1597 | 0.040* | |
C8 | 0.0364 (7) | 0.6875 (5) | 0.1713 (3) | 0.036 (2) | |
H8A | 0.0836 | 0.6911 | 0.2034 | 0.043* | |
H8B | −0.0435 | 0.7000 | 0.1800 | 0.043* | |
C9 | 0.0827 (7) | 0.7363 (4) | 0.1279 (3) | 0.0302 (19) | |
H9A | 0.0569 | 0.7871 | 0.1324 | 0.036* | |
H9B | 0.1671 | 0.7351 | 0.1268 | 0.036* | |
C10 | 0.0315 (6) | 0.7024 (4) | 0.0787 (3) | 0.0241 (16) | |
H10 | −0.0500 | 0.7177 | 0.0755 | 0.029* | |
C11 | 0.0952 (6) | 0.7245 (4) | 0.0299 (3) | 0.0248 (17) | |
O1 | 0.0838 (5) | 0.7867 (3) | 0.0140 (2) | 0.0348 (14) | |
N3 | 0.1639 (5) | 0.6708 (3) | 0.0105 (2) | 0.0196 (13) | |
C12 | 0.2143 (6) | 0.6765 (4) | −0.0392 (3) | 0.0218 (16) | |
C13 | 0.1789 (7) | 0.7300 (4) | −0.0754 (3) | 0.0268 (17) | |
H13 | 0.1222 | 0.7640 | −0.0652 | 0.032* | |
C14 | 0.2243 (6) | 0.7343 (4) | −0.1253 (3) | 0.0260 (18) | |
H14 | 0.1975 | 0.7706 | −0.1488 | 0.031* | |
C15 | 0.3078 (7) | 0.6868 (4) | −0.1412 (3) | 0.0266 (18) | |
H15 | 0.3400 | 0.6906 | −0.1753 | 0.032* | |
C16 | 0.3438 (6) | 0.6341 (4) | −0.1074 (3) | 0.0203 (16) | |
H16 | 0.4013 | 0.6012 | −0.1187 | 0.024* | |
C17 | 0.2986 (6) | 0.6265 (4) | −0.0559 (3) | 0.0222 (16) | |
C18 | 0.3438 (6) | 0.5671 (4) | −0.0234 (3) | 0.0205 (16) | |
C19 | 0.4374 (6) | 0.5220 (4) | −0.0472 (3) | 0.0203 (16) | |
C20 | 0.4081 (7) | 0.4645 (4) | −0.0800 (3) | 0.0260 (18) | |
H20 | 0.3301 | 0.4525 | −0.0853 | 0.031* | |
C21 | 0.4925 (7) | 0.4246 (4) | −0.1050 (3) | 0.032 (2) | |
H21 | 0.4722 | 0.3851 | −0.1270 | 0.038* | |
C22 | 0.6063 (7) | 0.4423 (5) | −0.0979 (3) | 0.035 (2) | |
H22 | 0.6640 | 0.4154 | −0.1155 | 0.042* | |
C23 | 0.6356 (6) | 0.4992 (4) | −0.0652 (3) | 0.0295 (19) | |
H23 | 0.7138 | 0.5105 | −0.0599 | 0.035* | |
C24 | 0.5532 (6) | 0.5397 (4) | −0.0400 (3) | 0.0227 (17) | |
H24 | 0.5743 | 0.5792 | −0.0181 | 0.027* | |
N4 | 0.2993 (5) | 0.5507 (3) | 0.0215 (2) | 0.0228 (14) | |
C25 | 0.3482 (6) | 0.4917 (4) | 0.0537 (3) | 0.0241 (16) | |
H25 | 0.3794 | 0.4530 | 0.0302 | 0.029* | |
C26 | 0.4440 (7) | 0.5186 (4) | 0.0911 (3) | 0.031 (2) | |
H26A | 0.4738 | 0.4763 | 0.1108 | 0.037* | |
H26B | 0.5074 | 0.5380 | 0.0696 | 0.037* | |
C27 | 0.4084 (6) | 0.5760 (4) | 0.1296 (3) | 0.0280 (18) | |
C28 | 0.4269 (7) | 0.6486 (4) | 0.1201 (4) | 0.038 (2) | |
H28 | 0.4617 | 0.6631 | 0.0881 | 0.046* | |
C29 | 0.3957 (8) | 0.7012 (5) | 0.1563 (4) | 0.052 (3) | |
H29 | 0.4091 | 0.7512 | 0.1489 | 0.063* | |
C30 | 0.3449 (9) | 0.6811 (5) | 0.2033 (4) | 0.051 (3) | |
H30 | 0.3237 | 0.7170 | 0.2282 | 0.061* | |
C31 | 0.3255 (8) | 0.6089 (5) | 0.2132 (3) | 0.044 (2) | |
H31 | 0.2903 | 0.5948 | 0.2452 | 0.053* | |
C32 | 0.3567 (7) | 0.5565 (4) | 0.1774 (3) | 0.032 (2) | |
H32 | 0.3431 | 0.5067 | 0.1850 | 0.038* | |
C33 | 0.2511 (7) | 0.4601 (4) | 0.0864 (3) | 0.0269 (18) | |
O2 | 0.1615 (5) | 0.5004 (3) | 0.08979 (19) | 0.0278 (12) | |
O3 | 0.2630 (5) | 0.4013 (3) | 0.1088 (2) | 0.0340 (14) | |
NiA | 0.67933 (8) | 0.29707 (5) | 0.15465 (4) | 0.0199 (2) | |
N1A | 0.8541 (6) | 0.3377 (4) | 0.2327 (3) | 0.041 (2) | |
C1A | 0.8582 (8) | 0.3726 (6) | 0.2788 (3) | 0.057 (3) | |
H1A | 0.8037 | 0.3597 | 0.3048 | 0.068* | |
C2A | 0.9366 (10) | 0.4260 (6) | 0.2910 (4) | 0.064 (4) | |
H2A | 0.9352 | 0.4494 | 0.3241 | 0.077* | |
C3A | 1.0167 (11) | 0.4444 (6) | 0.2540 (4) | 0.067 (4) | |
H3A | 1.0731 | 0.4801 | 0.2616 | 0.080* | |
C4A | 1.0144 (8) | 0.4106 (5) | 0.2058 (3) | 0.043 (2) | |
H4A | 1.0684 | 0.4226 | 0.1794 | 0.052* | |
C5A | 0.9310 (7) | 0.3587 (5) | 0.1968 (3) | 0.032 (2) | |
C6A | 0.9184 (6) | 0.3238 (5) | 0.1437 (3) | 0.031 (2) | |
H6A1 | 0.9807 | 0.3412 | 0.1207 | 0.038* | |
H6A2 | 0.9272 | 0.2705 | 0.1476 | 0.038* | |
N2A | 0.8075 (5) | 0.3391 (3) | 0.1180 (2) | 0.0210 (14) | |
C7A | 0.8096 (7) | 0.3103 (4) | 0.0620 (2) | 0.0253 (17) | |
H7A1 | 0.7384 | 0.2837 | 0.0538 | 0.030* | |
H7A2 | 0.8753 | 0.2773 | 0.0566 | 0.030* | |
C8A | 0.8207 (7) | 0.3781 (4) | 0.0279 (3) | 0.0291 (17) | |
H8A1 | 0.9008 | 0.3948 | 0.0256 | 0.035* | |
H8A2 | 0.7907 | 0.3697 | −0.0078 | 0.035* | |
C9A | 0.7470 (6) | 0.4319 (4) | 0.0581 (3) | 0.0261 (18) | |
H9A1 | 0.6649 | 0.4208 | 0.0540 | 0.031* | |
H9A2 | 0.7615 | 0.4825 | 0.0467 | 0.031* | |
C10A | 0.7868 (6) | 0.4194 (4) | 0.1142 (3) | 0.0210 (16) | |
H10A | 0.8604 | 0.4457 | 0.1199 | 0.025* | |
C11A | 0.7001 (6) | 0.4455 (4) | 0.1540 (3) | 0.0203 (16) | |
O1A | 0.6901 (5) | 0.5109 (3) | 0.1607 (2) | 0.0294 (13) | |
N3A | 0.6370 (5) | 0.3895 (3) | 0.1752 (2) | 0.0207 (14) | |
C12A | 0.5581 (6) | 0.4034 (4) | 0.2152 (3) | 0.0194 (16) | |
C13A | 0.5664 (7) | 0.4656 (4) | 0.2472 (3) | 0.0267 (18) | |
H13A | 0.6286 | 0.4981 | 0.2425 | 0.032* | |
C14A | 0.4854 (7) | 0.4804 (4) | 0.2855 (3) | 0.0273 (18) | |
H14A | 0.4930 | 0.5227 | 0.3065 | 0.033* | |
C15A | 0.3936 (7) | 0.4341 (4) | 0.2934 (3) | 0.030 (2) | |
H15A | 0.3357 | 0.4457 | 0.3180 | 0.036* | |
C16A | 0.3886 (6) | 0.3712 (4) | 0.2646 (3) | 0.0262 (18) | |
H16A | 0.3274 | 0.3384 | 0.2707 | 0.031* | |
C17A | 0.4710 (6) | 0.3532 (4) | 0.2263 (3) | 0.0202 (16) | |
C18A | 0.4618 (6) | 0.2809 (3) | 0.2025 (3) | 0.0191 (16) | |
C19A | 0.3548 (6) | 0.2378 (4) | 0.2123 (3) | 0.0203 (17) | |
C20A | 0.3522 (6) | 0.1808 (4) | 0.2477 (3) | 0.0207 (16) | |
H20A | 0.4182 | 0.1696 | 0.2677 | 0.025* | |
C21A | 0.2537 (6) | 0.1397 (4) | 0.2542 (3) | 0.0246 (17) | |
H21A | 0.2525 | 0.1004 | 0.2784 | 0.030* | |
C22A | 0.1573 (6) | 0.1565 (4) | 0.2252 (3) | 0.0233 (17) | |
H22A | 0.0901 | 0.1282 | 0.2292 | 0.028* | |
C23A | 0.1578 (6) | 0.2138 (4) | 0.1905 (3) | 0.0301 (18) | |
H23A | 0.0911 | 0.2251 | 0.1710 | 0.036* | |
C24A | 0.2554 (6) | 0.2548 (4) | 0.1842 (3) | 0.0250 (17) | |
H24A | 0.2553 | 0.2949 | 0.1607 | 0.030* | |
N4A | 0.5452 (5) | 0.2527 (3) | 0.1762 (2) | 0.0192 (14) | |
C25A | 0.5381 (6) | 0.1777 (4) | 0.1564 (3) | 0.0245 (17) | |
H25A | 0.5061 | 0.1459 | 0.1846 | 0.029* | |
C26A | 0.4649 (7) | 0.1685 (4) | 0.1063 (3) | 0.0291 (19) | |
H26C | 0.4577 | 0.1160 | 0.0985 | 0.035* | |
H26D | 0.3873 | 0.1875 | 0.1133 | 0.035* | |
C27A | 0.5116 (6) | 0.2062 (4) | 0.0588 (3) | 0.0231 (16) | |
C28A | 0.4828 (6) | 0.2779 (4) | 0.0471 (3) | 0.0297 (19) | |
H28A | 0.4332 | 0.3039 | 0.0698 | 0.036* | |
C29A | 0.5254 (7) | 0.3119 (4) | 0.0027 (3) | 0.0290 (19) | |
H29A | 0.5063 | 0.3611 | −0.0045 | 0.035* | |
C30A | 0.5965 (7) | 0.2735 (4) | −0.0311 (3) | 0.0291 (19) | |
H30A | 0.6244 | 0.2963 | −0.0620 | 0.035* | |
C31A | 0.6265 (7) | 0.2029 (5) | −0.0204 (3) | 0.0318 (19) | |
H31A | 0.6760 | 0.1773 | −0.0434 | 0.038* | |
C32A | 0.5841 (7) | 0.1688 (4) | 0.0243 (3) | 0.0295 (19) | |
H32A | 0.6045 | 0.1199 | 0.0315 | 0.035* | |
C33A | 0.6604 (7) | 0.1527 (4) | 0.1442 (3) | 0.0253 (17) | |
O2A | 0.7348 (4) | 0.2041 (3) | 0.1407 (2) | 0.0260 (12) | |
O3A | 0.6789 (5) | 0.0876 (3) | 0.1379 (2) | 0.0350 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0210 (5) | 0.0231 (5) | 0.0194 (4) | 0.0006 (5) | 0.0020 (4) | 0.0045 (4) |
N1 | 0.032 (4) | 0.027 (4) | 0.033 (4) | −0.004 (3) | 0.000 (3) | −0.003 (3) |
C1 | 0.025 (4) | 0.034 (5) | 0.037 (5) | −0.001 (4) | 0.006 (4) | −0.003 (4) |
C2 | 0.031 (5) | 0.039 (5) | 0.028 (4) | 0.002 (4) | −0.003 (4) | 0.004 (4) |
C3 | 0.033 (5) | 0.041 (5) | 0.036 (5) | 0.012 (4) | −0.007 (4) | 0.001 (4) |
C4 | 0.026 (5) | 0.037 (5) | 0.033 (4) | 0.001 (4) | 0.007 (4) | −0.006 (4) |
C5 | 0.018 (4) | 0.026 (4) | 0.035 (4) | −0.013 (4) | −0.001 (3) | 0.001 (4) |
C6 | 0.018 (4) | 0.035 (5) | 0.033 (4) | −0.004 (4) | 0.006 (3) | −0.001 (4) |
N2 | 0.020 (3) | 0.033 (4) | 0.019 (3) | −0.011 (3) | 0.003 (3) | −0.003 (3) |
C7 | 0.046 (5) | 0.032 (5) | 0.021 (4) | 0.001 (4) | 0.009 (4) | 0.004 (3) |
C8 | 0.031 (5) | 0.058 (6) | 0.019 (4) | 0.009 (5) | −0.002 (4) | 0.004 (4) |
C9 | 0.029 (5) | 0.038 (5) | 0.023 (4) | −0.003 (4) | −0.004 (4) | −0.009 (4) |
C10 | 0.019 (4) | 0.029 (4) | 0.024 (4) | 0.003 (4) | 0.000 (3) | 0.002 (4) |
C11 | 0.020 (4) | 0.024 (4) | 0.030 (4) | −0.004 (3) | 0.000 (3) | −0.003 (3) |
O1 | 0.040 (3) | 0.023 (3) | 0.041 (3) | 0.007 (3) | 0.015 (3) | 0.004 (3) |
N3 | 0.019 (3) | 0.024 (3) | 0.016 (3) | 0.001 (3) | 0.002 (3) | 0.004 (2) |
C12 | 0.020 (4) | 0.022 (4) | 0.023 (4) | −0.008 (3) | −0.007 (3) | 0.008 (3) |
C13 | 0.025 (4) | 0.032 (4) | 0.024 (4) | 0.005 (4) | −0.001 (4) | 0.004 (3) |
C14 | 0.024 (4) | 0.036 (5) | 0.018 (4) | −0.004 (4) | −0.005 (3) | 0.010 (3) |
C15 | 0.028 (4) | 0.038 (4) | 0.014 (3) | −0.012 (4) | −0.008 (3) | 0.006 (3) |
C16 | 0.015 (4) | 0.025 (4) | 0.021 (3) | 0.004 (3) | 0.004 (3) | −0.001 (3) |
C17 | 0.018 (4) | 0.027 (4) | 0.022 (4) | −0.008 (3) | −0.007 (3) | 0.000 (3) |
C18 | 0.022 (4) | 0.018 (4) | 0.021 (4) | −0.005 (3) | −0.002 (3) | −0.003 (3) |
C19 | 0.016 (4) | 0.024 (4) | 0.020 (4) | 0.002 (3) | −0.004 (3) | 0.000 (3) |
C20 | 0.026 (4) | 0.028 (4) | 0.025 (4) | −0.004 (4) | −0.002 (4) | 0.000 (3) |
C21 | 0.046 (5) | 0.021 (4) | 0.028 (4) | −0.008 (4) | 0.005 (4) | 0.000 (3) |
C22 | 0.044 (6) | 0.040 (5) | 0.022 (4) | 0.001 (4) | 0.010 (4) | −0.006 (4) |
C23 | 0.021 (4) | 0.035 (5) | 0.033 (4) | −0.001 (4) | 0.006 (3) | 0.007 (4) |
C24 | 0.021 (4) | 0.023 (4) | 0.024 (4) | 0.000 (3) | 0.001 (3) | −0.005 (3) |
N4 | 0.023 (4) | 0.023 (3) | 0.022 (3) | −0.002 (3) | −0.002 (3) | 0.003 (3) |
C25 | 0.027 (4) | 0.026 (4) | 0.019 (3) | 0.008 (3) | 0.005 (3) | 0.006 (3) |
C26 | 0.022 (4) | 0.042 (5) | 0.029 (4) | 0.006 (4) | −0.005 (4) | 0.007 (4) |
C27 | 0.020 (4) | 0.034 (5) | 0.030 (4) | 0.005 (4) | −0.013 (3) | 0.003 (4) |
C28 | 0.028 (5) | 0.038 (5) | 0.049 (6) | −0.009 (4) | −0.014 (5) | 0.015 (4) |
C29 | 0.055 (6) | 0.040 (5) | 0.062 (7) | 0.005 (5) | −0.035 (6) | −0.002 (6) |
C30 | 0.051 (7) | 0.047 (6) | 0.054 (6) | 0.017 (5) | −0.032 (6) | −0.023 (5) |
C31 | 0.033 (5) | 0.067 (7) | 0.032 (4) | 0.006 (5) | −0.012 (5) | −0.013 (4) |
C32 | 0.030 (5) | 0.031 (4) | 0.034 (4) | 0.000 (4) | −0.010 (4) | 0.003 (4) |
C33 | 0.043 (5) | 0.020 (4) | 0.018 (4) | −0.007 (4) | 0.000 (4) | 0.003 (3) |
O2 | 0.034 (3) | 0.022 (3) | 0.028 (3) | 0.002 (3) | 0.003 (3) | 0.007 (2) |
O3 | 0.053 (4) | 0.023 (3) | 0.026 (3) | 0.002 (3) | −0.005 (3) | 0.005 (2) |
NiA | 0.0179 (5) | 0.0192 (4) | 0.0227 (5) | 0.0006 (4) | 0.0040 (5) | 0.0000 (4) |
N1A | 0.033 (5) | 0.064 (5) | 0.027 (4) | 0.011 (4) | −0.007 (3) | 0.012 (4) |
C1A | 0.045 (6) | 0.097 (9) | 0.028 (5) | 0.034 (6) | −0.011 (5) | 0.004 (5) |
C2A | 0.096 (10) | 0.065 (8) | 0.032 (6) | 0.028 (7) | −0.032 (7) | −0.018 (6) |
C3A | 0.088 (10) | 0.057 (7) | 0.055 (7) | −0.009 (7) | −0.041 (7) | −0.002 (6) |
C4A | 0.040 (5) | 0.048 (6) | 0.042 (5) | −0.007 (5) | −0.020 (4) | 0.003 (5) |
C5A | 0.025 (4) | 0.043 (5) | 0.029 (4) | 0.007 (4) | −0.012 (4) | 0.007 (4) |
C6A | 0.013 (4) | 0.042 (5) | 0.038 (5) | 0.005 (4) | 0.000 (4) | 0.006 (4) |
N2A | 0.018 (3) | 0.027 (3) | 0.018 (3) | 0.003 (3) | −0.003 (3) | −0.001 (3) |
C7A | 0.024 (4) | 0.035 (4) | 0.018 (4) | −0.002 (4) | 0.001 (3) | −0.006 (3) |
C8A | 0.026 (4) | 0.042 (4) | 0.020 (3) | −0.004 (4) | 0.008 (4) | −0.006 (3) |
C9A | 0.022 (4) | 0.034 (4) | 0.023 (4) | 0.002 (3) | 0.001 (3) | 0.000 (3) |
C10A | 0.019 (4) | 0.022 (4) | 0.022 (4) | −0.011 (3) | 0.004 (3) | −0.002 (3) |
C11A | 0.026 (4) | 0.027 (4) | 0.009 (3) | −0.004 (3) | 0.001 (3) | 0.000 (3) |
O1A | 0.040 (3) | 0.020 (3) | 0.029 (3) | −0.006 (3) | 0.007 (3) | −0.001 (2) |
N3A | 0.021 (3) | 0.026 (3) | 0.015 (3) | −0.001 (3) | 0.000 (3) | 0.001 (2) |
C12A | 0.022 (4) | 0.020 (4) | 0.017 (3) | 0.003 (3) | 0.000 (3) | 0.000 (3) |
C13A | 0.026 (4) | 0.035 (5) | 0.020 (4) | −0.004 (4) | 0.008 (3) | −0.008 (3) |
C14A | 0.042 (5) | 0.019 (4) | 0.021 (4) | −0.001 (4) | 0.004 (4) | −0.002 (3) |
C15A | 0.033 (5) | 0.032 (5) | 0.026 (4) | 0.006 (4) | 0.005 (4) | −0.002 (4) |
C16A | 0.021 (4) | 0.027 (4) | 0.031 (4) | 0.004 (4) | 0.009 (4) | −0.005 (4) |
C17A | 0.020 (4) | 0.024 (4) | 0.017 (4) | 0.004 (3) | 0.004 (3) | −0.004 (3) |
C18A | 0.028 (4) | 0.016 (4) | 0.013 (3) | 0.001 (3) | 0.000 (3) | 0.001 (3) |
C19A | 0.021 (4) | 0.023 (4) | 0.017 (3) | 0.000 (3) | 0.010 (3) | −0.008 (3) |
C20A | 0.014 (4) | 0.030 (4) | 0.018 (3) | 0.003 (3) | −0.001 (3) | 0.002 (3) |
C21A | 0.028 (4) | 0.023 (4) | 0.023 (4) | −0.005 (4) | 0.004 (3) | −0.001 (3) |
C22A | 0.015 (4) | 0.026 (4) | 0.029 (4) | −0.003 (3) | 0.005 (3) | −0.004 (3) |
C23A | 0.019 (4) | 0.037 (5) | 0.033 (4) | 0.008 (4) | 0.003 (4) | 0.002 (4) |
C24A | 0.030 (4) | 0.023 (4) | 0.022 (4) | 0.005 (4) | 0.002 (4) | 0.003 (3) |
N4A | 0.020 (3) | 0.019 (3) | 0.018 (3) | 0.001 (3) | 0.004 (3) | −0.001 (3) |
C25A | 0.024 (4) | 0.019 (4) | 0.030 (4) | −0.004 (3) | 0.009 (4) | −0.001 (3) |
C26A | 0.026 (4) | 0.028 (4) | 0.034 (4) | −0.001 (4) | 0.006 (4) | −0.012 (4) |
C27A | 0.015 (3) | 0.028 (4) | 0.027 (4) | −0.008 (3) | −0.006 (3) | −0.007 (3) |
C28A | 0.017 (4) | 0.040 (5) | 0.033 (4) | −0.001 (4) | 0.001 (4) | −0.014 (4) |
C29A | 0.027 (4) | 0.032 (5) | 0.028 (4) | −0.001 (4) | −0.001 (4) | −0.003 (4) |
C30A | 0.030 (4) | 0.035 (5) | 0.023 (4) | −0.005 (4) | −0.006 (4) | 0.001 (3) |
C31A | 0.030 (4) | 0.038 (5) | 0.027 (4) | −0.003 (4) | 0.003 (4) | −0.012 (4) |
C32A | 0.024 (4) | 0.033 (4) | 0.032 (4) | −0.001 (4) | 0.001 (4) | −0.009 (4) |
C33A | 0.032 (5) | 0.024 (4) | 0.019 (4) | 0.007 (4) | 0.006 (4) | −0.002 (3) |
O2A | 0.020 (3) | 0.021 (3) | 0.038 (3) | −0.001 (2) | 0.010 (2) | 0.000 (2) |
O3A | 0.044 (3) | 0.021 (3) | 0.040 (3) | 0.008 (3) | 0.022 (3) | 0.004 (2) |
Ni—N2 | 1.932 (6) | NiA—N2A | 1.932 (6) |
Ni—N3 | 1.862 (5) | NiA—N3A | 1.846 (6) |
Ni—N4 | 1.833 (6) | NiA—N4A | 1.855 (6) |
Ni—O2 | 1.872 (5) | NiA—O2A | 1.863 (5) |
Ni—N1 | 2.861 (7) | NiA—N1A | 2.954 (8) |
N1—C5 | 1.343 (9) | N1A—C1A | 1.341 (10) |
N1—C1 | 1.358 (9) | N1A—C5A | 1.343 (10) |
C1—C2 | 1.373 (10) | C1A—C2A | 1.381 (13) |
C1—H1 | 0.9500 | C1A—H1A | 0.9500 |
C2—C3 | 1.372 (10) | C2A—C3A | 1.374 (14) |
C2—H2 | 0.9500 | C2A—H2A | 0.9500 |
C3—C4 | 1.371 (10) | C3A—C4A | 1.379 (12) |
C3—H3 | 0.9500 | C3A—H3A | 0.9500 |
C4—C5 | 1.388 (10) | C4A—C5A | 1.385 (10) |
C4—H4 | 0.9500 | C4A—H4A | 0.9500 |
C5—C6 | 1.511 (9) | C5A—C6A | 1.507 (10) |
C6—N2 | 1.486 (8) | C6A—N2A | 1.484 (8) |
C6—H6A | 0.9900 | C6A—H6A1 | 0.9900 |
C6—H6B | 0.9900 | C6A—H6A2 | 0.9900 |
N2—C10 | 1.494 (9) | N2A—C10A | 1.500 (8) |
N2—C7 | 1.511 (8) | N2A—C7A | 1.524 (8) |
C7—C8 | 1.523 (10) | C7A—C8A | 1.525 (9) |
C7—H7A | 0.9900 | C7A—H7A1 | 0.9900 |
C7—H7B | 0.9900 | C7A—H7A2 | 0.9900 |
C8—C9 | 1.527 (10) | C8A—C9A | 1.522 (9) |
C8—H8A | 0.9900 | C8A—H8A1 | 0.9900 |
C8—H8B | 0.9900 | C8A—H8A2 | 0.9900 |
C9—C10 | 1.523 (9) | C9A—C10A | 1.525 (9) |
C9—H9A | 0.9900 | C9A—H9A1 | 0.9900 |
C9—H9B | 0.9900 | C9A—H9A2 | 0.9900 |
C10—C11 | 1.509 (9) | C10A—C11A | 1.515 (9) |
C10—H10 | 1.0000 | C10A—H10A | 1.0000 |
C11—O1 | 1.222 (8) | C11A—O1A | 1.220 (8) |
C11—N3 | 1.366 (8) | C11A—N3A | 1.380 (8) |
N3—C12 | 1.404 (8) | N3A—C12A | 1.402 (8) |
C12—C13 | 1.413 (9) | C12A—C17A | 1.405 (9) |
C12—C17 | 1.417 (9) | C12A—C13A | 1.409 (9) |
C13—C14 | 1.382 (9) | C13A—C14A | 1.389 (9) |
C13—H13 | 0.9500 | C13A—H13A | 0.9500 |
C14—C15 | 1.374 (10) | C14A—C15A | 1.386 (10) |
C14—H14 | 0.9500 | C14A—H14A | 0.9500 |
C15—C16 | 1.365 (9) | C15A—C16A | 1.372 (10) |
C15—H15 | 0.9500 | C15A—H15A | 0.9500 |
C16—C17 | 1.423 (9) | C16A—C17A | 1.414 (9) |
C16—H16 | 0.9500 | C16A—H16A | 0.9500 |
C17—C18 | 1.470 (9) | C17A—C18A | 1.465 (9) |
C18—N4 | 1.294 (8) | C18A—N4A | 1.296 (8) |
C18—C19 | 1.505 (9) | C18A—C19A | 1.505 (9) |
C19—C20 | 1.391 (9) | C19A—C20A | 1.384 (9) |
C19—C24 | 1.407 (9) | C19A—C24A | 1.403 (9) |
C20—C21 | 1.386 (10) | C20A—C21A | 1.389 (9) |
C20—H20 | 0.9500 | C20A—H20A | 0.9500 |
C21—C22 | 1.385 (11) | C21A—C22A | 1.387 (10) |
C21—H21 | 0.9500 | C21A—H21A | 0.9500 |
C22—C23 | 1.382 (10) | C22A—C23A | 1.375 (9) |
C22—H22 | 0.9500 | C22A—H22A | 0.9500 |
C23—C24 | 1.379 (9) | C23A—C24A | 1.380 (10) |
C23—H23 | 0.9500 | C23A—H23A | 0.9500 |
C24—H24 | 0.9500 | C24A—H24A | 0.9500 |
N4—C25 | 1.477 (8) | N4A—C25A | 1.470 (8) |
C25—C33 | 1.526 (9) | C25A—C33A | 1.538 (9) |
C25—C26 | 1.555 (10) | C25A—C26A | 1.551 (10) |
C25—H25 | 1.0000 | C25A—H25A | 1.0000 |
C26—C27 | 1.502 (10) | C26A—C27A | 1.501 (10) |
C26—H26A | 0.9900 | C26A—H26C | 0.9900 |
C26—H26B | 0.9900 | C26A—H26D | 0.9900 |
C27—C28 | 1.375 (10) | C27A—C28A | 1.393 (10) |
C27—C32 | 1.409 (10) | C27A—C32A | 1.404 (9) |
C28—C29 | 1.387 (11) | C28A—C29A | 1.387 (10) |
C28—H28 | 0.9500 | C28A—H28A | 0.9500 |
C29—C30 | 1.390 (12) | C29A—C30A | 1.393 (10) |
C29—H29 | 0.9500 | C29A—H29A | 0.9500 |
C30—C31 | 1.372 (11) | C30A—C31A | 1.373 (10) |
C30—H30 | 0.9500 | C30A—H30A | 0.9500 |
C31—C32 | 1.378 (10) | C31A—C32A | 1.392 (10) |
C31—H31 | 0.9500 | C31A—H31A | 0.9500 |
C32—H32 | 0.9500 | C32A—H32A | 0.9500 |
C33—O3 | 1.232 (8) | C33A—O3A | 1.225 (8) |
C33—O2 | 1.288 (9) | C33A—O2A | 1.290 (8) |
N2—Ni—N3 | 88.2 (3) | N2A—NiA—N3A | 88.8 (2) |
N2—Ni—N4 | 175.1 (3) | N2A—NiA—N4A | 168.2 (2) |
N2—Ni—O2 | 89.5 (2) | N2A—NiA—O2A | 90.2 (2) |
N3—Ni—N4 | 95.4 (2) | N3A—NiA—N4A | 95.3 (3) |
N3—Ni—O2 | 175.0 (3) | N3A—NiA—O2A | 173.0 (3) |
N4—Ni—O2 | 87.0 (2) | N4A—NiA—O2A | 87.1 (2) |
C5—N1—C1 | 116.0 (7) | C1A—N1A—C5A | 116.0 (8) |
N1—C1—C2 | 124.0 (8) | N1A—C1A—C2A | 124.1 (10) |
N1—C1—H1 | 118.0 | N1A—C1A—H1A | 118.0 |
C2—C1—H1 | 118.0 | C2A—C1A—H1A | 118.0 |
C3—C2—C1 | 118.2 (7) | C3A—C2A—C1A | 118.5 (9) |
C3—C2—H2 | 120.9 | C3A—C2A—H2A | 120.8 |
C1—C2—H2 | 120.9 | C1A—C2A—H2A | 120.8 |
C4—C3—C2 | 119.7 (8) | C2A—C3A—C4A | 119.2 (10) |
C4—C3—H3 | 120.1 | C2A—C3A—H3A | 120.4 |
C2—C3—H3 | 120.1 | C4A—C3A—H3A | 120.4 |
C3—C4—C5 | 118.6 (7) | C3A—C4A—C5A | 118.2 (9) |
C3—C4—H4 | 120.7 | C3A—C4A—H4A | 120.9 |
C5—C4—H4 | 120.7 | C5A—C4A—H4A | 120.9 |
N1—C5—C4 | 123.3 (7) | N1A—C5A—C4A | 124.0 (8) |
N1—C5—C6 | 114.5 (7) | N1A—C5A—C6A | 115.2 (7) |
C4—C5—C6 | 122.2 (7) | C4A—C5A—C6A | 120.8 (7) |
N2—C6—C5 | 113.4 (6) | N2A—C6A—C5A | 113.8 (6) |
N2—C6—H6A | 108.9 | N2A—C6A—H6A1 | 108.8 |
C5—C6—H6A | 108.9 | C5A—C6A—H6A1 | 108.8 |
N2—C6—H6B | 108.9 | N2A—C6A—H6A2 | 108.8 |
C5—C6—H6B | 108.9 | C5A—C6A—H6A2 | 108.8 |
H6A—C6—H6B | 107.7 | H6A1—C6A—H6A2 | 107.7 |
C6—N2—C10 | 112.4 (6) | C6A—N2A—C10A | 110.9 (6) |
C6—N2—C7 | 110.0 (6) | C6A—N2A—C7A | 109.6 (6) |
C10—N2—C7 | 106.9 (5) | C10A—N2A—C7A | 106.5 (5) |
C6—N2—Ni | 108.0 (4) | C6A—N2A—NiA | 113.0 (4) |
C10—N2—Ni | 106.4 (4) | C10A—N2A—NiA | 107.4 (4) |
C7—N2—Ni | 113.1 (5) | C7A—N2A—NiA | 109.2 (4) |
N2—C7—C8 | 106.5 (6) | N2A—C7A—C8A | 104.6 (5) |
N2—C7—H7A | 110.4 | N2A—C7A—H7A1 | 110.8 |
C8—C7—H7A | 110.4 | C8A—C7A—H7A1 | 110.8 |
N2—C7—H7B | 110.4 | N2A—C7A—H7A2 | 110.8 |
C8—C7—H7B | 110.4 | C8A—C7A—H7A2 | 110.8 |
H7A—C7—H7B | 108.6 | H7A1—C7A—H7A2 | 108.9 |
C7—C8—C9 | 102.6 (6) | C9A—C8A—C7A | 101.2 (6) |
C7—C8—H8A | 111.3 | C9A—C8A—H8A1 | 111.5 |
C9—C8—H8A | 111.2 | C7A—C8A—H8A1 | 111.5 |
C7—C8—H8B | 111.2 | C9A—C8A—H8A2 | 111.5 |
C9—C8—H8B | 111.2 | C7A—C8A—H8A2 | 111.5 |
H8A—C8—H8B | 109.2 | H8A1—C8A—H8A2 | 109.3 |
C10—C9—C8 | 102.6 (6) | C8A—C9A—C10A | 101.8 (6) |
C10—C9—H9A | 111.2 | C8A—C9A—H9A1 | 111.4 |
C8—C9—H9A | 111.2 | C10A—C9A—H9A1 | 111.4 |
C10—C9—H9B | 111.2 | C8A—C9A—H9A2 | 111.4 |
C8—C9—H9B | 111.2 | C10A—C9A—H9A2 | 111.4 |
H9A—C9—H9B | 109.2 | H9A1—C9A—H9A2 | 109.3 |
N2—C10—C11 | 112.5 (6) | N2A—C10A—C11A | 112.2 (5) |
N2—C10—C9 | 104.5 (6) | N2A—C10A—C9A | 104.9 (5) |
C11—C10—C9 | 112.1 (6) | C11A—C10A—C9A | 112.1 (6) |
N2—C10—H10 | 109.2 | N2A—C10A—H10A | 109.2 |
C11—C10—H10 | 109.2 | C11A—C10A—H10A | 109.2 |
C9—C10—H10 | 109.2 | C9A—C10A—H10A | 109.2 |
O1—C11—N3 | 128.4 (7) | O1A—C11A—N3A | 129.1 (6) |
O1—C11—C10 | 118.2 (7) | O1A—C11A—C10A | 118.0 (6) |
N3—C11—C10 | 113.3 (6) | N3A—C11A—C10A | 112.7 (6) |
C11—N3—C12 | 121.4 (6) | C11A—N3A—C12A | 120.2 (6) |
C11—N3—Ni | 114.5 (4) | C11A—N3A—NiA | 115.6 (4) |
C12—N3—Ni | 123.6 (5) | C12A—N3A—NiA | 123.5 (5) |
N3—C12—C13 | 121.4 (6) | N3A—C12A—C17A | 120.4 (6) |
N3—C12—C17 | 121.2 (6) | N3A—C12A—C13A | 121.7 (6) |
C13—C12—C17 | 117.3 (6) | C17A—C12A—C13A | 117.8 (6) |
C14—C13—C12 | 122.0 (7) | C14A—C13A—C12A | 121.3 (7) |
C14—C13—H13 | 119.0 | C14A—C13A—H13A | 119.4 |
C12—C13—H13 | 119.0 | C12A—C13A—H13A | 119.4 |
C15—C14—C13 | 120.6 (7) | C15A—C14A—C13A | 120.9 (7) |
C15—C14—H14 | 119.7 | C15A—C14A—H14A | 119.6 |
C13—C14—H14 | 119.7 | C13A—C14A—H14A | 119.6 |
C16—C15—C14 | 119.0 (7) | C16A—C15A—C14A | 118.2 (7) |
C16—C15—H15 | 120.5 | C16A—C15A—H15A | 120.9 |
C14—C15—H15 | 120.5 | C14A—C15A—H15A | 120.9 |
C15—C16—C17 | 122.6 (7) | C15A—C16A—C17A | 122.6 (7) |
C15—C16—H16 | 118.7 | C15A—C16A—H16A | 118.7 |
C17—C16—H16 | 118.7 | C17A—C16A—H16A | 118.7 |
C12—C17—C16 | 118.3 (6) | C12A—C17A—C16A | 118.8 (6) |
C12—C17—C18 | 124.2 (6) | C12A—C17A—C18A | 124.5 (6) |
C16—C17—C18 | 117.4 (6) | C16A—C17A—C18A | 116.6 (6) |
N4—C18—C17 | 121.9 (6) | N4A—C18A—C17A | 121.6 (6) |
N4—C18—C19 | 121.6 (6) | N4A—C18A—C19A | 120.2 (6) |
C17—C18—C19 | 116.3 (6) | C17A—C18A—C19A | 118.1 (6) |
C20—C19—C24 | 119.5 (6) | C20A—C19A—C24A | 119.0 (6) |
C20—C19—C18 | 118.8 (6) | C20A—C19A—C18A | 121.7 (6) |
C24—C19—C18 | 121.5 (6) | C24A—C19A—C18A | 119.3 (6) |
C21—C20—C19 | 120.1 (7) | C19A—C20A—C21A | 120.5 (7) |
C21—C20—H20 | 120.0 | C19A—C20A—H20A | 119.7 |
C19—C20—H20 | 120.0 | C21A—C20A—H20A | 119.7 |
C22—C21—C20 | 120.3 (7) | C22A—C21A—C20A | 119.4 (6) |
C22—C21—H21 | 119.9 | C22A—C21A—H21A | 120.3 |
C20—C21—H21 | 119.9 | C20A—C21A—H21A | 120.3 |
C23—C22—C21 | 119.7 (8) | C23A—C22A—C21A | 120.8 (7) |
C23—C22—H22 | 120.2 | C23A—C22A—H22A | 119.6 |
C21—C22—H22 | 120.2 | C21A—C22A—H22A | 119.6 |
C24—C23—C22 | 121.1 (7) | C22A—C23A—C24A | 119.8 (7) |
C24—C23—H23 | 119.4 | C22A—C23A—H23A | 120.1 |
C22—C23—H23 | 119.4 | C24A—C23A—H23A | 120.1 |
C23—C24—C19 | 119.3 (7) | C23A—C24A—C19A | 120.4 (7) |
C23—C24—H24 | 120.4 | C23A—C24A—H24A | 119.8 |
C19—C24—H24 | 120.4 | C19A—C24A—H24A | 119.8 |
C18—N4—C25 | 120.5 (6) | C18A—N4A—C25A | 120.8 (6) |
C18—N4—Ni | 128.3 (5) | C18A—N4A—NiA | 128.1 (5) |
C25—N4—Ni | 111.1 (4) | C25A—N4A—NiA | 111.0 (4) |
N4—C25—C33 | 107.1 (6) | N4A—C25A—C33A | 107.3 (6) |
N4—C25—C26 | 112.8 (6) | N4A—C25A—C26A | 114.6 (6) |
C33—C25—C26 | 108.9 (6) | C33A—C25A—C26A | 108.4 (6) |
N4—C25—H25 | 109.3 | N4A—C25A—H25A | 108.8 |
C33—C25—H25 | 109.3 | C33A—C25A—H25A | 108.8 |
C26—C25—H25 | 109.3 | C26A—C25A—H25A | 108.8 |
C27—C26—C25 | 115.2 (6) | C27A—C26A—C25A | 114.5 (6) |
C27—C26—H26A | 108.5 | C27A—C26A—H26C | 108.6 |
C25—C26—H26A | 108.5 | C25A—C26A—H26C | 108.6 |
C27—C26—H26B | 108.5 | C27A—C26A—H26D | 108.6 |
C25—C26—H26B | 108.5 | C25A—C26A—H26D | 108.6 |
H26A—C26—H26B | 107.5 | H26C—C26A—H26D | 107.6 |
C28—C27—C32 | 117.9 (7) | C28A—C27A—C32A | 118.5 (7) |
C28—C27—C26 | 121.5 (7) | C28A—C27A—C26A | 121.4 (7) |
C32—C27—C26 | 120.5 (7) | C32A—C27A—C26A | 120.1 (7) |
C27—C28—C29 | 121.2 (8) | C29A—C28A—C27A | 120.9 (7) |
C27—C28—H28 | 119.4 | C29A—C28A—H28A | 119.6 |
C29—C28—H28 | 119.4 | C27A—C28A—H28A | 119.6 |
C28—C29—C30 | 120.2 (9) | C28A—C29A—C30A | 119.6 (7) |
C28—C29—H29 | 119.9 | C28A—C29A—H29A | 120.2 |
C30—C29—H29 | 119.9 | C30A—C29A—H29A | 120.2 |
C31—C30—C29 | 119.3 (9) | C31A—C30A—C29A | 120.6 (7) |
C31—C30—H30 | 120.4 | C31A—C30A—H30A | 119.7 |
C29—C30—H30 | 120.4 | C29A—C30A—H30A | 119.7 |
C30—C31—C32 | 120.7 (9) | C30A—C31A—C32A | 119.8 (8) |
C30—C31—H31 | 119.7 | C30A—C31A—H31A | 120.1 |
C32—C31—H31 | 119.7 | C32A—C31A—H31A | 120.1 |
C31—C32—C27 | 120.7 (8) | C31A—C32A—C27A | 120.6 (8) |
C31—C32—H32 | 119.6 | C31A—C32A—H32A | 119.7 |
C27—C32—H32 | 119.6 | C27A—C32A—H32A | 119.7 |
O3—C33—O2 | 124.4 (7) | O3A—C33A—O2A | 126.0 (7) |
O3—C33—C25 | 120.2 (7) | O3A—C33A—C25A | 118.9 (7) |
O2—C33—C25 | 115.3 (6) | O2A—C33A—C25A | 115.1 (6) |
C33—O2—Ni | 114.5 (5) | C33A—O2A—NiA | 115.1 (4) |
[Ni(C33H30N4O3)]·0.5H2O | F(000) = 2504 |
Mr = 598.33 | Dx = 1.434 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 32 reflections |
a = 11.522 (4) Å | θ = 12.4–13.7° |
b = 18.623 (6) Å | µ = 0.75 mm−1 |
c = 25.828 (7) Å | T = 150 K |
V = 5542 (3) Å3 | Tablet, dark red |
Z = 8 | 0.35 × 0.27 × 0.16 mm |
Stoe Stadi-4 four-circle diffractometer | 3785 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 23.5°, θmin = 2.6° |
ω/2θ scans | h = 0→12 |
Absorption correction: ψ scan (X-RED; Stoe & Cie, 1995) | k = −20→20 |
Tmin = 0.789, Tmax = 0.864 | l = 0→29 |
5291 measured reflections | 3 standard reflections every 60 min |
4765 independent reflections | intensity decay: variation +−5.2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.066 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + 16.36P] where P = (Fo2 + 2Fc2)/3 |
S = 1.29 | (Δ/σ)max = 0.004 |
4765 reflections | Δρmax = 0.48 e Å−3 |
748 parameters | Δρmin = −0.42 e Å−3 |
369 restraints | Absolute structure: Flack (1983) with 194 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (3) |
[Ni(C33H30N4O3)]·0.5H2O | V = 5542 (3) Å3 |
Mr = 598.33 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.522 (4) Å | µ = 0.75 mm−1 |
b = 18.623 (6) Å | T = 150 K |
c = 25.828 (7) Å | 0.35 × 0.27 × 0.16 mm |
Stoe Stadi-4 four-circle diffractometer | 3785 reflections with I > 2σ(I) |
Absorption correction: ψ scan (X-RED; Stoe & Cie, 1995) | Rint = 0.044 |
Tmin = 0.789, Tmax = 0.864 | θmax = 23.5° |
5291 measured reflections | 3 standard reflections every 60 min |
4765 independent reflections | intensity decay: variation +−5.2% |
R[F2 > 2σ(F2)] = 0.066 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + 16.36P] where P = (Fo2 + 2Fc2)/3 |
S = 1.29 | Δρmax = 0.48 e Å−3 |
4765 reflections | Δρmin = −0.42 e Å−3 |
748 parameters | Absolute structure: Flack (1983) with 194 Friedel pairs |
369 restraints | Absolute structure parameter: 0.01 (3) |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.81375 (12) | 0.30046 (7) | 0.34360 (5) | 0.0280 (4) | |
O1 | 0.8069 (7) | 0.5119 (3) | 0.3414 (3) | 0.036 (2) | |
O2 | 0.7548 (6) | 0.2086 (3) | 0.3552 (3) | 0.039 (3) | |
O3 | 0.8069 (7) | 0.0934 (3) | 0.3547 (3) | 0.051 (3) | |
N1 | 0.5019 (14) | 0.4648 (7) | 0.2469 (6) | 0.096 (6) | |
N2 | 0.6812 (8) | 0.3410 (4) | 0.3774 (3) | 0.030 (3) | |
N3 | 0.8538 (7) | 0.3929 (3) | 0.3239 (3) | 0.025 (3) | |
N4 | 0.9469 (7) | 0.2569 (4) | 0.3214 (3) | 0.028 (3) | |
C1 | 0.6316 (13) | 0.3460 (8) | 0.2546 (5) | 0.070 (6) | |
C2 | 0.6307 (14) | 0.3839 (10) | 0.2106 (5) | 0.093 (8) | |
C3 | 0.5629 (18) | 0.4429 (11) | 0.2069 (6) | 0.110 (9) | |
C4 | 0.4953 (12) | 0.4266 (7) | 0.2909 (5) | 0.061 (5) | |
C5 | 0.5649 (11) | 0.3668 (6) | 0.2973 (4) | 0.052 (5) | |
C6 | 0.5708 (9) | 0.3286 (6) | 0.3485 (4) | 0.043 (4) | |
C7 | 0.6687 (10) | 0.3097 (5) | 0.4316 (3) | 0.039 (4) | |
C8 | 0.6638 (11) | 0.3747 (5) | 0.4678 (3) | 0.043 (4) | |
C9 | 0.7443 (9) | 0.4271 (5) | 0.4406 (3) | 0.035 (4) | |
C10 | 0.7040 (8) | 0.4202 (4) | 0.3840 (3) | 0.027 (3) | |
C11 | 0.7940 (9) | 0.4471 (5) | 0.3468 (4) | 0.027 (3) | |
C12 | 0.9389 (9) | 0.4064 (5) | 0.2858 (3) | 0.029 (3) | |
C13 | 0.9346 (10) | 0.4701 (5) | 0.2564 (4) | 0.039 (4) | |
C14 | 1.0208 (12) | 0.4854 (5) | 0.2198 (4) | 0.051 (5) | |
C15 | 1.1107 (11) | 0.4391 (5) | 0.2108 (4) | 0.046 (4) | |
C16 | 1.1137 (10) | 0.3760 (5) | 0.2382 (4) | 0.039 (4) | |
C17 | 1.0280 (9) | 0.3566 (5) | 0.2749 (4) | 0.025 (3) | |
C18 | 1.0339 (8) | 0.2842 (4) | 0.2962 (3) | 0.023 (3) | |
C19 | 1.1431 (8) | 0.2406 (5) | 0.2865 (3) | 0.022 (3) | |
C20 | 1.2418 (9) | 0.2536 (5) | 0.3158 (4) | 0.034 (4) | |
C21 | 1.3396 (9) | 0.2115 (5) | 0.3090 (4) | 0.042 (4) | |
C22 | 1.3403 (10) | 0.1568 (5) | 0.2731 (4) | 0.038 (4) | |
C23 | 1.2431 (9) | 0.1448 (5) | 0.2431 (4) | 0.031 (3) | |
C24 | 1.1441 (9) | 0.1854 (5) | 0.2503 (3) | 0.027 (3) | |
C25 | 0.9547 (9) | 0.1807 (5) | 0.3393 (4) | 0.036 (4) | |
C26 | 1.0266 (10) | 0.1686 (6) | 0.3882 (4) | 0.048 (4) | |
C27 | 0.9804 (9) | 0.2049 (5) | 0.4366 (4) | 0.037 (3) | |
C28 | 1.0112 (9) | 0.2748 (6) | 0.4487 (4) | 0.042 (4) | |
C29 | 0.9695 (10) | 0.3076 (6) | 0.4931 (4) | 0.043 (4) | |
C30 | 0.8928 (10) | 0.2713 (6) | 0.5244 (4) | 0.046 (4) | |
C31 | 0.8589 (10) | 0.2029 (6) | 0.5125 (4) | 0.045 (4) | |
C32 | 0.9032 (10) | 0.1703 (6) | 0.4686 (4) | 0.045 (4) | |
C33 | 0.8283 (11) | 0.1580 (5) | 0.3494 (4) | 0.043 (4) | |
NIA | 0.66302 (13) | 0.08870 (6) | 0.04732 (5) | 0.0268 (4) | |
O1A | 0.5869 (7) | 0.2866 (3) | 0.0069 (3) | 0.043 (3) | |
O2A | 0.6452 (6) | 0.0025 (3) | 0.0839 (3) | 0.032 (3) | |
O3A | 0.7405 (7) | −0.0974 (3) | 0.1059 (3) | 0.038 (3) | |
N1A | 0.3458 (10) | 0.1478 (5) | −0.0792 (4) | 0.064 (4) | |
N2A | 0.5272 (8) | 0.1270 (4) | 0.0816 (3) | 0.032 (3) | |
N3A | 0.6657 (8) | 0.1705 (4) | 0.0066 (3) | 0.029 (3) | |
N4A | 0.7956 (7) | 0.0480 (4) | 0.0190 (3) | 0.028 (3) | |
C1A | 0.4757 (10) | 0.0434 (5) | −0.0284 (4) | 0.033 (3) | |
C2A | 0.4727 (11) | 0.0459 (6) | −0.0806 (4) | 0.043 (4) | |
C3A | 0.4110 (12) | 0.0988 (7) | −0.1037 (5) | 0.059 (5) | |
C4A | 0.3533 (11) | 0.1453 (6) | −0.0260 (5) | 0.051 (4) | |
C5A | 0.4156 (9) | 0.0939 (6) | 0.0012 (4) | 0.032 (3) | |
C6A | 0.4213 (9) | 0.0921 (6) | 0.0596 (4) | 0.040 (3) | |
C7A | 0.5290 (12) | 0.1166 (5) | 0.1401 (4) | 0.047 (4) | |
C8A | 0.5371 (10) | 0.1904 (6) | 0.1644 (4) | 0.044 (4) | |
C9A | 0.5876 (10) | 0.2364 (5) | 0.1209 (4) | 0.036 (3) | |
C10A | 0.5297 (9) | 0.2064 (5) | 0.0722 (3) | 0.033 (3) | |
C11A | 0.5968 (9) | 0.2246 (5) | 0.0239 (4) | 0.033 (4) | |
C12A | 0.7182 (8) | 0.1738 (4) | −0.0425 (4) | 0.026 (3) | |
C13A | 0.6863 (9) | 0.2262 (5) | −0.0790 (4) | 0.034 (3) | |
C14A | 0.7345 (9) | 0.2283 (6) | −0.1282 (4) | 0.036 (4) | |
C15A | 0.8167 (10) | 0.1786 (5) | −0.1428 (4) | 0.035 (3) | |
C16A | 0.8490 (9) | 0.1265 (5) | −0.1082 (3) | 0.033 (3) | |
C17A | 0.8018 (8) | 0.1226 (5) | −0.0578 (3) | 0.025 (3) | |
C18A | 0.8433 (8) | 0.0637 (4) | −0.0248 (3) | 0.025 (3) | |
C19A | 0.9418 (8) | 0.0185 (5) | −0.0461 (4) | 0.023 (3) | |
C20A | 0.9161 (10) | −0.0410 (5) | −0.0758 (4) | 0.034 (4) | |
C21A | 1.0051 (9) | −0.0797 (6) | −0.0988 (4) | 0.038 (4) | |
C22A | 1.1191 (10) | −0.0608 (6) | −0.0924 (4) | 0.043 (4) | |
C23A | 1.1431 (9) | −0.0016 (6) | −0.0621 (4) | 0.037 (4) | |
C24A | 1.0564 (9) | 0.0389 (5) | −0.0397 (4) | 0.034 (3) | |
C25A | 0.8377 (9) | −0.0129 (5) | 0.0512 (4) | 0.031 (3) | |
C26A | 0.9363 (9) | 0.0100 (5) | 0.0875 (4) | 0.037 (4) | |
C27A | 0.9078 (9) | 0.0710 (5) | 0.1233 (4) | 0.033 (3) | |
C28A | 0.9335 (11) | 0.1403 (5) | 0.1106 (5) | 0.049 (5) | |
C29A | 0.9075 (13) | 0.1955 (7) | 0.1442 (5) | 0.071 (5) | |
C30A | 0.8548 (12) | 0.1801 (8) | 0.1903 (6) | 0.074 (6) | |
C31A | 0.8270 (13) | 0.1116 (8) | 0.2037 (5) | 0.076 (6) | |
C32A | 0.8550 (11) | 0.0563 (7) | 0.1702 (4) | 0.052 (4) | |
C33A | 0.7334 (9) | −0.0396 (5) | 0.0834 (4) | 0.030 (3) | |
O1W | 0.6084 (12) | 0.0965 (10) | 0.2842 (5) | 0.158 (8) | |
H1 | 0.67840 | 0.30420 | 0.25690 | 0.0840* | |
H2 | 0.67740 | 0.36940 | 0.18210 | 0.1120* | |
H3 | 0.55920 | 0.46870 | 0.17520 | 0.1340* | |
H4 | 0.44310 | 0.44070 | 0.31750 | 0.0730* | |
H6A | 0.50500 | 0.34470 | 0.37030 | 0.0510* | |
H6B | 0.56150 | 0.27640 | 0.34250 | 0.0510* | |
H7A | 0.73580 | 0.27870 | 0.44010 | 0.0460* | |
H7B | 0.59670 | 0.28090 | 0.43440 | 0.0460* | |
H8A | 0.58400 | 0.39410 | 0.47050 | 0.0520* | |
H8B | 0.69260 | 0.36250 | 0.50280 | 0.0520* | |
H9A | 0.82660 | 0.41290 | 0.44460 | 0.0420* | |
H9B | 0.73380 | 0.47660 | 0.45380 | 0.0420* | |
H10 | 0.63010 | 0.44760 | 0.37900 | 0.0320* | |
H13 | 0.87260 | 0.50300 | 0.26150 | 0.0470* | |
H14 | 1.01680 | 0.52900 | 0.20080 | 0.0610* | |
H15 | 1.16940 | 0.45030 | 0.18620 | 0.0560* | |
H16 | 1.17620 | 0.34380 | 0.23220 | 0.0460* | |
H20 | 1.24240 | 0.29150 | 0.34040 | 0.0410* | |
H21 | 1.40680 | 0.22040 | 0.32920 | 0.0500* | |
H22 | 1.40720 | 0.12750 | 0.26910 | 0.0450* | |
H23 | 1.24430 | 0.10840 | 0.21730 | 0.0370* | |
H24 | 1.07650 | 0.17550 | 0.23050 | 0.0320* | |
H25 | 0.98710 | 0.15070 | 0.31070 | 0.0440* | |
H26A | 1.03130 | 0.11630 | 0.39480 | 0.0580* | |
H26B | 1.10650 | 0.18610 | 0.38180 | 0.0580* | |
H28 | 1.06160 | 0.30060 | 0.42630 | 0.0510* | |
H29 | 0.99370 | 0.35490 | 0.50190 | 0.0510* | |
H30 | 0.86310 | 0.29400 | 0.55450 | 0.0550* | |
H31 | 0.80570 | 0.17800 | 0.53420 | 0.0540* | |
H32 | 0.87950 | 0.12270 | 0.46030 | 0.0540* | |
H6A1 | 0.35180 | 0.11650 | 0.07360 | 0.0490* | |
H1A | 0.51920 | 0.00690 | −0.01160 | 0.0400* | |
H6A2 | 0.41890 | 0.04150 | 0.07110 | 0.0490* | |
H2A | 0.51300 | 0.01120 | −0.10070 | 0.0520* | |
H7A1 | 0.45730 | 0.09200 | 0.15160 | 0.0560* | |
H3A | 0.41420 | 0.10150 | −0.14040 | 0.0710* | |
H7A2 | 0.59650 | 0.08690 | 0.15030 | 0.0560* | |
H4A | 0.31330 | 0.18100 | −0.00680 | 0.0620* | |
H8A1 | 0.58890 | 0.19000 | 0.19490 | 0.0530* | |
H8A2 | 0.45960 | 0.20810 | 0.17490 | 0.0530* | |
H9A1 | 0.67310 | 0.23130 | 0.11910 | 0.0430* | |
H9A2 | 0.56810 | 0.28770 | 0.12590 | 0.0430* | |
H10A | 0.44860 | 0.22520 | 0.06940 | 0.0390* | |
H13A | 0.63020 | 0.26130 | −0.06970 | 0.0400* | |
H14A | 0.71060 | 0.26430 | −0.15200 | 0.0430* | |
H15A | 0.85050 | 0.18040 | −0.17630 | 0.0420* | |
H16A | 0.90510 | 0.09190 | −0.11840 | 0.0390* | |
H20A | 0.83770 | −0.05530 | −0.08050 | 0.0410* | |
H21A | 0.98660 | −0.12020 | −0.11950 | 0.0460* | |
H22A | 1.17960 | −0.08760 | −0.10820 | 0.0510* | |
H23A | 1.22180 | 0.01170 | −0.05660 | 0.0440* | |
H24A | 1.07520 | 0.08040 | −0.02000 | 0.0400* | |
H25A | 0.86550 | −0.05240 | 0.02810 | 0.0380* | |
H26C | 0.95960 | −0.03200 | 0.10860 | 0.0440* | |
H26D | 1.00400 | 0.02400 | 0.06610 | 0.0440* | |
H28A | 0.96970 | 0.15060 | 0.07840 | 0.0580* | |
H29A | 0.92590 | 0.24370 | 0.13550 | 0.0850* | |
H30A | 0.83720 | 0.21810 | 0.21360 | 0.0890* | |
H31A | 0.78890 | 0.10190 | 0.23560 | 0.0910* | |
H32A | 0.83800 | 0.00810 | 0.17940 | 0.0620* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0322 (8) | 0.0184 (6) | 0.0334 (8) | −0.0008 (7) | 0.0093 (7) | 0.0009 (6) |
O1 | 0.059 (5) | 0.022 (3) | 0.027 (4) | 0.005 (4) | 0.010 (4) | 0.005 (3) |
O2 | 0.038 (4) | 0.024 (4) | 0.055 (5) | −0.001 (4) | 0.026 (4) | −0.001 (4) |
O3 | 0.066 (6) | 0.017 (3) | 0.070 (5) | −0.013 (4) | 0.046 (5) | −0.004 (4) |
N1 | 0.124 (12) | 0.091 (10) | 0.074 (8) | −0.014 (8) | −0.058 (9) | 0.031 (8) |
N2 | 0.032 (5) | 0.030 (4) | 0.027 (4) | −0.003 (4) | 0.005 (4) | −0.001 (4) |
N3 | 0.034 (5) | 0.015 (4) | 0.025 (4) | −0.001 (4) | 0.010 (4) | 0.003 (3) |
N4 | 0.035 (5) | 0.016 (4) | 0.034 (5) | −0.004 (4) | 0.010 (4) | −0.007 (4) |
C1 | 0.082 (12) | 0.082 (10) | 0.047 (8) | −0.019 (9) | −0.010 (8) | −0.030 (7) |
C2 | 0.084 (13) | 0.171 (18) | 0.025 (7) | −0.043 (11) | −0.012 (8) | −0.018 (9) |
C3 | 0.131 (19) | 0.154 (17) | 0.038 (7) | 0.040 (11) | −0.051 (8) | −0.037 (10) |
C4 | 0.063 (10) | 0.062 (9) | 0.058 (8) | −0.004 (7) | −0.028 (7) | 0.005 (7) |
C5 | 0.051 (9) | 0.051 (8) | 0.055 (7) | −0.017 (7) | −0.016 (7) | −0.004 (6) |
C6 | 0.031 (6) | 0.041 (7) | 0.056 (7) | −0.004 (5) | 0.005 (6) | −0.004 (6) |
C7 | 0.035 (7) | 0.042 (6) | 0.039 (6) | 0.010 (6) | 0.018 (6) | 0.010 (5) |
C8 | 0.054 (8) | 0.050 (6) | 0.025 (6) | 0.016 (7) | 0.011 (6) | 0.006 (5) |
C9 | 0.039 (7) | 0.043 (6) | 0.022 (6) | 0.015 (5) | 0.009 (5) | 0.002 (5) |
C10 | 0.025 (6) | 0.023 (5) | 0.033 (5) | 0.004 (5) | −0.004 (5) | 0.000 (4) |
C11 | 0.029 (6) | 0.032 (5) | 0.021 (5) | −0.001 (5) | −0.001 (5) | 0.011 (5) |
C12 | 0.040 (6) | 0.028 (5) | 0.018 (5) | −0.009 (5) | 0.003 (5) | −0.007 (5) |
C13 | 0.052 (8) | 0.025 (6) | 0.040 (7) | 0.013 (6) | 0.016 (6) | −0.001 (5) |
C14 | 0.094 (11) | 0.017 (5) | 0.042 (7) | 0.006 (7) | 0.028 (8) | 0.004 (5) |
C15 | 0.075 (9) | 0.023 (6) | 0.041 (7) | 0.001 (6) | 0.028 (7) | 0.003 (5) |
C16 | 0.052 (8) | 0.030 (6) | 0.034 (7) | 0.004 (6) | 0.016 (6) | 0.000 (5) |
C17 | 0.035 (6) | 0.019 (5) | 0.021 (6) | −0.002 (5) | 0.007 (5) | −0.004 (4) |
C18 | 0.032 (6) | 0.021 (5) | 0.015 (5) | −0.005 (5) | 0.005 (5) | −0.005 (4) |
C19 | 0.022 (6) | 0.021 (5) | 0.022 (5) | −0.003 (4) | 0.002 (5) | 0.000 (4) |
C20 | 0.039 (7) | 0.026 (6) | 0.038 (7) | −0.006 (5) | 0.000 (6) | 0.001 (5) |
C21 | 0.028 (6) | 0.037 (6) | 0.062 (7) | −0.016 (6) | −0.007 (6) | 0.004 (6) |
C22 | 0.032 (7) | 0.032 (6) | 0.050 (7) | 0.002 (6) | 0.004 (6) | 0.008 (5) |
C23 | 0.037 (7) | 0.022 (5) | 0.035 (6) | 0.000 (5) | 0.015 (5) | −0.002 (5) |
C24 | 0.031 (6) | 0.033 (6) | 0.016 (5) | −0.003 (5) | 0.006 (5) | −0.002 (4) |
C25 | 0.044 (7) | 0.016 (5) | 0.049 (7) | 0.002 (5) | 0.023 (6) | 0.006 (5) |
C26 | 0.042 (7) | 0.038 (6) | 0.064 (8) | 0.021 (6) | 0.016 (6) | 0.029 (6) |
C27 | 0.033 (6) | 0.034 (6) | 0.044 (6) | 0.009 (6) | 0.005 (5) | 0.025 (5) |
C28 | 0.026 (6) | 0.054 (7) | 0.046 (7) | −0.003 (6) | 0.002 (6) | 0.025 (6) |
C29 | 0.046 (8) | 0.045 (7) | 0.037 (7) | 0.003 (7) | −0.010 (6) | 0.015 (6) |
C30 | 0.042 (8) | 0.054 (7) | 0.043 (7) | 0.015 (6) | 0.008 (6) | 0.012 (6) |
C31 | 0.047 (8) | 0.051 (7) | 0.037 (7) | 0.005 (7) | 0.005 (6) | 0.017 (6) |
C32 | 0.048 (8) | 0.032 (6) | 0.055 (8) | 0.002 (6) | 0.005 (6) | 0.017 (5) |
C33 | 0.061 (8) | 0.031 (6) | 0.038 (7) | −0.015 (6) | 0.023 (7) | −0.002 (5) |
NiA | 0.0317 (8) | 0.0216 (6) | 0.0272 (7) | −0.0012 (7) | 0.0017 (7) | 0.0045 (6) |
O1A | 0.051 (5) | 0.024 (4) | 0.054 (5) | 0.004 (4) | 0.002 (4) | 0.004 (4) |
O2A | 0.042 (5) | 0.028 (4) | 0.026 (4) | 0.000 (4) | 0.005 (4) | 0.000 (3) |
O3A | 0.062 (5) | 0.020 (4) | 0.032 (4) | −0.001 (4) | −0.002 (4) | 0.003 (3) |
N1A | 0.065 (8) | 0.048 (6) | 0.079 (7) | 0.006 (6) | −0.028 (7) | 0.012 (6) |
N2A | 0.041 (6) | 0.019 (4) | 0.036 (5) | −0.004 (4) | 0.006 (4) | 0.001 (4) |
N3A | 0.030 (5) | 0.021 (4) | 0.036 (5) | −0.001 (4) | 0.001 (4) | 0.004 (4) |
N4A | 0.034 (5) | 0.024 (4) | 0.026 (5) | 0.007 (4) | −0.007 (4) | 0.005 (4) |
C1A | 0.038 (7) | 0.019 (5) | 0.043 (6) | −0.012 (5) | −0.007 (6) | 0.001 (5) |
C2A | 0.045 (8) | 0.030 (6) | 0.055 (8) | 0.003 (6) | −0.007 (7) | −0.008 (6) |
C3A | 0.066 (10) | 0.050 (8) | 0.062 (8) | 0.009 (8) | −0.022 (8) | −0.003 (7) |
C4A | 0.043 (8) | 0.031 (6) | 0.080 (8) | 0.003 (6) | −0.017 (7) | 0.007 (6) |
C5A | 0.023 (6) | 0.029 (6) | 0.045 (6) | −0.009 (5) | 0.006 (5) | −0.008 (5) |
C6A | 0.034 (6) | 0.029 (5) | 0.058 (7) | −0.006 (6) | 0.015 (6) | −0.002 (6) |
C7A | 0.075 (10) | 0.036 (6) | 0.030 (6) | 0.009 (7) | 0.017 (6) | −0.004 (5) |
C8A | 0.041 (7) | 0.049 (7) | 0.043 (7) | −0.005 (7) | −0.014 (6) | 0.005 (6) |
C9A | 0.038 (7) | 0.028 (5) | 0.043 (6) | 0.001 (6) | 0.002 (6) | −0.011 (5) |
C10A | 0.037 (6) | 0.021 (5) | 0.040 (6) | −0.004 (5) | −0.002 (5) | −0.003 (5) |
C11A | 0.033 (7) | 0.028 (6) | 0.038 (6) | −0.006 (5) | −0.007 (5) | 0.006 (5) |
C12A | 0.029 (6) | 0.017 (5) | 0.032 (5) | −0.009 (4) | −0.008 (5) | 0.005 (4) |
C13A | 0.023 (6) | 0.034 (6) | 0.044 (6) | −0.002 (5) | −0.004 (5) | 0.017 (5) |
C14A | 0.037 (7) | 0.042 (6) | 0.028 (6) | −0.010 (6) | −0.017 (5) | 0.010 (5) |
C15A | 0.039 (7) | 0.043 (6) | 0.024 (5) | −0.011 (6) | −0.005 (6) | 0.014 (5) |
C16A | 0.035 (7) | 0.036 (6) | 0.027 (5) | −0.005 (6) | −0.004 (5) | 0.005 (5) |
C17A | 0.022 (6) | 0.026 (5) | 0.026 (5) | −0.005 (4) | −0.004 (5) | 0.004 (4) |
C18A | 0.022 (5) | 0.024 (5) | 0.028 (5) | −0.003 (5) | −0.009 (5) | −0.001 (4) |
C19A | 0.026 (5) | 0.022 (5) | 0.021 (5) | 0.000 (4) | −0.002 (5) | 0.003 (5) |
C20A | 0.036 (7) | 0.038 (6) | 0.028 (6) | −0.006 (6) | −0.002 (6) | −0.001 (5) |
C21A | 0.052 (7) | 0.041 (7) | 0.022 (6) | 0.000 (6) | 0.005 (6) | −0.003 (5) |
C22A | 0.039 (7) | 0.046 (7) | 0.043 (7) | 0.012 (6) | 0.007 (6) | −0.011 (6) |
C23A | 0.029 (6) | 0.050 (7) | 0.031 (6) | 0.005 (6) | 0.002 (5) | 0.003 (5) |
C24A | 0.037 (6) | 0.038 (6) | 0.027 (6) | −0.001 (5) | −0.010 (5) | −0.002 (5) |
C25A | 0.038 (6) | 0.027 (5) | 0.029 (5) | 0.006 (5) | 0.009 (5) | 0.006 (4) |
C26A | 0.034 (7) | 0.039 (6) | 0.037 (7) | 0.008 (6) | −0.002 (6) | 0.012 (5) |
C27A | 0.028 (6) | 0.047 (6) | 0.025 (6) | 0.008 (6) | −0.011 (5) | 0.013 (5) |
C28A | 0.053 (9) | 0.042 (7) | 0.051 (8) | −0.005 (7) | −0.021 (7) | 0.010 (6) |
C29A | 0.081 (11) | 0.049 (7) | 0.083 (10) | 0.024 (8) | −0.058 (9) | −0.004 (8) |
C30A | 0.049 (10) | 0.087 (10) | 0.087 (10) | 0.045 (9) | −0.045 (8) | −0.056 (9) |
C31A | 0.043 (9) | 0.139 (13) | 0.046 (8) | −0.017 (11) | 0.006 (8) | −0.033 (9) |
C32A | 0.062 (9) | 0.067 (8) | 0.026 (6) | −0.005 (8) | −0.007 (6) | −0.001 (6) |
C33A | 0.043 (7) | 0.025 (5) | 0.021 (6) | 0.001 (5) | 0.001 (5) | −0.001 (5) |
O1W | 0.105 (11) | 0.239 (17) | 0.131 (11) | −0.012 (13) | 0.029 (10) | 0.038 (13) |
Ni—N2 | 1.914 (9) | C13—H13 | 0.95 |
Ni—N3 | 1.853 (6) | C14—H14 | 0.95 |
Ni—N4 | 1.828 (8) | C15—H15 | 0.95 |
Ni—O2 | 1.865 (6) | C16—H16 | 0.95 |
Ni—N1 | 5.339 (15) | C20—H20 | 0.95 |
NiA—N2A | 1.934 (9) | C21—H21 | 0.95 |
NiA—N3A | 1.851 (8) | C22—H22 | 0.95 |
NiA—N4A | 1.856 (8) | C23—H23 | 0.95 |
NiA—O2A | 1.874 (6) | C24—H24 | 0.95 |
NiA—N1A | 5.024 (12) | C25—H25 | 1.00 |
O1—C11 | 1.224 (11) | C26—H26B | 0.99 |
O2—C33 | 1.276 (13) | C26—H26A | 0.99 |
O3—C33 | 1.236 (11) | C28—H28 | 0.95 |
O1A—C11A | 1.241 (11) | C29—H29 | 0.95 |
O2A—C33A | 1.284 (12) | C30—H30 | 0.95 |
O3A—C33A | 1.226 (11) | C31—H31 | 0.95 |
N1—C3 | 1.323 (18) | C32—H32 | 0.95 |
N1—C4 | 1.343 (14) | C1A—C2A | 1.349 (15) |
N2—C6 | 1.493 (14) | C1A—C5A | 1.396 (15) |
N2—C7 | 1.523 (11) | C2A—C3A | 1.353 (18) |
N2—C10 | 1.508 (11) | C4A—C5A | 1.387 (16) |
N3—C11 | 1.358 (12) | C5A—C6A | 1.510 (15) |
N3—C12 | 1.412 (12) | C7A—C8A | 1.514 (15) |
N4—C18 | 1.299 (12) | C8A—C9A | 1.528 (15) |
N4—C25 | 1.495 (12) | C9A—C10A | 1.529 (13) |
N1A—C4A | 1.378 (17) | C10A—C11A | 1.506 (13) |
N1A—C3A | 1.341 (17) | C12A—C13A | 1.406 (13) |
N2A—C6A | 1.495 (14) | C12A—C17A | 1.412 (13) |
N2A—C10A | 1.499 (12) | C13A—C14A | 1.387 (15) |
N2A—C7A | 1.523 (13) | C14A—C15A | 1.377 (15) |
N3A—C11A | 1.358 (13) | C15A—C16A | 1.371 (13) |
N3A—C12A | 1.406 (13) | C16A—C17A | 1.413 (11) |
N4A—C25A | 1.488 (12) | C17A—C18A | 1.469 (12) |
N4A—C18A | 1.291 (11) | C18A—C19A | 1.516 (13) |
C1—C5 | 1.399 (18) | C19A—C20A | 1.380 (14) |
C1—C2 | 1.336 (15) | C19A—C24A | 1.384 (14) |
C2—C3 | 1.347 (17) | C20A—C21A | 1.387 (15) |
C4—C5 | 1.382 (18) | C21A—C22A | 1.370 (16) |
C5—C6 | 1.503 (15) | C22A—C23A | 1.380 (15) |
C7—C8 | 1.531 (12) | C23A—C24A | 1.379 (15) |
C8—C9 | 1.519 (14) | C25A—C26A | 1.533 (15) |
C9—C10 | 1.539 (11) | C25A—C33A | 1.544 (15) |
C10—C11 | 1.500 (13) | C26A—C27A | 1.501 (14) |
C12—C13 | 1.409 (13) | C27A—C28A | 1.364 (14) |
C12—C17 | 1.412 (14) | C27A—C32A | 1.383 (15) |
C13—C14 | 1.400 (16) | C28A—C29A | 1.378 (17) |
C14—C15 | 1.368 (17) | C29A—C30A | 1.37 (2) |
C15—C16 | 1.372 (14) | C30A—C31A | 1.36 (2) |
C16—C17 | 1.416 (15) | C31A—C32A | 1.383 (19) |
C17—C18 | 1.458 (12) | C1A—H1A | 0.95 |
C18—C19 | 1.518 (13) | C2A—H2A | 0.95 |
C19—C24 | 1.390 (12) | C3A—H3A | 0.95 |
C19—C20 | 1.387 (14) | C4A—H4A | 0.95 |
C20—C21 | 1.384 (14) | C6A—H6A1 | 0.99 |
C21—C22 | 1.378 (14) | C6A—H6A2 | 0.99 |
C22—C23 | 1.380 (15) | C7A—H7A1 | 0.99 |
C23—C24 | 1.381 (14) | C7A—H7A2 | 0.99 |
C25—C26 | 1.527 (15) | C8A—H8A1 | 0.99 |
C25—C33 | 1.539 (16) | C8A—H8A2 | 0.99 |
C26—C27 | 1.518 (15) | C9A—H9A1 | 0.99 |
C27—C28 | 1.385 (15) | C9A—H9A2 | 0.99 |
C27—C32 | 1.375 (15) | C10A—H10A | 1.00 |
C28—C29 | 1.385 (15) | C13A—H13A | 0.95 |
C29—C30 | 1.375 (16) | C14A—H14A | 0.95 |
C30—C31 | 1.367 (16) | C15A—H15A | 0.95 |
C31—C32 | 1.384 (15) | C16A—H16A | 0.95 |
C1—H1 | 0.95 | C20A—H20A | 0.95 |
C2—H2 | 0.95 | C21A—H21A | 0.95 |
C3—H3 | 0.95 | C22A—H22A | 0.95 |
C4—H4 | 0.95 | C23A—H23A | 0.95 |
C6—H6A | 0.99 | C24A—H24A | 0.95 |
C6—H6B | 0.99 | C25A—H25A | 1.00 |
C7—H7A | 0.99 | C26A—H26C | 0.99 |
C7—H7B | 0.99 | C26A—H26D | 0.99 |
C8—H8A | 0.99 | C28A—H28A | 0.95 |
C8—H8B | 0.99 | C29A—H29A | 0.95 |
C9—H9A | 0.99 | C30A—H30A | 0.95 |
C9—H9B | 0.99 | C31A—H31A | 0.95 |
C10—H10 | 1.00 | C32A—H32A | 0.95 |
N2—Ni—N3 | 87.6 (3) | C23—C24—H24 | 119.90 |
N2—Ni—N4 | 171.0 (3) | C19—C24—H24 | 119.94 |
N2—Ni—O2 | 89.9 (3) | N4—C25—H25 | 108.95 |
N3—Ni—N4 | 96.7 (3) | C26—C25—H25 | 109.05 |
N3—Ni—O2 | 170.7 (3) | C33—C25—H25 | 109.00 |
N4—Ni—O2 | 87.1 (3) | H26A—C26—H26B | 107.55 |
N2A—NiA—N3A | 88.3 (4) | C25—C26—H26A | 108.49 |
N2A—NiA—N4A | 175.6 (3) | C25—C26—H26B | 108.52 |
N2A—NiA—O2A | 89.8 (3) | C27—C26—H26B | 108.48 |
N3A—NiA—N4A | 95.6 (4) | C27—C26—H26A | 108.39 |
N3A—NiA—O2A | 173.3 (4) | C29—C28—H28 | 119.54 |
N4A—NiA—O2A | 86.5 (3) | C27—C28—H28 | 119.64 |
Ni—O2—C33 | 114.6 (7) | C28—C29—H29 | 120.29 |
NiA—O2A—C33A | 115.6 (6) | C30—C29—H29 | 120.19 |
C3—N1—C4 | 122.1 (15) | C29—C30—H30 | 119.63 |
Ni—N2—C6 | 113.0 (6) | C31—C30—H30 | 119.75 |
Ni—N2—C7 | 110.1 (6) | C32—C31—H31 | 120.44 |
Ni—N2—C10 | 107.4 (6) | C30—C31—H31 | 120.38 |
C6—N2—C7 | 108.6 (8) | C31—C32—H32 | 119.16 |
C6—N2—C10 | 110.9 (7) | C27—C32—H32 | 119.12 |
C7—N2—C10 | 106.7 (7) | C2A—C1A—C5A | 120.7 (10) |
C11—N3—C12 | 121.6 (7) | C1A—C2A—C3A | 118.6 (11) |
Ni—N3—C11 | 116.4 (6) | N1A—C3A—C2A | 125.6 (12) |
Ni—N3—C12 | 122.0 (6) | N1A—C4A—C5A | 124.1 (11) |
Ni—N4—C25 | 112.0 (6) | C1A—C5A—C4A | 116.4 (10) |
Ni—N4—C18 | 129.1 (6) | C1A—C5A—C6A | 120.7 (9) |
C18—N4—C25 | 118.7 (8) | C4A—C5A—C6A | 122.9 (10) |
C3A—N1A—C4A | 114.4 (10) | N2A—C6A—C5A | 113.9 (8) |
NiA—N2A—C10A | 105.9 (6) | N2A—C7A—C8A | 107.3 (8) |
NiA—N2A—C7A | 113.3 (7) | C7A—C8A—C9A | 103.2 (8) |
NiA—N2A—C6A | 109.0 (6) | C8A—C9A—C10A | 103.5 (8) |
C6A—N2A—C7A | 109.4 (8) | N2A—C10A—C9A | 103.6 (7) |
C6A—N2A—C10A | 112.5 (8) | N2A—C10A—C11A | 111.5 (7) |
C7A—N2A—C10A | 106.6 (7) | C9A—C10A—C11A | 112.0 (8) |
NiA—N3A—C11A | 114.4 (7) | O1A—C11A—N3A | 128.9 (10) |
NiA—N3A—C12A | 123.7 (6) | O1A—C11A—C10A | 117.1 (9) |
C11A—N3A—C12A | 121.0 (8) | N3A—C11A—C10A | 113.9 (8) |
NiA—N4A—C18A | 127.1 (6) | N3A—C12A—C13A | 121.5 (8) |
NiA—N4A—C25A | 111.1 (6) | N3A—C12A—C17A | 121.1 (8) |
C18A—N4A—C25A | 121.6 (8) | C13A—C12A—C17A | 117.4 (9) |
C2—C1—C5 | 121.3 (14) | C12A—C13A—C14A | 121.9 (9) |
C1—C2—C3 | 119.6 (14) | C13A—C14A—C15A | 120.5 (10) |
N1—C3—C2 | 120.4 (15) | C14A—C15A—C16A | 119.0 (10) |
N1—C4—C5 | 119.7 (12) | C15A—C16A—C17A | 122.2 (9) |
C1—C5—C4 | 116.6 (11) | C12A—C17A—C16A | 119.1 (8) |
C1—C5—C6 | 122.5 (11) | C12A—C17A—C18A | 124.3 (8) |
C4—C5—C6 | 120.8 (10) | C16A—C17A—C18A | 116.6 (8) |
N2—C6—C5 | 113.9 (9) | N4A—C18A—C17A | 122.6 (8) |
N2—C7—C8 | 105.2 (7) | N4A—C18A—C19A | 120.7 (8) |
C7—C8—C9 | 101.7 (7) | C17A—C18A—C19A | 116.6 (7) |
C8—C9—C10 | 101.6 (7) | C18A—C19A—C20A | 119.1 (9) |
N2—C10—C9 | 104.0 (6) | C18A—C19A—C24A | 121.2 (8) |
N2—C10—C11 | 112.0 (7) | C20A—C19A—C24A | 119.4 (9) |
C9—C10—C11 | 111.8 (8) | C19A—C20A—C21A | 119.8 (10) |
N3—C11—C10 | 112.4 (8) | C20A—C21A—C22A | 121.6 (10) |
O1—C11—N3 | 128.4 (10) | C21A—C22A—C23A | 117.8 (10) |
O1—C11—C10 | 119.1 (9) | C22A—C23A—C24A | 122.0 (10) |
N3—C12—C17 | 121.8 (8) | C19A—C24A—C23A | 119.4 (9) |
N3—C12—C13 | 120.1 (9) | N4A—C25A—C26A | 111.8 (8) |
C13—C12—C17 | 118.1 (9) | N4A—C25A—C33A | 107.0 (8) |
C12—C13—C14 | 120.7 (10) | C26A—C25A—C33A | 109.7 (8) |
C13—C14—C15 | 121.6 (9) | C25A—C26A—C27A | 115.2 (8) |
C14—C15—C16 | 118.1 (10) | C26A—C27A—C28A | 121.4 (10) |
C15—C16—C17 | 123.1 (10) | C26A—C27A—C32A | 119.1 (9) |
C12—C17—C18 | 124.5 (9) | C28A—C27A—C32A | 119.6 (10) |
C12—C17—C16 | 118.2 (9) | C27A—C28A—C29A | 120.5 (12) |
C16—C17—C18 | 117.1 (9) | C28A—C29A—C30A | 119.2 (12) |
C17—C18—C19 | 118.1 (8) | C29A—C30A—C31A | 121.5 (14) |
N4—C18—C17 | 121.0 (8) | C30A—C31A—C32A | 119.0 (13) |
N4—C18—C19 | 120.9 (7) | C27A—C32A—C31A | 120.2 (12) |
C18—C19—C24 | 120.9 (8) | O2A—C33A—O3A | 125.8 (10) |
C20—C19—C24 | 119.3 (9) | O2A—C33A—C25A | 115.2 (8) |
C18—C19—C20 | 119.7 (8) | O3A—C33A—C25A | 119.1 (9) |
C19—C20—C21 | 120.0 (9) | C2A—C1A—H1A | 119.66 |
C20—C21—C22 | 120.6 (10) | C5A—C1A—H1A | 119.60 |
C21—C22—C23 | 119.5 (10) | C1A—C2A—H2A | 120.66 |
C22—C23—C24 | 120.4 (9) | C3A—C2A—H2A | 120.72 |
C19—C24—C23 | 120.2 (9) | N1A—C3A—H3A | 117.17 |
N4—C25—C33 | 104.8 (8) | C2A—C3A—H3A | 117.26 |
C26—C25—C33 | 109.4 (8) | N1A—C4A—H4A | 117.85 |
N4—C25—C26 | 115.4 (8) | C5A—C4A—H4A | 118.04 |
C25—C26—C27 | 115.2 (9) | N2A—C6A—H6A1 | 108.79 |
C28—C27—C32 | 118.1 (10) | N2A—C6A—H6A2 | 108.85 |
C26—C27—C28 | 121.0 (9) | C5A—C6A—H6A1 | 108.65 |
C26—C27—C32 | 120.9 (9) | C5A—C6A—H6A2 | 108.67 |
C27—C28—C29 | 120.8 (10) | H6A1—C6A—H6A2 | 107.79 |
C28—C29—C30 | 119.5 (10) | N2A—C7A—H7A1 | 110.18 |
C29—C30—C31 | 120.6 (10) | N2A—C7A—H7A2 | 110.22 |
C30—C31—C32 | 119.2 (10) | C8A—C7A—H7A1 | 110.31 |
C27—C32—C31 | 121.7 (10) | C8A—C7A—H7A2 | 110.39 |
O2—C33—C25 | 116.4 (8) | H7A1—C7A—H7A2 | 108.49 |
O3—C33—C25 | 118.4 (10) | C7A—C8A—H8A1 | 111.15 |
O2—C33—O3 | 125.0 (11) | C7A—C8A—H8A2 | 111.12 |
C5—C1—H1 | 119.34 | C9A—C8A—H8A1 | 111.12 |
C2—C1—H1 | 119.37 | C9A—C8A—H8A2 | 111.00 |
C3—C2—H2 | 120.21 | H8A1—C8A—H8A2 | 109.20 |
C1—C2—H2 | 120.22 | C8A—C9A—H9A1 | 111.06 |
C2—C3—H3 | 119.86 | C8A—C9A—H9A2 | 111.02 |
N1—C3—H3 | 119.76 | C10A—C9A—H9A1 | 111.11 |
N1—C4—H4 | 120.09 | C10A—C9A—H9A2 | 111.15 |
C5—C4—H4 | 120.23 | H9A1—C9A—H9A2 | 108.92 |
N2—C6—H6A | 108.73 | N2A—C10A—H10A | 109.82 |
N2—C6—H6B | 108.80 | C9A—C10A—H10A | 109.82 |
C5—C6—H6A | 108.79 | C11A—C10A—H10A | 109.92 |
C5—C6—H6B | 108.79 | C12A—C13A—H13A | 119.07 |
H6A—C6—H6B | 107.65 | C14A—C13A—H13A | 118.98 |
C8—C7—H7A | 110.78 | C13A—C14A—H14A | 119.76 |
H7A—C7—H7B | 108.80 | C15A—C14A—H14A | 119.76 |
N2—C7—H7B | 110.70 | C14A—C15A—H15A | 120.53 |
C8—C7—H7B | 110.66 | C16A—C15A—H15A | 120.52 |
N2—C7—H7A | 110.69 | C15A—C16A—H16A | 118.95 |
C7—C8—H8A | 111.46 | C17A—C16A—H16A | 118.86 |
H8A—C8—H8B | 109.32 | C19A—C20A—H20A | 120.03 |
C9—C8—H8B | 111.43 | C21A—C20A—H20A | 120.19 |
C7—C8—H8B | 111.35 | C20A—C21A—H21A | 119.23 |
C9—C8—H8A | 111.42 | C22A—C21A—H21A | 119.19 |
C10—C9—H9A | 111.46 | C21A—C22A—H22A | 121.13 |
C10—C9—H9B | 111.58 | C23A—C22A—H22A | 121.10 |
H9A—C9—H9B | 109.26 | C22A—C23A—H23A | 118.95 |
C8—C9—H9B | 111.36 | C24A—C23A—H23A | 119.06 |
C8—C9—H9A | 111.42 | C19A—C24A—H24A | 120.31 |
N2—C10—H10 | 109.62 | C23A—C24A—H24A | 120.29 |
C11—C10—H10 | 109.58 | N4A—C25A—H25A | 109.38 |
C9—C10—H10 | 109.67 | C26A—C25A—H25A | 109.40 |
C12—C13—H13 | 119.63 | C33A—C25A—H25A | 109.51 |
C14—C13—H13 | 119.70 | C25A—C26A—H26C | 108.52 |
C15—C14—H14 | 119.20 | C25A—C26A—H26D | 108.38 |
C13—C14—H14 | 119.23 | C27A—C26A—H26C | 108.54 |
C14—C15—H15 | 120.92 | C27A—C26A—H26D | 108.46 |
C16—C15—H15 | 120.96 | H26C—C26A—H26D | 107.54 |
C17—C16—H16 | 118.49 | C27A—C28A—H28A | 119.79 |
C15—C16—H16 | 118.40 | C29A—C28A—H28A | 119.74 |
C21—C20—H20 | 120.00 | C28A—C29A—H29A | 120.51 |
C19—C20—H20 | 120.04 | C30A—C29A—H29A | 120.25 |
C22—C21—H21 | 119.66 | C29A—C30A—H30A | 119.33 |
C20—C21—H21 | 119.74 | C31A—C30A—H30A | 119.13 |
C21—C22—H22 | 120.18 | C30A—C31A—H31A | 120.49 |
C23—C22—H22 | 120.29 | C32A—C31A—H31A | 120.55 |
C22—C23—H23 | 119.82 | C27A—C32A—H32A | 119.83 |
C24—C23—H23 | 119.79 | C31A—C32A—H32A | 119.97 |
[Ni(C29H29N3O3)] | F(000) = 1104 |
Mr = 526.26 | Dx = 1.377 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 35 reflections |
a = 9.692 (3) Å | θ = 12.5–14.5° |
b = 10.047 (2) Å | µ = 0.80 mm−1 |
c = 26.060 (6) Å | T = 220 K |
V = 2537.6 (11) Å3 | Block, dark red |
Z = 4 | 0.78 × 0.47 × 0.39 mm |
Stoe Stadi-4 four-circle diffractometer | 2358 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.011 |
Graphite monochromator | θmax = 25.0°, θmin = 2.6° |
ω/θ learnt profile scans | h = 0→11 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1995) | k = 0→11 |
Tmin = 0.568, Tmax = 0.765 | l = 0→31 |
2570 measured reflections | 3 standard reflections every 60 min |
2560 independent reflections | intensity decay: variation +−3.6% |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.074P)2 + 2.47P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.050 | (Δ/σ)max = 0.002 |
wR(F2) = 0.135 | Δρmax = 0.93 e Å−3 |
S = 1.08 | Δρmin = −0.56 e Å−3 |
2560 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
326 parameters | Extinction coefficient: 0.012 (2) |
109 restraints | Absolute structure: (Flack, 1983) with x Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (3) |
Hydrogen site location: inferred from neighbouring sites |
[Ni(C29H29N3O3)] | V = 2537.6 (11) Å3 |
Mr = 526.26 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.692 (3) Å | µ = 0.80 mm−1 |
b = 10.047 (2) Å | T = 220 K |
c = 26.060 (6) Å | 0.78 × 0.47 × 0.39 mm |
Stoe Stadi-4 four-circle diffractometer | 2358 reflections with I > 2σ(I) |
Absorption correction: numerical (X-RED; Stoe & Cie, 1995) | Rint = 0.011 |
Tmin = 0.568, Tmax = 0.765 | 3 standard reflections every 60 min |
2570 measured reflections | intensity decay: variation +−3.6% |
2560 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.135 | Δρmax = 0.93 e Å−3 |
S = 1.08 | Δρmin = −0.56 e Å−3 |
2560 reflections | Absolute structure: (Flack, 1983) with x Friedel pairs |
326 parameters | Absolute structure parameter: −0.03 (3) |
109 restraints |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.44496 (7) | 0.17379 (7) | 0.88010 (2) | 0.0465 (3) | |
O1 | 0.7891 (5) | −0.0177 (6) | 0.8913 (2) | 0.0803 (15) | |
O2 | 0.2827 (5) | 0.2460 (5) | 0.90524 (15) | 0.0624 (12) | |
N2 | 0.5474 (7) | 0.2202 (5) | 0.94171 (19) | 0.0682 (14) | |
O3 | 0.0574 (5) | 0.2615 (6) | 0.88950 (17) | 0.0869 (17) | |
N3 | 0.6087 (5) | 0.1066 (5) | 0.85640 (18) | 0.0497 (11) | |
N4 | 0.3456 (5) | 0.1311 (5) | 0.82188 (17) | 0.0477 (11) | |
C1 | 0.6231 (12) | 0.3483 (8) | 0.9328 (4) | 0.122 (4) | |
H1A | 0.6746 | 0.3704 | 0.9640 | 0.146* | |
H1B | 0.6905 | 0.3342 | 0.9053 | 0.146* | |
C2 | 0.5372 (12) | 0.4626 (9) | 0.9191 (4) | 0.115 (3) | |
H2A | 0.5955 | 0.5394 | 0.9129 | 0.173* | |
H2B | 0.4742 | 0.4820 | 0.9471 | 0.173* | |
H2C | 0.4849 | 0.4422 | 0.8884 | 0.173* | |
C7 | 0.4801 (10) | 0.2292 (11) | 0.9879 (3) | 0.095 (2) | |
H7A | 0.3924 | 0.2772 | 0.9850 | 0.114* | |
H7B | 0.5376 | 0.2707 | 1.0144 | 0.114* | |
C8 | 0.4599 (10) | 0.0876 (10) | 0.9971 (3) | 0.094 (2) | |
H8A | 0.3918 | 0.0508 | 0.9732 | 0.113* | |
H8B | 0.4282 | 0.0718 | 1.0323 | 0.113* | |
C9 | 0.6071 (14) | 0.0222 (10) | 0.9880 (3) | 0.123 (4) | |
H9A | 0.6003 | −0.0686 | 0.9745 | 0.148* | |
H9B | 0.6638 | 0.0226 | 1.0192 | 0.148* | |
C10 | 0.6624 (7) | 0.1251 (7) | 0.9459 (2) | 0.0604 (15) | |
H10 | 0.7451 | 0.1715 | 0.9593 | 0.072* | |
C11 | 0.6953 (6) | 0.0629 (7) | 0.8943 (2) | 0.0570 (14) | |
C12 | 0.6417 (6) | 0.0877 (6) | 0.8046 (2) | 0.0517 (13) | |
C13 | 0.7807 (8) | 0.0781 (9) | 0.7900 (3) | 0.076 (2) | |
H13 | 0.8504 | 0.0844 | 0.8150 | 0.091* | |
C14 | 0.8164 (8) | 0.0594 (10) | 0.7386 (3) | 0.086 (2) | |
H14 | 0.9098 | 0.0517 | 0.7294 | 0.103* | |
C15 | 0.7169 (9) | 0.0523 (10) | 0.7014 (3) | 0.085 (2) | |
H15 | 0.7412 | 0.0377 | 0.6669 | 0.102* | |
C16 | 0.5816 (8) | 0.0668 (8) | 0.7151 (3) | 0.0692 (19) | |
H16 | 0.5133 | 0.0631 | 0.6896 | 0.083* | |
C17 | 0.5415 (6) | 0.0870 (6) | 0.7664 (2) | 0.0508 (13) | |
C18 | 0.3919 (6) | 0.1005 (6) | 0.7763 (2) | 0.0479 (13) | |
C19 | 0.2948 (6) | 0.0864 (7) | 0.7319 (2) | 0.0489 (13) | |
C20 | 0.2497 (7) | −0.0409 (7) | 0.7172 (2) | 0.0607 (16) | |
H20 | 0.2812 | −0.1168 | 0.7347 | 0.073* | |
C21 | 0.1588 (8) | −0.0536 (9) | 0.6766 (3) | 0.0756 (19) | |
H21 | 0.1281 | −0.1382 | 0.6663 | 0.091* | |
C22 | 0.1131 (7) | 0.0590 (10) | 0.6513 (2) | 0.079 (2) | |
H22 | 0.0487 | 0.0505 | 0.6245 | 0.095* | |
C23 | 0.1599 (8) | 0.1819 (10) | 0.6646 (2) | 0.0779 (19) | |
H23 | 0.1307 | 0.2571 | 0.6461 | 0.093* | |
C24 | 0.2518 (7) | 0.1967 (7) | 0.7059 (2) | 0.0621 (16) | |
H24 | 0.2833 | 0.2816 | 0.7155 | 0.074* | |
C25 | 0.1949 (6) | 0.1368 (7) | 0.8314 (2) | 0.0564 (15) | |
H25 | 0.1483 | 0.1784 | 0.8017 | 0.068* | |
C26 | 0.1343 (6) | −0.0042 (8) | 0.8406 (3) | 0.0682 (17) | |
H26A | 0.0353 | 0.0050 | 0.8474 | 0.082* | |
H26B | 0.1442 | −0.0554 | 0.8088 | 0.082* | |
C27 | 0.1972 (7) | −0.0832 (7) | 0.8835 (3) | 0.0613 (14) | |
C28 | 0.3234 (8) | −0.1473 (7) | 0.8772 (3) | 0.0789 (19) | |
H28 | 0.3716 | −0.1391 | 0.8460 | 0.095* | |
C29 | 0.3779 (11) | −0.2226 (9) | 0.9163 (4) | 0.100 (3) | |
H29 | 0.4635 | −0.2650 | 0.9119 | 0.120* | |
C30 | 0.3094 (10) | −0.2361 (8) | 0.9612 (4) | 0.094 (2) | |
H30 | 0.3468 | −0.2894 | 0.9874 | 0.113* | |
C31 | 0.1866 (10) | −0.1731 (9) | 0.9689 (3) | 0.087 (2) | |
H31 | 0.1409 | −0.1814 | 1.0005 | 0.105* | |
C32 | 0.1293 (8) | −0.0971 (8) | 0.9303 (3) | 0.0712 (18) | |
H32 | 0.0441 | −0.0545 | 0.9356 | 0.085* | |
C33 | 0.1734 (7) | 0.2229 (7) | 0.8788 (2) | 0.0620 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0469 (4) | 0.0511 (4) | 0.0415 (4) | 0.0131 (3) | −0.0033 (3) | −0.0021 (3) |
O1 | 0.059 (3) | 0.099 (4) | 0.083 (3) | 0.032 (3) | −0.006 (2) | 0.003 (3) |
O2 | 0.063 (2) | 0.080 (3) | 0.044 (2) | 0.033 (2) | −0.0041 (19) | −0.009 (2) |
N2 | 0.081 (4) | 0.073 (3) | 0.051 (3) | 0.027 (3) | −0.024 (3) | −0.013 (2) |
O3 | 0.065 (3) | 0.137 (5) | 0.059 (3) | 0.054 (3) | 0.001 (2) | −0.004 (3) |
N3 | 0.039 (2) | 0.058 (3) | 0.052 (2) | 0.003 (2) | −0.0038 (19) | −0.004 (2) |
N4 | 0.047 (2) | 0.055 (3) | 0.042 (2) | 0.013 (2) | 0.0015 (19) | −0.004 (2) |
C1 | 0.155 (10) | 0.085 (5) | 0.125 (7) | −0.015 (5) | −0.049 (6) | −0.023 (5) |
C2 | 0.155 (10) | 0.098 (5) | 0.094 (6) | −0.024 (7) | −0.005 (7) | 0.009 (5) |
C7 | 0.100 (6) | 0.114 (5) | 0.071 (4) | 0.033 (5) | −0.014 (4) | −0.024 (4) |
C8 | 0.091 (5) | 0.115 (6) | 0.076 (5) | −0.039 (6) | 0.013 (5) | −0.016 (5) |
C9 | 0.214 (11) | 0.099 (6) | 0.056 (4) | 0.072 (7) | −0.003 (5) | 0.017 (4) |
C10 | 0.047 (3) | 0.074 (4) | 0.060 (3) | 0.006 (3) | −0.012 (3) | −0.001 (3) |
C11 | 0.042 (3) | 0.065 (4) | 0.064 (3) | 0.006 (3) | −0.003 (3) | 0.003 (3) |
C12 | 0.044 (3) | 0.052 (3) | 0.059 (3) | 0.001 (3) | 0.008 (2) | −0.001 (3) |
C13 | 0.052 (4) | 0.101 (6) | 0.075 (4) | 0.010 (4) | 0.007 (3) | 0.005 (4) |
C14 | 0.058 (4) | 0.114 (7) | 0.085 (5) | 0.014 (5) | 0.024 (3) | 0.014 (5) |
C15 | 0.078 (5) | 0.105 (6) | 0.071 (4) | 0.005 (5) | 0.029 (4) | −0.002 (4) |
C16 | 0.068 (4) | 0.085 (5) | 0.054 (3) | 0.009 (4) | 0.011 (3) | −0.008 (4) |
C17 | 0.054 (3) | 0.048 (3) | 0.050 (3) | −0.007 (3) | 0.005 (2) | −0.005 (2) |
C18 | 0.053 (3) | 0.048 (3) | 0.043 (3) | 0.003 (3) | 0.000 (2) | −0.001 (2) |
C19 | 0.050 (3) | 0.058 (3) | 0.039 (3) | 0.002 (3) | 0.004 (2) | −0.005 (2) |
C20 | 0.059 (4) | 0.068 (4) | 0.055 (3) | 0.003 (3) | 0.002 (3) | −0.014 (3) |
C21 | 0.055 (4) | 0.109 (5) | 0.063 (4) | −0.011 (4) | 0.005 (3) | −0.034 (4) |
C22 | 0.054 (4) | 0.140 (6) | 0.045 (3) | 0.001 (4) | −0.002 (3) | −0.022 (4) |
C23 | 0.071 (4) | 0.114 (5) | 0.049 (3) | 0.020 (5) | −0.004 (3) | 0.003 (4) |
C24 | 0.064 (4) | 0.076 (4) | 0.046 (3) | 0.004 (3) | 0.000 (3) | 0.004 (3) |
C25 | 0.044 (3) | 0.082 (4) | 0.043 (3) | 0.018 (3) | −0.004 (2) | 0.005 (3) |
C26 | 0.044 (3) | 0.102 (5) | 0.059 (3) | 0.002 (3) | 0.005 (3) | −0.007 (3) |
C27 | 0.055 (3) | 0.062 (3) | 0.066 (3) | −0.007 (3) | 0.007 (3) | −0.004 (3) |
C28 | 0.077 (4) | 0.070 (4) | 0.090 (5) | 0.015 (4) | 0.016 (4) | 0.005 (4) |
C29 | 0.101 (6) | 0.074 (5) | 0.125 (7) | 0.026 (5) | 0.012 (5) | 0.024 (5) |
C30 | 0.099 (6) | 0.069 (5) | 0.114 (6) | −0.009 (4) | −0.015 (5) | 0.033 (5) |
C31 | 0.095 (5) | 0.078 (5) | 0.089 (5) | −0.019 (5) | 0.011 (4) | 0.021 (4) |
C32 | 0.065 (4) | 0.071 (4) | 0.077 (4) | −0.008 (4) | 0.009 (3) | 0.006 (3) |
C33 | 0.061 (3) | 0.080 (4) | 0.045 (3) | 0.030 (3) | 0.000 (3) | 0.010 (3) |
Ni—N2 | 1.944 (5) | C14—H14 | 0.9400 |
Ni—N3 | 1.832 (5) | C15—C16 | 1.368 (10) |
Ni—N4 | 1.847 (5) | C15—H15 | 0.9400 |
Ni—O2 | 1.851 (4) | C16—C17 | 1.405 (9) |
O1—C11 | 1.220 (7) | C16—H16 | 0.9400 |
O2—C33 | 1.284 (8) | C17—C18 | 1.479 (9) |
N2—C7 | 1.373 (10) | C18—C19 | 1.500 (8) |
N2—C10 | 1.472 (8) | C19—C24 | 1.364 (9) |
N2—C1 | 1.499 (8) | C19—C20 | 1.404 (9) |
O3—C33 | 1.221 (7) | C20—C21 | 1.382 (10) |
N3—C11 | 1.368 (7) | C20—H20 | 0.9400 |
N3—C12 | 1.400 (8) | C21—C22 | 1.382 (12) |
N4—C18 | 1.305 (7) | C21—H21 | 0.9400 |
N4—C25 | 1.483 (7) | C22—C23 | 1.360 (12) |
C1—C2 | 1.463 (8) | C22—H22 | 0.9400 |
C1—H1A | 0.9800 | C23—C24 | 1.406 (9) |
C1—H1B | 0.9800 | C23—H23 | 0.9400 |
C2—H2A | 0.9700 | C24—H24 | 0.9400 |
C2—H2B | 0.9700 | C25—C33 | 1.522 (9) |
C2—H2C | 0.9700 | C25—C26 | 1.551 (10) |
C7—C8 | 1.456 (14) | C25—H25 | 0.9900 |
C7—H7A | 0.9800 | C26—C27 | 1.502 (10) |
C7—H7B | 0.9800 | C26—H26A | 0.9800 |
C8—C9 | 1.589 (14) | C26—H26B | 0.9800 |
C8—H8A | 0.9800 | C27—C28 | 1.392 (10) |
C8—H8B | 0.9800 | C27—C32 | 1.393 (9) |
C9—C10 | 1.600 (11) | C28—C29 | 1.376 (11) |
C9—H9A | 0.9800 | C28—H28 | 0.9400 |
C9—H9B | 0.9800 | C29—C30 | 1.352 (13) |
C10—C11 | 1.518 (9) | C29—H29 | 0.9400 |
C10—H10 | 0.9900 | C30—C31 | 1.363 (12) |
C12—C17 | 1.392 (8) | C30—H30 | 0.9400 |
C12—C13 | 1.404 (9) | C31—C32 | 1.380 (11) |
C13—C14 | 1.396 (11) | C31—H31 | 0.9400 |
C13—H13 | 0.9400 | C32—H32 | 0.9400 |
C14—C15 | 1.369 (11) | ||
N2—Ni—N3 | 85.7 (2) | C15—C14—H14 | 119.6 |
N2—Ni—N4 | 179.2 (2) | C13—C14—H14 | 119.6 |
N2—Ni—O2 | 92.7 (2) | C16—C15—C14 | 118.9 (7) |
N3—Ni—N4 | 95.1 (2) | C16—C15—H15 | 120.5 |
N3—Ni—O2 | 178.1 (2) | C14—C15—H15 | 120.5 |
N4—Ni—O2 | 86.5 (2) | C15—C16—C17 | 122.0 (7) |
C33—O2—Ni | 116.1 (4) | C15—C16—H16 | 119.0 |
C7—N2—C10 | 109.7 (6) | C17—C16—H16 | 119.0 |
C7—N2—C1 | 108.1 (7) | C12—C17—C16 | 119.2 (6) |
C10—N2—C1 | 101.4 (6) | C12—C17—C18 | 123.9 (5) |
C7—N2—Ni | 119.9 (6) | C16—C17—C18 | 116.8 (6) |
C10—N2—Ni | 107.0 (4) | N4—C18—C17 | 121.2 (5) |
C1—N2—Ni | 109.2 (5) | N4—C18—C19 | 120.6 (5) |
C11—N3—C12 | 120.8 (5) | C17—C18—C19 | 118.1 (5) |
C11—N3—Ni | 114.0 (4) | C24—C19—C20 | 120.6 (6) |
C12—N3—Ni | 125.0 (4) | C24—C19—C18 | 119.9 (6) |
C18—N4—C25 | 120.0 (5) | C20—C19—C18 | 119.5 (6) |
C18—N4—Ni | 128.5 (4) | C21—C20—C19 | 119.4 (7) |
C25—N4—Ni | 111.5 (3) | C21—C20—H20 | 120.3 |
C2—C1—N2 | 115.7 (8) | C19—C20—H20 | 120.3 |
C2—C1—H1A | 108.4 | C20—C21—C22 | 119.6 (7) |
N2—C1—H1A | 108.4 | C20—C21—H21 | 120.2 |
C2—C1—H1B | 108.4 | C22—C21—H21 | 120.2 |
N2—C1—H1B | 108.4 | C23—C22—C21 | 121.0 (6) |
H1A—C1—H1B | 107.4 | C23—C22—H22 | 119.5 |
C1—C2—H2A | 109.5 | C21—C22—H22 | 119.5 |
C1—C2—H2B | 109.5 | C22—C23—C24 | 120.2 (8) |
H2A—C2—H2B | 109.5 | C22—C23—H23 | 119.9 |
C1—C2—H2C | 109.5 | C24—C23—H23 | 119.9 |
H2A—C2—H2C | 109.5 | C19—C24—C23 | 119.2 (7) |
H2B—C2—H2C | 109.5 | C19—C24—H24 | 120.4 |
N2—C7—C8 | 98.3 (7) | C23—C24—H24 | 120.4 |
N2—C7—H7A | 112.1 | N4—C25—C33 | 107.0 (5) |
C8—C7—H7A | 112.1 | N4—C25—C26 | 111.3 (5) |
N2—C7—H7B | 112.1 | C33—C25—C26 | 110.0 (5) |
C8—C7—H7B | 112.1 | N4—C25—H25 | 109.5 |
H7A—C7—H7B | 109.7 | C33—C25—H25 | 109.5 |
C7—C8—C9 | 105.0 (8) | C26—C25—H25 | 109.5 |
C7—C8—H8A | 110.8 | C27—C26—C25 | 116.3 (5) |
C9—C8—H8A | 110.8 | C27—C26—H26A | 108.2 |
C7—C8—H8B | 110.7 | C25—C26—H26A | 108.2 |
C9—C8—H8B | 110.7 | C27—C26—H26B | 108.2 |
H8A—C8—H8B | 108.8 | C25—C26—H26B | 108.2 |
C8—C9—C10 | 97.8 (6) | H26A—C26—H26B | 107.4 |
C8—C9—H9A | 112.2 | C28—C27—C32 | 118.2 (7) |
C10—C9—H9A | 112.2 | C28—C27—C26 | 120.9 (6) |
C8—C9—H9B | 112.2 | C32—C27—C26 | 120.9 (6) |
C10—C9—H9B | 112.2 | C29—C28—C27 | 120.2 (8) |
H9A—C9—H9B | 109.8 | C29—C28—H28 | 119.9 |
N2—C10—C11 | 111.1 (5) | C27—C28—H28 | 119.9 |
N2—C10—C9 | 102.6 (6) | C30—C29—C28 | 120.6 (9) |
C11—C10—C9 | 114.3 (6) | C30—C29—H29 | 119.7 |
N2—C10—H10 | 109.5 | C28—C29—H29 | 119.7 |
C11—C10—H10 | 109.5 | C29—C30—C31 | 120.6 (8) |
C9—C10—H10 | 109.5 | C29—C30—H30 | 119.7 |
O1—C11—N3 | 128.6 (6) | C31—C30—H30 | 119.7 |
O1—C11—C10 | 119.2 (6) | C30—C31—C32 | 120.2 (8) |
N3—C11—C10 | 112.2 (5) | C30—C31—H31 | 119.9 |
C17—C12—N3 | 122.1 (5) | C32—C31—H31 | 119.9 |
C17—C12—C13 | 118.3 (6) | C31—C32—C27 | 120.2 (8) |
N3—C12—C13 | 119.4 (6) | C31—C32—H32 | 119.9 |
C14—C13—C12 | 120.5 (7) | C27—C32—H32 | 119.9 |
C14—C13—H13 | 119.8 | O3—C33—O2 | 125.4 (6) |
C12—C13—H13 | 119.8 | O3—C33—C25 | 119.4 (6) |
C15—C14—C13 | 120.8 (7) | O2—C33—C25 | 115.1 (5) |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | [Ni(C33H30N4O3)] | [Ni(C33H30N4O3)]·0.5H2O | [Ni(C29H29N3O3)] |
Mr | 589.32 | 598.33 | 526.26 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 150 | 150 | 220 |
a, b, c (Å) | 11.722 (2), 18.391 (14), 25.528 (6) | 11.522 (4), 18.623 (6), 25.828 (7) | 9.692 (3), 10.047 (2), 26.060 (6) |
V (Å3) | 5503 (4) | 5542 (3) | 2537.6 (11) |
Z | 8 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.75 | 0.75 | 0.80 |
Crystal size (mm) | 0.42 × 0.33 × 0.29 | 0.35 × 0.27 × 0.16 | 0.78 × 0.47 × 0.39 |
Data collection | |||
Diffractometer | Stoe Stadi-4 four-circle diffractometer | Stoe Stadi-4 four-circle diffractometer | Stoe Stadi-4 four-circle diffractometer |
Absorption correction | ψ scan (X-RED; Stoe & Cie, 1995) | ψ scan (X-RED; Stoe & Cie, 1995) | Numerical (X-RED; Stoe & Cie, 1995) |
Tmin, Tmax | 0.730, 0.825 | 0.789, 0.864 | 0.568, 0.765 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6352, 5359, 4490 | 5291, 4765, 3785 | 2570, 2560, 2358 |
Rint | 0.136 | 0.044 | 0.011 |
θmax (°) | 25.1 | 23.5 | 25.0 |
(sin θ/λ)max (Å−1) | 0.596 | 0.561 | 0.595 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.115, 1.18 | 0.066, 0.126, 1.29 | 0.050, 0.135, 1.08 |
No. of reflections | 5355 | 4765 | 2560 |
No. of parameters | 740 | 748 | 326 |
No. of restraints | 109 | 369 | 109 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0088P)2 + 15.94P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + 16.36P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.074P)2 + 2.47P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.48, −0.46 | 0.48, −0.42 | 0.93, −0.56 |
Absolute structure | Flack (1983) with x Friedel pairs | Flack (1983) with 194 Friedel pairs | (Flack, 1983) with x Friedel pairs |
Absolute structure parameter | −0.03 (2) | 0.01 (3) | −0.03 (3) |
Computer programs: STADI4 (Stoe & Cie, 1995), STADI4, X-RED (Stoe & Cie, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Bruker, 1997), SHELXL97 and PLATON (Spek, 2002).
Ni—N2 | 1.932 (6) | NiA—N2A | 1.932 (6) |
Ni—N3 | 1.862 (5) | NiA—N3A | 1.846 (6) |
Ni—N4 | 1.833 (6) | NiA—N4A | 1.855 (6) |
Ni—O2 | 1.872 (5) | NiA—O2A | 1.863 (5) |
Ni—N1 | 2.861 (7) | NiA—N1A | 2.954 (8) |
N2—Ni—N3 | 88.2 (3) | N2A—NiA—N3A | 88.8 (2) |
N2—Ni—N4 | 175.1 (3) | N2A—NiA—N4A | 168.2 (2) |
N2—Ni—O2 | 89.5 (2) | N2A—NiA—O2A | 90.2 (2) |
N3—Ni—N4 | 95.4 (2) | N3A—NiA—N4A | 95.3 (3) |
N3—Ni—O2 | 175.0 (3) | N3A—NiA—O2A | 173.0 (3) |
N4—Ni—O2 | 87.0 (2) | N4A—NiA—O2A | 87.1 (2) |
Ni—N2 | 1.914 (9) | NiA—N2A | 1.934 (9) |
Ni—N3 | 1.853 (6) | NiA—N3A | 1.851 (8) |
Ni—N4 | 1.828 (8) | NiA—N4A | 1.856 (8) |
Ni—O2 | 1.865 (6) | NiA—O2A | 1.874 (6) |
Ni—N1 | 5.339 (15) | NiA—N1A | 5.024 (12) |
N2—Ni—N3 | 87.6 (3) | N2A—NiA—N3A | 88.3 (4) |
N2—Ni—N4 | 171.0 (3) | N2A—NiA—N4A | 175.6 (3) |
N2—Ni—O2 | 89.9 (3) | N2A—NiA—O2A | 89.8 (3) |
N3—Ni—N4 | 96.7 (3) | N3A—NiA—N4A | 95.6 (4) |
N3—Ni—O2 | 170.7 (3) | N3A—NiA—O2A | 173.3 (4) |
N4—Ni—O2 | 87.1 (3) | N4A—NiA—O2A | 86.5 (3) |
Ni—N2 | 1.944 (5) | Ni—N4 | 1.847 (5) |
Ni—N3 | 1.832 (5) | Ni—O2 | 1.851 (4) |
N2—Ni—N3 | 85.7 (2) | N3—Ni—N4 | 95.1 (2) |
N2—Ni—N4 | 179.2 (2) | N3—Ni—O2 | 178.1 (2) |
N2—Ni—O2 | 92.7 (2) | N4—Ni—O2 | 86.5 (2) |
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The asymmetric synthesis of α-amino acids has been an area of intense interest over the past few decades. A number of elegant approaches have established themselves for use in research or industrial scale syntheses. However, many industrial processes still involve classical resolutions in which large amounts of chemical waste in the form of amino acids of the wrong stereochemistry are produced. Belokon et al. (1983) reported the first example of a process they termed retroracemization, in which a racemic α-amino acid mixture could be enriched in one of its enantiomeric forms by selective protonation of a prochiral amino acid enolate generated in an asymmetric environment formed from the amino acid, CuII or NiII, and either (S)-2-[N-benzylprolyl)amino]benzaldehyde, acetophenone or benzophenone. The combination of NiII and (S)-2-[N-benzylprolyl)amino]benzophenone [(S)-BPB] proved the most successful in the retroracemizations, and in the stereoselective alkylation of complexes containing the glycine enolate. More recently, a number of modified forms of the original Belokon ligands have been investigated. These include a variety of ligands in which the N-benzyl group has been replaced by the bulkier naphthalen-1-ylmethyl group, the smaller ethyl derivative, and 2-picolyl or 3-picolyl groups, which may offer a further coordination site for binding to the metal in the complex (De & Thomas, 1997). N-(2-benzoylphenyl)pyridine-2-carbamide (PBP) was studied by Belokon et al. (2001), who have investigated glycine enolate alkylation reactions under phase-transfer catalysis (PTC) conditions, and Popkov et al. (2000), who have reported the use of (S)-2-[N-(2,4,6-trimethylbenzylprolyl)amino]benzophenone [(S)-TMBPB] to give improved diastereoselectivity and enantioselectivity in the synthesis of (S)-alanine when compared with (S)-BPB.
In our investigation, two approaches to improving the diastereoselectivity of the retroracemization process were investigated. Initially, we examined the possibility of increasing the steric bulk of the prolyl substituent by replacing the N-benzyl group of (S)-BPB with diphenylmethyl, trityl or naphthalen-1-ylmethyl groups. It proved to be impossible to form the Schiff base complexes with either (S)-2-[(N-1-diphenylmethylprolyl)amino]- or (S)-[(N-1-tritylprolyl)amino]benzophenone and either racemic phenylalanine or glycine. In the case of (S)-[(N-1-(naphthalen-1'-ylmethyl)prolyl)amino]benzophenone, a small increase in the enantiomeric excess of the product α-amino acid was observed after conducting the retroracemization procedure and decomposing the complex, when compared with the use of (S)-BPB. However, the yield of the amino acid product was generally 10–15% lower. As an alternative strategy, we investigated the introduction of prolyl substituents, which should be capable of providing a further coordination site for the metal in the Schiff base complex, such that one face of the prochiral α-amino acid enolate generated during the retroracemization process would be rendered totally inaccessible to protonation or alkylation. This was inspired by the fact that the square-planar CuII complex of pyruvyl Gly-D-Phe reacts with imidazole-4-carboxaldehyde to give a square-pyramidyl intermediate (Owa et al., 1988). It was anticipated that inclusion of a 2-picolyl or 3-picolyl substituent in the (S)-2-[N-alkylprolyl)amino]benzophenone would cause the Schiff base formed with NiII or CuII and an α-amino acid to adopt a square-pyramidal or octahedral geometry, the latter involving a solvent ligand. Thus the three title compounds, (I), (II) and (III), were prepared and their crystal structures are presented here. \sch
Both picolyl complexes, (I) and (II), crystallize with two independent molecules in the asymmetric unit. Each NiII atom adopts an approximately square-planar geometry (Figs. 1 and 2, Tables 1 and 2), with the distance from the Ni atom to the sp3-hybridized N2 atom being longer than the other three distances. However, there are significant differences in the detailed geometry of the independent molecules. In the first molecule of (I), the tetrahedral distortion is much less than in the second (r.m.s. deviation of the constituent atoms from the N3O donor-atom plane 0.064 Å in the second molecule versus 0.148 Å in the first), as is the displacement of the NiII centre from this plane [0.008 (3) versus 0.038 (3) Å, the latter in the direction of atom N1A].
In (II), the two molecules also have different degrees of tetrahedral distortion, indicated by r.m.s. deviations of 0.139 and 0.074 Å, as well as different displacements of 0.001 (5) and 0.044 (4) Å (away from N1A), of the metal centre from the N3O plane. Interestingly, there is no correlation between the degree of tetrahedral distortion and the displacement of the metal centre. In (I), the greater distortion is associated with the greater displacement, but this is not the case in (II). We believe that the origin of these differences in the coordination geometries lies in the different conformations of the ligands (see below).
The N atoms of both the 2-picolyl and 3-picolyl substituents are too remote from the metal centres to form Ni—N bonds. In both of these complexes with picolyl substituents, (I) and (II), there are two independent molecules with similar, but slightly different, conformations (Figs. 3 and 4). In the 2-picolyl complex, (I), the pyridyl N—Ni distances are 2.861 (7) and 2.954 (8) Å, while in the 3-picolyl complex, (II), these are even longer, at 5.339 (15) and 5.024 (12) Å. Despite these differences, and the presence in (II) of a poorly defined water molecule which is hydrogen bonded to the complex via atom N1 [N1···O1W 2.88 (2) Å], the space groups are the same, the unit-cell dimensions are similar and the unit-cell volumes differ by only 0.7%. We believe that the differences in the coordination geometry at the Ni atom in (I) and (II) can be traced to the different ligand conformations (Figs. 3 and 4), which induce differing types and degrees of distortion. In turn, the adoption of these ligand conformations allows efficient packing between adjacent symmetry-independent molecules. This packing involves a number of interactions between aromatic rings, including some face-to-edge interactions.
These two crystal structures show a significant similarity with those of (S)-BPB/NiII and a wide variety of α-amino acids that have been reported previously [(S)-BPB with NiII and (2S,3S)-2-(trifluoromethyl)threonine (Soloshonok et al., 1993); (S)-BPB with NiII and ω-ethyl-(2S,3S)-3-trifluoromethylglutamate (Soloshonok et al., 1997); (S)-BPB with NiII and (2S,3S,4R)-3-trifluoromethyl-4-methylpyroglutamic acid (Soloshonok et al., 1999); (S)-BPB with NiII and dehydroaminobutanoic acid (Belokon et al., 1990); (S)-2-N-(N'-benzylprolyl)aminoacetophenone with CuII and glycine (Belokon et al., 1983); (S)-2-N-(N'-benzylprolyl)aminoacetophenone with NiII and (R)-valine (Lindeman et al., 1985)].
Square-planar geometry around NiII is also observed in the third complex, (III), where the picolyl substituents have been replaced by a less sterically demanding ethyl group. Here, there is only one molecule per asymmetric unit, and the distance from the Ni atom to the sp3-hybridized N2 atom is again longer than the other three Ni—N/O distances, in this case by approximately 0.1 Å. There is no significant tetrahedral distortion (the r.m.s. deviation of the constituent atoms from the N3O donor-atom plane is only 0.016 Å) and the metal centre lies in this plane [calculated deviation 0.003 (4) Å].
NB Belokon is spelled Belokon' in our database. With which spelling were this author's other papers published?