Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805042224/kp6076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805042224/kp6076Isup2.hkl |
CCDC reference: 296722
The crystals of the title compound were obtained as a side product by dissolving zinc-tetraphenylporphyrin in N,N'-dimethylformamide in the presence of tris(acetoneperoxide) while attempting to formulate new porphyrin complexes.
H atoms were placeded in calculated positions and were constrained to ride on their parent atoms, with C—H distances in the range 0.95–0.98 Å and with Uiso(H) = 1.2 or 1.5 times Ueq(C).
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-III (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Zn(C44H28N4)(C3H7NO)] | F(000) = 1560 |
Mr = 751.17 | Dx = 1.371 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8468 reflections |
a = 13.7419 (3) Å | θ = 2.3–28.2° |
b = 9.2278 (2) Å | µ = 0.72 mm−1 |
c = 29.3016 (7) Å | T = 110 K |
β = 101.7186 (13)° | Prism, red |
V = 3638.22 (14) Å3 | 0.20 × 0.15 × 0.15 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 5627 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.059 |
Graphite monochromator | θmax = 28.2°, θmin = 2.3° |
Detector resolution: 56 microns pixels mm-1 | h = −18→18 |
ϕ and ω scans | k = −12→12 |
29748 measured reflections | l = −38→37 |
8697 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.058P)2 + 1.2438P] where P = (Fo2 + 2Fc2)/3 |
8697 reflections | (Δ/σ)max = 0.003 |
489 parameters | Δρmax = 0.85 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
[Zn(C44H28N4)(C3H7NO)] | V = 3638.22 (14) Å3 |
Mr = 751.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.7419 (3) Å | µ = 0.72 mm−1 |
b = 9.2278 (2) Å | T = 110 K |
c = 29.3016 (7) Å | 0.20 × 0.15 × 0.15 mm |
β = 101.7186 (13)° |
Nonius KappaCCD diffractometer | 5627 reflections with I > 2σ(I) |
29748 measured reflections | Rint = 0.059 |
8697 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.85 e Å−3 |
8697 reflections | Δρmin = −0.64 e Å−3 |
489 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Zn | 0.27658 (2) | 0.24348 (3) | 0.894088 (10) | 0.02084 (10) | |
C1 | 0.04751 (18) | 0.2034 (3) | 0.88257 (9) | 0.0231 (6) | |
C2 | −0.0296 (2) | 0.1944 (3) | 0.90945 (9) | 0.0300 (7) | |
H2 | −0.0977 | 0.1731 | 0.8977 | 0.036* | |
C3 | 0.0130 (2) | 0.2218 (3) | 0.95413 (9) | 0.0293 (7) | |
H3 | −0.0195 | 0.2233 | 0.9798 | 0.035* | |
C4 | 0.11684 (19) | 0.2483 (3) | 0.95587 (9) | 0.0232 (6) | |
C5 | 0.18809 (19) | 0.2700 (3) | 0.99681 (9) | 0.0238 (6) | |
C6 | 0.29151 (19) | 0.2725 (3) | 1.00014 (9) | 0.0230 (6) | |
C7 | 0.3634 (2) | 0.2901 (3) | 1.04308 (9) | 0.0285 (7) | |
H7 | 0.3495 | 0.3074 | 1.0731 | 0.034* | |
C8 | 0.4543 (2) | 0.2772 (3) | 1.03261 (9) | 0.0281 (7) | |
H8 | 0.5163 | 0.2837 | 1.0539 | 0.034* | |
C9 | 0.43969 (18) | 0.2517 (3) | 0.98299 (8) | 0.0221 (6) | |
C10 | 0.51630 (18) | 0.2214 (3) | 0.95946 (9) | 0.0222 (6) | |
C11 | 0.50308 (18) | 0.1851 (3) | 0.91205 (9) | 0.0227 (6) | |
C12 | 0.58215 (19) | 0.1554 (3) | 0.88778 (9) | 0.0271 (6) | |
H12 | 0.6512 | 0.1535 | 0.9011 | 0.033* | |
C13 | 0.54055 (18) | 0.1309 (3) | 0.84283 (9) | 0.0257 (6) | |
H13 | 0.5746 | 0.1089 | 0.8185 | 0.031* | |
C14 | 0.43358 (18) | 0.1444 (3) | 0.83833 (9) | 0.0218 (6) | |
C15 | 0.36284 (18) | 0.1337 (3) | 0.79652 (9) | 0.0219 (6) | |
C16 | 0.25902 (18) | 0.1433 (3) | 0.79266 (8) | 0.0216 (6) | |
C17 | 0.18718 (18) | 0.1212 (3) | 0.74991 (9) | 0.0239 (6) | |
H17 | 0.2012 | 0.1014 | 0.7201 | 0.029* | |
C18 | 0.09645 (18) | 0.1340 (3) | 0.76037 (8) | 0.0234 (6) | |
H18 | 0.0345 | 0.1256 | 0.7391 | 0.028* | |
C19 | 0.11052 (18) | 0.1624 (3) | 0.80944 (8) | 0.0221 (6) | |
C20 | 0.03357 (17) | 0.1770 (3) | 0.83449 (8) | 0.0215 (6) | |
N21 | 0.13662 (15) | 0.2360 (2) | 0.91168 (7) | 0.0224 (5) | |
N22 | 0.33965 (15) | 0.2524 (2) | 0.96387 (7) | 0.0214 (5) | |
N23 | 0.41256 (15) | 0.1766 (2) | 0.88132 (7) | 0.0218 (5) | |
N24 | 0.21054 (14) | 0.1700 (3) | 0.82855 (7) | 0.0221 (5) | |
C25 | 0.1518 (2) | 0.2820 (3) | 1.04185 (9) | 0.0274 (7) | |
C26 | 0.1004 (2) | 0.4026 (4) | 1.05195 (10) | 0.0342 (7) | |
H26 | 0.0869 | 0.4795 | 1.0300 | 0.041* | |
C27 | 0.0680 (2) | 0.4127 (4) | 1.09381 (11) | 0.0427 (8) | |
H27 | 0.0321 | 0.4955 | 1.1003 | 0.051* | |
C28 | 0.0883 (2) | 0.3026 (4) | 1.12576 (11) | 0.0463 (9) | |
H28 | 0.0672 | 0.3103 | 1.1546 | 0.056* | |
C29 | 0.1386 (2) | 0.1820 (4) | 1.11649 (11) | 0.0475 (9) | |
H29 | 0.1520 | 0.1059 | 1.1387 | 0.057* | |
C30 | 0.1705 (2) | 0.1706 (4) | 1.07419 (10) | 0.0411 (8) | |
H30 | 0.2050 | 0.0864 | 1.0676 | 0.049* | |
C31 | 0.62109 (19) | 0.2259 (3) | 0.98724 (9) | 0.0237 (6) | |
C32 | 0.6652 (2) | 0.3566 (3) | 1.00331 (10) | 0.0318 (7) | |
H32 | 0.6284 | 0.4441 | 0.9975 | 0.038* | |
C33 | 0.76340 (19) | 0.3599 (3) | 1.02803 (10) | 0.0315 (7) | |
H33 | 0.7934 | 0.4499 | 1.0385 | 0.038* | |
C34 | 0.8170 (2) | 0.2336 (3) | 1.03736 (9) | 0.0288 (7) | |
H34 | 0.8841 | 0.2363 | 1.0537 | 0.035* | |
C35 | 0.7725 (2) | 0.1032 (4) | 1.02281 (10) | 0.0375 (7) | |
H35 | 0.8084 | 0.0154 | 1.0301 | 0.045* | |
C36 | 0.6752 (2) | 0.0996 (3) | 0.99752 (10) | 0.0344 (7) | |
H36 | 0.6455 | 0.0092 | 0.9872 | 0.041* | |
C37 | 0.39887 (17) | 0.1146 (3) | 0.75206 (9) | 0.0227 (6) | |
C38 | 0.45292 (17) | −0.0066 (3) | 0.74393 (9) | 0.0255 (6) | |
H38 | 0.4690 | −0.0788 | 0.7674 | 0.031* | |
C39 | 0.48369 (18) | −0.0235 (3) | 0.70193 (10) | 0.0306 (7) | |
H39 | 0.5218 | −0.1059 | 0.6972 | 0.037* | |
C40 | 0.45926 (19) | 0.0787 (4) | 0.66696 (10) | 0.0330 (7) | |
H40 | 0.4785 | 0.0650 | 0.6379 | 0.040* | |
C41 | 0.4069 (2) | 0.2004 (4) | 0.67459 (10) | 0.0317 (7) | |
H41 | 0.3915 | 0.2721 | 0.6510 | 0.038* | |
C42 | 0.37632 (19) | 0.2189 (3) | 0.71677 (9) | 0.0262 (6) | |
H42 | 0.3399 | 0.3030 | 0.7216 | 0.031* | |
C43 | −0.07116 (17) | 0.1582 (3) | 0.80790 (8) | 0.0217 (6) | |
C44 | −0.10151 (18) | 0.0328 (3) | 0.78242 (9) | 0.0250 (6) | |
H44 | −0.0553 | −0.0435 | 0.7820 | 0.030* | |
C45 | −0.19850 (19) | 0.0183 (3) | 0.75757 (9) | 0.0288 (6) | |
H45 | −0.2179 | −0.0669 | 0.7399 | 0.035* | |
C46 | −0.2667 (2) | 0.1274 (4) | 0.75856 (10) | 0.0329 (7) | |
H46 | −0.3331 | 0.1171 | 0.7417 | 0.040* | |
C47 | −0.2383 (2) | 0.2517 (3) | 0.78414 (10) | 0.0325 (7) | |
H47 | −0.2853 | 0.3265 | 0.7851 | 0.039* | |
C48 | −0.14061 (19) | 0.2674 (3) | 0.80847 (10) | 0.0283 (6) | |
H48 | −0.1213 | 0.3537 | 0.8256 | 0.034* | |
O49 | 0.29027 (15) | 0.4680 (2) | 0.87671 (7) | 0.0377 (5) | |
C50 | 0.2233 (2) | 0.5474 (4) | 0.86032 (10) | 0.0376 (8) | |
H50 | 0.1587 | 0.5066 | 0.8519 | 0.045* | |
N51 | 0.23272 (17) | 0.6899 (3) | 0.85300 (8) | 0.0305 (5) | |
C52 | 0.1458 (2) | 0.7731 (4) | 0.83234 (12) | 0.0443 (9) | |
H52A | 0.0877 | 0.7092 | 0.8259 | 0.066* | |
H52B | 0.1559 | 0.8169 | 0.8032 | 0.066* | |
H52C | 0.1350 | 0.8496 | 0.8540 | 0.066* | |
C53 | 0.3246 (2) | 0.7675 (4) | 0.86449 (12) | 0.0428 (8) | |
H53A | 0.3795 | 0.6987 | 0.8733 | 0.064* | |
H53B | 0.3229 | 0.8331 | 0.8906 | 0.064* | |
H53C | 0.3343 | 0.8238 | 0.8374 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.02044 (16) | 0.02527 (19) | 0.01600 (16) | 0.00285 (13) | 0.00177 (12) | 0.00048 (13) |
C1 | 0.0214 (13) | 0.0271 (16) | 0.0203 (14) | 0.0037 (11) | 0.0035 (11) | 0.0024 (11) |
C2 | 0.0235 (13) | 0.0405 (19) | 0.0257 (15) | −0.0013 (13) | 0.0047 (12) | −0.0011 (13) |
C3 | 0.0255 (13) | 0.041 (2) | 0.0225 (14) | 0.0003 (12) | 0.0073 (12) | −0.0018 (13) |
C4 | 0.0256 (13) | 0.0235 (15) | 0.0210 (13) | 0.0033 (11) | 0.0056 (11) | 0.0015 (12) |
C5 | 0.0287 (13) | 0.0254 (16) | 0.0181 (13) | 0.0007 (11) | 0.0064 (11) | 0.0015 (11) |
C6 | 0.0266 (13) | 0.0235 (16) | 0.0186 (13) | 0.0010 (11) | 0.0034 (11) | 0.0006 (11) |
C7 | 0.0306 (14) | 0.0365 (18) | 0.0175 (14) | −0.0012 (12) | 0.0024 (12) | −0.0010 (12) |
C8 | 0.0262 (14) | 0.0359 (19) | 0.0191 (14) | 0.0000 (12) | −0.0027 (11) | −0.0007 (12) |
C9 | 0.0239 (12) | 0.0244 (15) | 0.0155 (12) | −0.0007 (11) | −0.0019 (10) | 0.0006 (11) |
C10 | 0.0230 (13) | 0.0221 (16) | 0.0188 (13) | 0.0001 (11) | −0.0020 (11) | 0.0015 (11) |
C11 | 0.0222 (12) | 0.0217 (15) | 0.0225 (14) | 0.0014 (11) | 0.0007 (11) | 0.0028 (11) |
C12 | 0.0208 (13) | 0.0329 (18) | 0.0263 (15) | 0.0002 (12) | 0.0016 (11) | 0.0005 (13) |
C13 | 0.0200 (12) | 0.0325 (17) | 0.0241 (14) | 0.0031 (11) | 0.0033 (11) | 0.0014 (12) |
C14 | 0.0207 (12) | 0.0222 (15) | 0.0232 (14) | 0.0007 (11) | 0.0061 (11) | −0.0016 (11) |
C15 | 0.0233 (12) | 0.0229 (15) | 0.0195 (13) | 0.0010 (11) | 0.0046 (11) | 0.0002 (11) |
C16 | 0.0219 (12) | 0.0229 (15) | 0.0194 (13) | 0.0015 (11) | 0.0024 (11) | 0.0020 (11) |
C17 | 0.0239 (13) | 0.0292 (16) | 0.0189 (13) | 0.0010 (11) | 0.0052 (11) | 0.0004 (12) |
C18 | 0.0199 (12) | 0.0316 (17) | 0.0169 (13) | 0.0002 (11) | −0.0005 (10) | 0.0011 (12) |
C19 | 0.0213 (12) | 0.0246 (16) | 0.0191 (13) | 0.0029 (11) | 0.0015 (11) | 0.0014 (11) |
C20 | 0.0190 (12) | 0.0268 (16) | 0.0184 (13) | 0.0031 (11) | 0.0030 (10) | 0.0000 (11) |
N21 | 0.0194 (10) | 0.0303 (14) | 0.0163 (11) | 0.0035 (9) | 0.0010 (9) | 0.0007 (10) |
N22 | 0.0221 (10) | 0.0241 (13) | 0.0172 (11) | 0.0005 (9) | 0.0020 (9) | 0.0009 (10) |
N23 | 0.0218 (10) | 0.0260 (13) | 0.0162 (11) | 0.0023 (9) | 0.0009 (9) | −0.0003 (10) |
N24 | 0.0201 (10) | 0.0281 (14) | 0.0182 (11) | 0.0034 (9) | 0.0046 (9) | −0.0014 (10) |
C25 | 0.0285 (14) | 0.0363 (19) | 0.0170 (13) | −0.0061 (12) | 0.0036 (11) | −0.0038 (12) |
C26 | 0.0305 (15) | 0.045 (2) | 0.0277 (16) | −0.0031 (14) | 0.0068 (13) | −0.0075 (14) |
C27 | 0.0361 (17) | 0.060 (2) | 0.0352 (18) | −0.0090 (16) | 0.0134 (14) | −0.0187 (17) |
C28 | 0.0391 (17) | 0.081 (3) | 0.0226 (16) | −0.0206 (18) | 0.0147 (14) | −0.0158 (18) |
C29 | 0.053 (2) | 0.068 (3) | 0.0222 (16) | −0.0129 (19) | 0.0106 (15) | 0.0085 (17) |
C30 | 0.0495 (18) | 0.047 (2) | 0.0291 (17) | −0.0015 (16) | 0.0131 (15) | 0.0019 (15) |
C31 | 0.0218 (12) | 0.0295 (17) | 0.0190 (13) | −0.0022 (11) | 0.0026 (11) | −0.0009 (11) |
C32 | 0.0323 (15) | 0.0258 (17) | 0.0334 (16) | 0.0019 (13) | −0.0024 (13) | 0.0022 (13) |
C33 | 0.0274 (14) | 0.0323 (18) | 0.0318 (16) | −0.0055 (13) | −0.0012 (12) | −0.0012 (13) |
C34 | 0.0225 (13) | 0.0388 (19) | 0.0237 (14) | −0.0001 (13) | 0.0013 (11) | −0.0021 (13) |
C35 | 0.0335 (15) | 0.0307 (19) | 0.0421 (18) | 0.0043 (14) | −0.0072 (14) | −0.0016 (15) |
C36 | 0.0317 (15) | 0.0270 (18) | 0.0373 (17) | −0.0013 (13) | −0.0098 (13) | −0.0023 (14) |
C37 | 0.0168 (12) | 0.0294 (16) | 0.0207 (14) | −0.0036 (11) | 0.0010 (10) | −0.0041 (12) |
C38 | 0.0164 (12) | 0.0334 (17) | 0.0253 (14) | −0.0013 (11) | 0.0011 (11) | −0.0036 (12) |
C39 | 0.0201 (13) | 0.0369 (19) | 0.0349 (17) | 0.0015 (12) | 0.0060 (12) | −0.0108 (14) |
C40 | 0.0280 (14) | 0.049 (2) | 0.0227 (15) | −0.0069 (14) | 0.0076 (12) | −0.0090 (14) |
C41 | 0.0319 (15) | 0.0414 (19) | 0.0218 (15) | −0.0058 (14) | 0.0052 (12) | −0.0023 (13) |
C42 | 0.0234 (13) | 0.0348 (18) | 0.0200 (14) | −0.0007 (12) | 0.0037 (11) | −0.0035 (12) |
C43 | 0.0197 (12) | 0.0301 (17) | 0.0156 (13) | −0.0004 (11) | 0.0040 (10) | 0.0033 (11) |
C44 | 0.0256 (13) | 0.0305 (17) | 0.0195 (13) | 0.0002 (12) | 0.0057 (11) | 0.0028 (12) |
C45 | 0.0322 (14) | 0.0340 (18) | 0.0200 (14) | −0.0105 (13) | 0.0049 (12) | 0.0001 (12) |
C46 | 0.0225 (13) | 0.046 (2) | 0.0284 (15) | −0.0091 (13) | 0.0005 (12) | 0.0043 (14) |
C47 | 0.0203 (13) | 0.042 (2) | 0.0341 (16) | 0.0052 (13) | 0.0032 (12) | −0.0002 (15) |
C48 | 0.0231 (13) | 0.0314 (18) | 0.0297 (15) | 0.0024 (12) | 0.0035 (12) | −0.0017 (13) |
O49 | 0.0475 (12) | 0.0383 (14) | 0.0270 (11) | 0.0116 (11) | 0.0073 (10) | 0.0032 (10) |
C50 | 0.0302 (15) | 0.054 (2) | 0.0288 (17) | −0.0022 (15) | 0.0059 (13) | −0.0073 (15) |
N51 | 0.0428 (14) | 0.0229 (14) | 0.0255 (13) | 0.0003 (11) | 0.0062 (11) | 0.0015 (11) |
C52 | 0.0319 (16) | 0.056 (2) | 0.044 (2) | 0.0019 (15) | 0.0048 (14) | −0.0003 (17) |
C53 | 0.0323 (16) | 0.049 (2) | 0.0438 (19) | 0.0049 (15) | 0.0003 (14) | −0.0047 (16) |
Zn—N22 | 2.054 (2) | C27—H27 | 0.9500 |
Zn—N24 | 2.065 (2) | C28—C29 | 1.367 (5) |
Zn—N23 | 2.073 (2) | C28—H28 | 0.9500 |
Zn—N21 | 2.091 (2) | C29—C30 | 1.400 (4) |
Zn—O49 | 2.150 (2) | C29—H29 | 0.9500 |
C1—N21 | 1.376 (3) | C30—H30 | 0.9500 |
C1—C20 | 1.404 (3) | C31—C36 | 1.383 (4) |
C1—C2 | 1.445 (4) | C31—C32 | 1.388 (4) |
C2—C3 | 1.345 (4) | C32—C33 | 1.396 (4) |
C2—H2 | 0.9500 | C32—H32 | 0.9500 |
C3—C4 | 1.438 (4) | C33—C34 | 1.376 (4) |
C3—H3 | 0.9500 | C33—H33 | 0.9500 |
C4—N21 | 1.381 (3) | C34—C35 | 1.378 (4) |
C4—C5 | 1.400 (4) | C34—H34 | 0.9500 |
C5—C6 | 1.405 (4) | C35—C36 | 1.391 (4) |
C5—C25 | 1.506 (3) | C35—H35 | 0.9500 |
C6—N22 | 1.374 (3) | C36—H36 | 0.9500 |
C6—C7 | 1.442 (4) | C37—C38 | 1.389 (4) |
C7—C8 | 1.350 (4) | C37—C42 | 1.401 (4) |
C7—H7 | 0.9500 | C38—C39 | 1.389 (4) |
C8—C9 | 1.446 (4) | C38—H38 | 0.9500 |
C8—H8 | 0.9500 | C39—C40 | 1.383 (4) |
C9—N22 | 1.375 (3) | C39—H39 | 0.9500 |
C9—C10 | 1.399 (4) | C40—C41 | 1.376 (4) |
C10—C11 | 1.404 (4) | C40—H40 | 0.9500 |
C10—C31 | 1.504 (3) | C41—C42 | 1.395 (4) |
C11—N23 | 1.382 (3) | C41—H41 | 0.9500 |
C11—C12 | 1.441 (4) | C42—H42 | 0.9500 |
C12—C13 | 1.344 (4) | C43—C48 | 1.390 (4) |
C12—H12 | 0.9500 | C43—C44 | 1.394 (4) |
C13—C14 | 1.454 (3) | C44—C45 | 1.389 (4) |
C13—H13 | 0.9500 | C44—H44 | 0.9500 |
C14—N23 | 1.381 (3) | C45—C46 | 1.380 (4) |
C14—C15 | 1.404 (3) | C45—H45 | 0.9500 |
C15—C16 | 1.411 (3) | C46—C47 | 1.383 (4) |
C15—C37 | 1.495 (3) | C46—H46 | 0.9500 |
C16—N24 | 1.377 (3) | C47—C48 | 1.393 (4) |
C16—C17 | 1.443 (4) | C47—H47 | 0.9500 |
C17—C18 | 1.348 (3) | C48—H48 | 0.9500 |
C17—H17 | 0.9500 | O49—C50 | 1.199 (3) |
C18—C19 | 1.435 (3) | C50—N51 | 1.342 (4) |
C18—H18 | 0.9500 | C50—H50 | 0.9500 |
C19—N24 | 1.377 (3) | N51—C53 | 1.431 (4) |
C19—C20 | 1.411 (3) | N51—C52 | 1.445 (4) |
C20—C43 | 1.501 (3) | C52—H52A | 0.9800 |
C25—C26 | 1.383 (4) | C52—H52B | 0.9800 |
C25—C30 | 1.386 (4) | C52—H52C | 0.9800 |
C26—C27 | 1.390 (4) | C53—H53A | 0.9800 |
C26—H26 | 0.9500 | C53—H53B | 0.9800 |
C27—C28 | 1.371 (5) | C53—H53C | 0.9800 |
N22—Zn—N24 | 162.90 (9) | C27—C26—H26 | 119.6 |
N22—Zn—N23 | 88.74 (8) | C28—C27—C26 | 119.7 (3) |
N24—Zn—N23 | 88.64 (8) | C28—C27—H27 | 120.1 |
N22—Zn—N21 | 88.81 (8) | C26—C27—H27 | 120.1 |
N24—Zn—N21 | 88.04 (8) | C29—C28—C27 | 120.6 (3) |
N23—Zn—N21 | 160.51 (9) | C29—C28—H28 | 119.7 |
N22—Zn—O49 | 99.08 (8) | C27—C28—H28 | 119.7 |
N24—Zn—O49 | 98.01 (8) | C28—C29—C30 | 119.9 (3) |
N23—Zn—O49 | 96.81 (8) | C28—C29—H29 | 120.0 |
N21—Zn—O49 | 102.67 (8) | C30—C29—H29 | 120.0 |
N21—C1—C20 | 125.6 (2) | C25—C30—C29 | 120.2 (3) |
N21—C1—C2 | 109.5 (2) | C25—C30—H30 | 119.9 |
C20—C1—C2 | 124.8 (2) | C29—C30—H30 | 119.9 |
C3—C2—C1 | 107.3 (2) | C36—C31—C32 | 118.7 (2) |
C3—C2—H2 | 126.3 | C36—C31—C10 | 120.5 (2) |
C1—C2—H2 | 126.3 | C32—C31—C10 | 120.8 (2) |
C2—C3—C4 | 107.4 (2) | C31—C32—C33 | 120.3 (3) |
C2—C3—H3 | 126.3 | C31—C32—H32 | 119.8 |
C4—C3—H3 | 126.3 | C33—C32—H32 | 119.8 |
N21—C4—C5 | 125.4 (2) | C34—C33—C32 | 120.4 (3) |
N21—C4—C3 | 109.6 (2) | C34—C33—H33 | 119.8 |
C5—C4—C3 | 124.8 (2) | C32—C33—H33 | 119.8 |
C4—C5—C6 | 125.7 (2) | C33—C34—C35 | 119.5 (3) |
C4—C5—C25 | 117.6 (2) | C33—C34—H34 | 120.3 |
C6—C5—C25 | 116.6 (2) | C35—C34—H34 | 120.3 |
N22—C6—C5 | 125.7 (2) | C34—C35—C36 | 120.3 (3) |
N22—C6—C7 | 109.7 (2) | C34—C35—H35 | 119.9 |
C5—C6—C7 | 124.5 (2) | C36—C35—H35 | 119.9 |
C8—C7—C6 | 107.0 (2) | C31—C36—C35 | 120.8 (3) |
C8—C7—H7 | 126.5 | C31—C36—H36 | 119.6 |
C6—C7—H7 | 126.5 | C35—C36—H36 | 119.6 |
C7—C8—C9 | 107.3 (2) | C38—C37—C42 | 118.2 (2) |
C7—C8—H8 | 126.4 | C38—C37—C15 | 121.8 (2) |
C9—C8—H8 | 126.4 | C42—C37—C15 | 120.0 (2) |
N22—C9—C10 | 126.2 (2) | C39—C38—C37 | 120.8 (3) |
N22—C9—C8 | 109.4 (2) | C39—C38—H38 | 119.6 |
C10—C9—C8 | 124.3 (2) | C37—C38—H38 | 119.6 |
C9—C10—C11 | 125.2 (2) | C40—C39—C38 | 120.6 (3) |
C9—C10—C31 | 117.5 (2) | C40—C39—H39 | 119.7 |
C11—C10—C31 | 117.3 (2) | C38—C39—H39 | 119.7 |
N23—C11—C10 | 125.2 (2) | C41—C40—C39 | 119.5 (3) |
N23—C11—C12 | 109.7 (2) | C41—C40—H40 | 120.3 |
C10—C11—C12 | 125.1 (2) | C39—C40—H40 | 120.3 |
C13—C12—C11 | 107.6 (2) | C40—C41—C42 | 120.4 (3) |
C13—C12—H12 | 126.2 | C40—C41—H41 | 119.8 |
C11—C12—H12 | 126.2 | C42—C41—H41 | 119.8 |
C12—C13—C14 | 107.2 (2) | C41—C42—C37 | 120.6 (3) |
C12—C13—H13 | 126.4 | C41—C42—H42 | 119.7 |
C14—C13—H13 | 126.4 | C37—C42—H42 | 119.7 |
N23—C14—C15 | 125.1 (2) | C48—C43—C44 | 118.5 (2) |
N23—C14—C13 | 109.3 (2) | C48—C43—C20 | 119.9 (2) |
C15—C14—C13 | 125.5 (2) | C44—C43—C20 | 121.7 (2) |
C14—C15—C16 | 125.1 (2) | C45—C44—C43 | 120.8 (3) |
C14—C15—C37 | 118.4 (2) | C45—C44—H44 | 119.6 |
C16—C15—C37 | 116.5 (2) | C43—C44—H44 | 119.6 |
N24—C16—C15 | 126.0 (2) | C46—C45—C44 | 120.1 (3) |
N24—C16—C17 | 109.7 (2) | C46—C45—H45 | 119.9 |
C15—C16—C17 | 124.3 (2) | C44—C45—H45 | 119.9 |
C18—C17—C16 | 107.0 (2) | C45—C46—C47 | 119.9 (3) |
C18—C17—H17 | 126.5 | C45—C46—H46 | 120.0 |
C16—C17—H17 | 126.5 | C47—C46—H46 | 120.0 |
C17—C18—C19 | 107.5 (2) | C46—C47—C48 | 120.0 (3) |
C17—C18—H18 | 126.2 | C46—C47—H47 | 120.0 |
C19—C18—H18 | 126.2 | C48—C47—H47 | 120.0 |
N24—C19—C20 | 125.1 (2) | C43—C48—C47 | 120.7 (3) |
N24—C19—C18 | 109.7 (2) | C43—C48—H48 | 119.6 |
C20—C19—C18 | 125.2 (2) | C47—C48—H48 | 119.6 |
C1—C20—C19 | 125.1 (2) | C50—O49—Zn | 126.0 (2) |
C1—C20—C43 | 117.5 (2) | O49—C50—N51 | 124.9 (3) |
C19—C20—C43 | 117.4 (2) | O49—C50—H50 | 117.6 |
C1—N21—C4 | 106.2 (2) | N51—C50—H50 | 117.6 |
C1—N21—Zn | 127.01 (16) | C50—N51—C53 | 124.2 (3) |
C4—N21—Zn | 126.48 (17) | C50—N51—C52 | 119.3 (3) |
C6—N22—C9 | 106.5 (2) | C53—N51—C52 | 116.5 (3) |
C6—N22—Zn | 127.12 (17) | N51—C52—H52A | 109.5 |
C9—N22—Zn | 126.17 (16) | N51—C52—H52B | 109.5 |
C14—N23—C11 | 106.22 (19) | H52A—C52—H52B | 109.5 |
C14—N23—Zn | 126.31 (16) | N51—C52—H52C | 109.5 |
C11—N23—Zn | 126.21 (17) | H52A—C52—H52C | 109.5 |
C19—N24—C16 | 106.2 (2) | H52B—C52—H52C | 109.5 |
C19—N24—Zn | 127.51 (16) | N51—C53—H53A | 109.5 |
C16—N24—Zn | 125.43 (16) | N51—C53—H53B | 109.5 |
C26—C25—C30 | 118.8 (3) | H53A—C53—H53B | 109.5 |
C26—C25—C5 | 121.4 (3) | N51—C53—H53C | 109.5 |
C30—C25—C5 | 119.7 (3) | H53A—C53—H53C | 109.5 |
C25—C26—C27 | 120.8 (3) | H53B—C53—H53C | 109.5 |
C25—C26—H26 | 119.6 |
Experimental details
Crystal data | |
Chemical formula | [Zn(C44H28N4)(C3H7NO)] |
Mr | 751.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 110 |
a, b, c (Å) | 13.7419 (3), 9.2278 (2), 29.3016 (7) |
β (°) | 101.7186 (13) |
V (Å3) | 3638.22 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.20 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29748, 8697, 5627 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.132, 1.03 |
No. of reflections | 8697 |
No. of parameters | 489 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −0.64 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-III (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002).
Zn—N22 | 2.054 (2) | Zn—N21 | 2.091 (2) |
Zn—N24 | 2.065 (2) | Zn—O49 | 2.150 (2) |
Zn—N23 | 2.073 (2) | ||
N22—Zn—N24 | 162.90 (9) | N22—Zn—O49 | 99.08 (8) |
N22—Zn—N23 | 88.74 (8) | N24—Zn—O49 | 98.01 (8) |
N24—Zn—N23 | 88.64 (8) | N23—Zn—O49 | 96.81 (8) |
N22—Zn—N21 | 88.81 (8) | N21—Zn—O49 | 102.67 (8) |
N24—Zn—N21 | 88.04 (8) | C50—O49—Zn | 126.0 (2) |
N23—Zn—N21 | 160.51 (9) |
Numerous four-coordinate, five-coordinate and six-coordinate complexes of metallo-tetraphenylporphyrin have been reported with a wide variety of crystallization solvents (many of these compounds form clathrates) and axial ligands coordinated to the metal centre (Byrn, et al., 1991; Byrn et al., 1993). Porphyrin complexes with dimethylformamide as an axial ligand include ZnII-tetra(4-hydroxyphenyl)porphyrin (Goldberg et al., 1995), MnIII-tetraphenylporphyrin perchlorate (Hill & Williamson, 1985), ZrIV-tetraphenylporphyrin dichloride (Tutass et al., 2002), and ZnII-tetraphenylporphyrin (Droege et al., 1994). The latter crystallized as a dichloromethane solvate. The present report provides information on the five-coordinate complex of the title compound, (I) (Fig. 1), determined at low temperature (ca 110 K).
In the crystal structure, the porphyrin core is slightly saddled with the inner pyrrole N atoms deviating ±0.023 (1) Å from their mean plane. The zinc ion is shifted by 0.329 (1) Å from this N4 plane towards the axial ligand, imparting to the metalloporphyrin entity a domed structure (Fig. 2), which is typical of many five-coordinate complexes of metallated tetraarylporphyrins (Allen, 2002).
Efficient crystal packing of the molecular units of (I) (Fig. 3) is realised by waved layers of the metalloporphyrin species running perpendicular to the b axis. Adjacent inversion-related layers fit tightly into one another; the axial ligands of one layer are inserted between the porphyrin frameworks of neighbouring layers. The parallel offset of these layers allows a close van der Waals contact between the concave surface of a given metalloporphyrin core and a phenyl ring from another layer. The corresponding shortest non-bonding distances include: C4···C35(1 − x, −y, 2 − z) = 3.583 (2) Å, N22···C36(1 − x, −y, 2 − z) = 3.459 (2) Å, and C6···C36(1 − x, −y, 2 − z) = 3.463 (2) Å. This concave surface is in van der Waals contact with one of the methyl residues from the nearest layer translated along b. The axial ligand from one layer penetrates through the nearest layer approaching the porphyrin core [N24···C52(x, 1 + y, z) =3.776 (3) Å]. The geometry of the coordination around the zinc ion (Table 1) shows already known values (Allen, 2002, Vinodu & Goldberg, 2004).