The crystal structure of the title compound, [Zn(C40H24N8)]·1.6C2H4O2 has been determined at ca 110 K. The centrosymmetric metalloporphyrin compound forms a self-assembled honeycomb architecture, with open channels extending parallel to the c axis of the unit cell. The compound crystallizes as an acetic acid clathrate. The guest species, which are included in the interporphyrin channels, hydrogen bond to the porphyrin framework.
Supporting information
CCDC reference: 282624
Key indicators
- Single-crystal X-ray study
- T = 110 K
- Mean (C-C) = 0.005 Å
- Disorder in solvent or counterion
- R factor = 0.055
- wR factor = 0.165
- Data-to-parameter ratio = 17.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.90
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) ..... 20 Ang.
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C25
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 80.00 Perc.
Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
From the CIF: _diffrn_reflns_theta_max 27.87
From the CIF: _reflns_number_total 4514
From the CIF: _diffrn_reflns_limit_ max hkl 36. 43. 11.
From the CIF: _diffrn_reflns_limit_ min hkl -36. -43. -11.
TEST1: Expected hkl limits for theta max
Calculated maximum hkl 43. 43. 11.
Calculated minimum hkl -43. -43. -11.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
4 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: Collect (Nonius , 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: DIRDIF96 (Beurskens et al., 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), Mercury (Bruno et al.,
2002) and DS ViewerPro (Accelrys, 2002); software used to prepare material for publication: SHELXL97.
Crystal data top
[Zn(C10H6N2)]4·1.6C2H4O2 | Dx = 1.365 Mg m−3 |
Mr = 778.79 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 8992 reflections |
a = 33.0359 (2) Å | θ = 2.1–27.9° |
c = 9.0191 (3) Å | µ = 0.70 mm−1 |
V = 8524.4 (3) Å3 | T = 110 K |
Z = 9 | Prism, red–violet |
F(000) = 3613.7 | 0.25 × 0.20 × 0.20 mm |
Data collection top
Nonius KappaCCD diffractometer | 3055 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 27.9°, θmin = 2.1° |
φ scans | h = −36→36 |
21174 measured reflections | k = −43→43 |
4514 independent reflections | l = −11→11 |
Refinement top
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0988P)2 + 2.8002P] where P = (Fo2 + 2Fc2)/3 |
4514 reflections | (Δ/σ)max < 0.001 |
261 parameters | Δρmax = 1.38 e Å−3 |
1 restraint | Δρmin = −0.47 e Å−3 |
Special details top
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. The acetic acid guest appears severely disordered in the interporphyrin
channels. It was refined with a partial occupancy of 0.805. The residual
electron density map shows two relatively high peaks of 1.38 e.Å-3 at
0,0,0 and 0.91 e.Å-3 at 0.0117,0.0364,-0.0310 (on and near centers of
inversion), which may reflect presence of traces of disordered water at this
site. The remaining peaks and troughs were below 0.65 e.Å-3. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Zn | 0.1667 | 0.3333 | 0.3333 | 0.02767 (17) | |
C1 | 0.22205 (10) | 0.30817 (10) | 0.5496 (3) | 0.0340 (6) | |
C2 | 0.25109 (11) | 0.32486 (11) | 0.6802 (4) | 0.0429 (8) | |
H2 | 0.2688 | 0.3122 | 0.7218 | 0.051* | |
C3 | 0.08485 (11) | 0.30484 (11) | −0.0661 (4) | 0.0416 (7) | |
H3 | 0.0695 | 0.2867 | −0.1512 | 0.050* | |
C4 | 0.11562 (10) | 0.29820 (10) | 0.0326 (3) | 0.0339 (6) | |
C5 | 0.12502 (9) | 0.26110 (10) | 0.0243 (3) | 0.0323 (6) | |
C6 | 0.14991 (9) | 0.25098 (10) | 0.1292 (3) | 0.0324 (6) | |
C7 | 0.16307 (11) | 0.21527 (11) | 0.1134 (4) | 0.0388 (7) | |
H7 | 0.1551 | 0.1937 | 0.0340 | 0.047* | |
C8 | 0.18902 (11) | 0.21889 (10) | 0.2345 (4) | 0.0390 (7) | |
H8 | 0.2029 | 0.2003 | 0.2554 | 0.047* | |
C9 | 0.19172 (10) | 0.25601 (10) | 0.3258 (3) | 0.0328 (6) | |
C10 | 0.21742 (10) | 0.27191 (10) | 0.4585 (3) | 0.0335 (6) | |
N11 | 0.13161 (8) | 0.33175 (8) | 0.1407 (3) | 0.0315 (5) | |
N12 | 0.16707 (8) | 0.27437 (8) | 0.2602 (3) | 0.0313 (5) | |
C13 | 0.10609 (10) | 0.22892 (10) | −0.1065 (3) | 0.0372 (7) | |
C14 | 0.12124 (12) | 0.24496 (12) | −0.2489 (4) | 0.0429 (7) | |
H14 | 0.1429 | 0.2771 | −0.2659 | 0.052* | |
C15 | 0.10457 (13) | 0.21387 (14) | −0.3665 (4) | 0.0546 (9) | |
H15 | 0.1161 | 0.2253 | −0.4631 | 0.066* | |
N16 | 0.07300 (12) | 0.16863 (11) | −0.3506 (4) | 0.0625 (9) | |
C17 | 0.05760 (15) | 0.15353 (13) | −0.2130 (5) | 0.0629 (11) | |
H17 | 0.0346 | 0.1216 | −0.1999 | 0.076* | |
C18 | 0.07328 (12) | 0.18187 (11) | −0.0888 (4) | 0.0479 (8) | |
H18 | 0.0618 | 0.1694 | 0.0069 | 0.057* | |
C19 | 0.24354 (10) | 0.24740 (10) | 0.5026 (3) | 0.0347 (7) | |
C20 | 0.28606 (11) | 0.25925 (11) | 0.4367 (4) | 0.0408 (7) | |
H20 | 0.2997 | 0.2839 | 0.3665 | 0.049* | |
C21 | 0.30806 (11) | 0.23475 (11) | 0.4747 (4) | 0.0406 (7) | |
H21 | 0.3370 | 0.2429 | 0.4286 | 0.049* | |
N22 | 0.29054 (9) | 0.19986 (8) | 0.5736 (3) | 0.0360 (6) | |
C23 | 0.25012 (11) | 0.18905 (11) | 0.6378 (4) | 0.0412 (7) | |
H23 | 0.2374 | 0.1645 | 0.7086 | 0.049* | |
C24 | 0.22557 (11) | 0.21200 (11) | 0.6064 (4) | 0.0413 (7) | |
H24 | 0.1970 | 0.2035 | 0.6555 | 0.050* | |
C25 | 0.0392 (2) | 0.1124 (2) | 0.3047 (7) | 0.0782 (18) | 0.805 (8) |
C26 | 0.0282 (2) | 0.0845 (3) | 0.1785 (8) | 0.109 (3) | 0.805 (8) |
H26A | 0.0081 | 0.0907 | 0.1134 | 0.164* | 0.805 (8) |
H26B | 0.0117 | 0.0515 | 0.2075 | 0.164* | 0.805 (8) |
H26C | 0.0570 | 0.0918 | 0.1258 | 0.164* | 0.805 (8) |
O27 | 0.0394 (3) | 0.1470 (2) | 0.2995 (10) | 0.178 (4) | 0.805 (8) |
O28 | 0.0523 (4) | 0.1032 (4) | 0.4242 (9) | 0.233 (5) | 0.805 (8) |
H28 | 0.0598 | 0.1267 | 0.5067 | 0.100* | 0.805 (8) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn | 0.0241 (3) | 0.0292 (3) | 0.0329 (3) | 0.01571 (19) | −0.00058 (17) | −0.00048 (17) |
C1 | 0.0358 (15) | 0.0375 (15) | 0.0360 (16) | 0.0239 (13) | −0.0054 (12) | −0.0008 (12) |
C2 | 0.0462 (18) | 0.0509 (19) | 0.0460 (19) | 0.0351 (16) | −0.0126 (14) | −0.0076 (15) |
C3 | 0.0411 (17) | 0.0450 (18) | 0.0442 (18) | 0.0257 (15) | −0.0130 (14) | −0.0063 (14) |
C4 | 0.0331 (15) | 0.0351 (15) | 0.0367 (16) | 0.0194 (12) | −0.0026 (12) | −0.0033 (12) |
C5 | 0.0281 (14) | 0.0329 (14) | 0.0371 (16) | 0.0163 (12) | −0.0002 (11) | −0.0005 (12) |
C6 | 0.0278 (14) | 0.0317 (14) | 0.0386 (16) | 0.0156 (12) | −0.0001 (11) | −0.0027 (12) |
C7 | 0.0434 (17) | 0.0387 (16) | 0.0428 (18) | 0.0269 (14) | −0.0061 (13) | −0.0075 (13) |
C8 | 0.0404 (16) | 0.0375 (16) | 0.0481 (19) | 0.0263 (14) | −0.0053 (14) | −0.0064 (13) |
C9 | 0.0324 (14) | 0.0321 (14) | 0.0404 (16) | 0.0210 (12) | −0.0016 (12) | −0.0017 (12) |
C10 | 0.0321 (14) | 0.0361 (15) | 0.0386 (17) | 0.0217 (12) | −0.0037 (12) | 0.0000 (12) |
N11 | 0.0291 (12) | 0.0322 (12) | 0.0378 (14) | 0.0187 (10) | −0.0013 (10) | 0.0002 (10) |
N12 | 0.0272 (12) | 0.0302 (12) | 0.0389 (14) | 0.0161 (10) | −0.0016 (10) | −0.0015 (10) |
C13 | 0.0374 (16) | 0.0375 (16) | 0.0420 (18) | 0.0228 (13) | −0.0084 (13) | −0.0069 (13) |
C14 | 0.0479 (18) | 0.0434 (18) | 0.0421 (19) | 0.0263 (15) | −0.0032 (14) | −0.0037 (14) |
C15 | 0.063 (2) | 0.068 (2) | 0.045 (2) | 0.042 (2) | −0.0071 (17) | −0.0070 (17) |
N16 | 0.074 (2) | 0.059 (2) | 0.060 (2) | 0.0370 (18) | −0.0238 (18) | −0.0235 (17) |
C17 | 0.066 (2) | 0.0411 (19) | 0.071 (3) | 0.0190 (18) | −0.017 (2) | −0.0119 (18) |
C18 | 0.051 (2) | 0.0393 (18) | 0.049 (2) | 0.0194 (15) | −0.0124 (16) | −0.0045 (15) |
C19 | 0.0377 (16) | 0.0369 (16) | 0.0376 (17) | 0.0245 (13) | −0.0056 (12) | −0.0050 (12) |
C20 | 0.0435 (17) | 0.0457 (17) | 0.0429 (18) | 0.0297 (15) | 0.0040 (14) | 0.0078 (14) |
C21 | 0.0406 (17) | 0.0506 (19) | 0.0397 (17) | 0.0296 (15) | 0.0064 (13) | 0.0058 (14) |
N22 | 0.0393 (13) | 0.0360 (13) | 0.0389 (14) | 0.0234 (11) | −0.0018 (11) | 0.0010 (11) |
C23 | 0.0381 (16) | 0.0417 (17) | 0.0479 (19) | 0.0229 (14) | 0.0028 (14) | 0.0084 (14) |
C24 | 0.0387 (16) | 0.0458 (17) | 0.0480 (19) | 0.0275 (15) | 0.0013 (14) | 0.0048 (14) |
C25 | 0.076 (4) | 0.089 (5) | 0.073 (4) | 0.045 (4) | 0.001 (3) | −0.019 (3) |
C26 | 0.079 (5) | 0.130 (6) | 0.076 (5) | 0.020 (4) | −0.011 (4) | −0.012 (4) |
O27 | 0.176 (7) | 0.074 (4) | 0.277 (10) | 0.058 (4) | 0.067 (6) | −0.021 (5) |
O28 | 0.371 (14) | 0.270 (11) | 0.135 (7) | 0.216 (11) | −0.121 (8) | −0.096 (7) |
Geometric parameters (Å, º) top
Zn—N12 | 2.063 (2) | C13—C14 | 1.384 (5) |
Zn—N12i | 2.063 (2) | C13—C18 | 1.390 (5) |
Zn—N11i | 2.074 (2) | C14—C15 | 1.384 (5) |
Zn—N11 | 2.074 (2) | C14—H14 | 0.9500 |
Zn—N22ii | 2.336 (2) | C15—N16 | 1.335 (5) |
Zn—N22iii | 2.336 (2) | C15—H15 | 0.9500 |
C1—N11i | 1.368 (3) | N16—C17 | 1.340 (5) |
C1—C10 | 1.397 (4) | C17—C18 | 1.384 (5) |
C1—C2 | 1.444 (4) | C17—H17 | 0.9500 |
C2—C3i | 1.352 (4) | C18—H18 | 0.9500 |
C2—H2 | 0.9500 | C19—C24 | 1.379 (4) |
C3—C2i | 1.352 (4) | C19—C20 | 1.389 (4) |
C3—C4 | 1.448 (4) | C20—C21 | 1.374 (4) |
C3—H3 | 0.9500 | C20—H20 | 0.9500 |
C4—N11 | 1.369 (4) | C21—N22 | 1.339 (4) |
C4—C5 | 1.409 (4) | C21—H21 | 0.9500 |
C5—C6 | 1.399 (4) | N22—C23 | 1.330 (4) |
C5—C13 | 1.499 (4) | N22—Zniv | 2.336 (2) |
C6—N12 | 1.370 (4) | C23—C24 | 1.388 (4) |
C6—C7 | 1.454 (4) | C23—H23 | 0.9500 |
C7—C8 | 1.356 (4) | C24—H24 | 0.9500 |
C7—H7 | 0.9500 | C25—O27 | 1.141 (8) |
C8—C9 | 1.442 (4) | C25—O28 | 1.254 (9) |
C8—H8 | 0.9500 | C25—C26 | 1.392 (7) |
C9—N12 | 1.370 (3) | C26—H26A | 0.9800 |
C9—C10 | 1.408 (4) | C26—H26B | 0.9800 |
C10—C19 | 1.502 (4) | C26—H26C | 0.9800 |
N11—C1i | 1.368 (3) | O28—H28 | 1.0130 |
| | | |
N12—Zn—N12i | 180.0 | C9—N12—C6 | 107.0 (2) |
N12—Zn—N11i | 91.42 (9) | C9—N12—Zn | 124.47 (19) |
N12i—Zn—N11i | 88.58 (9) | C6—N12—Zn | 127.77 (18) |
N12—Zn—N11 | 88.59 (9) | C14—C13—C18 | 117.7 (3) |
N12i—Zn—N11 | 91.41 (9) | C14—C13—C5 | 121.0 (3) |
N11i—Zn—N11 | 180.0 | C18—C13—C5 | 121.2 (3) |
N12—Zn—N22ii | 86.80 (9) | C13—C14—C15 | 119.6 (3) |
N12i—Zn—N22ii | 93.20 (9) | C13—C14—H14 | 120.2 |
N11i—Zn—N22ii | 82.42 (9) | C15—C14—H14 | 120.2 |
N11—Zn—N22ii | 97.59 (9) | N16—C15—C14 | 123.1 (4) |
N12—Zn—N22iii | 93.21 (9) | N16—C15—H15 | 118.4 |
N12i—Zn—N22iii | 86.79 (9) | C14—C15—H15 | 118.4 |
N11i—Zn—N22iii | 97.58 (9) | C15—N16—C17 | 117.0 (3) |
N11—Zn—N22iii | 82.41 (9) | N16—C17—C18 | 123.7 (4) |
N22ii—Zn—N22iii | 180.0 | N16—C17—H17 | 118.2 |
N11i—C1—C10 | 125.7 (3) | C18—C17—H17 | 118.2 |
N11i—C1—C2 | 109.1 (3) | C17—C18—C13 | 118.8 (4) |
C10—C1—C2 | 125.1 (3) | C17—C18—H18 | 120.6 |
C3i—C2—C1 | 107.5 (3) | C13—C18—H18 | 120.6 |
C3i—C2—H2 | 126.3 | C24—C19—C20 | 118.4 (3) |
C1—C2—H2 | 126.3 | C24—C19—C10 | 121.1 (3) |
C2i—C3—C4 | 106.8 (3) | C20—C19—C10 | 120.5 (3) |
C2i—C3—H3 | 126.6 | C21—C20—C19 | 119.0 (3) |
C4—C3—H3 | 126.6 | C21—C20—H20 | 120.5 |
N11—C4—C5 | 125.4 (3) | C19—C20—H20 | 120.5 |
N11—C4—C3 | 109.3 (2) | N22—C21—C20 | 123.0 (3) |
C5—C4—C3 | 125.2 (3) | N22—C21—H21 | 118.5 |
C6—C5—C4 | 125.7 (3) | C20—C21—H21 | 118.5 |
C6—C5—C13 | 116.7 (2) | C23—N22—C21 | 117.7 (3) |
C4—C5—C13 | 117.6 (2) | C23—N22—Zniv | 118.7 (2) |
N12—C6—C5 | 125.1 (3) | C21—N22—Zniv | 122.7 (2) |
N12—C6—C7 | 109.6 (2) | N22—C23—C24 | 123.1 (3) |
C5—C6—C7 | 125.3 (3) | N22—C23—H23 | 118.4 |
C8—C7—C6 | 106.4 (3) | C24—C23—H23 | 118.4 |
C8—C7—H7 | 126.8 | C19—C24—C23 | 118.7 (3) |
C6—C7—H7 | 126.8 | C19—C24—H24 | 120.6 |
C7—C8—C9 | 107.6 (3) | C23—C24—H24 | 120.6 |
C7—C8—H8 | 126.2 | O27—C25—O28 | 116.5 (8) |
C9—C8—H8 | 126.2 | O27—C25—C26 | 119.8 (9) |
N12—C9—C10 | 125.7 (3) | O28—C25—C26 | 123.4 (8) |
N12—C9—C8 | 109.4 (2) | C25—C26—H26A | 109.5 |
C10—C9—C8 | 124.9 (3) | C25—C26—H26B | 109.5 |
C1—C10—C9 | 127.4 (3) | H26A—C26—H26B | 109.5 |
C1—C10—C19 | 117.4 (3) | C25—C26—H26C | 109.5 |
C9—C10—C19 | 115.2 (2) | H26A—C26—H26C | 109.5 |
C1i—N11—C4 | 107.3 (2) | H26B—C26—H26C | 109.5 |
C1i—N11—Zn | 124.25 (19) | C25—O28—H28 | 115.3 |
C4—N11—Zn | 126.99 (18) | | |
Symmetry codes: (i) −x+1/3, −y+2/3, −z+2/3; (ii) −x+y+1/3, −x+2/3, z−1/3; (iii) x−y, x, −z+1; (iv) −y+2/3, x−y+1/3, z+1/3. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O28—H28···N16v | 1.01 | 1.78 | 2.790 (8) | 179 |
Symmetry code: (v) x, y, z+1. |