In the title compound, [Co(C48H28N4O8)(C5H5N)2]·4C5H5N·H2O, the Co atom lies on a fourfold inversion axis, with the N atom and one C atom of the axial pyridine ligand on a twofold axis. Four pyridine solvent molecules hydrogen bond to the carboxylate groups of the porphyrin. The structure generates a hydrophobic void that incorporates a disordered solvent water molecule whose O atom lies on another fourfold inversion axis.
Supporting information
CCDC reference: 647335
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.004 Å
- H-atom completeness 97%
- R factor = 0.097
- wR factor = 0.326
- Data-to-parameter ratio = 16.3
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) ....... O1W
| Author Response: The hydrogen atoms on water could not be located from Fourier
difference maps.
|
Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for O1 - C12 .. 12.85 su
| Author Response: Outer atoms moving about the metal centre.
|
PLAT230_ALERT_2_B Hirshfeld Test Diff for C6 - C11 .. 9.34 su
| Author Response: Outer atoms moving about the metal centre.
|
PLAT230_ALERT_2_B Hirshfeld Test Diff for C9 - C10 .. 11.38 su
| Author Response: Outer atoms moving about the metal centre.
|
Alert level C
RFACR01_ALERT_3_C The value of the weighted R factor is > 0.25
Weighted R factor given 0.326
RINTA01_ALERT_3_C The value of Rint is greater than 0.10
Rint given 0.102
SHFSU01_ALERT_2_C The absolute value of parameter shift to su ratio > 0.05
Absolute value of the parameter shift to su ratio given 0.057
Additional refinement cycles may be required.
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.10
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.04
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT080_ALERT_2_C Maximum Shift/Error ............................ 0.06
PLAT084_ALERT_2_C High R2 Value .................................. 0.33
PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... C16
PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... C17
PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... C18
PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... C19
PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... C20
PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... N3
PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... C16
PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... C17
PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... C18
PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... C19
PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... C20
PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... N3
PLAT165_ALERT_3_C Nr. of Status R Flagged Non-Hydrogen Atoms ..... 6
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.78 Ratio
PLAT221_ALERT_4_C Large Solvent/Anion C Ueq(max)/Ueq(min) ... 3.07 Ratio
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.38 Ratio
PLAT223_ALERT_4_C Large Solvent/Anion H Ueq(max)/Ueq(min) ... 3.09 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Co1 - N1 .. 5.61 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C9
PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for C16
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N3
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C17
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C19
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.60
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.72
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C9 - C12 ... 1.55 Ang.
PLAT757_ALERT_4_C D...A Calc 2.66353, Rep 2.664(3) ...... Senseless su
O1 -N3 1.555 1.555
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C78 H60 Co1 N10 O9
Atom count from the _atom_site data: C78 H58 Co1 N10 O9
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C78 H60 Co N10 O9
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 312.00 312.00 0.00
H 240.00 232.00 8.00
Co 4.00 4.00 0.00
N 40.00 40.00 0.00
O 36.00 36.00 0.00
1 ALERT level A = In general: serious problem
3 ALERT level B = Potentially serious problem
37 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
14 ALERT type 2 Indicator that the structure model may be wrong or deficient
5 ALERT type 3 Indicator that the structure quality may be low
20 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Dipyridine[5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinato]cobalt(II) pyridine
tetrasolvate monohydrate
top
Crystal data top
[Co(C48H28N4O8)(C5H5N)2]·4C5H5N·H2O | Dx = 1.444 Mg m−3 |
Mr = 1340.29 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 26109 reflections |
Hall symbol: -I 4ad | θ = 1.6–27.0° |
a = 19.093 (4) Å | µ = 0.35 mm−1 |
c = 16.916 (6) Å | T = 150 K |
V = 6167 (3) Å3 | Block, purple |
Z = 4 | 0.26 × 0.15 × 0.12 mm |
F(000) = 2788 | |
Data collection top
Bruker SMART CCD 1000 diffractometer | 3342 independent reflections |
Radiation source: fine-focus sealed tube | 1975 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.103 |
φ and ω scans | θmax = 27.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −23→24 |
Tmin = 0.872, Tmax = 0.917 | k = −24→24 |
26109 measured reflections | l = −21→21 |
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)] = 0.097 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.326 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.1577P)2 + 26.3219P] where P = (Fo2 + 2Fc2)/3 |
3342 reflections | (Δ/σ)max = 0.057 |
205 parameters | Δρmax = 1.20 e Å−3 |
2 restraints | Δρmin = −0.69 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.0000 | 0.2500 | 0.6250 | 0.04441 (14) | |
N1 | −0.04395 (8) | 0.34282 (8) | 0.62367 (10) | 0.0446 (4) | |
N2 | 0.0000 | 0.2500 | 0.74072 (16) | 0.0477 (7) | |
O1 | 0.13244 (19) | 0.72827 (14) | 0.7717 (2) | 0.1599 (14) | |
H1A | 0.1493 | 0.7687 | 0.7765 | 0.240* | |
O2 | 0.18363 (16) | 0.73253 (12) | 0.6568 (2) | 0.1558 (13) | |
O1W | 0.5000 | 0.7500 | 0.6250 | 0.253 (6) | |
C1 | −0.11245 (10) | 0.35767 (10) | 0.60549 (14) | 0.0526 (6) | |
C2 | −0.12243 (12) | 0.43213 (10) | 0.60185 (17) | 0.0642 (7) | |
H2B | −0.1644 | 0.4560 | 0.5882 | 0.077* | |
C3 | −0.06106 (11) | 0.46149 (11) | 0.62148 (15) | 0.0600 (7) | |
H3A | −0.0520 | 0.5102 | 0.6265 | 0.072* | |
C4 | −0.01171 (10) | 0.40610 (10) | 0.63352 (14) | 0.0505 (6) | |
C5 | 0.05863 (10) | 0.41617 (10) | 0.65032 (15) | 0.0519 (6) | |
C6 | 0.08346 (11) | 0.48950 (10) | 0.66660 (16) | 0.0584 (7) | |
C7 | 0.11643 (18) | 0.52773 (13) | 0.6087 (2) | 0.0903 (10) | |
H7A | 0.1241 | 0.5072 | 0.5583 | 0.108* | |
C8 | 0.13872 (18) | 0.59585 (14) | 0.6225 (2) | 0.0967 (12) | |
H8A | 0.1605 | 0.6219 | 0.5815 | 0.116* | |
C9 | 0.12939 (17) | 0.62465 (14) | 0.6939 (2) | 0.0920 (11) | |
C10 | 0.09094 (16) | 0.59008 (14) | 0.7513 (2) | 0.0889 (10) | |
H10A | 0.0803 | 0.6125 | 0.8000 | 0.107* | |
C11 | 0.06797 (13) | 0.52162 (13) | 0.73668 (19) | 0.0745 (9) | |
H11A | 0.0415 | 0.4974 | 0.7756 | 0.089* | |
C12 | 0.1554 (3) | 0.70027 (19) | 0.7083 (3) | 0.1404 (18) | |
C13 | −0.05442 (12) | 0.27569 (12) | 0.78213 (16) | 0.0595 (7) | |
H13A | −0.0937 | 0.2934 | 0.7541 | 0.071* | |
C14 | −0.05537 (15) | 0.27732 (16) | 0.86262 (17) | 0.0770 (9) | |
H14A | −0.0940 | 0.2972 | 0.8900 | 0.092* | |
C15 | 0.0000 | 0.2500 | 0.90361 (11) | 0.0863 (14) | |
H15 | 0.0000 | 0.2500 | 0.9598 | 0.104* | |
C16 | 0.0938 | 0.9059 | 0.80896 (11) | 0.393 (4) | |
H16A | 0.0491 | 0.8870 | 0.8214 | 0.472* | |
C17 | 0.1039 | 0.9776 | 0.81751 (11) | 0.186 (3) | |
H17A | 0.0687 | 1.0052 | 0.8422 | 0.223* | |
C18 | 0.1657 | 1.0101 | 0.79019 (11) | 0.1666 (19) | |
H18A | 0.1726 | 1.0591 | 0.7958 | 0.200* | |
C19 | 0.2165 | 0.9675 | 0.75442 (11) | 0.1278 (17) | |
H19A | 0.2594 | 0.9856 | 0.7345 | 0.153* | |
C20 | 0.1985 | 0.8936 | 0.75025 (11) | 0.157 (2) | |
H20A | 0.2283 | 0.8626 | 0.7219 | 0.189* | |
N3 | 0.1389 | 0.8670 | 0.78656 (11) | 0.206 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.02882 (13) | 0.02882 (13) | 0.0756 (3) | 0.000 | 0.000 | 0.000 |
N1 | 0.0314 (7) | 0.0341 (7) | 0.0684 (10) | 0.0004 (6) | −0.0013 (7) | −0.0012 (7) |
N2 | 0.0323 (10) | 0.0297 (9) | 0.0810 (16) | −0.0054 (8) | 0.000 | 0.000 |
O1 | 0.206 (3) | 0.0677 (13) | 0.207 (3) | −0.0203 (17) | −0.041 (2) | −0.0350 (16) |
O2 | 0.142 (2) | 0.0594 (11) | 0.266 (3) | −0.0407 (12) | 0.051 (2) | −0.0249 (17) |
O1W | 0.308 (8) | 0.308 (8) | 0.142 (7) | 0.000 | 0.000 | 0.000 |
C1 | 0.0375 (9) | 0.0351 (9) | 0.0852 (15) | 0.0074 (7) | −0.0004 (9) | 0.0001 (9) |
C2 | 0.0447 (10) | 0.0336 (9) | 0.1145 (19) | 0.0082 (8) | −0.0113 (12) | 0.0025 (11) |
C3 | 0.0457 (10) | 0.0330 (9) | 0.1014 (17) | 0.0048 (8) | −0.0019 (11) | 0.0018 (10) |
C4 | 0.0396 (9) | 0.0299 (8) | 0.0819 (14) | −0.0002 (7) | 0.0018 (9) | 0.0007 (9) |
C5 | 0.0401 (9) | 0.0329 (8) | 0.0825 (14) | −0.0036 (7) | 0.0009 (10) | −0.0010 (9) |
C6 | 0.0485 (10) | 0.0337 (9) | 0.0930 (16) | −0.0055 (8) | −0.0039 (11) | −0.0041 (10) |
C7 | 0.1008 (19) | 0.0470 (12) | 0.123 (2) | −0.0258 (12) | 0.0227 (18) | −0.0025 (14) |
C8 | 0.0973 (19) | 0.0442 (12) | 0.148 (3) | −0.0193 (13) | 0.0227 (19) | −0.0026 (15) |
C9 | 0.0854 (18) | 0.0481 (12) | 0.142 (3) | −0.0189 (12) | 0.0003 (18) | −0.0078 (15) |
C10 | 0.0814 (17) | 0.0544 (13) | 0.131 (2) | 0.0086 (13) | −0.0140 (17) | −0.0230 (15) |
C11 | 0.0613 (13) | 0.0475 (12) | 0.115 (2) | 0.0017 (11) | −0.0070 (14) | −0.0066 (13) |
C12 | 0.164 (3) | 0.0658 (17) | 0.191 (4) | −0.043 (2) | 0.031 (3) | −0.031 (2) |
C13 | 0.0454 (10) | 0.0521 (11) | 0.0809 (15) | −0.0044 (9) | 0.0051 (11) | −0.0038 (11) |
C14 | 0.0640 (14) | 0.0852 (17) | 0.0818 (17) | −0.0096 (13) | 0.0081 (13) | −0.0053 (14) |
C15 | 0.080 (2) | 0.113 (3) | 0.066 (2) | −0.017 (2) | 0.000 | 0.000 |
C16 | 0.478 (7) | 0.124 (4) | 0.577 (9) | 0.136 (4) | −0.384 (6) | −0.129 (5) |
C17 | 0.085 (2) | 0.335 (7) | 0.137 (4) | 0.077 (3) | −0.017 (2) | −0.036 (4) |
C18 | 0.191 (4) | 0.123 (3) | 0.185 (4) | 0.047 (3) | −0.103 (3) | −0.040 (3) |
C19 | 0.076 (2) | 0.120 (3) | 0.188 (4) | −0.005 (2) | −0.012 (2) | −0.018 (3) |
C20 | 0.189 (5) | 0.120 (3) | 0.163 (4) | 0.021 (4) | 0.001 (4) | −0.020 (3) |
N3 | 0.214 (4) | 0.218 (4) | 0.185 (4) | −0.098 (3) | −0.069 (3) | 0.007 (3) |
Geometric parameters (Å, º) top
Co1—N2i | 1.957 (3) | C7—H7A | 0.9500 |
Co1—N2 | 1.957 (3) | C8—C9 | 1.339 (5) |
Co1—N1ii | 1.9610 (16) | C8—H8A | 0.9500 |
Co1—N1 | 1.9610 (16) | C9—C10 | 1.385 (5) |
Co1—N1i | 1.9610 (16) | C9—C12 | 1.546 (5) |
Co1—N1iii | 1.9610 (16) | C10—C11 | 1.401 (4) |
N1—C4 | 1.366 (2) | C10—H10A | 0.9500 |
N1—C1 | 1.373 (2) | C11—H11A | 0.9500 |
N2—C13 | 1.346 (3) | C13—C14 | 1.362 (4) |
N2—C13iii | 1.346 (3) | C13—H13A | 0.9500 |
O1—C12 | 1.276 (6) | C14—C15 | 1.368 (3) |
O1—H1A | 0.8400 | C14—H14A | 0.9500 |
O2—C12 | 1.195 (6) | C15—C14iii | 1.368 (3) |
C1—C5ii | 1.392 (3) | C15—H15 | 0.9500 |
C1—C2 | 1.436 (3) | C16—N3 | 1.1990 |
C2—C3 | 1.341 (3) | C16—C17 | 1.3899 |
C2—H2B | 0.9500 | C16—H16A | 0.9500 |
C3—C4 | 1.431 (3) | C17—C18 | 1.4097 |
C3—H3A | 0.9500 | C17—H17A | 0.9500 |
C4—C5 | 1.386 (3) | C18—C19 | 1.4032 |
C5—C1i | 1.392 (3) | C18—H18A | 0.9500 |
C5—C6 | 1.504 (3) | C19—C20 | 1.4544 |
C6—C11 | 1.367 (4) | C19—H19A | 0.9500 |
C6—C7 | 1.374 (4) | C20—N3 | 1.3899 |
C7—C8 | 1.388 (4) | C20—H20A | 0.9500 |
| | | |
N2i—Co1—N2 | 180.0 | C9—C8—C7 | 119.7 (3) |
N2i—Co1—N1ii | 90.66 (5) | C9—C8—H8A | 120.1 |
N2—Co1—N1ii | 89.34 (5) | C7—C8—H8A | 120.1 |
N2i—Co1—N1 | 89.34 (5) | C8—C9—C10 | 120.5 (3) |
N2—Co1—N1 | 90.66 (5) | C8—C9—C12 | 118.9 (3) |
N1ii—Co1—N1 | 90.008 (1) | C10—C9—C12 | 120.3 (3) |
N2i—Co1—N1i | 90.66 (5) | C9—C10—C11 | 119.1 (3) |
N2—Co1—N1i | 89.34 (5) | C9—C10—H10A | 120.5 |
N1ii—Co1—N1i | 178.68 (10) | C11—C10—H10A | 120.5 |
N1—Co1—N1i | 90.008 (2) | C6—C11—C10 | 120.3 (3) |
N2i—Co1—N1iii | 89.34 (5) | C6—C11—H11A | 119.9 |
N2—Co1—N1iii | 90.66 (5) | C10—C11—H11A | 119.9 |
N1ii—Co1—N1iii | 90.008 (1) | O2—C12—O1 | 123.5 (4) |
N1—Co1—N1iii | 178.68 (10) | O2—C12—C9 | 120.7 (4) |
N1i—Co1—N1iii | 90.007 (1) | O1—C12—C9 | 114.4 (4) |
C4—N1—C1 | 105.89 (15) | N2—C13—C14 | 122.6 (2) |
C4—N1—Co1 | 127.23 (12) | N2—C13—H13A | 118.7 |
C1—N1—Co1 | 126.65 (13) | C14—C13—H13A | 118.7 |
C13—N2—C13iii | 117.3 (3) | C13—C14—C15 | 119.2 (2) |
C13—N2—Co1 | 121.37 (15) | C13—C14—H14A | 120.4 |
C13iii—N2—Co1 | 121.37 (15) | C15—C14—H14A | 120.4 |
C12—O1—H1A | 109.5 | C14—C15—C14iii | 119.1 (3) |
N1—C1—C5ii | 125.34 (17) | C14—C15—C14iv | 59.09 (13) |
N1—C1—C2 | 109.91 (17) | C14iii—C15—C14iv | 119.80 (13) |
C5ii—C1—C2 | 124.42 (18) | C14—C15—H15 | 120.5 |
C3—C2—C1 | 106.71 (19) | C14iii—C15—H15 | 120.5 |
C3—C2—H2B | 126.6 | C14iv—C15—H15 | 90.9 |
C1—C2—H2B | 126.6 | N3—C16—C17 | 122.9 |
C2—C3—C4 | 107.55 (18) | N3—C16—H16A | 118.6 |
C2—C3—H3A | 126.2 | C17—C16—H16A | 118.6 |
C4—C3—H3A | 126.2 | C16—C17—C18 | 121.1 |
N1—C4—C5 | 125.75 (17) | C16—C17—H17A | 119.5 |
N1—C4—C3 | 109.85 (17) | C18—C17—H17A | 119.5 |
C5—C4—C3 | 124.37 (18) | C19—C18—C17 | 117.7 |
C4—C5—C1i | 122.35 (18) | C19—C18—H18A | 121.1 |
C4—C5—C6 | 118.18 (17) | C17—C18—H18A | 121.1 |
C1i—C5—C6 | 119.13 (18) | C18—C19—C20 | 114.8 |
C11—C6—C7 | 118.6 (2) | C18—C19—H19A | 122.6 |
C11—C6—C5 | 120.5 (2) | C20—C19—H19A | 122.6 |
C7—C6—C5 | 120.6 (2) | N3—C20—C19 | 121.8 |
C6—C7—C8 | 121.2 (3) | N3—C20—H20A | 119.1 |
C6—C7—H7A | 119.4 | C19—C20—H20A | 119.1 |
C8—C7—H7A | 119.4 | C16—N3—C20 | 120.1 |
Symmetry codes: (i) y−1/4, −x+1/4, −z+5/4; (ii) −y+1/4, x+1/4, −z+5/4; (iii) −x, −y+1/2, z; (iv) −x−2, −y−1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N3 | 0.84 | 1.90 | 2.664 (3) | 151 |