Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106035840/ga3024sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106035840/ga3024Isup2.hkl |
CCDC reference: 625682
The title porphyrin moiety was synthesized by standard literature procedures (Lindsey et al., 1987; Adler et al., 1970). The initially obtained free base porphyrin derivative was fully characterized by 1H NMR, UV–vis and MS techniques. Crystals of (I) were obtained by dissolving the metallated product in N,N'-dimethylacetamide, followed by slow evaporation.
The H atoms were located 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) = 1.2Ueq(C) or 1.5Ueq(C).
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
[Zn(C52H36N4O8)]·2C4H9NO | F(000) = 1132 |
Mr = 1084.46 | Dx = 1.387 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.8014 (4) Å | Cell parameters from 5531 reflections |
b = 8.9030 (4) Å | θ = 1.4–27.9° |
c = 21.1399 (9) Å | µ = 0.54 mm−1 |
β = 91.675 (3)° | T = 110 K |
V = 2596.43 (18) Å3 | Needle, red |
Z = 2 | 0.45 × 0.10 × 0.10 mm |
Nonius KappaCCD area-detector diffractometer | 4518 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.081 |
Graphite monochromator | θmax = 27.9°, θmin = 2.4° |
Detector resolution: 12.8 pixels mm-1 | h = −18→18 |
1° ϕ scans | k = −11→11 |
19518 measured reflections | l = −27→27 |
6135 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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0204P)2 + 3.6188P] where P = (Fo2 + 2Fc2)/3 |
6135 reflections | (Δ/σ)max = 0.002 |
354 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
[Zn(C52H36N4O8)]·2C4H9NO | V = 2596.43 (18) Å3 |
Mr = 1084.46 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.8014 (4) Å | µ = 0.54 mm−1 |
b = 8.9030 (4) Å | T = 110 K |
c = 21.1399 (9) Å | 0.45 × 0.10 × 0.10 mm |
β = 91.675 (3)° |
Nonius KappaCCD area-detector diffractometer | 4518 reflections with I > 2σ(I) |
19518 measured reflections | Rint = 0.081 |
6135 independent reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.63 e Å−3 |
6135 reflections | Δρmin = −0.54 e Å−3 |
354 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 | 0.5000 | 0.5000 | 0.5000 | 0.01652 (12) | |
C1 | 0.50651 (18) | 0.7233 (3) | 0.61000 (12) | 0.0178 (6) | |
C2 | 0.55096 (19) | 0.8623 (3) | 0.63019 (13) | 0.0223 (6) | |
H2 | 0.5421 | 0.9116 | 0.6695 | 0.027* | |
C3 | 0.60761 (19) | 0.9098 (3) | 0.58306 (13) | 0.0221 (6) | |
H3 | 0.6458 | 0.9986 | 0.5829 | 0.027* | |
C4 | 0.59897 (18) | 0.8000 (3) | 0.53307 (12) | 0.0181 (6) | |
C5 | 0.64958 (18) | 0.8049 (3) | 0.47596 (12) | 0.0174 (5) | |
C6 | 0.64447 (18) | 0.6959 (3) | 0.42805 (12) | 0.0170 (5) | |
C7 | 0.69243 (19) | 0.7061 (3) | 0.36823 (13) | 0.0215 (6) | |
H7 | 0.7334 | 0.7851 | 0.3550 | 0.026* | |
C8 | 0.66763 (19) | 0.5813 (3) | 0.33466 (13) | 0.0207 (6) | |
H8 | 0.6885 | 0.5561 | 0.2936 | 0.025* | |
C9 | 0.60354 (17) | 0.4940 (3) | 0.37303 (11) | 0.0168 (5) | |
C10 | 0.55909 (18) | 0.3588 (3) | 0.35461 (12) | 0.0176 (5) | |
N11 | 0.53677 (14) | 0.6880 (2) | 0.55030 (10) | 0.0167 (5) | |
N12 | 0.59107 (15) | 0.5663 (2) | 0.42966 (10) | 0.0157 (5) | |
C13 | 0.71720 (18) | 0.9338 (3) | 0.46742 (12) | 0.0167 (5) | |
C14 | 0.81698 (19) | 0.9071 (3) | 0.46342 (13) | 0.0203 (6) | |
H14 | 0.8412 | 0.8075 | 0.4673 | 0.024* | |
C15 | 0.88033 (18) | 1.0248 (3) | 0.45392 (12) | 0.0209 (6) | |
H15 | 0.9478 | 1.0055 | 0.4514 | 0.025* | |
C16 | 0.84606 (18) | 1.1710 (3) | 0.44803 (12) | 0.0184 (6) | |
C17 | 0.74705 (18) | 1.1991 (3) | 0.45322 (12) | 0.0182 (6) | |
H17 | 0.7231 | 1.2989 | 0.4499 | 0.022* | |
C18 | 0.68365 (19) | 1.0811 (3) | 0.46330 (12) | 0.0189 (6) | |
H18 | 0.6165 | 1.1011 | 0.4674 | 0.023* | |
C19 | 0.91657 (19) | 1.2924 (3) | 0.43530 (13) | 0.0217 (6) | |
O20 | 1.00352 (14) | 1.2801 (2) | 0.44232 (11) | 0.0351 (5) | |
O21 | 0.87361 (13) | 1.4178 (2) | 0.41391 (10) | 0.0277 (5) | |
C22 | 0.9374 (2) | 1.5408 (3) | 0.39855 (17) | 0.0342 (8) | |
H22A | 0.9691 | 1.5788 | 0.4374 | 0.051* | |
H22B | 0.8995 | 1.6215 | 0.3782 | 0.051* | |
H22C | 0.9866 | 1.5052 | 0.3696 | 0.051* | |
C23 | 0.58595 (18) | 0.2923 (3) | 0.29207 (12) | 0.0173 (5) | |
C24 | 0.6668 (2) | 0.1985 (4) | 0.28915 (13) | 0.0337 (8) | |
H24 | 0.7042 | 0.1779 | 0.3266 | 0.040* | |
C25 | 0.6928 (2) | 0.1353 (4) | 0.23242 (13) | 0.0324 (8) | |
H25 | 0.7473 | 0.0703 | 0.2311 | 0.039* | |
C26 | 0.63931 (18) | 0.1666 (3) | 0.17711 (12) | 0.0188 (6) | |
C27 | 0.55851 (19) | 0.2590 (3) | 0.17987 (12) | 0.0197 (6) | |
H27 | 0.5216 | 0.2809 | 0.1424 | 0.024* | |
C28 | 0.53155 (19) | 0.3195 (3) | 0.23715 (12) | 0.0206 (6) | |
H28 | 0.4751 | 0.3803 | 0.2388 | 0.025* | |
C29 | 0.66900 (18) | 0.1086 (3) | 0.11456 (12) | 0.0177 (6) | |
O30 | 0.62883 (13) | 0.1405 (2) | 0.06465 (8) | 0.0213 (4) | |
O31 | 0.74769 (13) | 0.0207 (2) | 0.11978 (8) | 0.0246 (5) | |
C32 | 0.7877 (2) | −0.0283 (4) | 0.06075 (13) | 0.0279 (7) | |
H32A | 0.7356 | −0.0676 | 0.0329 | 0.042* | |
H32B | 0.8358 | −0.1073 | 0.0692 | 0.042* | |
H32C | 0.8188 | 0.0569 | 0.0401 | 0.042* | |
O33 | 1.0124 (2) | 0.3466 (3) | 0.16201 (13) | 0.0611 (8) | |
C34 | 0.9438 (3) | 0.4405 (5) | 0.16349 (16) | 0.0443 (9) | |
C35 | 0.8486 (3) | 0.4059 (5) | 0.1322 (2) | 0.0632 (12) | |
H35A | 0.8517 | 0.3074 | 0.1117 | 0.095* | |
H35B | 0.8331 | 0.4829 | 0.1004 | 0.095* | |
H35C | 0.7983 | 0.4046 | 0.1639 | 0.095* | |
N36 | 0.9567 (2) | 0.5682 (4) | 0.19365 (15) | 0.0463 (8) | |
C37 | 1.0521 (2) | 0.6100 (5) | 0.22035 (19) | 0.0535 (11) | |
H37A | 1.0989 | 0.5304 | 0.2116 | 0.080* | |
H37B | 1.0479 | 0.6234 | 0.2662 | 0.080* | |
H37C | 1.0733 | 0.7041 | 0.2011 | 0.080* | |
C38 | 0.8806 (3) | 0.6828 (5) | 0.1978 (2) | 0.0608 (12) | |
H38A | 0.8951 | 0.7666 | 0.1696 | 0.091* | |
H38B | 0.8782 | 0.7195 | 0.2415 | 0.091* | |
H38C | 0.8179 | 0.6388 | 0.1853 | 0.091* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0173 (2) | 0.0173 (2) | 0.0151 (2) | −0.0031 (2) | 0.00324 (15) | −0.00225 (19) |
C1 | 0.0176 (12) | 0.0192 (14) | 0.0165 (13) | 0.0012 (11) | 0.0008 (10) | −0.0018 (11) |
C2 | 0.0241 (14) | 0.0232 (15) | 0.0198 (14) | −0.0026 (12) | 0.0026 (11) | −0.0060 (12) |
C3 | 0.0230 (14) | 0.0209 (15) | 0.0226 (14) | −0.0056 (12) | 0.0012 (11) | −0.0043 (12) |
C4 | 0.0159 (12) | 0.0196 (14) | 0.0187 (13) | −0.0014 (11) | 0.0004 (10) | −0.0015 (11) |
C5 | 0.0153 (12) | 0.0173 (14) | 0.0195 (13) | 0.0002 (11) | −0.0011 (10) | 0.0017 (11) |
C6 | 0.0151 (12) | 0.0185 (14) | 0.0175 (13) | −0.0015 (11) | −0.0009 (10) | 0.0028 (11) |
C7 | 0.0195 (13) | 0.0243 (15) | 0.0210 (14) | −0.0047 (12) | 0.0039 (11) | 0.0023 (12) |
C8 | 0.0214 (13) | 0.0244 (15) | 0.0166 (13) | −0.0014 (12) | 0.0040 (11) | 0.0011 (11) |
C9 | 0.0157 (11) | 0.0176 (13) | 0.0171 (12) | 0.0021 (12) | 0.0008 (9) | 0.0011 (12) |
C10 | 0.0160 (12) | 0.0214 (14) | 0.0155 (13) | 0.0027 (11) | 0.0000 (10) | −0.0016 (11) |
N11 | 0.0155 (10) | 0.0174 (12) | 0.0173 (11) | −0.0010 (9) | 0.0012 (9) | 0.0000 (9) |
N12 | 0.0165 (10) | 0.0169 (11) | 0.0137 (11) | 0.0005 (9) | 0.0003 (8) | −0.0017 (9) |
C13 | 0.0172 (12) | 0.0203 (14) | 0.0124 (12) | −0.0025 (11) | 0.0006 (10) | −0.0003 (11) |
C14 | 0.0203 (13) | 0.0168 (14) | 0.0238 (14) | 0.0014 (11) | 0.0018 (11) | 0.0006 (11) |
C15 | 0.0158 (12) | 0.0255 (17) | 0.0217 (13) | −0.0013 (11) | 0.0034 (10) | −0.0007 (11) |
C16 | 0.0189 (13) | 0.0206 (14) | 0.0158 (13) | −0.0050 (11) | 0.0012 (10) | −0.0011 (11) |
C17 | 0.0197 (13) | 0.0165 (14) | 0.0183 (13) | −0.0003 (11) | −0.0010 (10) | 0.0005 (11) |
C18 | 0.0170 (13) | 0.0221 (15) | 0.0175 (13) | 0.0019 (12) | −0.0001 (10) | −0.0006 (11) |
C19 | 0.0205 (14) | 0.0231 (15) | 0.0217 (14) | −0.0046 (12) | 0.0013 (11) | −0.0019 (12) |
O20 | 0.0191 (10) | 0.0311 (13) | 0.0550 (15) | −0.0070 (9) | 0.0003 (10) | 0.0092 (11) |
O21 | 0.0231 (10) | 0.0225 (11) | 0.0378 (12) | −0.0048 (9) | 0.0035 (9) | 0.0076 (9) |
C22 | 0.0314 (16) | 0.0241 (17) | 0.048 (2) | −0.0083 (13) | 0.0091 (15) | 0.0060 (14) |
C23 | 0.0157 (12) | 0.0188 (14) | 0.0177 (13) | −0.0027 (11) | 0.0034 (10) | −0.0020 (11) |
C24 | 0.0286 (15) | 0.057 (2) | 0.0156 (14) | 0.0174 (16) | −0.0051 (12) | −0.0049 (14) |
C25 | 0.0271 (15) | 0.049 (2) | 0.0212 (15) | 0.0183 (15) | −0.0042 (12) | −0.0067 (14) |
C26 | 0.0186 (13) | 0.0204 (14) | 0.0175 (13) | −0.0018 (11) | 0.0019 (10) | −0.0017 (11) |
C27 | 0.0210 (13) | 0.0213 (14) | 0.0166 (13) | 0.0015 (11) | −0.0022 (11) | 0.0013 (11) |
C28 | 0.0188 (13) | 0.0225 (15) | 0.0204 (14) | 0.0037 (12) | 0.0016 (11) | −0.0004 (11) |
C29 | 0.0165 (12) | 0.0173 (14) | 0.0195 (14) | −0.0023 (11) | 0.0018 (11) | −0.0017 (11) |
O30 | 0.0205 (9) | 0.0270 (11) | 0.0163 (9) | 0.0017 (8) | 0.0000 (8) | −0.0015 (8) |
O31 | 0.0226 (9) | 0.0321 (12) | 0.0191 (9) | 0.0110 (9) | 0.0004 (8) | −0.0044 (9) |
C32 | 0.0234 (14) | 0.037 (2) | 0.0235 (14) | 0.0082 (13) | 0.0044 (11) | −0.0095 (13) |
O33 | 0.083 (2) | 0.0431 (16) | 0.0587 (18) | 0.0222 (16) | 0.0258 (15) | 0.0088 (14) |
C34 | 0.060 (2) | 0.046 (2) | 0.0272 (18) | −0.016 (2) | 0.0064 (17) | 0.0057 (16) |
C35 | 0.064 (3) | 0.076 (3) | 0.048 (2) | −0.032 (2) | −0.002 (2) | −0.003 (2) |
N36 | 0.0447 (17) | 0.0466 (19) | 0.0476 (19) | 0.0016 (15) | −0.0013 (14) | −0.0045 (16) |
C37 | 0.039 (2) | 0.073 (3) | 0.047 (2) | −0.008 (2) | −0.0070 (17) | −0.011 (2) |
C38 | 0.059 (2) | 0.052 (3) | 0.072 (3) | 0.022 (2) | 0.019 (2) | 0.010 (2) |
Zn—N11 | 2.039 (2) | C19—O20 | 1.210 (3) |
Zn—N11i | 2.039 (2) | C19—O21 | 1.336 (3) |
Zn—N12i | 2.061 (2) | O21—C22 | 1.447 (3) |
Zn—N12 | 2.061 (2) | C22—H22A | 0.9800 |
Zn—O30ii | 2.540 (2) | C22—H22B | 0.9800 |
Zn—O30iii | 2.540 (2) | C22—H22C | 0.9800 |
C1—N11 | 1.377 (3) | C23—C28 | 1.385 (4) |
C1—C10i | 1.398 (4) | C23—C24 | 1.396 (4) |
C1—C2 | 1.440 (4) | C24—C25 | 1.382 (4) |
C2—C3 | 1.352 (4) | C24—H24 | 0.9500 |
C2—H2 | 0.9500 | C25—C26 | 1.393 (4) |
C3—C4 | 1.442 (4) | C25—H25 | 0.9500 |
C3—H3 | 0.9500 | C26—C27 | 1.389 (4) |
C4—N11 | 1.372 (3) | C26—C29 | 1.488 (4) |
C4—C5 | 1.413 (3) | C27—C28 | 1.386 (4) |
C5—C6 | 1.403 (4) | C27—H27 | 0.9500 |
C5—C13 | 1.493 (4) | C28—H28 | 0.9500 |
C6—N12 | 1.370 (3) | C29—O30 | 1.211 (3) |
C6—C7 | 1.447 (3) | C29—O31 | 1.340 (3) |
C7—C8 | 1.357 (4) | O31—C32 | 1.447 (3) |
C7—H7 | 0.9500 | C32—H32A | 0.9800 |
C8—C9 | 1.445 (4) | C32—H32B | 0.9800 |
C8—H8 | 0.9500 | C32—H32C | 0.9800 |
C9—N12 | 1.374 (3) | O33—C34 | 1.264 (5) |
C9—C10 | 1.401 (4) | C34—N36 | 1.313 (5) |
C10—C1i | 1.398 (4) | C34—C35 | 1.486 (5) |
C10—C23 | 1.505 (3) | C35—H35A | 0.9800 |
C13—C18 | 1.393 (4) | C35—H35B | 0.9800 |
C13—C14 | 1.403 (4) | C35—H35C | 0.9800 |
C14—C15 | 1.383 (4) | N36—C37 | 1.466 (4) |
C14—H14 | 0.9500 | N36—C38 | 1.468 (5) |
C15—C16 | 1.389 (4) | C37—H37A | 0.9800 |
C15—H15 | 0.9500 | C37—H37B | 0.9800 |
C16—C17 | 1.397 (4) | C37—H37C | 0.9800 |
C16—C19 | 1.484 (4) | C38—H38A | 0.9800 |
C17—C18 | 1.387 (4) | C38—H38B | 0.9800 |
C17—H17 | 0.9500 | C38—H38C | 0.9800 |
C18—H18 | 0.9500 | ||
N11—Zn—N11i | 180.0 | O20—C19—C16 | 124.4 (3) |
N11—Zn—N12i | 90.37 (8) | O21—C19—C16 | 112.5 (2) |
N11i—Zn—N12i | 89.63 (8) | C19—O21—C22 | 116.2 (2) |
N11—Zn—N12 | 89.63 (8) | O21—C22—H22A | 109.5 |
N11i—Zn—N12 | 90.37 (8) | O21—C22—H22B | 109.5 |
N12i—Zn—N12 | 180.0 | H22A—C22—H22B | 109.5 |
N11—C1—C10i | 126.1 (2) | O21—C22—H22C | 109.5 |
N11—C1—C2 | 109.3 (2) | H22A—C22—H22C | 109.5 |
C10i—C1—C2 | 124.6 (2) | H22B—C22—H22C | 109.5 |
C3—C2—C1 | 107.5 (2) | C28—C23—C24 | 118.8 (2) |
C3—C2—H2 | 126.2 | C28—C23—C10 | 121.8 (2) |
C1—C2—H2 | 126.2 | C24—C23—C10 | 119.4 (2) |
C2—C3—C4 | 106.9 (2) | C25—C24—C23 | 120.7 (3) |
C2—C3—H3 | 126.6 | C25—C24—H24 | 119.7 |
C4—C3—H3 | 126.6 | C23—C24—H24 | 119.7 |
N11—C4—C5 | 125.3 (2) | C24—C25—C26 | 120.2 (3) |
N11—C4—C3 | 109.7 (2) | C24—C25—H25 | 119.9 |
C5—C4—C3 | 124.9 (2) | C26—C25—H25 | 119.9 |
C6—C5—C4 | 125.4 (2) | C27—C26—C25 | 119.3 (2) |
C6—C5—C13 | 117.6 (2) | C27—C26—C29 | 119.0 (2) |
C4—C5—C13 | 117.0 (2) | C25—C26—C29 | 121.6 (2) |
N12—C6—C5 | 125.5 (2) | C28—C27—C26 | 120.2 (2) |
N12—C6—C7 | 109.6 (2) | C28—C27—H27 | 119.9 |
C5—C6—C7 | 124.9 (2) | C26—C27—H27 | 119.9 |
C8—C7—C6 | 106.9 (2) | C23—C28—C27 | 120.8 (2) |
C8—C7—H7 | 126.6 | C23—C28—H28 | 119.6 |
C6—C7—H7 | 126.6 | C27—C28—H28 | 119.6 |
C7—C8—C9 | 107.2 (2) | O30—C29—O31 | 123.9 (2) |
C7—C8—H8 | 126.4 | O30—C29—C26 | 124.2 (2) |
C9—C8—H8 | 126.4 | O31—C29—C26 | 111.9 (2) |
N12—C9—C10 | 125.4 (2) | C29—O31—C32 | 115.7 (2) |
N12—C9—C8 | 109.4 (2) | O31—C32—H32A | 109.5 |
C10—C9—C8 | 125.2 (2) | O31—C32—H32B | 109.5 |
C1i—C10—C9 | 125.9 (2) | H32A—C32—H32B | 109.5 |
C1i—C10—C23 | 116.4 (2) | O31—C32—H32C | 109.5 |
C9—C10—C23 | 117.7 (2) | H32A—C32—H32C | 109.5 |
C4—N11—C1 | 106.6 (2) | H32B—C32—H32C | 109.5 |
C4—N11—Zn | 127.32 (17) | O33—C34—N36 | 119.6 (4) |
C1—N11—Zn | 126.01 (17) | O33—C34—C35 | 120.4 (4) |
C6—N12—C9 | 106.9 (2) | N36—C34—C35 | 120.0 (4) |
C6—N12—Zn | 126.79 (17) | C34—C35—H35A | 109.5 |
C9—N12—Zn | 126.08 (18) | C34—C35—H35B | 109.5 |
C18—C13—C14 | 118.8 (2) | H35A—C35—H35B | 109.5 |
C18—C13—C5 | 121.6 (2) | C34—C35—H35C | 109.5 |
C14—C13—C5 | 119.7 (2) | H35A—C35—H35C | 109.5 |
C15—C14—C13 | 120.4 (3) | H35B—C35—H35C | 109.5 |
C15—C14—H14 | 119.8 | C34—N36—C37 | 120.9 (3) |
C13—C14—H14 | 119.8 | C34—N36—C38 | 123.0 (3) |
C14—C15—C16 | 120.5 (2) | C37—N36—C38 | 115.9 (3) |
C14—C15—H15 | 119.7 | N36—C37—H37A | 109.5 |
C16—C15—H15 | 119.7 | N36—C37—H37B | 109.5 |
C15—C16—C17 | 119.5 (2) | H37A—C37—H37B | 109.5 |
C15—C16—C19 | 118.4 (2) | N36—C37—H37C | 109.5 |
C17—C16—C19 | 122.1 (3) | H37A—C37—H37C | 109.5 |
C18—C17—C16 | 120.0 (3) | H37B—C37—H37C | 109.5 |
C18—C17—H17 | 120.0 | N36—C38—H38A | 109.5 |
C16—C17—H17 | 120.0 | N36—C38—H38B | 109.5 |
C17—C18—C13 | 120.8 (2) | H38A—C38—H38B | 109.5 |
C17—C18—H18 | 119.6 | N36—C38—H38C | 109.5 |
C13—C18—H18 | 119.6 | H38A—C38—H38C | 109.5 |
O20—C19—O21 | 123.1 (3) | H38B—C38—H38C | 109.5 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C52H36N4O8)]·2C4H9NO |
Mr | 1084.46 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 110 |
a, b, c (Å) | 13.8014 (4), 8.9030 (4), 21.1399 (9) |
β (°) | 91.675 (3) |
V (Å3) | 2596.43 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.45 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19518, 6135, 4518 |
Rint | 0.081 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.116, 1.08 |
No. of reflections | 6135 |
No. of parameters | 354 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.54 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
Zn—N11 | 2.039 (2) | Zn—O30i | 2.540 (2) |
Zn—N12 | 2.061 (2) | ||
N11—Zn—N12 | 89.63 (8) | N11ii—Zn—N12 | 90.37 (8) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1. |
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The formulation of porphyrin network and framework solids has received increasing attention in recent years (Goldberg, 2005; Kosal et al., 2002; Diskin-Posner et al., 2000; Krupitsky et al., 1994; Abrahams et al., 1994), due to their potential application to problems of materials storage and separation as well as heterogeneous catalysis. Most of the supramolecular architectures reported to date involve external auxiliaries (metal ions or organic ligands) as linkers between the porphyrin units. Only a few examples of direct networking between suitably functionalized metalloporphyrins have been observed thus far, including our first robust porous solid consisting of a three-dimensional coordination polymer of the zinc–tetra(4-pyridyl)porphyrin (Krupitsky et al., 1994; Shmilovits et al., 2004a; George et al., 2006). As part of our systematic investigation of porphyrin-based solids, we report here the direct coordination polymerization of the title porphyrin derivative and the intercalate-type crystal structure it forms with N,N'-dimethylacetamide solvent, (I) (Fig. 1).
The carbomethoxy function has not been utilized before in the supramolecular assembly of porphyrin arrays. The bond lengths and angles in (I) (Table 1) show standard values [Cambridge Structural Database, Version 5.27; Mercury (Macrae et al., 2006); Allen, 2002], in particular for the Zn—N(pyrrole) distances (Shmilovits et al., 2004b).
The inter-porphyrin coordination pattern in (I) is illustrated in Fig. 2. It represents a unique two-dimensional coordination polymer obtained by direct coordination of two trans-related peripheral carbomethoxy groups of one porphyrin to the metal core of neighbouring moieties. Thus, formation of the polymeric array is effected by axial coordination of the Zn centres from above and below to the carbomethoxy groups of two perching unitsacross inversion at Zn—O(═C) of 2.540 (2) Å. Two trans-related carbomethoxyphenyl arms along a roughly perpendicular direction of the central molecule associate with the metal centres of two other neighbouring entities. Each porphyrin unit (located on an inversion centre) is thus involved in a four-point connection to the surrounding species, affording a condensed two-dimensional coordination polymer assembly. The supramolecular Zn—O coordinative interactions operate between molecular units related to each other by the screw/glide symmetry (thus forming a herringbone pattern). There are fortuitous C—H···π interactions [PLATON (Spek, 2003)] between the adjacent carbomethoxy methyl atom H32A and the Zn-pyrrole ring (Zn/N11/C4–C6/N12) at (x, 1/2 − y, z − 1/2) of 2.45 Å (C—H···π angle 167°). The resulting polymeric arrays have corrugated surfaces.
Similar polymer constructions have been reported previously only for the Mn–tetrakis(4'-carboxyphenyl)porphyrin, with the embedded Mn ions having a distinct preference for a six-coordinate environment and exhibiting considerably shorter Mn—O axial interactions (2.2–2.3 Å; Shmilovits et al., 2004a; George et al., 2006). Octahedral coordination is less common for the d10 Zn ions, with lower affinity for oxo ligands than Mn, thus representing somewhat weaker though still significant interactions at Zn—O near 2.5 Å (Krishna Kumar et al., 1998). The crystal structure of (I) consists of a stacked arrangement of the polymeric layers along the a axis, which do not interact directly (except by dispersion). The corresponding shortest non-bonding distance involves the terminal carbomethoxy substituents, with C32···O20(2 − x, y − 3/2, 1/2 − z) = 3.351 (3) Å.
Overall, this represents an intercalated pattern, with the N,N'-dimethylacetamide solvent species incorporated into the interface regions parallel to the layered arrays (Fig. 3). Thus, the structure of (I) consists of uniquely assembled two-dimensional multi-porphyrin arrays via direct coordination polymerization, which is rarely observed.