Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109005691/gd3276sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109005691/gd3276Isup2.hkl |
CCDC reference: 728203
All reactants were obtained commercially. The procedure detailed below was intended to yield co-crystals of ZnTPyP with 3,5-pyridinedicarboxylic acid, with potential hydrogen bonding and/or coordination between the interacting components. However, it turned out that the dicarboxylic acid was not incorporated into the formed products. In the applied reaction, a solution of 3,5-pyridinedicarboxylic acid (1.5 × 10-2 M, 4 ml) in dimethylformamide was carefully layered onto a solution of ZnTPyP dissolved in a 3:1 mixture of 1,2-dichlorobenzene and methanol (1.47 × 10-3 M, 10 ml). This mixture was left at room temperature for several days. The crystallized material was recovered by filtration, washed with dichlorobenzene and dried in air. Two types of crystals of different morphology were found: thin red needles and square blocks. The needle-shaped crystals were found to be isomorphous and isometric with the crystal structures of the methanol, water and acetic acid clathrates of ZnTPyP, wherein the metalloporphyrin moiety itself assembles in the form of a three-dimensional coordination framework (Krupitsky et al., 1994; George & Goldberg, 2005). The square-block-type crystals of (I) represent a new material and are the subject matter of this report. IR (KBr, cm-1): 1593 (m), 1521 (m), 1486 (w), 1440 (m), 1342 (m), 1342 (m), 1204 (w), 1066 (m), 1010 (m), 993 (s), 795 (s), 753 (s), 717 (m), 705 (s), 670 (m).
H atoms were located in calculated positions and were constrained to ride on their parent atoms with C—H distances of 0.95 Å and with Uiso(H) values of 1.2Ueq(C).
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Zn(C40H24N8)]·2C6H4Cl2 | F(000) = 996 |
Mr = 976.03 | Dx = 1.503 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4704 reflections |
a = 11.0295 (2) Å | θ = 1.4–27.9° |
b = 13.8207 (2) Å | µ = 0.87 mm−1 |
c = 14.1529 (3) Å | T = 110 K |
β = 90.2383 (7)° | Square block, red |
V = 2157.39 (7) Å3 | 0.30 × 0.25 × 0.15 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 5115 independent reflections |
Radiation source: fine-focus sealed tube | 3970 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 12.8 pixels mm-1 | θmax = 27.9°, θmin = 2.4° |
1° ϕ scans | h = 0→14 |
Absorption correction: multi-scan (Blessing, 1995) | k = −17→17 |
Tmin = 0.781, Tmax = 0.881 | l = −18→18 |
16059 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0614P)2 + 0.9105P] where P = (Fo2 + 2Fc2)/3 |
5115 reflections | (Δ/σ)max < 0.001 |
295 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.74 e Å−3 |
[Zn(C40H24N8)]·2C6H4Cl2 | V = 2157.39 (7) Å3 |
Mr = 976.03 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.0295 (2) Å | µ = 0.87 mm−1 |
b = 13.8207 (2) Å | T = 110 K |
c = 14.1529 (3) Å | 0.30 × 0.25 × 0.15 mm |
β = 90.2383 (7)° |
Nonius KappaCCD diffractometer | 5115 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3970 reflections with I > 2σ(I) |
Tmin = 0.781, Tmax = 0.881 | Rint = 0.041 |
16059 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.41 e Å−3 |
5115 reflections | Δρmin = −0.74 e Å−3 |
295 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 | ||
Zn1 | 0.0000 | 0.5000 | 0.5000 | 0.01447 (11) | |
C1 | −0.21505 (19) | 0.63951 (14) | 0.47345 (14) | 0.0168 (4) | |
C2 | −0.2546 (2) | 0.72216 (15) | 0.41873 (15) | 0.0199 (4) | |
H2 | −0.3292 | 0.7558 | 0.4253 | 0.024* | |
C3 | −0.16555 (19) | 0.74265 (15) | 0.35657 (15) | 0.0189 (4) | |
H3 | −0.1661 | 0.7930 | 0.3109 | 0.023* | |
C4 | −0.06888 (19) | 0.67337 (14) | 0.37269 (14) | 0.0163 (4) | |
C5 | 0.04325 (18) | 0.67082 (14) | 0.32510 (14) | 0.0156 (4) | |
C6 | 0.13771 (19) | 0.60363 (14) | 0.33994 (14) | 0.0163 (4) | |
C7 | 0.24989 (19) | 0.60068 (15) | 0.28690 (15) | 0.0189 (4) | |
H7 | 0.2738 | 0.6439 | 0.2383 | 0.023* | |
C8 | 0.3139 (2) | 0.52414 (15) | 0.32026 (15) | 0.0195 (4) | |
H8 | 0.3907 | 0.5026 | 0.2985 | 0.023* | |
C9 | 0.24303 (18) | 0.48127 (14) | 0.39555 (14) | 0.0155 (4) | |
C10 | 0.27971 (18) | 0.40194 (14) | 0.45126 (14) | 0.0164 (4) | |
N11 | −0.10274 (15) | 0.61094 (12) | 0.44339 (12) | 0.0155 (3) | |
N12 | 0.13679 (15) | 0.53132 (12) | 0.40536 (12) | 0.0155 (4) | |
C13 | 0.06132 (18) | 0.74640 (15) | 0.25129 (14) | 0.0164 (4) | |
C14 | 0.07091 (19) | 0.72181 (15) | 0.15608 (14) | 0.0177 (4) | |
H14 | 0.0736 | 0.6558 | 0.1376 | 0.021* | |
C15 | 0.07647 (19) | 0.79411 (15) | 0.08886 (15) | 0.0192 (4) | |
H15 | 0.0824 | 0.7760 | 0.0243 | 0.023* | |
N16 | 0.07393 (16) | 0.88808 (13) | 0.11004 (12) | 0.0190 (4) | |
C17 | 0.07074 (19) | 0.91193 (15) | 0.20145 (15) | 0.0197 (4) | |
H17 | 0.0723 | 0.9786 | 0.2177 | 0.024* | |
C18 | 0.0654 (2) | 0.84467 (15) | 0.27368 (15) | 0.0199 (4) | |
H18 | 0.0644 | 0.8651 | 0.3378 | 0.024* | |
C19 | 0.39785 (19) | 0.35487 (14) | 0.42642 (15) | 0.0180 (4) | |
C20 | 0.5027 (2) | 0.36887 (18) | 0.47905 (17) | 0.0267 (5) | |
H20 | 0.5020 | 0.4099 | 0.5329 | 0.032* | |
C21 | 0.6086 (2) | 0.32235 (19) | 0.45236 (18) | 0.0312 (5) | |
H21 | 0.6795 | 0.3337 | 0.4890 | 0.037* | |
N22 | 0.61716 (18) | 0.26284 (15) | 0.37886 (14) | 0.0289 (5) | |
C23 | 0.5162 (2) | 0.24968 (19) | 0.32870 (18) | 0.0339 (6) | |
H23 | 0.5196 | 0.2076 | 0.2757 | 0.041* | |
C24 | 0.4062 (2) | 0.29363 (18) | 0.34906 (18) | 0.0297 (5) | |
H24 | 0.3372 | 0.2819 | 0.3103 | 0.036* | |
Cl25 | 0.65049 (6) | 0.52317 (5) | 0.26423 (5) | 0.03981 (18) | |
Cl26 | 0.53532 (13) | 0.38155 (10) | 0.11492 (8) | 0.1045 (5) | |
C27 | 0.7049 (2) | 0.51767 (18) | 0.14968 (19) | 0.0307 (5) | |
C28 | 0.6557 (3) | 0.4547 (2) | 0.0851 (2) | 0.0479 (8) | |
C29 | 0.7026 (4) | 0.4503 (3) | −0.0060 (2) | 0.0615 (10) | |
H29 | 0.6690 | 0.4063 | −0.0506 | 0.074* | |
C30 | 0.7973 (3) | 0.5093 (2) | −0.0316 (2) | 0.0436 (7) | |
H30 | 0.8291 | 0.5064 | −0.0938 | 0.052* | |
C31 | 0.8460 (3) | 0.5727 (2) | 0.0336 (2) | 0.0373 (6) | |
H31 | 0.9114 | 0.6135 | 0.0159 | 0.045* | |
C32 | 0.8011 (2) | 0.57769 (19) | 0.12369 (18) | 0.0323 (6) | |
H32 | 0.8352 | 0.6216 | 0.1681 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01424 (18) | 0.01427 (18) | 0.01493 (18) | 0.00194 (12) | 0.00336 (12) | 0.00131 (13) |
C1 | 0.0176 (10) | 0.0145 (9) | 0.0183 (10) | 0.0020 (7) | −0.0003 (8) | −0.0002 (8) |
C2 | 0.0183 (11) | 0.0197 (10) | 0.0218 (10) | 0.0056 (8) | 0.0018 (8) | 0.0023 (9) |
C3 | 0.0188 (11) | 0.0175 (10) | 0.0204 (10) | 0.0018 (8) | 0.0008 (8) | 0.0032 (8) |
C4 | 0.0179 (10) | 0.0151 (9) | 0.0158 (9) | 0.0004 (7) | 0.0009 (8) | 0.0003 (8) |
C5 | 0.0179 (10) | 0.0145 (9) | 0.0144 (9) | −0.0008 (7) | 0.0011 (8) | 0.0002 (8) |
C6 | 0.0164 (10) | 0.0172 (10) | 0.0152 (9) | −0.0014 (7) | 0.0019 (8) | −0.0001 (8) |
C7 | 0.0174 (11) | 0.0220 (10) | 0.0175 (10) | −0.0004 (8) | 0.0058 (8) | 0.0041 (8) |
C8 | 0.0162 (11) | 0.0223 (10) | 0.0202 (10) | 0.0006 (8) | 0.0054 (8) | 0.0004 (9) |
C9 | 0.0127 (10) | 0.0189 (10) | 0.0149 (10) | 0.0002 (7) | 0.0025 (8) | −0.0005 (8) |
C10 | 0.0138 (10) | 0.0175 (10) | 0.0179 (10) | 0.0025 (7) | 0.0015 (8) | −0.0009 (8) |
N11 | 0.0146 (9) | 0.0152 (8) | 0.0166 (8) | 0.0012 (6) | 0.0023 (7) | −0.0008 (7) |
N12 | 0.0151 (9) | 0.0146 (8) | 0.0170 (9) | 0.0004 (6) | 0.0024 (7) | 0.0020 (7) |
C13 | 0.0141 (10) | 0.0185 (10) | 0.0166 (10) | 0.0009 (7) | 0.0010 (8) | 0.0042 (8) |
C14 | 0.0177 (10) | 0.0162 (10) | 0.0193 (10) | 0.0014 (7) | 0.0028 (8) | 0.0002 (8) |
C15 | 0.0185 (11) | 0.0209 (10) | 0.0182 (10) | 0.0015 (8) | 0.0009 (8) | 0.0014 (8) |
N16 | 0.0173 (9) | 0.0198 (9) | 0.0198 (9) | −0.0001 (7) | 0.0011 (7) | 0.0039 (7) |
C17 | 0.0220 (11) | 0.0163 (10) | 0.0210 (10) | −0.0025 (8) | −0.0014 (8) | 0.0005 (9) |
C18 | 0.0235 (11) | 0.0191 (10) | 0.0171 (10) | −0.0014 (8) | 0.0002 (8) | 0.0006 (8) |
C19 | 0.0162 (10) | 0.0169 (10) | 0.0210 (10) | 0.0034 (8) | 0.0050 (8) | 0.0046 (8) |
C20 | 0.0199 (12) | 0.0310 (12) | 0.0293 (12) | 0.0048 (9) | 0.0002 (9) | −0.0069 (10) |
C21 | 0.0178 (12) | 0.0396 (14) | 0.0362 (14) | 0.0063 (10) | −0.0027 (10) | −0.0056 (11) |
N22 | 0.0217 (10) | 0.0310 (11) | 0.0340 (11) | 0.0078 (8) | 0.0065 (8) | −0.0014 (9) |
C23 | 0.0276 (14) | 0.0379 (14) | 0.0361 (14) | 0.0111 (10) | 0.0046 (11) | −0.0138 (12) |
C24 | 0.0195 (12) | 0.0376 (14) | 0.0322 (13) | 0.0059 (10) | −0.0014 (10) | −0.0109 (11) |
Cl25 | 0.0288 (4) | 0.0550 (4) | 0.0357 (4) | −0.0007 (3) | 0.0067 (3) | −0.0042 (3) |
Cl26 | 0.1194 (10) | 0.1229 (10) | 0.0716 (7) | −0.0962 (9) | 0.0275 (6) | −0.0274 (6) |
C27 | 0.0289 (14) | 0.0323 (13) | 0.0310 (13) | 0.0035 (10) | −0.0003 (10) | −0.0004 (11) |
C28 | 0.054 (2) | 0.0434 (17) | 0.0466 (17) | −0.0208 (14) | 0.0067 (15) | −0.0040 (14) |
C29 | 0.087 (3) | 0.054 (2) | 0.0429 (18) | −0.0329 (19) | 0.0103 (18) | −0.0192 (16) |
C30 | 0.060 (2) | 0.0369 (15) | 0.0338 (15) | −0.0059 (13) | 0.0095 (14) | −0.0046 (12) |
C31 | 0.0382 (16) | 0.0331 (14) | 0.0405 (15) | −0.0039 (11) | 0.0006 (12) | 0.0043 (12) |
C32 | 0.0346 (14) | 0.0309 (13) | 0.0315 (13) | −0.0005 (10) | −0.0050 (11) | −0.0016 (11) |
Zn1—N11i | 2.0662 (16) | C14—H14 | 0.9500 |
Zn1—N11 | 2.0663 (16) | C15—N16 | 1.333 (3) |
Zn1—N12 | 2.0675 (17) | C15—H15 | 0.9500 |
Zn1—N12i | 2.0675 (17) | N16—C17 | 1.336 (3) |
Zn1—N16ii | 2.3393 (17) | N16—Zn1iv | 2.3393 (17) |
Zn1—N16iii | 2.3393 (17) | C17—C18 | 1.383 (3) |
C1—N11 | 1.370 (3) | C17—H17 | 0.9500 |
C1—C10i | 1.407 (3) | C18—H18 | 0.9500 |
C1—C2 | 1.446 (3) | C19—C20 | 1.386 (3) |
C2—C3 | 1.351 (3) | C19—C24 | 1.387 (3) |
C2—H2 | 0.9500 | C20—C21 | 1.387 (3) |
C3—C4 | 1.450 (3) | C20—H20 | 0.9500 |
C3—H3 | 0.9500 | C21—N22 | 1.330 (3) |
C4—N11 | 1.374 (3) | C21—H21 | 0.9500 |
C4—C5 | 1.411 (3) | N22—C23 | 1.331 (3) |
C5—C6 | 1.411 (3) | C23—C24 | 1.388 (3) |
C5—C13 | 1.491 (3) | C23—H23 | 0.9500 |
C6—N12 | 1.362 (3) | C24—H24 | 0.9500 |
C6—C7 | 1.450 (3) | Cl25—C27 | 1.733 (3) |
C7—C8 | 1.356 (3) | Cl26—C28 | 1.723 (3) |
C7—H7 | 0.9500 | C27—C28 | 1.372 (4) |
C8—C9 | 1.451 (3) | C27—C32 | 1.398 (4) |
C8—H8 | 0.9500 | C28—C29 | 1.392 (4) |
C9—N12 | 1.368 (3) | C29—C30 | 1.375 (4) |
C9—C10 | 1.409 (3) | C29—H29 | 0.9500 |
C10—C1i | 1.407 (3) | C30—C31 | 1.380 (4) |
C10—C19 | 1.499 (3) | C30—H30 | 0.9500 |
C13—C14 | 1.394 (3) | C31—C32 | 1.371 (4) |
C13—C18 | 1.395 (3) | C31—H31 | 0.9500 |
C14—C15 | 1.381 (3) | C32—H32 | 0.9500 |
N11i—Zn1—N11 | 180.00 (8) | C14—C13—C5 | 121.15 (18) |
N11i—Zn1—N12 | 90.35 (7) | C18—C13—C5 | 121.79 (18) |
N11—Zn1—N12 | 89.65 (7) | C15—C14—C13 | 119.54 (19) |
N11i—Zn1—N12i | 89.65 (7) | C15—C14—H14 | 120.2 |
N11—Zn1—N12i | 90.35 (7) | C13—C14—H14 | 120.2 |
N12—Zn1—N12i | 180.00 (6) | N16—C15—C14 | 123.3 (2) |
N11i—Zn1—N16ii | 92.49 (6) | N16—C15—H15 | 118.4 |
N11—Zn1—N16ii | 87.51 (6) | C14—C15—H15 | 118.4 |
N12—Zn1—N16ii | 92.27 (6) | C15—N16—C17 | 117.32 (18) |
N12i—Zn1—N16ii | 87.73 (6) | C15—N16—Zn1iv | 120.13 (14) |
N11i—Zn1—N16iii | 87.51 (6) | C17—N16—Zn1iv | 118.11 (14) |
N11—Zn1—N16iii | 92.49 (6) | N16—C17—C18 | 123.46 (19) |
N12—Zn1—N16iii | 87.73 (6) | N16—C17—H17 | 118.3 |
N12i—Zn1—N16iii | 92.27 (7) | C18—C17—H17 | 118.3 |
N16ii—Zn1—N16iii | 180.0 | C17—C18—C13 | 119.2 (2) |
N11—C1—C10i | 125.45 (18) | C17—C18—H18 | 120.4 |
N11—C1—C2 | 109.41 (18) | C13—C18—H18 | 120.4 |
C10i—C1—C2 | 125.07 (19) | C20—C19—C24 | 116.8 (2) |
C3—C2—C1 | 107.20 (18) | C20—C19—C10 | 122.50 (19) |
C3—C2—H2 | 126.4 | C24—C19—C10 | 120.7 (2) |
C1—C2—H2 | 126.4 | C19—C20—C21 | 119.4 (2) |
C2—C3—C4 | 107.16 (18) | C19—C20—H20 | 120.3 |
C2—C3—H3 | 126.4 | C21—C20—H20 | 120.3 |
C4—C3—H3 | 126.4 | N22—C21—C20 | 124.2 (2) |
N11—C4—C5 | 124.98 (18) | N22—C21—H21 | 117.9 |
N11—C4—C3 | 109.10 (17) | C20—C21—H21 | 117.9 |
C5—C4—C3 | 125.91 (19) | C21—N22—C23 | 116.1 (2) |
C6—C5—C4 | 126.40 (18) | N22—C23—C24 | 124.0 (2) |
C6—C5—C13 | 117.69 (18) | N22—C23—H23 | 118.0 |
C4—C5—C13 | 115.91 (18) | C24—C23—H23 | 118.0 |
N12—C6—C5 | 125.20 (18) | C19—C24—C23 | 119.4 (2) |
N12—C6—C7 | 109.87 (18) | C19—C24—H24 | 120.3 |
C5—C6—C7 | 124.92 (18) | C23—C24—H24 | 120.3 |
C8—C7—C6 | 106.60 (18) | C28—C27—C32 | 120.0 (3) |
C8—C7—H7 | 126.7 | C28—C27—Cl25 | 120.9 (2) |
C6—C7—H7 | 126.7 | C32—C27—Cl25 | 119.1 (2) |
C7—C8—C9 | 107.05 (18) | C27—C28—C29 | 119.8 (3) |
C7—C8—H8 | 126.5 | C27—C28—Cl26 | 120.8 (2) |
C9—C8—H8 | 126.5 | C29—C28—Cl26 | 119.4 (2) |
N12—C9—C10 | 125.50 (18) | C30—C29—C28 | 120.2 (3) |
N12—C9—C8 | 109.41 (18) | C30—C29—H29 | 119.9 |
C10—C9—C8 | 125.08 (19) | C28—C29—H29 | 119.9 |
C1i—C10—C9 | 126.56 (19) | C29—C30—C31 | 119.6 (3) |
C1i—C10—C19 | 116.41 (18) | C29—C30—H30 | 120.2 |
C9—C10—C19 | 117.01 (18) | C31—C30—H30 | 120.2 |
C1—N11—C4 | 107.11 (16) | C32—C31—C30 | 120.8 (3) |
C1—N11—Zn1 | 126.06 (13) | C32—C31—H31 | 119.6 |
C4—N11—Zn1 | 126.73 (13) | C30—C31—H31 | 119.6 |
C6—N12—C9 | 107.04 (17) | C31—C32—C27 | 119.5 (2) |
C6—N12—Zn1 | 126.97 (14) | C31—C32—H32 | 120.3 |
C9—N12—Zn1 | 125.98 (14) | C27—C32—H32 | 120.3 |
C14—C13—C18 | 117.03 (19) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C40H24N8)]·2C6H4Cl2 |
Mr | 976.03 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 110 |
a, b, c (Å) | 11.0295 (2), 13.8207 (2), 14.1529 (3) |
β (°) | 90.2383 (7) |
V (Å3) | 2157.39 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.87 |
Crystal size (mm) | 0.30 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.781, 0.881 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16059, 5115, 3970 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.116, 1.05 |
No. of reflections | 5115 |
No. of parameters | 295 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.74 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006).
Zn1—N11i | 2.0662 (16) | Zn1—N16ii | 2.3393 (17) |
Zn1—N11 | 2.0663 (16) | Zn1—N16iii | 2.3393 (17) |
Zn1—N12 | 2.0675 (17) | N16—Zn1iv | 2.3393 (17) |
Zn1—N12i | 2.0675 (17) | ||
N11i—Zn1—N11 | 180.00 (8) | N12—Zn1—N16ii | 92.27 (6) |
N11i—Zn1—N12 | 90.35 (7) | N12i—Zn1—N16ii | 87.73 (6) |
N11—Zn1—N12 | 89.65 (7) | N11i—Zn1—N16iii | 87.51 (6) |
N11i—Zn1—N12i | 89.65 (7) | N11—Zn1—N16iii | 92.49 (6) |
N11—Zn1—N12i | 90.35 (7) | N12—Zn1—N16iii | 87.73 (6) |
N12—Zn1—N12i | 180.00 (6) | N12i—Zn1—N16iii | 92.27 (7) |
N11i—Zn1—N16ii | 92.49 (6) | N16ii—Zn1—N16iii | 180.0 |
N11—Zn1—N16ii | 87.51 (6) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x, y+1/2, −z+1/2. |
The tetra(pyridyl)porphyrin moiety in its free-base (TPyP) and metalated forms (MTPyP) is one of the most widely used building blocks in the design of porphyrin-based coordination networks. It has a planar and rigid structure, bearing laterally diverging pyridyl groups prone to coordination interaction with metal centres of neighbouring entities. There are two types of binding modes to this end. Thus, TPyP and MTPyP molecules may self-assemble readily through exocyclic metal ion nodes that can bridge between the lateral pyridyl sites of neighbouring units. A wide variety of such aggregation modes through diverse metal ion connectors have been reported (e.g. Abrahams et al., 1994; Hagrman et al., 1999; Sharma et al., 1999; Carlucci et al., 2003; Ohmura et al., 2006). Alternatively, those MTPyP scaffolds in which the metal ion inserted into the porphyrin centre has an additional axial coordination capacity may self-associate into homogeneous polymeric arrays without resorting to external foreign ion auxiliaries. Here, the pyridyl groups of one porphyrin unit coordinate directly to the metal centres of adjacent porphyrin entities, leading to either one-, two- or three-dimensional multiporphyrin aggregates (Fleischer & Shachter, 1991; Krupitsky et al., 1994; Lin, 1999; Diskin-Posner et al., 2001; Pan et al., 2002; George & Goldberg, 2005). The extended two-dimensional and three-dimensional coordination networks of the metalloporphyrins are of particular interest owing to their promising application in practical areas such as, for example, heterogeneous catalysis, molecular sieving and separation, as well as solid sensors. Indeed, the three-dimensional honeycomb coordination polymers of MTPyP were found to reveal attractive sorption and desorption features (Lin, 1999).
This study relates to the ZnTPyP compound and its direct self-assembly into coordination networks. In an earlier report (Krupitsky et al. 1994) we demonstrated the construction of isostructural three-dimensional single-framework ZnTPyP-polymers with intralattice channels accommodated by water or a mixture of water and methanol. In that structure-type (labeled as II) the zinc ion is six-coordinate. Every porphyrin framework is bound axially to two adjacent units through the zinc and equatorially to two additional porphyrins through two trans-related pyridyl substituents. A similarly structured acetic acid clathrate of ZnTPyP has been reported more recently (George & Goldberg, 2005). Another ladder-type one-dimensional coordination polymer composed of a mixture of five-coordinate and six-coordinate ZnTPyP moieties has also been reported (Diskin-Posner et al., 2001). In the present investigation we describe a two-dimensional mode of interporphyrin association of the ZnTPyP units, as observed in the title compound, (I). The latter represents a supramolecular isomer of the three-dimensionally interconnected framework of type (II) described earlier. In (I), the porphyrin moiety is located on a crystallographic inversion at (0,1/2,1/2), while the dichlorobenzene solvent resides in a general position (Fig. 1). The geometry around the zinc ion is also octahedral, the axial positions being occupied by two pyridine N atoms of two adjacent ZnTPyP molecules (Table 1). The mutual orientation of the neighboring porphyrins is roughly perpendicular, the dihedral angle between the mean planes of the respective macrocyclic core rings (atoms C1—C10/N11/N12) being 79 (1)° (Fig. 2). The slight deviation from strictly perpendicular mutual orientation of adjacent ZnTPyPs is reflected also in the non-linear Zn1···N16i···Zn1i (i= x,3/2-y,1/2+z) angle of 153.55 (5)°. Then, the inclined approach of the axially coordinated pyridyl group to the zinc ion finds its mark in the sum of bond angles around N16 to C15, C17 and Zn1(-x,y+1/2,1/2-z)" of 355.6°. The zinc–zinc distances in the multi-porphyrin assembly are 9.981 (2) Å. The observed approximate square-grid porphyrin assembly is similar to the `paddle-wheel-like' pattern found for the Fe(TPyP) structure (Pan et al., 2002). In the crystal, the ZnTPyP arrays are aligned parallel to the bc plane. As the self-assembly process took place in the presence of the dichlorobenzene solvent as a template, the two-dimensional coordination networks stack one on top of the other along the a axis in a parallel fashion, creating intra-lattice channel voids which accommodate molecules of the dichlorobenzene solvent (Fig. 2).
Fig. 3 shows projection of the crystal structure down the b axis, and reveals the lipophilic interface between adjacent polymeric arrays and the tight steric fit between them. The inter-layer stacking is thus mainly stabilized by dispersion forces. The important role of the dichlorobenzene solvent as templating agent in the creation of a clathrate-type structure can be appreciated by comparing the parallel stacking of the ZnTPyP coordination networks with the offset-stacked arrangements in a solvent-free structure of the FeTPyP flat polymeric arrays (Pan et al., 2002). In the latter case, the adjacent layers are shifted with respect to one another by about one-half of the grid size (approximately 7 Å). As a result, the pendant pyridine rings from the porphyrin entities in each FeTPyP layer effectively occupy the interporphyrin voids in the adjacent layers, without incorporating any additional solvent within the lattice.
As mentioned above the supramolecular aggregation modes of ZnTPyP in (I) and in its earlier reported clathrates, exhibiting ZnTPyP assembly mode of type (II) (Krupitsky et al., 1994; George & Goldberg, 2005), represent supramolecular isomers. As the two structure types crystallize concomitantly (see Experimental) from the crystallization mixture, the free energies of their formation should be comparable. In both structures, the coordination geometry around each zinc is octahedral, and every metalloporphyrin scaffold is coordinated to four adjacent units. The coordination geometries at every zinc site are almost identical in the two structure types. The central zinc ion binds axially from above and below to the pyridyl functions of two adjacent porphyrins, while two of the (trans-related) pyridyl groups coordinate to the metal centers of two other units. The two other pyridyl arms of each porphyrin remain non-coordinated in either isomeric arrangement. The main difference between the two structures lies in the relative orientation of the coordinated porphyrins, a degree of freedom which arises from the possible rotation of one framework with respect to the other about the intermolecular Zn—N bond. A fragment of the porphyrin framework in structure type (II) is illustrated in Fig. 4 (Krupitsky et al., 1994; George & Goldberg, 2005). Comparison of the spatial orientation of the assembled porphyrins reveals the following features. In the porphyrin framework of (I), molecules A and B, as well as A and C (as marked in Fig. 2), are nearly perpendicular to one another, while molecule B is parallel to C (and molecule A is parallel to D). On the other hand, in (II) the porphyrin cores B and C are nearly perpendicular [(rather than parallel, as in (I)] to each other, the corresponding dihedral angle between their respective mean planes being 83.5 (5)° (Fig. 4). The same applies to the next nearest neighbors A and D in (II). The actual structure that forms in a given experiment is affected by the crystallization environment. It appears that the three-dimensional coordination frameworking is preferred in hydrophilic solvents [such as water, acetic acid and small alcohols (Krupitsky et al., 1994; Lin, 1999; George & Goldberg, 2005)]. In such case the non-coordinated pyridyl groups are solvated by the hydrophilic agent, inducing the trigonal structure type (II), where all the non-coordinated pyridyl groups line the walls of the interporphyrin channels formed around the trigonal axes. The solvent species are accommodated in these channels. In crystallization environments lacking foreign species that can interact with the `free' N-atom sites of the pyridyl arms, the two-dimensional aggregation seems to be preferred, as in (I) and in FeTPyP. The `free' pyridyl arms are then oriented towards the surface of the coordination layers (Fig. 3), being involved in dispersive aryl–aryl interactions between the layers.
In summary, compound (I) reveals an interesting self-coordinated two-dimensional network of ZnTPyP, with a nearly square-grid geometry. It represents a supramolecular isomer of a three-dimensional coordination framework of ZnTPyP (Krupitsky et al., 1994; George & Goldberg, 2005). Compound (I) is a clathrate-type structure, wherein the dichlorobenzene solvent is accommodated within intra-lattice channels created in the parallel-stacked arrangement of the coordination networks.