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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805018556/sg6017sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805018556/sg6017Isup2.hkl
Contains datablock I

CCDC reference: 282624

Key indicators

  • Single-crystal X-ray study
  • T = 110 K
  • Mean [sigma](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

Computing details top

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.

(I) top
Crystal data top
[Zn(C10H6N2)]4·1.6C2H4O2Dx = 1.365 Mg m3
Mr = 778.79Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 8992 reflections
a = 33.0359 (2) Åθ = 2.1–27.9°
c = 9.0191 (3) ŵ = 0.70 mm1
V = 8524.4 (3) Å3T = 110 K
Z = 9Prism, red–violet
F(000) = 3613.70.25 × 0.20 × 0.20 mm
Data collection top
Nonius KappaCCD
diffractometer
3055 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.041
Graphite monochromatorθmax = 27.9°, θmin = 2.1°
φ scansh = 3636
21174 measured reflectionsk = 4343
4514 independent reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165H-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 parametersΔρmax = 1.38 e Å3
1 restraintΔρmin = 0.47 e Å3
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
xyzUiso*/UeqOcc. (<1)
Zn0.16670.33330.33330.02767 (17)
C10.22205 (10)0.30817 (10)0.5496 (3)0.0340 (6)
C20.25109 (11)0.32486 (11)0.6802 (4)0.0429 (8)
H20.26880.31220.72180.051*
C30.08485 (11)0.30484 (11)0.0661 (4)0.0416 (7)
H30.06950.28670.15120.050*
C40.11562 (10)0.29820 (10)0.0326 (3)0.0339 (6)
C50.12502 (9)0.26110 (10)0.0243 (3)0.0323 (6)
C60.14991 (9)0.25098 (10)0.1292 (3)0.0324 (6)
C70.16307 (11)0.21527 (11)0.1134 (4)0.0388 (7)
H70.15510.19370.03400.047*
C80.18902 (11)0.21889 (10)0.2345 (4)0.0390 (7)
H80.20290.20030.25540.047*
C90.19172 (10)0.25601 (10)0.3258 (3)0.0328 (6)
C100.21742 (10)0.27191 (10)0.4585 (3)0.0335 (6)
N110.13161 (8)0.33175 (8)0.1407 (3)0.0315 (5)
N120.16707 (8)0.27437 (8)0.2602 (3)0.0313 (5)
C130.10609 (10)0.22892 (10)0.1065 (3)0.0372 (7)
C140.12124 (12)0.24496 (12)0.2489 (4)0.0429 (7)
H140.14290.27710.26590.052*
C150.10457 (13)0.21387 (14)0.3665 (4)0.0546 (9)
H150.11610.22530.46310.066*
N160.07300 (12)0.16863 (11)0.3506 (4)0.0625 (9)
C170.05760 (15)0.15353 (13)0.2130 (5)0.0629 (11)
H170.03460.12160.19990.076*
C180.07328 (12)0.18187 (11)0.0888 (4)0.0479 (8)
H180.06180.16940.00690.057*
C190.24354 (10)0.24740 (10)0.5026 (3)0.0347 (7)
C200.28606 (11)0.25925 (11)0.4367 (4)0.0408 (7)
H200.29970.28390.36650.049*
C210.30806 (11)0.23475 (11)0.4747 (4)0.0406 (7)
H210.33700.24290.42860.049*
N220.29054 (9)0.19986 (8)0.5736 (3)0.0360 (6)
C230.25012 (11)0.18905 (11)0.6378 (4)0.0412 (7)
H230.23740.16450.70860.049*
C240.22557 (11)0.21200 (11)0.6064 (4)0.0413 (7)
H240.19700.20350.65550.050*
C250.0392 (2)0.1124 (2)0.3047 (7)0.0782 (18)0.805 (8)
C260.0282 (2)0.0845 (3)0.1785 (8)0.109 (3)0.805 (8)
H26A0.00810.09070.11340.164*0.805 (8)
H26B0.01170.05150.20750.164*0.805 (8)
H26C0.05700.09180.12580.164*0.805 (8)
O270.0394 (3)0.1470 (2)0.2995 (10)0.178 (4)0.805 (8)
O280.0523 (4)0.1032 (4)0.4242 (9)0.233 (5)0.805 (8)
H280.05980.12670.50670.100*0.805 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.0241 (3)0.0292 (3)0.0329 (3)0.01571 (19)0.00058 (17)0.00048 (17)
C10.0358 (15)0.0375 (15)0.0360 (16)0.0239 (13)0.0054 (12)0.0008 (12)
C20.0462 (18)0.0509 (19)0.0460 (19)0.0351 (16)0.0126 (14)0.0076 (15)
C30.0411 (17)0.0450 (18)0.0442 (18)0.0257 (15)0.0130 (14)0.0063 (14)
C40.0331 (15)0.0351 (15)0.0367 (16)0.0194 (12)0.0026 (12)0.0033 (12)
C50.0281 (14)0.0329 (14)0.0371 (16)0.0163 (12)0.0002 (11)0.0005 (12)
C60.0278 (14)0.0317 (14)0.0386 (16)0.0156 (12)0.0001 (11)0.0027 (12)
C70.0434 (17)0.0387 (16)0.0428 (18)0.0269 (14)0.0061 (13)0.0075 (13)
C80.0404 (16)0.0375 (16)0.0481 (19)0.0263 (14)0.0053 (14)0.0064 (13)
C90.0324 (14)0.0321 (14)0.0404 (16)0.0210 (12)0.0016 (12)0.0017 (12)
C100.0321 (14)0.0361 (15)0.0386 (17)0.0217 (12)0.0037 (12)0.0000 (12)
N110.0291 (12)0.0322 (12)0.0378 (14)0.0187 (10)0.0013 (10)0.0002 (10)
N120.0272 (12)0.0302 (12)0.0389 (14)0.0161 (10)0.0016 (10)0.0015 (10)
C130.0374 (16)0.0375 (16)0.0420 (18)0.0228 (13)0.0084 (13)0.0069 (13)
C140.0479 (18)0.0434 (18)0.0421 (19)0.0263 (15)0.0032 (14)0.0037 (14)
C150.063 (2)0.068 (2)0.045 (2)0.042 (2)0.0071 (17)0.0070 (17)
N160.074 (2)0.059 (2)0.060 (2)0.0370 (18)0.0238 (18)0.0235 (17)
C170.066 (2)0.0411 (19)0.071 (3)0.0190 (18)0.017 (2)0.0119 (18)
C180.051 (2)0.0393 (18)0.049 (2)0.0194 (15)0.0124 (16)0.0045 (15)
C190.0377 (16)0.0369 (16)0.0376 (17)0.0245 (13)0.0056 (12)0.0050 (12)
C200.0435 (17)0.0457 (17)0.0429 (18)0.0297 (15)0.0040 (14)0.0078 (14)
C210.0406 (17)0.0506 (19)0.0397 (17)0.0296 (15)0.0064 (13)0.0058 (14)
N220.0393 (13)0.0360 (13)0.0389 (14)0.0234 (11)0.0018 (11)0.0010 (11)
C230.0381 (16)0.0417 (17)0.0479 (19)0.0229 (14)0.0028 (14)0.0084 (14)
C240.0387 (16)0.0458 (17)0.0480 (19)0.0275 (15)0.0013 (14)0.0048 (14)
C250.076 (4)0.089 (5)0.073 (4)0.045 (4)0.001 (3)0.019 (3)
C260.079 (5)0.130 (6)0.076 (5)0.020 (4)0.011 (4)0.012 (4)
O270.176 (7)0.074 (4)0.277 (10)0.058 (4)0.067 (6)0.021 (5)
O280.371 (14)0.270 (11)0.135 (7)0.216 (11)0.121 (8)0.096 (7)
Geometric parameters (Å, º) top
Zn—N122.063 (2)C13—C141.384 (5)
Zn—N12i2.063 (2)C13—C181.390 (5)
Zn—N11i2.074 (2)C14—C151.384 (5)
Zn—N112.074 (2)C14—H140.9500
Zn—N22ii2.336 (2)C15—N161.335 (5)
Zn—N22iii2.336 (2)C15—H150.9500
C1—N11i1.368 (3)N16—C171.340 (5)
C1—C101.397 (4)C17—C181.384 (5)
C1—C21.444 (4)C17—H170.9500
C2—C3i1.352 (4)C18—H180.9500
C2—H20.9500C19—C241.379 (4)
C3—C2i1.352 (4)C19—C201.389 (4)
C3—C41.448 (4)C20—C211.374 (4)
C3—H30.9500C20—H200.9500
C4—N111.369 (4)C21—N221.339 (4)
C4—C51.409 (4)C21—H210.9500
C5—C61.399 (4)N22—C231.330 (4)
C5—C131.499 (4)N22—Zniv2.336 (2)
C6—N121.370 (4)C23—C241.388 (4)
C6—C71.454 (4)C23—H230.9500
C7—C81.356 (4)C24—H240.9500
C7—H70.9500C25—O271.141 (8)
C8—C91.442 (4)C25—O281.254 (9)
C8—H80.9500C25—C261.392 (7)
C9—N121.370 (3)C26—H26A0.9800
C9—C101.408 (4)C26—H26B0.9800
C10—C191.502 (4)C26—H26C0.9800
N11—C1i1.368 (3)O28—H281.0130
N12—Zn—N12i180.0C9—N12—C6107.0 (2)
N12—Zn—N11i91.42 (9)C9—N12—Zn124.47 (19)
N12i—Zn—N11i88.58 (9)C6—N12—Zn127.77 (18)
N12—Zn—N1188.59 (9)C14—C13—C18117.7 (3)
N12i—Zn—N1191.41 (9)C14—C13—C5121.0 (3)
N11i—Zn—N11180.0C18—C13—C5121.2 (3)
N12—Zn—N22ii86.80 (9)C13—C14—C15119.6 (3)
N12i—Zn—N22ii93.20 (9)C13—C14—H14120.2
N11i—Zn—N22ii82.42 (9)C15—C14—H14120.2
N11—Zn—N22ii97.59 (9)N16—C15—C14123.1 (4)
N12—Zn—N22iii93.21 (9)N16—C15—H15118.4
N12i—Zn—N22iii86.79 (9)C14—C15—H15118.4
N11i—Zn—N22iii97.58 (9)C15—N16—C17117.0 (3)
N11—Zn—N22iii82.41 (9)N16—C17—C18123.7 (4)
N22ii—Zn—N22iii180.0N16—C17—H17118.2
N11i—C1—C10125.7 (3)C18—C17—H17118.2
N11i—C1—C2109.1 (3)C17—C18—C13118.8 (4)
C10—C1—C2125.1 (3)C17—C18—H18120.6
C3i—C2—C1107.5 (3)C13—C18—H18120.6
C3i—C2—H2126.3C24—C19—C20118.4 (3)
C1—C2—H2126.3C24—C19—C10121.1 (3)
C2i—C3—C4106.8 (3)C20—C19—C10120.5 (3)
C2i—C3—H3126.6C21—C20—C19119.0 (3)
C4—C3—H3126.6C21—C20—H20120.5
N11—C4—C5125.4 (3)C19—C20—H20120.5
N11—C4—C3109.3 (2)N22—C21—C20123.0 (3)
C5—C4—C3125.2 (3)N22—C21—H21118.5
C6—C5—C4125.7 (3)C20—C21—H21118.5
C6—C5—C13116.7 (2)C23—N22—C21117.7 (3)
C4—C5—C13117.6 (2)C23—N22—Zniv118.7 (2)
N12—C6—C5125.1 (3)C21—N22—Zniv122.7 (2)
N12—C6—C7109.6 (2)N22—C23—C24123.1 (3)
C5—C6—C7125.3 (3)N22—C23—H23118.4
C8—C7—C6106.4 (3)C24—C23—H23118.4
C8—C7—H7126.8C19—C24—C23118.7 (3)
C6—C7—H7126.8C19—C24—H24120.6
C7—C8—C9107.6 (3)C23—C24—H24120.6
C7—C8—H8126.2O27—C25—O28116.5 (8)
C9—C8—H8126.2O27—C25—C26119.8 (9)
N12—C9—C10125.7 (3)O28—C25—C26123.4 (8)
N12—C9—C8109.4 (2)C25—C26—H26A109.5
C10—C9—C8124.9 (3)C25—C26—H26B109.5
C1—C10—C9127.4 (3)H26A—C26—H26B109.5
C1—C10—C19117.4 (3)C25—C26—H26C109.5
C9—C10—C19115.2 (2)H26A—C26—H26C109.5
C1i—N11—C4107.3 (2)H26B—C26—H26C109.5
C1i—N11—Zn124.25 (19)C25—O28—H28115.3
C4—N11—Zn126.99 (18)
Symmetry codes: (i) x+1/3, y+2/3, z+2/3; (ii) x+y+1/3, x+2/3, z1/3; (iii) xy, x, z+1; (iv) y+2/3, xy+1/3, z+1/3.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O28—H28···N16v1.011.782.790 (8)179
Symmetry code: (v) x, y, z+1.
 

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