The title cobalt coordination polymers,
catena-poly[[[aquatripyridinecobalt(II)]-μ-tetrachloroterephthalato] pyridine solvate], {[Co(C
8Cl
4O
4)(C
5H
5N)
3(H
2O)]·C
5H
5N}
n, (I), and
catena-poly[[[diaquadipyridinecobalt(II)]-μ-tetrachloroterephthalato] 1,4-dioxane trihydrate], {[Co(C
8Cl
4O
4)(C
5H
5N)
2(H
2O)
2]·C
4H
8O
2·3H
2O}
n, (II), have been prepared with tetrachloroterephthalic acid (H
2BDC-Cl
4) under different solvent media. Both complexes form infinite cobalt(II)–tetrachloroterephthalate polymeric chains. In (I), two independent Co
II ions are six-coordinated through N
3O
3 donor sets in slightly distorted octahedral geometries provided by two carboxylate and three pyridine ligands, and one water molecule. The structure of (II) contains two independent Co
II atoms, each lying on a twofold axis, which adopt a tetragonally distorted N
2O
4 octahedral geometry
via two carboxylate groups, two pyridine ligands and two water molecules. The different stoichiometry of coordinated and solvent guest molecules leads to different two-dimensional supramolecular networks, with (I) utilizing C—H
π and weak π–π interactions and (II) utilizing mainly conventional hydrogen bonding.
Supporting information
CCDC references: 724190; 724191
To a solution of CoCl2.6H2O (23.8 mg, 0.1 mmol) in a mixture of pyridine and
water (v/v 1:1, 10 ml) was added a solution of H2BDC-Cl4
(30.4 mg, 0.1 mmol) in water (5 ml). After stirring for 30 min, the reaction
mixture was filtered and left to stand at room temperature. After 3 d, pink
block-shaped crystals of (I) suitable for X-ray diffraction were obtained by
slow evaporation of the filtrate in a yield of 78% (54.2 mg, based on
H2BDC-Cl4). Analysis found: C 48.42, H 3.18, N 8.13%; calculated for
C56H44Cl8Co2N8O10: C 48.37, H 3.19, N 8.06%. For the preparation
of (II), an aqueous solution (5 ml) of CoCl2.6H2O (23.8 mg, 0.1 mmol) was
added to a dioxane and water solution (v/v 1:1, 10 ml) of
H2BDC-Cl4 (30.4 mg, 0.1 mmol) with stirring for 30 min. Pyridine (0.5 ml)
was then added and allowed to diffuse into the mixture at room temperature.
After 7 d, pink block-shaped crystals of (II) suitable for X-ray diffraction
were collected by slow evaporation of the filtrate in a yield of 67% (46.4 mg,
based on H2BDC-Cl4). Analysis found: C 37.73, H 3.94, N 4.09%; calculated
for C22H28Cl4CoN2O11: C 37.90, H 4.05, N 4.02%.
H atoms bonded to C atoms were positioned geometrically (C—H = 0.93 and 0.97 Å for pyridine and dioxane H atoms, respectively) and included in the
refinement in the riding-model approximation. All of the water H atoms were
located in difference maps and refined as riding. Uiso(H)
values for all H atoms were set at 1.2Ueq(C,O). The
electron density trough in (II) (-0.62 e.Å-3) is 0.66 Å from atom Co1.
For both compounds, data collection: APEX2 (Bruker, 2003); cell refinement: APEX2 (Bruker, 2003) and SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
(I)
catena-poly[[[aquatripyridinecobalt(II)]-µ-tetrachloroterephthalato]
pyridine solvate]
top
Crystal data top
[Co(C8Cl4O4)(C5H5N)3(H2O)]·C5H5N | Z = 4 |
Mr = 695.23 | F(000) = 1412 |
Triclinic, P1 | Dx = 1.535 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7128 (10) Å | Cell parameters from 9967 reflections |
b = 17.8408 (17) Å | θ = 2.4–27.7° |
c = 21.227 (2) Å | µ = 0.97 mm−1 |
α = 67.879 (1)° | T = 291 K |
β = 79.839 (2)° | Block, pink |
γ = 84.962 (1)° | 0.30 × 0.26 × 0.24 mm |
V = 3007.9 (5) Å3 | |
Data collection top
Bruker SMART APEX CCD diffractometer | 11691 independent reflections |
Radiation source: sealed tube | 8460 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
phi and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.76, Tmax = 0.79 | k = −22→21 |
23660 measured reflections | l = −26→26 |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.050P)2 + 0.880P] where P = (Fo2 + 2Fc2)/3 |
11691 reflections | (Δ/σ)max < 0.001 |
757 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.62 e Å−3 |
Crystal data top
[Co(C8Cl4O4)(C5H5N)3(H2O)]·C5H5N | γ = 84.962 (1)° |
Mr = 695.23 | V = 3007.9 (5) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.7128 (10) Å | Mo Kα radiation |
b = 17.8408 (17) Å | µ = 0.97 mm−1 |
c = 21.227 (2) Å | T = 291 K |
α = 67.879 (1)° | 0.30 × 0.26 × 0.24 mm |
β = 79.839 (2)° | |
Data collection top
Bruker SMART APEX CCD diffractometer | 11691 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 8460 reflections with I > 2σ(I) |
Tmin = 0.76, Tmax = 0.79 | Rint = 0.027 |
23660 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.27 e Å−3 |
11691 reflections | Δρmin = −0.62 e Å−3 |
757 parameters | |
Special details top
Experimental. IR (KBr, υ, cm-1): 3133 (bs), 1650 (s), 1608 (vs), 1495
(m), 1413 (s), 1383 (m), 1340 (vs), 1250
(m), 1113 (m), 798 (m), 678 (s), 619 (s). |
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 | |
C1 | 0.8462 (3) | 0.85114 (18) | −0.13517 (14) | 0.0313 (6) | |
C2 | 0.7901 (3) | 0.79935 (18) | −0.06148 (15) | 0.0348 (7) | |
C3 | 0.6318 (3) | 0.80117 (17) | −0.03282 (15) | 0.0329 (6) | |
C4 | 0.5781 (3) | 0.75106 (18) | 0.03454 (14) | 0.0310 (6) | |
C5 | 0.6781 (3) | 0.69760 (17) | 0.07618 (14) | 0.0325 (6) | |
C6 | 0.8360 (3) | 0.69622 (18) | 0.04746 (15) | 0.0335 (6) | |
C7 | 0.8899 (3) | 0.74689 (17) | −0.01986 (15) | 0.0325 (6) | |
C8 | 0.6203 (3) | 0.64243 (17) | 0.14873 (14) | 0.0298 (6) | |
C9 | 0.2889 (3) | 0.32289 (19) | 0.34797 (15) | 0.0349 (7) | |
C10 | 0.2516 (3) | 0.28377 (18) | 0.42552 (15) | 0.0342 (7) | |
C11 | 0.1137 (3) | 0.30136 (18) | 0.46246 (15) | 0.0348 (7) | |
C12 | 0.0791 (3) | 0.26337 (18) | 0.53421 (15) | 0.0363 (7) | |
C13 | 0.1830 (4) | 0.20799 (17) | 0.57205 (15) | 0.0361 (7) | |
C14 | 0.3194 (3) | 0.19136 (18) | 0.53514 (15) | 0.0366 (7) | |
C15 | 0.3540 (3) | 0.22823 (18) | 0.46375 (14) | 0.0334 (6) | |
C16 | 0.1483 (4) | 0.16751 (18) | 0.64926 (15) | 0.0367 (7) | |
C17 | 0.2447 (4) | 0.62283 (19) | 0.25021 (16) | 0.0392 (7) | |
H17 | 0.3404 | 0.6462 | 0.2436 | 0.047* | |
C18 | 0.1114 (4) | 0.6674 (2) | 0.25993 (17) | 0.0428 (8) | |
H18 | 0.1171 | 0.7189 | 0.2607 | 0.051* | |
C19 | −0.0318 (4) | 0.6332 (2) | 0.26853 (16) | 0.0425 (8) | |
H19 | −0.1244 | 0.6618 | 0.2741 | 0.051* | |
C20 | −0.0339 (3) | 0.55571 (19) | 0.26865 (15) | 0.0395 (7) | |
H20 | −0.1280 | 0.5309 | 0.2751 | 0.047* | |
C21 | 0.1057 (3) | 0.51591 (19) | 0.25903 (15) | 0.0353 (7) | |
H21 | 0.1034 | 0.4639 | 0.2590 | 0.042* | |
C22 | 0.3849 (4) | 0.3770 (2) | 0.15766 (16) | 0.0396 (7) | |
H22 | 0.4139 | 0.3349 | 0.1958 | 0.048* | |
C23 | 0.3544 (4) | 0.3598 (2) | 0.10299 (17) | 0.0433 (8) | |
H23 | 0.3614 | 0.3066 | 0.1051 | 0.052* | |
C24 | 0.3140 (4) | 0.4205 (2) | 0.04593 (18) | 0.0431 (8) | |
H24 | 0.2965 | 0.4100 | 0.0081 | 0.052* | |
C25 | 0.3001 (4) | 0.4977 (2) | 0.04630 (17) | 0.0420 (7) | |
H25 | 0.2703 | 0.5405 | 0.0088 | 0.050* | |
C26 | 0.3306 (3) | 0.51112 (19) | 0.10259 (15) | 0.0360 (7) | |
H26 | 0.3203 | 0.5636 | 0.1022 | 0.043* | |
C27 | 0.7562 (4) | 0.4231 (2) | 0.16352 (18) | 0.0440 (8) | |
H27 | 0.7166 | 0.4568 | 0.1242 | 0.053* | |
C28 | 0.9010 (4) | 0.38457 (19) | 0.15619 (17) | 0.0418 (8) | |
H28 | 0.9575 | 0.3935 | 0.1126 | 0.050* | |
C29 | 0.9588 (4) | 0.3336 (2) | 0.21347 (18) | 0.0426 (8) | |
H29 | 1.0539 | 0.3063 | 0.2096 | 0.051* | |
C30 | 0.8738 (4) | 0.32327 (19) | 0.27703 (17) | 0.0389 (7) | |
H30 | 0.9108 | 0.2890 | 0.3169 | 0.047* | |
C31 | 0.7327 (4) | 0.36443 (19) | 0.28104 (17) | 0.0407 (7) | |
H31 | 0.6772 | 0.3578 | 0.3244 | 0.049* | |
C32 | −0.2697 (4) | 0.12233 (19) | 0.71839 (16) | 0.0392 (7) | |
H32 | −0.2169 | 0.1247 | 0.6756 | 0.047* | |
C33 | −0.4071 (4) | 0.1660 (2) | 0.72113 (17) | 0.0435 (8) | |
H33 | −0.4449 | 0.1976 | 0.6807 | 0.052* | |
C34 | −0.4885 (4) | 0.1629 (2) | 0.78363 (18) | 0.0476 (8) | |
H34 | −0.5814 | 0.1922 | 0.7864 | 0.057* | |
C35 | −0.4284 (4) | 0.1149 (2) | 0.84212 (17) | 0.0418 (8) | |
H35 | −0.4799 | 0.1114 | 0.8854 | 0.050* | |
C36 | −0.2892 (4) | 0.07189 (19) | 0.83543 (17) | 0.0408 (7) | |
H36 | −0.2511 | 0.0384 | 0.8752 | 0.049* | |
C37 | 0.3631 (3) | −0.02126 (19) | 0.74271 (16) | 0.0367 (7) | |
H37 | 0.3614 | 0.0322 | 0.7397 | 0.044* | |
C38 | 0.5052 (4) | −0.0575 (2) | 0.73164 (16) | 0.0392 (7) | |
H38 | 0.5969 | −0.0295 | 0.7221 | 0.047* | |
C39 | 0.5095 (4) | −0.1363 (2) | 0.73494 (17) | 0.0423 (8) | |
H39 | 0.6036 | −0.1625 | 0.7269 | 0.051* | |
C40 | 0.3697 (4) | −0.1749 (2) | 0.75058 (16) | 0.0383 (7) | |
H40 | 0.3687 | −0.2285 | 0.7541 | 0.046* | |
C41 | 0.2324 (4) | −0.1345 (2) | 0.76095 (16) | 0.0406 (7) | |
H41 | 0.1393 | −0.1613 | 0.7708 | 0.049* | |
C42 | 0.1498 (4) | −0.0078 (2) | 0.89425 (15) | 0.0384 (7) | |
H42 | 0.1643 | −0.0605 | 0.8954 | 0.046* | |
C43 | 0.1872 (4) | 0.0086 (2) | 0.94846 (17) | 0.0410 (7) | |
H43 | 0.2262 | −0.0320 | 0.9849 | 0.049* | |
C44 | 0.1649 (4) | 0.0867 (2) | 0.94703 (17) | 0.0398 (7) | |
H44 | 0.1861 | 0.0997 | 0.9831 | 0.048* | |
C45 | 0.1105 (4) | 0.1455 (2) | 0.89090 (18) | 0.0457 (8) | |
H45 | 0.0961 | 0.1989 | 0.8881 | 0.055* | |
C46 | 0.0782 (4) | 0.12326 (19) | 0.83941 (18) | 0.0411 (7) | |
H46 | 0.0433 | 0.1632 | 0.8015 | 0.049* | |
C47 | 0.9492 (4) | 0.1167 (2) | 0.43452 (18) | 0.0450 (8) | |
H47 | 1.0237 | 0.1563 | 0.4121 | 0.054* | |
H48 | 0.9403 | 0.1255 | 0.5266 | 0.054* | |
C48 | 0.9004 (4) | 0.0982 (2) | 0.50350 (17) | 0.0406 (7) | |
C49 | 0.7908 (4) | 0.0394 (2) | 0.53715 (17) | 0.0431 (8) | |
H49 | 0.7586 | 0.0231 | 0.5844 | 0.052* | |
C50 | 0.7318 (4) | 0.00624 (19) | 0.49930 (16) | 0.0394 (7) | |
H50 | 0.6538 | −0.0317 | 0.5200 | 0.047* | |
C51 | 0.7861 (4) | 0.0283 (2) | 0.43077 (18) | 0.0448 (8) | |
H51 | 0.7434 | 0.0045 | 0.4058 | 0.054* | |
C52 | 0.4964 (4) | 0.4126 (2) | 0.47055 (18) | 0.0477 (8) | |
H52 | 0.5933 | 0.4015 | 0.4490 | 0.057* | |
C53 | 0.4510 (4) | 0.3639 (2) | 0.53794 (17) | 0.0413 (7) | |
H53 | 0.5131 | 0.3205 | 0.5608 | 0.050* | |
C54 | 0.3160 (4) | 0.3813 (2) | 0.56874 (17) | 0.0420 (8) | |
H54 | 0.2827 | 0.3499 | 0.6146 | 0.050* | |
C55 | 0.2251 (4) | 0.4430 (2) | 0.53591 (19) | 0.0505 (9) | |
H55 | 0.1301 | 0.4558 | 0.5579 | 0.061* | |
C56 | 0.2804 (4) | 0.4872 (2) | 0.46666 (17) | 0.0449 (8) | |
H56 | 0.2184 | 0.5294 | 0.4420 | 0.054* | |
Cl1 | 1.08649 (8) | 0.74542 (5) | −0.05327 (4) | 0.0433 (2) | |
Cl2 | 0.96200 (9) | 0.62941 (5) | 0.09719 (4) | 0.0445 (2) | |
Cl3 | 0.50547 (9) | 0.86625 (5) | −0.08360 (4) | 0.0488 (2) | |
Cl4 | 0.38215 (8) | 0.75212 (5) | 0.06803 (4) | 0.04241 (19) | |
Cl5 | −0.01658 (10) | 0.37221 (5) | 0.41810 (4) | 0.0505 (2) | |
Cl6 | −0.09346 (10) | 0.28776 (5) | 0.57784 (4) | 0.0513 (2) | |
Cl7 | 0.52658 (9) | 0.20347 (5) | 0.42020 (4) | 0.0495 (2) | |
Cl8 | 0.45660 (9) | 0.12642 (5) | 0.58018 (4) | 0.0450 (2) | |
Co1 | 0.45643 (4) | 0.47938 (2) | 0.23727 (2) | 0.03219 (11) | |
Co2 | 0.01039 (4) | 0.01012 (2) | 0.765790 (19) | 0.03243 (11) | |
N1 | 0.2451 (3) | 0.54853 (16) | 0.24963 (12) | 0.0351 (6) | |
N2 | 0.3743 (3) | 0.45198 (15) | 0.15768 (13) | 0.0362 (6) | |
N3 | 0.6719 (3) | 0.41329 (17) | 0.22562 (14) | 0.0416 (6) | |
N4 | −0.2082 (3) | 0.07630 (15) | 0.77496 (13) | 0.0380 (6) | |
N5 | 0.2269 (3) | −0.05772 (16) | 0.75754 (13) | 0.0379 (6) | |
N6 | 0.0941 (3) | 0.04765 (14) | 0.84056 (13) | 0.0340 (6) | |
N7 | 0.8963 (3) | 0.08156 (17) | 0.39802 (14) | 0.0446 (7) | |
N8 | 0.4161 (3) | 0.47188 (16) | 0.43500 (14) | 0.0396 (6) | |
O1 | 0.6363 (2) | 0.66500 (12) | 0.19639 (10) | 0.0340 (5) | |
O2 | 0.5589 (3) | 0.58016 (13) | 0.15312 (11) | 0.0433 (5) | |
O3 | 0.9125 (3) | 0.91503 (13) | −0.14355 (11) | 0.0419 (5) | |
O4 | 0.8250 (2) | 0.82567 (12) | −0.17965 (10) | 0.0357 (5) | |
O5 | 0.1862 (3) | 0.20301 (14) | 0.68327 (11) | 0.0436 (5) | |
O6 | 0.0863 (2) | 0.09859 (13) | 0.67153 (10) | 0.0409 (5) | |
O7 | 0.3689 (2) | 0.38528 (12) | 0.32531 (10) | 0.0363 (5) | |
O8 | 0.2373 (3) | 0.29009 (14) | 0.31466 (11) | 0.0442 (5) | |
O9 | 0.5608 (2) | 0.51868 (12) | 0.30226 (11) | 0.0392 (5) | |
H9A | 0.5059 | 0.5159 | 0.3403 | 0.047* | |
H9B | 0.5882 | 0.5671 | 0.2791 | 0.047* | |
O10 | −0.0886 (2) | −0.04343 (12) | 0.70756 (10) | 0.0358 (5) | |
H10B | −0.1266 | −0.0861 | 0.7393 | 0.043* | |
H10A | −0.0190 | −0.0561 | 0.6795 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0265 (14) | 0.0348 (16) | 0.0247 (14) | −0.0039 (12) | −0.0018 (11) | −0.0024 (12) |
C2 | 0.0322 (15) | 0.0321 (16) | 0.0325 (15) | −0.0067 (12) | −0.0060 (12) | −0.0016 (12) |
C3 | 0.0307 (14) | 0.0227 (14) | 0.0364 (16) | −0.0028 (11) | −0.0066 (12) | 0.0002 (12) |
C4 | 0.0257 (13) | 0.0325 (15) | 0.0265 (14) | −0.0036 (11) | −0.0005 (11) | −0.0025 (12) |
C5 | 0.0328 (15) | 0.0264 (15) | 0.0295 (15) | −0.0128 (12) | −0.0007 (12) | 0.0004 (12) |
C6 | 0.0300 (14) | 0.0343 (16) | 0.0304 (15) | −0.0017 (12) | −0.0090 (12) | −0.0034 (12) |
C7 | 0.0273 (14) | 0.0272 (15) | 0.0352 (15) | −0.0050 (11) | 0.0004 (11) | −0.0039 (12) |
C8 | 0.0283 (14) | 0.0266 (15) | 0.0264 (14) | 0.0003 (11) | −0.0048 (11) | −0.0004 (12) |
C9 | 0.0327 (15) | 0.0363 (17) | 0.0300 (15) | −0.0052 (13) | −0.0043 (12) | −0.0052 (13) |
C10 | 0.0358 (15) | 0.0309 (16) | 0.0296 (15) | −0.0087 (12) | −0.0010 (12) | −0.0040 (12) |
C11 | 0.0351 (15) | 0.0306 (16) | 0.0294 (15) | 0.0001 (12) | −0.0071 (12) | 0.0001 (12) |
C12 | 0.0351 (15) | 0.0323 (16) | 0.0283 (15) | −0.0018 (12) | 0.0078 (12) | −0.0018 (12) |
C13 | 0.0410 (16) | 0.0250 (15) | 0.0312 (15) | −0.0081 (12) | 0.0025 (12) | 0.0003 (12) |
C14 | 0.0362 (16) | 0.0290 (16) | 0.0292 (15) | 0.0031 (12) | −0.0070 (12) | 0.0068 (12) |
C15 | 0.0320 (15) | 0.0308 (15) | 0.0268 (14) | 0.0013 (12) | 0.0018 (11) | −0.0020 (12) |
C16 | 0.0454 (17) | 0.0237 (15) | 0.0297 (15) | 0.0008 (13) | −0.0006 (13) | 0.0001 (12) |
C17 | 0.0390 (17) | 0.0388 (18) | 0.0373 (17) | 0.0068 (14) | −0.0061 (13) | −0.0129 (14) |
C18 | 0.0391 (17) | 0.0420 (19) | 0.0437 (18) | 0.0150 (14) | −0.0161 (14) | −0.0110 (15) |
C19 | 0.0394 (17) | 0.0448 (19) | 0.0396 (17) | 0.0132 (14) | −0.0093 (14) | −0.0129 (15) |
C20 | 0.0287 (15) | 0.0401 (18) | 0.0341 (16) | 0.0011 (13) | −0.0006 (12) | 0.0016 (13) |
C21 | 0.0333 (15) | 0.0319 (16) | 0.0321 (15) | −0.0036 (12) | −0.0071 (12) | −0.0003 (13) |
C22 | 0.0477 (18) | 0.0366 (17) | 0.0361 (16) | −0.0075 (14) | 0.0011 (14) | −0.0170 (14) |
C23 | 0.0440 (18) | 0.0379 (18) | 0.0477 (19) | −0.0241 (14) | 0.0018 (15) | −0.0143 (15) |
C24 | 0.0448 (18) | 0.0440 (19) | 0.0461 (19) | −0.0127 (15) | −0.0097 (15) | −0.0191 (16) |
C25 | 0.0488 (19) | 0.0374 (18) | 0.0407 (17) | −0.0061 (14) | −0.0124 (14) | −0.0117 (14) |
C26 | 0.0389 (16) | 0.0320 (16) | 0.0364 (16) | −0.0024 (13) | −0.0140 (13) | −0.0080 (13) |
C27 | 0.0435 (18) | 0.0409 (19) | 0.0432 (18) | 0.0025 (14) | 0.0041 (14) | −0.0160 (15) |
C28 | 0.0397 (17) | 0.0386 (18) | 0.0425 (18) | −0.0004 (14) | 0.0065 (14) | −0.0156 (15) |
C29 | 0.0304 (15) | 0.0414 (18) | 0.054 (2) | 0.0091 (13) | −0.0083 (14) | −0.0162 (16) |
C30 | 0.0439 (17) | 0.0349 (17) | 0.0407 (17) | 0.0080 (13) | −0.0146 (14) | −0.0153 (14) |
C31 | 0.0411 (17) | 0.0317 (17) | 0.0451 (18) | 0.0025 (13) | −0.0147 (14) | −0.0066 (14) |
C32 | 0.0399 (17) | 0.0350 (17) | 0.0377 (17) | 0.0003 (13) | 0.0012 (13) | −0.0111 (14) |
C33 | 0.0426 (18) | 0.0425 (19) | 0.0441 (18) | 0.0084 (14) | −0.0162 (14) | −0.0124 (15) |
C34 | 0.0427 (18) | 0.047 (2) | 0.055 (2) | 0.0111 (15) | −0.0078 (16) | −0.0231 (17) |
C35 | 0.0383 (17) | 0.0410 (18) | 0.0394 (17) | 0.0038 (14) | 0.0084 (13) | −0.0148 (15) |
C36 | 0.0462 (18) | 0.0291 (16) | 0.0436 (18) | 0.0040 (13) | −0.0120 (14) | −0.0083 (14) |
C37 | 0.0382 (16) | 0.0308 (16) | 0.0413 (17) | 0.0073 (13) | −0.0175 (13) | −0.0103 (13) |
C38 | 0.0302 (15) | 0.0461 (19) | 0.0374 (17) | −0.0050 (13) | −0.0047 (12) | −0.0103 (14) |
C39 | 0.0413 (17) | 0.0351 (17) | 0.0467 (19) | 0.0108 (14) | −0.0148 (14) | −0.0096 (14) |
C40 | 0.0404 (17) | 0.0362 (17) | 0.0394 (17) | 0.0132 (13) | −0.0187 (13) | −0.0130 (14) |
C41 | 0.0353 (16) | 0.0425 (19) | 0.0398 (17) | −0.0004 (13) | −0.0083 (13) | −0.0093 (14) |
C42 | 0.0433 (17) | 0.0387 (18) | 0.0327 (16) | 0.0038 (14) | −0.0066 (13) | −0.0132 (14) |
C43 | 0.0403 (17) | 0.0400 (18) | 0.0440 (18) | −0.0037 (14) | −0.0183 (14) | −0.0109 (15) |
C44 | 0.0425 (17) | 0.0432 (19) | 0.0424 (17) | −0.0089 (14) | −0.0142 (14) | −0.0205 (15) |
C45 | 0.0469 (19) | 0.0409 (19) | 0.050 (2) | −0.0154 (15) | −0.0087 (15) | −0.0141 (16) |
C46 | 0.0433 (17) | 0.0293 (16) | 0.0520 (19) | −0.0047 (13) | −0.0021 (14) | −0.0178 (15) |
C47 | 0.0452 (18) | 0.0376 (18) | 0.052 (2) | 0.0089 (14) | −0.0122 (15) | −0.0163 (16) |
C48 | 0.0424 (17) | 0.0408 (18) | 0.0440 (18) | 0.0160 (14) | −0.0165 (14) | −0.0212 (15) |
C49 | 0.0439 (18) | 0.046 (2) | 0.0372 (17) | 0.0212 (15) | −0.0153 (14) | −0.0136 (15) |
C50 | 0.0390 (17) | 0.0330 (17) | 0.0416 (17) | 0.0114 (13) | 0.0000 (13) | −0.0139 (14) |
C51 | 0.0433 (18) | 0.0417 (19) | 0.0475 (19) | −0.0011 (15) | −0.0119 (15) | −0.0123 (16) |
C52 | 0.0478 (19) | 0.0421 (19) | 0.048 (2) | −0.0111 (16) | 0.0037 (16) | −0.0134 (16) |
C53 | 0.0461 (18) | 0.0361 (17) | 0.0427 (18) | −0.0164 (14) | −0.0125 (14) | −0.0098 (14) |
C54 | 0.0469 (19) | 0.0354 (18) | 0.0440 (18) | −0.0190 (14) | −0.0116 (15) | −0.0090 (14) |
C55 | 0.051 (2) | 0.045 (2) | 0.052 (2) | −0.0175 (16) | 0.0061 (16) | −0.0153 (17) |
C56 | 0.0442 (18) | 0.0394 (19) | 0.0448 (19) | −0.0001 (14) | −0.0126 (15) | −0.0061 (15) |
Cl1 | 0.0303 (4) | 0.0428 (4) | 0.0404 (4) | 0.0017 (3) | 0.0021 (3) | −0.0007 (3) |
Cl2 | 0.0425 (4) | 0.0363 (4) | 0.0355 (4) | 0.0114 (3) | −0.0113 (3) | 0.0080 (3) |
Cl3 | 0.0419 (4) | 0.0427 (5) | 0.0387 (4) | 0.0110 (3) | −0.0113 (3) | 0.0106 (3) |
Cl4 | 0.0297 (4) | 0.0410 (4) | 0.0406 (4) | 0.0004 (3) | 0.0016 (3) | −0.0004 (3) |
Cl5 | 0.0421 (4) | 0.0472 (5) | 0.0393 (4) | 0.0150 (4) | −0.0063 (3) | 0.0065 (4) |
Cl6 | 0.0446 (4) | 0.0405 (4) | 0.0419 (4) | 0.0174 (4) | 0.0146 (3) | 0.0019 (3) |
Cl7 | 0.0407 (4) | 0.0448 (5) | 0.0366 (4) | 0.0189 (3) | 0.0100 (3) | 0.0034 (3) |
Cl8 | 0.0392 (4) | 0.0418 (4) | 0.0341 (4) | 0.0148 (3) | −0.0087 (3) | 0.0064 (3) |
Co1 | 0.0286 (2) | 0.0313 (2) | 0.0278 (2) | −0.00365 (16) | −0.00186 (15) | −0.00133 (16) |
Co2 | 0.0300 (2) | 0.0308 (2) | 0.0269 (2) | −0.00426 (16) | −0.00143 (15) | −0.00045 (16) |
N1 | 0.0318 (13) | 0.0398 (15) | 0.0309 (13) | 0.0010 (11) | −0.0049 (10) | −0.0103 (11) |
N2 | 0.0398 (14) | 0.0330 (14) | 0.0319 (13) | −0.0066 (11) | −0.0041 (11) | −0.0069 (11) |
N3 | 0.0290 (13) | 0.0458 (16) | 0.0406 (15) | 0.0004 (11) | −0.0066 (11) | −0.0052 (12) |
N4 | 0.0348 (13) | 0.0285 (13) | 0.0405 (14) | 0.0004 (10) | −0.0024 (11) | −0.0029 (11) |
N5 | 0.0354 (14) | 0.0371 (15) | 0.0329 (13) | 0.0025 (11) | −0.0056 (10) | −0.0041 (11) |
N6 | 0.0359 (13) | 0.0243 (12) | 0.0369 (14) | −0.0032 (10) | 0.0009 (10) | −0.0079 (10) |
N7 | 0.0505 (17) | 0.0418 (16) | 0.0442 (16) | 0.0060 (13) | −0.0156 (13) | −0.0169 (13) |
N8 | 0.0402 (14) | 0.0338 (15) | 0.0466 (15) | −0.0143 (12) | 0.0056 (12) | −0.0195 (13) |
O1 | 0.0384 (11) | 0.0318 (11) | 0.0267 (10) | −0.0102 (9) | −0.0015 (8) | −0.0044 (9) |
O2 | 0.0474 (13) | 0.0395 (13) | 0.0332 (11) | −0.0170 (10) | −0.0017 (10) | −0.0010 (10) |
O3 | 0.0438 (12) | 0.0386 (13) | 0.0321 (11) | −0.0122 (10) | −0.0041 (9) | 0.0014 (9) |
O4 | 0.0427 (12) | 0.0311 (11) | 0.0246 (10) | −0.0170 (9) | −0.0021 (9) | 0.0016 (8) |
O5 | 0.0509 (13) | 0.0427 (13) | 0.0309 (11) | −0.0165 (10) | 0.0006 (10) | −0.0062 (10) |
O6 | 0.0350 (11) | 0.0419 (13) | 0.0289 (11) | −0.0056 (9) | 0.0028 (9) | 0.0037 (9) |
O7 | 0.0386 (11) | 0.0302 (11) | 0.0286 (10) | −0.0069 (9) | −0.0024 (9) | 0.0024 (9) |
O8 | 0.0490 (13) | 0.0469 (14) | 0.0320 (11) | −0.0133 (11) | −0.0070 (10) | −0.0061 (10) |
O9 | 0.0429 (12) | 0.0288 (11) | 0.0364 (11) | −0.0107 (9) | −0.0046 (9) | 0.0002 (9) |
O10 | 0.0408 (11) | 0.0308 (11) | 0.0276 (10) | −0.0057 (9) | −0.0046 (9) | −0.0008 (8) |
Geometric parameters (Å, º) top
C1—O4 | 1.237 (4) | C33—H33 | 0.9300 |
C1—O3 | 1.261 (4) | C34—C35 | 1.378 (5) |
C1—C2 | 1.503 (4) | C34—H34 | 0.9300 |
C2—C7 | 1.385 (4) | C35—C36 | 1.392 (4) |
C2—C3 | 1.409 (4) | C35—H35 | 0.9300 |
C3—C4 | 1.392 (4) | C36—N4 | 1.329 (4) |
C3—Cl3 | 1.725 (3) | C36—H36 | 0.9300 |
C4—C5 | 1.393 (4) | C37—N5 | 1.334 (4) |
C4—Cl4 | 1.731 (3) | C37—C38 | 1.370 (4) |
C5—C6 | 1.406 (4) | C37—H37 | 0.9300 |
C5—C8 | 1.505 (4) | C38—C39 | 1.379 (5) |
C6—C7 | 1.395 (4) | C38—H38 | 0.9300 |
C6—Cl2 | 1.724 (3) | C39—C40 | 1.379 (5) |
C7—Cl1 | 1.736 (3) | C39—H39 | 0.9300 |
C8—O2 | 1.240 (4) | C40—C41 | 1.370 (4) |
C8—O1 | 1.254 (4) | C40—H40 | 0.9300 |
C9—O8 | 1.231 (4) | C41—N5 | 1.341 (4) |
C9—O7 | 1.254 (4) | C41—H41 | 0.9300 |
C9—C10 | 1.513 (4) | C42—N6 | 1.332 (4) |
C10—C15 | 1.390 (4) | C42—C43 | 1.385 (4) |
C10—C11 | 1.394 (4) | C42—H42 | 0.9300 |
C11—C12 | 1.402 (4) | C43—C44 | 1.380 (4) |
C11—Cl5 | 1.733 (3) | C43—H43 | 0.9300 |
C12—C13 | 1.394 (4) | C44—C45 | 1.384 (5) |
C12—Cl6 | 1.733 (3) | C44—H44 | 0.9300 |
C13—C14 | 1.378 (4) | C45—C46 | 1.373 (5) |
C13—C16 | 1.507 (4) | C45—H45 | 0.9300 |
C14—C15 | 1.394 (4) | C46—N6 | 1.335 (4) |
C14—Cl8 | 1.735 (3) | C46—H46 | 0.9300 |
C15—Cl7 | 1.735 (3) | C47—N7 | 1.323 (4) |
C16—O5 | 1.223 (4) | C47—C48 | 1.369 (5) |
C16—O6 | 1.271 (4) | C47—H47 | 0.9300 |
C17—N1 | 1.330 (4) | C48—C49 | 1.376 (5) |
C17—C18 | 1.379 (4) | C48—H48 | 0.9318 |
C17—H17 | 0.9300 | C49—C50 | 1.348 (5) |
C18—C19 | 1.391 (5) | C49—H49 | 0.9300 |
C18—H18 | 0.9300 | C50—C51 | 1.362 (5) |
C19—C20 | 1.383 (5) | C50—H50 | 0.9300 |
C19—H19 | 0.9300 | C51—N7 | 1.317 (4) |
C20—C21 | 1.376 (4) | C51—H51 | 0.9300 |
C20—H20 | 0.9300 | C52—N8 | 1.278 (4) |
C21—N1 | 1.343 (4) | C52—C53 | 1.371 (5) |
C21—H21 | 0.9300 | C52—H52 | 0.9300 |
C22—N2 | 1.332 (4) | C53—C54 | 1.313 (5) |
C22—C23 | 1.380 (5) | C53—H53 | 0.9300 |
C22—H22 | 0.9300 | C54—C55 | 1.337 (5) |
C23—C24 | 1.364 (5) | C54—H54 | 0.9300 |
C23—H23 | 0.9300 | C55—C56 | 1.400 (5) |
C24—C25 | 1.376 (5) | C55—H55 | 0.9300 |
C24—H24 | 0.9300 | C56—N8 | 1.313 (4) |
C25—C26 | 1.376 (4) | C56—H56 | 0.9300 |
C25—H25 | 0.9300 | Co1—O7 | 2.0619 (19) |
C26—N2 | 1.335 (4) | Co1—O9 | 2.122 (2) |
C26—H26 | 0.9300 | Co1—O2 | 2.126 (2) |
C27—N3 | 1.347 (4) | Co1—N3 | 2.155 (3) |
C27—C28 | 1.395 (4) | Co1—N1 | 2.158 (2) |
C27—H27 | 0.9300 | Co1—N2 | 2.171 (3) |
C28—C29 | 1.365 (5) | Co2—O6 | 2.066 (2) |
C28—H28 | 0.9300 | Co2—O3i | 2.127 (2) |
C29—C30 | 1.374 (5) | Co2—O10 | 2.144 (2) |
C29—H29 | 0.9300 | Co2—N5 | 2.167 (3) |
C30—C31 | 1.382 (4) | Co2—N4 | 2.170 (2) |
C30—H30 | 0.9300 | Co2—N6 | 2.190 (3) |
C31—N3 | 1.338 (4) | O3—Co2ii | 2.127 (2) |
C31—H31 | 0.9300 | O9—H9A | 0.8497 |
C32—N4 | 1.345 (4) | O9—H9B | 0.8493 |
C32—C33 | 1.375 (4) | O10—H10B | 0.8498 |
C32—H32 | 0.9300 | O10—H10A | 0.8499 |
C33—C34 | 1.373 (5) | | |
| | | |
O4—C1—O3 | 128.1 (3) | C38—C39—C40 | 117.9 (3) |
O4—C1—C2 | 116.9 (3) | C38—C39—H39 | 121.0 |
O3—C1—C2 | 115.0 (3) | C40—C39—H39 | 121.0 |
C7—C2—C3 | 117.5 (3) | C41—C40—C39 | 119.9 (3) |
C7—C2—C1 | 121.8 (3) | C41—C40—H40 | 120.0 |
C3—C2—C1 | 120.7 (3) | C39—C40—H40 | 120.0 |
C4—C3—C2 | 120.9 (3) | N5—C41—C40 | 122.6 (3) |
C4—C3—Cl3 | 120.7 (2) | N5—C41—H41 | 118.7 |
C2—C3—Cl3 | 118.3 (2) | C40—C41—H41 | 118.7 |
C3—C4—C5 | 121.6 (3) | N6—C42—C43 | 123.8 (3) |
C3—C4—Cl4 | 120.2 (2) | N6—C42—H42 | 118.1 |
C5—C4—Cl4 | 118.2 (2) | C43—C42—H42 | 118.1 |
C4—C5—C6 | 117.3 (2) | C44—C43—C42 | 118.2 (3) |
C4—C5—C8 | 121.8 (2) | C44—C43—H43 | 120.9 |
C6—C5—C8 | 120.9 (3) | C42—C43—H43 | 120.9 |
C7—C6—C5 | 121.1 (3) | C43—C44—C45 | 118.8 (3) |
C7—C6—Cl2 | 120.5 (2) | C43—C44—H44 | 120.6 |
C5—C6—Cl2 | 118.4 (2) | C45—C44—H44 | 120.6 |
C2—C7—C6 | 121.6 (3) | C46—C45—C44 | 118.5 (3) |
C2—C7—Cl1 | 118.4 (2) | C46—C45—H45 | 120.7 |
C6—C7—Cl1 | 120.0 (2) | C44—C45—H45 | 120.7 |
O2—C8—O1 | 128.3 (3) | N6—C46—C45 | 123.9 (3) |
O2—C8—C5 | 114.3 (3) | N6—C46—H46 | 118.1 |
O1—C8—C5 | 117.4 (3) | C45—C46—H46 | 118.1 |
O8—C9—O7 | 127.7 (3) | N7—C47—C48 | 123.7 (3) |
O8—C9—C10 | 116.6 (3) | N7—C47—H47 | 118.1 |
O7—C9—C10 | 115.7 (3) | C48—C47—H47 | 118.1 |
C15—C10—C11 | 116.4 (3) | C47—C48—C49 | 118.5 (3) |
C15—C10—C9 | 121.4 (3) | C47—C48—H48 | 120.2 |
C11—C10—C9 | 122.1 (3) | C49—C48—H48 | 121.3 |
C10—C11—C12 | 121.6 (3) | C50—C49—C48 | 117.8 (3) |
C10—C11—Cl5 | 118.8 (2) | C50—C49—H49 | 121.1 |
C12—C11—Cl5 | 119.7 (2) | C48—C49—H49 | 121.1 |
C13—C12—C11 | 121.5 (3) | C49—C50—C51 | 120.1 (3) |
C13—C12—Cl6 | 118.7 (2) | C49—C50—H50 | 120.0 |
C11—C12—Cl6 | 119.8 (2) | C51—C50—H50 | 120.0 |
C14—C13—C12 | 116.5 (3) | N7—C51—C50 | 123.3 (3) |
C14—C13—C16 | 121.3 (3) | N7—C51—H51 | 118.4 |
C12—C13—C16 | 122.1 (3) | C50—C51—H51 | 118.4 |
C13—C14—C15 | 122.3 (3) | N8—C52—C53 | 125.2 (3) |
C13—C14—Cl8 | 118.3 (2) | N8—C52—H52 | 117.4 |
C15—C14—Cl8 | 119.3 (2) | C53—C52—H52 | 117.4 |
C10—C15—C14 | 121.6 (3) | C54—C53—C52 | 117.1 (3) |
C10—C15—Cl7 | 118.3 (2) | C54—C53—H53 | 121.4 |
C14—C15—Cl7 | 120.0 (2) | C52—C53—H53 | 121.4 |
O5—C16—O6 | 127.4 (3) | C53—C54—C55 | 121.8 (3) |
O5—C16—C13 | 117.1 (3) | C53—C54—H54 | 119.1 |
O6—C16—C13 | 115.5 (3) | C55—C54—H54 | 119.1 |
N1—C17—C18 | 124.2 (3) | C54—C55—C56 | 116.4 (3) |
N1—C17—H17 | 117.9 | C54—C55—H55 | 121.8 |
C18—C17—H17 | 117.9 | C56—C55—H55 | 121.8 |
C17—C18—C19 | 118.0 (3) | N8—C56—C55 | 123.0 (3) |
C17—C18—H18 | 121.0 | N8—C56—H56 | 118.5 |
C19—C18—H18 | 121.0 | C55—C56—H56 | 118.5 |
C20—C19—C18 | 118.7 (3) | O7—Co1—O9 | 86.56 (8) |
C20—C19—H19 | 120.7 | O7—Co1—O2 | 174.01 (9) |
C18—C19—H19 | 120.7 | O9—Co1—O2 | 87.46 (8) |
C21—C20—C19 | 118.9 (3) | O7—Co1—N3 | 91.71 (9) |
C21—C20—H20 | 120.6 | O9—Co1—N3 | 86.25 (10) |
C19—C20—H20 | 120.6 | O2—Co1—N3 | 87.54 (10) |
N1—C21—C20 | 123.2 (3) | O7—Co1—N1 | 89.07 (9) |
N1—C21—H21 | 118.4 | O9—Co1—N1 | 91.97 (9) |
C20—C21—H21 | 118.4 | O2—Co1—N1 | 91.49 (9) |
N2—C22—C23 | 122.3 (3) | N3—Co1—N1 | 178.00 (11) |
N2—C22—H22 | 118.9 | O7—Co1—N2 | 102.09 (9) |
C23—C22—H22 | 118.9 | O9—Co1—N2 | 171.04 (8) |
C24—C23—C22 | 120.2 (3) | O2—Co1—N2 | 83.87 (9) |
C24—C23—H23 | 119.9 | N3—Co1—N2 | 91.08 (10) |
C22—C23—H23 | 119.9 | N1—Co1—N2 | 90.55 (10) |
C23—C24—C25 | 117.7 (3) | O6—Co2—O3i | 172.82 (9) |
C23—C24—H24 | 121.2 | O6—Co2—O10 | 85.27 (9) |
C25—C24—H24 | 121.2 | O3i—Co2—O10 | 87.88 (8) |
C24—C25—C26 | 119.5 (3) | O6—Co2—N5 | 90.00 (9) |
C24—C25—H25 | 120.3 | O3i—Co2—N5 | 92.26 (9) |
C26—C25—H25 | 120.3 | O10—Co2—N5 | 90.98 (9) |
N2—C26—C25 | 122.8 (3) | O6—Co2—N4 | 90.76 (9) |
N2—C26—H26 | 118.6 | O3i—Co2—N4 | 86.93 (9) |
C25—C26—H26 | 118.6 | O10—Co2—N4 | 88.63 (9) |
N3—C27—C28 | 122.3 (3) | N5—Co2—N4 | 179.11 (10) |
N3—C27—H27 | 118.9 | O6—Co2—N6 | 104.47 (9) |
C28—C27—H27 | 118.9 | O3i—Co2—N6 | 82.39 (9) |
C29—C28—C27 | 119.4 (3) | O10—Co2—N6 | 170.26 (8) |
C29—C28—H28 | 120.3 | N5—Co2—N6 | 89.28 (10) |
C27—C28—H28 | 120.3 | N4—Co2—N6 | 90.96 (10) |
C28—C29—C30 | 118.7 (3) | C17—N1—C21 | 117.0 (3) |
C28—C29—H29 | 120.7 | C17—N1—Co1 | 123.0 (2) |
C30—C29—H29 | 120.7 | C21—N1—Co1 | 120.0 (2) |
C29—C30—C31 | 119.2 (3) | C22—N2—C26 | 117.5 (3) |
C29—C30—H30 | 120.4 | C22—N2—Co1 | 121.0 (2) |
C31—C30—H30 | 120.4 | C26—N2—Co1 | 120.9 (2) |
N3—C31—C30 | 123.2 (3) | C31—N3—C27 | 117.2 (3) |
N3—C31—H31 | 118.4 | C31—N3—Co1 | 120.4 (2) |
C30—C31—H31 | 118.4 | C27—N3—Co1 | 122.3 (2) |
N4—C32—C33 | 122.8 (3) | C36—N4—C32 | 117.1 (3) |
N4—C32—H32 | 118.6 | C36—N4—Co2 | 122.5 (2) |
C33—C32—H32 | 118.6 | C32—N4—Co2 | 120.3 (2) |
C34—C33—C32 | 119.9 (3) | C37—N5—C41 | 116.7 (3) |
C34—C33—H33 | 120.0 | C37—N5—Co2 | 120.0 (2) |
C32—C33—H33 | 120.0 | C41—N5—Co2 | 123.0 (2) |
C33—C34—C35 | 118.0 (3) | C42—N6—C46 | 116.8 (3) |
C33—C34—H34 | 121.0 | C42—N6—Co2 | 119.7 (2) |
C35—C34—H34 | 121.0 | C46—N6—Co2 | 123.2 (2) |
C34—C35—C36 | 119.0 (3) | C51—N7—C47 | 116.6 (3) |
C34—C35—H35 | 120.5 | C52—N8—C56 | 116.4 (3) |
C36—C35—H35 | 120.5 | C8—O2—Co1 | 133.6 (2) |
N4—C36—C35 | 123.2 (3) | C1—O3—Co2ii | 131.5 (2) |
N4—C36—H36 | 118.4 | C16—O6—Co2 | 137.5 (2) |
C35—C36—H36 | 118.4 | C9—O7—Co1 | 144.1 (2) |
N5—C37—C38 | 124.2 (3) | Co1—O9—H9A | 116.8 |
N5—C37—H37 | 117.9 | Co1—O9—H9B | 107.0 |
C38—C37—H37 | 117.9 | H9A—O9—H9B | 109.8 |
C37—C38—C39 | 118.6 (3) | Co2—O10—H10B | 101.0 |
C37—C38—H38 | 120.7 | Co2—O10—H10A | 111.6 |
C39—C38—H38 | 120.7 | H10B—O10—H10A | 109.7 |
| | | |
O4—C1—C2—C7 | 97.7 (4) | C18—C17—N1—C21 | 0.2 (5) |
O3—C1—C2—C7 | −81.0 (4) | C18—C17—N1—Co1 | −178.1 (2) |
O4—C1—C2—C3 | −80.7 (4) | C20—C21—N1—C17 | 0.3 (4) |
O3—C1—C2—C3 | 100.7 (3) | C20—C21—N1—Co1 | 178.7 (2) |
C7—C2—C3—C4 | −1.0 (5) | O7—Co1—N1—C17 | 127.2 (2) |
C1—C2—C3—C4 | 177.5 (3) | O9—Co1—N1—C17 | 40.7 (2) |
C7—C2—C3—Cl3 | 179.8 (2) | O2—Co1—N1—C17 | −46.8 (2) |
C1—C2—C3—Cl3 | −1.8 (4) | N2—Co1—N1—C17 | −130.7 (2) |
C2—C3—C4—C5 | 0.2 (5) | O7—Co1—N1—C21 | −51.1 (2) |
Cl3—C3—C4—C5 | 179.4 (2) | O9—Co1—N1—C21 | −137.6 (2) |
C2—C3—C4—Cl4 | −178.1 (2) | O2—Co1—N1—C21 | 134.9 (2) |
Cl3—C3—C4—Cl4 | 1.1 (4) | N2—Co1—N1—C21 | 51.0 (2) |
C3—C4—C5—C6 | 0.0 (5) | C23—C22—N2—C26 | 0.8 (5) |
Cl4—C4—C5—C6 | 178.4 (2) | C23—C22—N2—Co1 | −170.7 (2) |
C3—C4—C5—C8 | −179.1 (3) | C25—C26—N2—C22 | −1.4 (5) |
Cl4—C4—C5—C8 | −0.7 (4) | C25—C26—N2—Co1 | 170.0 (2) |
C4—C5—C6—C7 | 0.4 (5) | O7—Co1—N2—C22 | −44.7 (2) |
C8—C5—C6—C7 | 179.6 (3) | O2—Co1—N2—C22 | 134.7 (2) |
C4—C5—C6—Cl2 | −178.9 (2) | N3—Co1—N2—C22 | 47.3 (2) |
C8—C5—C6—Cl2 | 0.3 (4) | N1—Co1—N2—C22 | −133.9 (2) |
C3—C2—C7—C6 | 1.5 (5) | O7—Co1—N2—C26 | 144.1 (2) |
C1—C2—C7—C6 | −177.0 (3) | O2—Co1—N2—C26 | −36.5 (2) |
C3—C2—C7—Cl1 | −178.3 (2) | N3—Co1—N2—C26 | −123.9 (2) |
C1—C2—C7—Cl1 | 3.3 (4) | N1—Co1—N2—C26 | 54.9 (2) |
C5—C6—C7—C2 | −1.2 (5) | C30—C31—N3—C27 | −1.4 (5) |
Cl2—C6—C7—C2 | 178.1 (3) | C30—C31—N3—Co1 | −177.0 (3) |
C5—C6—C7—Cl1 | 178.6 (2) | C28—C27—N3—C31 | 0.1 (5) |
Cl2—C6—C7—Cl1 | −2.1 (4) | C28—C27—N3—Co1 | 175.5 (3) |
C4—C5—C8—O2 | 80.9 (4) | O7—Co1—N3—C31 | −35.4 (3) |
C6—C5—C8—O2 | −98.2 (3) | O9—Co1—N3—C31 | 51.0 (2) |
C4—C5—C8—O1 | −97.6 (4) | O2—Co1—N3—C31 | 138.7 (3) |
C6—C5—C8—O1 | 83.2 (4) | N2—Co1—N3—C31 | −137.5 (3) |
O8—C9—C10—C15 | 94.1 (4) | O7—Co1—N3—C27 | 149.3 (3) |
O7—C9—C10—C15 | −86.0 (4) | O9—Co1—N3—C27 | −124.2 (3) |
O8—C9—C10—C11 | −86.0 (4) | O2—Co1—N3—C27 | −36.6 (3) |
O7—C9—C10—C11 | 93.9 (4) | N2—Co1—N3—C27 | 47.2 (3) |
C15—C10—C11—C12 | −1.5 (5) | C35—C36—N4—C32 | −2.9 (5) |
C9—C10—C11—C12 | 178.6 (3) | C35—C36—N4—Co2 | 179.0 (3) |
C15—C10—C11—Cl5 | 178.3 (2) | C33—C32—N4—C36 | 2.3 (5) |
C9—C10—C11—Cl5 | −1.6 (4) | C33—C32—N4—Co2 | −179.5 (3) |
C10—C11—C12—C13 | 1.9 (5) | O6—Co2—N4—C36 | −150.8 (3) |
Cl5—C11—C12—C13 | −177.9 (3) | O3i—Co2—N4—C36 | 36.0 (3) |
C10—C11—C12—Cl6 | 179.6 (3) | O10—Co2—N4—C36 | 123.9 (3) |
Cl5—C11—C12—Cl6 | −0.1 (4) | N6—Co2—N4—C36 | −46.3 (3) |
C11—C12—C13—C14 | −1.4 (5) | O6—Co2—N4—C32 | 31.1 (2) |
Cl6—C12—C13—C14 | −179.2 (3) | O3i—Co2—N4—C32 | −142.1 (2) |
C11—C12—C13—C16 | 179.2 (3) | O10—Co2—N4—C32 | −54.1 (2) |
Cl6—C12—C13—C16 | 1.4 (4) | N6—Co2—N4—C32 | 135.6 (2) |
C12—C13—C14—C15 | 0.7 (5) | C38—C37—N5—C41 | −0.6 (5) |
C16—C13—C14—C15 | −179.8 (3) | C38—C37—N5—Co2 | −175.2 (2) |
C12—C13—C14—Cl8 | 177.1 (2) | C40—C41—N5—C37 | 0.6 (5) |
C16—C13—C14—Cl8 | −3.5 (4) | C40—C41—N5—Co2 | 175.0 (2) |
C11—C10—C15—C14 | 0.8 (5) | O6—Co2—N5—C37 | 50.7 (2) |
C9—C10—C15—C14 | −179.3 (3) | O3i—Co2—N5—C37 | −136.1 (2) |
C11—C10—C15—Cl7 | 179.4 (2) | O10—Co2—N5—C37 | 136.0 (2) |
C9—C10—C15—Cl7 | −0.7 (4) | N6—Co2—N5—C37 | −53.7 (2) |
C13—C14—C15—C10 | −0.5 (5) | O6—Co2—N5—C41 | −123.5 (2) |
Cl8—C14—C15—C10 | −176.8 (2) | O3i—Co2—N5—C41 | 49.7 (2) |
C13—C14—C15—Cl7 | −179.0 (3) | O10—Co2—N5—C41 | −38.2 (2) |
Cl8—C14—C15—Cl7 | 4.7 (4) | N6—Co2—N5—C41 | 132.1 (2) |
C14—C13—C16—O5 | 92.9 (4) | C43—C42—N6—C46 | 1.7 (5) |
C12—C13—C16—O5 | −87.6 (4) | C43—C42—N6—Co2 | −171.7 (2) |
C14—C13—C16—O6 | −85.2 (4) | C45—C46—N6—C42 | −2.4 (5) |
C12—C13—C16—O6 | 94.2 (4) | C45—C46—N6—Co2 | 170.8 (2) |
N1—C17—C18—C19 | −1.2 (5) | O6—Co2—N6—C42 | −140.5 (2) |
C17—C18—C19—C20 | 1.6 (5) | O3i—Co2—N6—C42 | 41.7 (2) |
C18—C19—C20—C21 | −1.2 (5) | N5—Co2—N6—C42 | −50.7 (2) |
C19—C20—C21—N1 | 0.2 (5) | N4—Co2—N6—C42 | 128.5 (2) |
N2—C22—C23—C24 | 1.0 (5) | O6—Co2—N6—C46 | 46.5 (2) |
C22—C23—C24—C25 | −2.2 (5) | O3i—Co2—N6—C46 | −131.3 (2) |
C23—C24—C25—C26 | 1.5 (5) | N5—Co2—N6—C46 | 136.4 (2) |
C24—C25—C26—N2 | 0.3 (5) | N4—Co2—N6—C46 | −44.5 (2) |
N3—C27—C28—C29 | 1.4 (5) | C50—C51—N7—C47 | −3.0 (5) |
C27—C28—C29—C30 | −1.5 (5) | C48—C47—N7—C51 | 2.7 (5) |
C28—C29—C30—C31 | 0.2 (5) | C53—C52—N8—C56 | 0.9 (5) |
C29—C30—C31—N3 | 1.3 (5) | C55—C56—N8—C52 | 1.1 (5) |
N4—C32—C33—C34 | −0.8 (5) | O1—C8—O2—Co1 | −1.8 (5) |
C32—C33—C34—C35 | −0.3 (5) | C5—C8—O2—Co1 | 179.8 (2) |
C33—C34—C35—C36 | −0.2 (5) | O9—Co1—O2—C8 | −14.1 (3) |
C34—C35—C36—N4 | 1.9 (5) | N3—Co1—O2—C8 | −100.5 (3) |
N5—C37—C38—C39 | 1.0 (5) | N1—Co1—O2—C8 | 77.8 (3) |
C37—C38—C39—C40 | −1.2 (5) | N2—Co1—O2—C8 | 168.2 (3) |
C38—C39—C40—C41 | 1.2 (5) | O4—C1—O3—Co2ii | 2.5 (5) |
C39—C40—C41—N5 | −1.0 (5) | C2—C1—O3—Co2ii | −179.06 (19) |
N6—C42—C43—C44 | 0.3 (5) | O5—C16—O6—Co2 | 1.5 (5) |
C42—C43—C44—C45 | −1.7 (5) | C13—C16—O6—Co2 | 179.4 (2) |
C43—C44—C45—C46 | 1.1 (5) | O10—Co2—O6—C16 | 170.4 (3) |
C44—C45—C46—N6 | 1.0 (5) | N5—Co2—O6—C16 | −98.6 (3) |
N7—C47—C48—C49 | 0.4 (5) | N4—Co2—O6—C16 | 81.8 (3) |
C47—C48—C49—C50 | −3.3 (4) | N6—Co2—O6—C16 | −9.3 (3) |
C48—C49—C50—C51 | 3.2 (4) | O8—C9—O7—Co1 | 7.2 (6) |
C49—C50—C51—N7 | 0.1 (5) | C10—C9—O7—Co1 | −172.6 (2) |
N8—C52—C53—C54 | −2.0 (5) | O9—Co1—O7—C9 | −179.1 (3) |
C52—C53—C54—C55 | 0.9 (5) | N3—Co1—O7—C9 | −93.0 (3) |
C53—C54—C55—C56 | 0.9 (5) | N1—Co1—O7—C9 | 88.9 (3) |
C54—C55—C56—N8 | −2.0 (5) | N2—Co1—O7—C9 | −1.5 (4) |
Symmetry codes: (i) x−1, y−1, z+1; (ii) x+1, y+1, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9A···N8 | 0.85 | 1.91 | 2.718 (3) | 159 |
O9—H9B···O1 | 0.85 | 1.97 | 2.768 (3) | 157 |
O10—H10B···O4i | 0.85 | 1.85 | 2.686 (3) | 166 |
O10—H10A···N7iii | 0.85 | 1.98 | 2.814 (3) | 167 |
C40—H40···Cg1iii | 0.93 | 2.99 | 3.813 (4) | 149 |
C44—H44···Cg2iv | 0.93 | 2.94 | 3.638 (4) | 133 |
Symmetry codes: (i) x−1, y−1, z+1; (iii) −x+1, −y, −z+1; (iv) −x+1, −y+1, −z+1. |
(II)
catena-poly[[[diaquadipyridinecobalt(II)]-µ-tetrachloroterephthalato]
1,4-dioxane trihydrate]
top
Crystal data top
[Co(C8Cl4O4)(C5H5N)2(H2O)2]·C4H8O2·3H2O | F(000) = 2856 |
Mr = 697.19 | Dx = 1.489 Mg m−3 |
Orthorhombic, Pcca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2a 2ac | Cell parameters from 9681 reflections |
a = 21.4257 (19) Å | θ = 2.4–27.5° |
b = 8.6567 (8) Å | µ = 0.95 mm−1 |
c = 33.537 (3) Å | T = 291 K |
V = 6220.3 (10) Å3 | Block, pink |
Z = 8 | 0.28 × 0.24 × 0.22 mm |
Data collection top
Bruker SMART APEX CCD diffractometer | 6133 independent reflections |
Radiation source: sealed tube | 4296 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
phi and ω scans | θmax = 26.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −25→26 |
Tmin = 0.77, Tmax = 0.81 | k = −10→10 |
46466 measured reflections | l = −41→41 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.03P)2] where P = (Fo2 + 2Fc2)/3 |
6133 reflections | (Δ/σ)max < 0.001 |
366 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
[Co(C8Cl4O4)(C5H5N)2(H2O)2]·C4H8O2·3H2O | V = 6220.3 (10) Å3 |
Mr = 697.19 | Z = 8 |
Orthorhombic, Pcca | Mo Kα radiation |
a = 21.4257 (19) Å | µ = 0.95 mm−1 |
b = 8.6567 (8) Å | T = 291 K |
c = 33.537 (3) Å | 0.28 × 0.24 × 0.22 mm |
Data collection top
Bruker SMART APEX CCD diffractometer | 6133 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4296 reflections with I > 2σ(I) |
Tmin = 0.77, Tmax = 0.81 | Rint = 0.066 |
46466 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.48 e Å−3 |
6133 reflections | Δρmin = −0.42 e Å−3 |
366 parameters | |
Special details top
Experimental. IR (KBr, υ, cm-1): 3391 (s), 3082 (m), 2964 (m), 2928
(m), 1643 (s), 1605 (versus), 1499 (m), 1417
(s), 1378 (m), 1316 (versus), 1248 (m), 1115
(m), 1050 (m), 874 (m), 699 (m), 632 (s). |
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 | |
C1 | 0.63102 (12) | 0.6993 (3) | 0.13145 (8) | 0.0387 (6) | |
C2 | 0.56117 (12) | 0.7107 (3) | 0.12591 (7) | 0.0364 (5) | |
C3 | 0.52189 (12) | 0.7346 (3) | 0.15828 (8) | 0.0400 (6) | |
C4 | 0.45812 (12) | 0.7532 (3) | 0.15319 (7) | 0.0383 (6) | |
C5 | 0.43093 (12) | 0.7521 (3) | 0.11557 (8) | 0.0375 (6) | |
C6 | 0.47023 (12) | 0.7270 (3) | 0.08318 (7) | 0.0352 (5) | |
C7 | 0.53431 (12) | 0.7054 (3) | 0.08827 (7) | 0.0348 (5) | |
C8 | 0.36151 (12) | 0.7757 (3) | 0.11034 (8) | 0.0393 (6) | |
C9 | 0.71463 (12) | 0.4034 (3) | 0.04717 (8) | 0.0408 (6) | |
H9 | 0.6892 | 0.3346 | 0.0610 | 0.049* | |
C10 | 0.71399 (13) | 0.4005 (3) | 0.00584 (8) | 0.0464 (6) | |
H10 | 0.6888 | 0.3300 | −0.0075 | 0.056* | |
C11 | 0.7500 | 0.5000 | −0.01501 (12) | 0.0422 (9) | |
H11 | 0.7500 | 0.5000 | −0.0427 | 0.051* | |
C12 | 0.69701 (13) | 0.4854 (3) | 0.21836 (8) | 0.0433 (6) | |
H12 | 0.6597 | 0.4730 | 0.2046 | 0.052* | |
C13 | 0.69560 (13) | 0.4881 (3) | 0.25938 (8) | 0.0426 (6) | |
H13 | 0.6576 | 0.4819 | 0.2727 | 0.051* | |
C14 | 0.7500 | 0.5000 | 0.28065 (12) | 0.0477 (9) | |
H14 | 0.7500 | 0.5000 | 0.3084 | 0.057* | |
C15 | 0.29491 (13) | 1.0678 (3) | 0.18747 (8) | 0.0444 (6) | |
H15 | 0.3271 | 1.1151 | 0.1734 | 0.053* | |
C16 | 0.29575 (13) | 1.0711 (3) | 0.22906 (8) | 0.0468 (7) | |
H16 | 0.3278 | 1.1221 | 0.2424 | 0.056* | |
C17 | 0.2500 | 1.0000 | 0.25012 (11) | 0.0427 (9) | |
H17 | 0.2500 | 1.0000 | 0.2779 | 0.051* | |
C18 | 0.30259 (13) | 1.0242 (3) | 0.01827 (8) | 0.0423 (6) | |
H18 | 0.3396 | 1.0407 | 0.0321 | 0.051* | |
C19 | 0.30376 (13) | 1.0253 (3) | −0.02284 (8) | 0.0431 (6) | |
H19 | 0.3410 | 1.0433 | −0.0363 | 0.052* | |
C20 | 0.2500 | 1.0000 | −0.04379 (12) | 0.0434 (9) | |
H20 | 0.2500 | 1.0000 | −0.0715 | 0.052* | |
C21 | 0.47215 (12) | 0.1269 (3) | 0.04907 (8) | 0.0411 (6) | |
H21A | 0.4460 | 0.0681 | 0.0672 | 0.049* | |
H21B | 0.4592 | 0.1035 | 0.0220 | 0.049* | |
C22 | 0.46389 (12) | 0.2956 (3) | 0.05690 (8) | 0.0431 (6) | |
H22A | 0.4878 | 0.3546 | 0.0376 | 0.052* | |
H22B | 0.4202 | 0.3230 | 0.0539 | 0.052* | |
C23 | 0.54786 (13) | 0.2896 (3) | 0.10159 (8) | 0.0459 (6) | |
H23A | 0.5611 | 0.3124 | 0.1286 | 0.055* | |
H23B | 0.5740 | 0.3483 | 0.0834 | 0.055* | |
C24 | 0.55548 (14) | 0.1196 (3) | 0.09346 (8) | 0.0461 (6) | |
H24A | 0.5990 | 0.0910 | 0.0966 | 0.055* | |
H24B | 0.5312 | 0.0609 | 0.1126 | 0.055* | |
Cl1 | 0.55413 (3) | 0.74018 (7) | 0.205766 (18) | 0.04123 (15) | |
Cl2 | 0.40961 (3) | 0.77913 (7) | 0.193944 (18) | 0.03949 (14) | |
Cl3 | 0.58195 (3) | 0.67111 (7) | 0.047696 (18) | 0.03850 (14) | |
Cl4 | 0.43824 (3) | 0.72156 (7) | 0.036001 (18) | 0.04005 (15) | |
Co1 | 0.2500 | 1.0000 | 0.103012 (14) | 0.03502 (12) | |
Co2 | 0.7500 | 0.5000 | 0.132603 (15) | 0.03916 (13) | |
N1 | 0.7500 | 0.5000 | 0.06784 (9) | 0.0376 (7) | |
N2 | 0.7500 | 0.5000 | 0.19752 (9) | 0.0441 (7) | |
N3 | 0.2500 | 1.0000 | 0.16773 (9) | 0.0430 (7) | |
N4 | 0.2500 | 1.0000 | 0.03903 (9) | 0.0357 (6) | |
O1 | 0.65428 (8) | 0.56641 (18) | 0.13157 (5) | 0.0413 (4) | |
O2 | 0.65952 (8) | 0.82454 (18) | 0.13507 (5) | 0.0428 (4) | |
O3 | 0.32825 (8) | 0.65701 (19) | 0.11257 (5) | 0.0445 (4) | |
O4 | 0.34350 (8) | 0.91098 (18) | 0.10431 (5) | 0.0420 (4) | |
O5 | 0.72222 (9) | 0.26689 (17) | 0.13148 (5) | 0.0408 (4) | |
H5A | 0.6875 | 0.2555 | 0.1434 | 0.049* | |
H5B | 0.7509 | 0.2176 | 0.1435 | 0.049* | |
O6 | 0.28590 (8) | 1.22506 (17) | 0.09998 (5) | 0.0407 (4) | |
H6B | 0.2928 | 1.2522 | 0.1239 | 0.049* | |
H6A | 0.2679 | 1.3015 | 0.0889 | 0.049* | |
O7 | 0.48434 (9) | 0.3339 (2) | 0.09657 (6) | 0.0516 (5) | |
O8 | 0.53549 (8) | 0.08335 (19) | 0.05435 (5) | 0.0444 (4) | |
O9 | 0.37596 (8) | 0.36886 (18) | 0.13815 (5) | 0.0425 (4) | |
H9A | 0.3787 | 0.4613 | 0.1298 | 0.051* | |
H9B | 0.4103 | 0.3221 | 0.1343 | 0.051* | |
O10 | 0.65448 (9) | 0.02484 (19) | 0.18134 (5) | 0.0458 (4) | |
H10A | 0.6467 | −0.0501 | 0.1969 | 0.055* | |
H10B | 0.6863 | 0.0035 | 0.1673 | 0.055* | |
O11 | 0.55676 (9) | 0.20707 (19) | 0.23599 (5) | 0.0464 (4) | |
H11A | 0.5871 | 0.1751 | 0.2219 | 0.056* | |
H11B | 0.5268 | 0.2332 | 0.2208 | 0.056* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0371 (14) | 0.0381 (14) | 0.0408 (14) | 0.0041 (11) | −0.0036 (11) | 0.0011 (10) |
C2 | 0.0394 (14) | 0.0306 (11) | 0.0392 (14) | 0.0046 (11) | −0.0028 (11) | 0.0058 (10) |
C3 | 0.0455 (16) | 0.0407 (14) | 0.0336 (14) | 0.0061 (11) | −0.0054 (11) | 0.0071 (11) |
C4 | 0.0412 (15) | 0.0418 (13) | 0.0319 (14) | 0.0056 (10) | 0.0036 (11) | 0.0046 (10) |
C5 | 0.0433 (15) | 0.0320 (11) | 0.0372 (14) | 0.0041 (10) | −0.0004 (11) | 0.0023 (9) |
C6 | 0.0459 (15) | 0.0302 (12) | 0.0294 (13) | 0.0043 (10) | −0.0037 (10) | 0.0011 (9) |
C7 | 0.0411 (14) | 0.0322 (11) | 0.0313 (13) | 0.0052 (11) | 0.0051 (10) | 0.0034 (10) |
C8 | 0.0387 (14) | 0.0405 (14) | 0.0388 (14) | 0.0041 (11) | 0.0014 (11) | 0.0009 (11) |
C9 | 0.0432 (15) | 0.0385 (13) | 0.0406 (15) | −0.0007 (11) | 0.0087 (12) | 0.0023 (10) |
C10 | 0.0468 (17) | 0.0468 (13) | 0.0455 (16) | −0.0067 (12) | 0.0010 (13) | −0.0128 (12) |
C11 | 0.044 (2) | 0.0417 (19) | 0.041 (2) | 0.0119 (16) | 0.000 | 0.000 |
C12 | 0.0432 (15) | 0.0397 (13) | 0.0470 (16) | 0.0081 (11) | 0.0083 (13) | 0.0030 (11) |
C13 | 0.0447 (16) | 0.0424 (14) | 0.0406 (14) | 0.0005 (11) | 0.0137 (13) | 0.0042 (10) |
C14 | 0.052 (3) | 0.046 (2) | 0.045 (2) | −0.0134 (17) | 0.000 | 0.000 |
C15 | 0.0428 (16) | 0.0452 (14) | 0.0451 (16) | −0.0105 (12) | 0.0117 (12) | −0.0011 (11) |
C16 | 0.0445 (16) | 0.0453 (14) | 0.0506 (17) | −0.0182 (12) | −0.0094 (13) | −0.0003 (12) |
C17 | 0.050 (2) | 0.0414 (19) | 0.037 (2) | −0.0100 (15) | 0.000 | 0.000 |
C18 | 0.0393 (15) | 0.0445 (14) | 0.0430 (15) | −0.0063 (11) | 0.0062 (11) | −0.0005 (11) |
C19 | 0.0416 (15) | 0.0470 (15) | 0.0406 (15) | −0.0114 (12) | 0.0104 (12) | 0.0003 (11) |
C20 | 0.051 (2) | 0.0370 (18) | 0.042 (2) | −0.0097 (16) | 0.000 | 0.000 |
C21 | 0.0431 (15) | 0.0373 (14) | 0.0431 (16) | −0.0062 (11) | −0.0071 (12) | 0.0027 (11) |
C22 | 0.0399 (15) | 0.0411 (13) | 0.0484 (16) | 0.0100 (11) | −0.0058 (12) | 0.0052 (12) |
C23 | 0.0488 (16) | 0.0465 (14) | 0.0425 (16) | 0.0005 (12) | −0.0085 (12) | −0.0032 (12) |
C24 | 0.0453 (17) | 0.0484 (14) | 0.0446 (16) | 0.0153 (12) | −0.0094 (13) | −0.0013 (12) |
Cl1 | 0.0393 (3) | 0.0491 (3) | 0.0352 (3) | 0.0107 (3) | −0.0098 (3) | 0.0023 (3) |
Cl2 | 0.0344 (3) | 0.0458 (3) | 0.0383 (3) | 0.0120 (2) | 0.0085 (3) | 0.0016 (3) |
Cl3 | 0.0305 (3) | 0.0462 (3) | 0.0388 (3) | 0.0127 (2) | 0.0078 (2) | 0.0034 (2) |
Cl4 | 0.0357 (3) | 0.0461 (3) | 0.0384 (3) | 0.0147 (3) | −0.0108 (3) | −0.0071 (3) |
Co1 | 0.0376 (3) | 0.0313 (2) | 0.0361 (3) | 0.00368 (18) | 0.000 | 0.000 |
Co2 | 0.0464 (3) | 0.0321 (2) | 0.0390 (3) | 0.00450 (19) | 0.000 | 0.000 |
N1 | 0.0318 (17) | 0.0395 (15) | 0.0415 (17) | 0.0071 (12) | 0.000 | 0.000 |
N2 | 0.0378 (18) | 0.0543 (18) | 0.0403 (18) | 0.0113 (14) | 0.000 | 0.000 |
N3 | 0.044 (2) | 0.0448 (17) | 0.0405 (17) | 0.0049 (13) | 0.000 | 0.000 |
N4 | 0.0293 (15) | 0.0391 (15) | 0.0385 (16) | −0.0003 (11) | 0.000 | 0.000 |
O1 | 0.0424 (11) | 0.0351 (9) | 0.0464 (10) | 0.0043 (8) | −0.0048 (8) | 0.0019 (7) |
O2 | 0.0432 (11) | 0.0372 (9) | 0.0481 (10) | 0.0026 (8) | −0.0073 (8) | −0.0042 (8) |
O3 | 0.0424 (10) | 0.0408 (9) | 0.0504 (11) | 0.0004 (8) | −0.0059 (8) | 0.0060 (8) |
O4 | 0.0412 (10) | 0.0366 (9) | 0.0484 (11) | 0.0073 (8) | −0.0030 (8) | 0.0031 (8) |
O5 | 0.0470 (11) | 0.0344 (8) | 0.0411 (9) | 0.0005 (7) | 0.0044 (8) | 0.0063 (7) |
O6 | 0.0457 (10) | 0.0353 (8) | 0.0410 (9) | 0.0008 (8) | −0.0023 (8) | −0.0017 (7) |
O7 | 0.0519 (12) | 0.0552 (11) | 0.0477 (12) | 0.0120 (9) | −0.0003 (9) | −0.0107 (9) |
O8 | 0.0482 (11) | 0.0437 (9) | 0.0413 (11) | 0.0127 (8) | −0.0075 (8) | −0.0091 (8) |
O9 | 0.0404 (10) | 0.0372 (9) | 0.0500 (11) | 0.0055 (7) | −0.0028 (8) | 0.0016 (8) |
O10 | 0.0444 (11) | 0.0420 (9) | 0.0510 (11) | 0.0019 (8) | −0.0016 (9) | 0.0006 (8) |
O11 | 0.0464 (11) | 0.0402 (9) | 0.0526 (11) | 0.0089 (8) | −0.0003 (9) | 0.0037 (8) |
Geometric parameters (Å, º) top
C1—O2 | 1.250 (3) | C20—C19ii | 1.367 (3) |
C1—O1 | 1.254 (3) | C20—H20 | 0.9300 |
C1—C2 | 1.511 (3) | C21—O8 | 1.420 (3) |
C2—C7 | 1.388 (3) | C21—C22 | 1.495 (3) |
C2—C3 | 1.389 (4) | C21—H21A | 0.9700 |
C3—C4 | 1.386 (4) | C21—H21B | 0.9700 |
C3—Cl1 | 1.737 (3) | C22—O7 | 1.440 (3) |
C4—C5 | 1.390 (3) | C22—H22A | 0.9700 |
C4—Cl2 | 1.732 (2) | C22—H22B | 0.9700 |
C5—C6 | 1.391 (4) | C23—O7 | 1.424 (3) |
C5—C8 | 1.512 (4) | C23—C24 | 1.506 (3) |
C6—C7 | 1.396 (4) | C23—H23A | 0.9700 |
C6—Cl4 | 1.725 (2) | C23—H23B | 0.9700 |
C7—Cl3 | 1.727 (2) | C24—O8 | 1.415 (3) |
C8—O4 | 1.250 (3) | C24—H24A | 0.9700 |
C8—O3 | 1.252 (3) | C24—H24B | 0.9700 |
C9—N1 | 1.325 (3) | Co1—O6ii | 2.0971 (15) |
C9—C10 | 1.387 (4) | Co1—O6 | 2.0971 (15) |
C9—H9 | 0.9300 | Co1—N4 | 2.146 (3) |
C10—C11 | 1.352 (3) | Co1—O4ii | 2.1469 (17) |
C10—H10 | 0.9300 | Co1—O4 | 2.1469 (17) |
C11—C10i | 1.352 (3) | Co1—N3 | 2.171 (3) |
C11—H11 | 0.9300 | Co2—O5i | 2.1043 (15) |
C12—N2 | 1.339 (3) | Co2—O5 | 2.1043 (15) |
C12—C13 | 1.376 (4) | Co2—O1i | 2.1302 (17) |
C12—H12 | 0.9300 | Co2—O1 | 2.1302 (17) |
C13—C14 | 1.370 (3) | Co2—N1 | 2.172 (3) |
C13—H13 | 0.9300 | Co2—N2 | 2.177 (3) |
C14—C13i | 1.370 (3) | N1—C9i | 1.325 (3) |
C14—H14 | 0.9300 | N2—C12i | 1.339 (3) |
C15—N3 | 1.307 (3) | N3—C15ii | 1.307 (3) |
C15—C16 | 1.395 (4) | N4—C18ii | 1.341 (3) |
C15—H15 | 0.9300 | O5—H5A | 0.8500 |
C16—C17 | 1.356 (3) | O5—H5B | 0.8500 |
C16—H16 | 0.9300 | O6—H6B | 0.8500 |
C17—C16ii | 1.356 (3) | O6—H6A | 0.8501 |
C17—H17 | 0.9300 | O9—H9A | 0.8499 |
C18—N4 | 1.341 (3) | O9—H9B | 0.8500 |
C18—C19 | 1.379 (4) | O10—H10A | 0.8500 |
C18—H18 | 0.9300 | O10—H10B | 0.8501 |
C19—C20 | 1.367 (3) | O11—H11A | 0.8501 |
C19—H19 | 0.9300 | O11—H11B | 0.8501 |
| | | |
O2—C1—O1 | 127.0 (2) | C21—C22—H22B | 109.5 |
O2—C1—C2 | 116.0 (2) | H22A—C22—H22B | 108.1 |
O1—C1—C2 | 117.0 (2) | O7—C23—C24 | 110.2 (2) |
C7—C2—C3 | 117.7 (2) | O7—C23—H23A | 109.6 |
C7—C2—C1 | 121.4 (2) | C24—C23—H23A | 109.6 |
C3—C2—C1 | 120.9 (2) | O7—C23—H23B | 109.6 |
C4—C3—C2 | 121.2 (2) | C24—C23—H23B | 109.6 |
C4—C3—Cl1 | 120.1 (2) | H23A—C23—H23B | 108.1 |
C2—C3—Cl1 | 118.68 (19) | O8—C24—C23 | 110.6 (2) |
C3—C4—C5 | 121.6 (2) | O8—C24—H24A | 109.5 |
C3—C4—Cl2 | 120.62 (19) | C23—C24—H24A | 109.5 |
C5—C4—Cl2 | 117.8 (2) | O8—C24—H24B | 109.5 |
C4—C5—C6 | 117.1 (2) | C23—C24—H24B | 109.5 |
C4—C5—C8 | 121.1 (2) | H24A—C24—H24B | 108.1 |
C6—C5—C8 | 121.7 (2) | O6ii—Co1—O6 | 174.44 (9) |
C5—C6—C7 | 121.4 (2) | O6ii—Co1—N4 | 87.22 (5) |
C5—C6—Cl4 | 118.7 (2) | O6—Co1—N4 | 87.22 (5) |
C7—C6—Cl4 | 119.96 (19) | O6ii—Co1—O4ii | 89.55 (6) |
C2—C7—C6 | 121.0 (2) | O6—Co1—O4ii | 90.56 (6) |
C2—C7—Cl3 | 118.49 (19) | N4—Co1—O4ii | 91.16 (5) |
C6—C7—Cl3 | 120.52 (19) | O6ii—Co1—O4 | 90.56 (6) |
O4—C8—O3 | 127.1 (2) | O6—Co1—O4 | 89.55 (6) |
O4—C8—C5 | 116.7 (2) | N4—Co1—O4 | 91.16 (5) |
O3—C8—C5 | 116.3 (2) | O4ii—Co1—O4 | 177.68 (10) |
N1—C9—C10 | 122.7 (2) | O6ii—Co1—N3 | 92.78 (5) |
N1—C9—H9 | 118.6 | O6—Co1—N3 | 92.78 (5) |
C10—C9—H9 | 118.6 | N4—Co1—N3 | 180.0 |
C11—C10—C9 | 120.0 (3) | O4ii—Co1—N3 | 88.84 (5) |
C11—C10—H10 | 120.0 | O4—Co1—N3 | 88.84 (5) |
C9—C10—H10 | 120.0 | O5i—Co2—O5 | 177.94 (9) |
C10i—C11—C10 | 117.7 (4) | O5i—Co2—O1i | 89.21 (7) |
C10i—C11—H11 | 121.1 | O5—Co2—O1i | 90.75 (7) |
C10—C11—H11 | 121.1 | O5i—Co2—O1 | 90.75 (7) |
N2—C12—C13 | 122.6 (3) | O5—Co2—O1 | 89.21 (7) |
N2—C12—H12 | 118.7 | O1i—Co2—O1 | 178.13 (10) |
C13—C12—H12 | 118.7 | O5i—Co2—N1 | 88.97 (5) |
C14—C13—C12 | 120.2 (3) | O5—Co2—N1 | 88.97 (5) |
C14—C13—H13 | 119.9 | O1i—Co2—N1 | 89.06 (5) |
C12—C13—H13 | 119.9 | O1—Co2—N1 | 89.06 (5) |
C13—C14—C13i | 117.3 (4) | O5i—Co2—N2 | 91.03 (5) |
C13—C14—H14 | 121.4 | O5—Co2—N2 | 91.03 (5) |
C13i—C14—H14 | 121.4 | O1i—Co2—N2 | 90.94 (5) |
N3—C15—C16 | 121.7 (2) | O1—Co2—N2 | 90.94 (5) |
N3—C15—H15 | 119.2 | N1—Co2—N2 | 180.000 (1) |
C16—C15—H15 | 119.2 | C9—N1—C9i | 116.9 (3) |
C17—C16—C15 | 120.2 (3) | C9—N1—Co2 | 121.55 (15) |
C17—C16—H16 | 119.9 | C9i—N1—Co2 | 121.55 (15) |
C15—C16—H16 | 119.9 | C12i—N2—C12 | 117.1 (3) |
C16—C17—C16ii | 117.2 (3) | C12i—N2—Co2 | 121.45 (17) |
C16—C17—H17 | 121.4 | C12—N2—Co2 | 121.45 (17) |
C16ii—C17—H17 | 121.4 | C15ii—N3—C15 | 119.1 (3) |
N4—C18—C19 | 122.4 (3) | C15ii—N3—Co1 | 120.43 (16) |
N4—C18—H18 | 118.8 | C15—N3—Co1 | 120.43 (16) |
C19—C18—H18 | 118.8 | C18—N4—C18ii | 117.4 (3) |
C20—C19—C18 | 119.8 (3) | C18—N4—Co1 | 121.29 (16) |
C20—C19—H19 | 120.1 | C18ii—N4—Co1 | 121.29 (16) |
C18—C19—H19 | 120.1 | C1—O1—Co2 | 129.08 (16) |
C19ii—C20—C19 | 118.1 (4) | C8—O4—Co1 | 128.88 (16) |
C19ii—C20—H20 | 120.9 | Co2—O5—H5A | 110.5 |
C19—C20—H20 | 120.9 | Co2—O5—H5B | 105.6 |
O8—C21—C22 | 110.5 (2) | H5A—O5—H5B | 110.6 |
O8—C21—H21A | 109.5 | Co1—O6—H6B | 106.0 |
C22—C21—H21A | 109.5 | Co1—O6—H6A | 125.3 |
O8—C21—H21B | 109.5 | H6B—O6—H6A | 106.0 |
C22—C21—H21B | 109.5 | C23—O7—C22 | 109.79 (19) |
H21A—C21—H21B | 108.1 | C24—O8—C21 | 110.26 (19) |
O7—C22—C21 | 110.6 (2) | H9A—O9—H9B | 109.8 |
O7—C22—H22A | 109.5 | H10A—O10—H10B | 109.5 |
C21—C22—H22A | 109.5 | H11A—O11—H11B | 109.5 |
O7—C22—H22B | 109.5 | | |
| | | |
O2—C1—C2—C7 | 96.8 (3) | O5—Co2—N1—C9i | −154.24 (13) |
O1—C1—C2—C7 | −82.5 (3) | O1i—Co2—N1—C9i | −63.48 (13) |
O2—C1—C2—C3 | −80.0 (3) | O1—Co2—N1—C9i | 116.52 (13) |
O1—C1—C2—C3 | 100.7 (3) | C13—C12—N2—C12i | 1.29 (16) |
C7—C2—C3—C4 | −0.2 (4) | C13—C12—N2—Co2 | −178.71 (16) |
C1—C2—C3—C4 | 176.6 (2) | O5i—Co2—N2—C12i | −67.27 (12) |
C7—C2—C3—Cl1 | 179.45 (17) | O5—Co2—N2—C12i | 112.73 (12) |
C1—C2—C3—Cl1 | −3.7 (3) | O1i—Co2—N2—C12i | 21.97 (12) |
C2—C3—C4—C5 | −1.5 (4) | O1—Co2—N2—C12i | −158.03 (12) |
Cl1—C3—C4—C5 | 178.86 (19) | O5i—Co2—N2—C12 | 112.73 (12) |
C2—C3—C4—Cl2 | 178.69 (19) | O5—Co2—N2—C12 | −67.27 (12) |
Cl1—C3—C4—Cl2 | −1.0 (3) | O1i—Co2—N2—C12 | −158.03 (12) |
C3—C4—C5—C6 | 1.9 (4) | O1—Co2—N2—C12 | 21.97 (12) |
Cl2—C4—C5—C6 | −178.27 (17) | C16—C15—N3—C15ii | −0.71 (19) |
C3—C4—C5—C8 | −178.8 (2) | C16—C15—N3—Co1 | 179.29 (19) |
Cl2—C4—C5—C8 | 1.1 (3) | O6—Co1—N3—C15 | −37.09 (14) |
C4—C5—C6—C7 | −0.7 (3) | O6ii—Co1—N3—C15 | 142.91 (14) |
C8—C5—C6—C7 | 180.0 (2) | O4ii—Co1—N3—C15 | −127.59 (14) |
C4—C5—C6—Cl4 | 178.97 (17) | O4—Co1—N3—C15 | 52.41 (14) |
C8—C5—C6—Cl4 | −0.4 (3) | O6—Co1—N3—C15ii | 142.91 (14) |
C3—C2—C7—C6 | 1.4 (3) | O6ii—Co1—N3—C15ii | −37.09 (14) |
C1—C2—C7—C6 | −175.4 (2) | O4ii—Co1—N3—C15ii | 52.41 (14) |
C3—C2—C7—Cl3 | −178.50 (17) | O4—Co1—N3—C15ii | −127.59 (14) |
C1—C2—C7—Cl3 | 4.6 (3) | C19—C18—N4—C18ii | 0.26 (18) |
C5—C6—C7—C2 | −1.0 (3) | C19—C18—N4—Co1 | −179.74 (18) |
Cl4—C6—C7—C2 | 179.37 (18) | O6—Co1—N4—C18 | 57.96 (13) |
C5—C6—C7—Cl3 | 178.93 (18) | O6ii—Co1—N4—C18 | −122.04 (13) |
Cl4—C6—C7—Cl3 | −0.7 (3) | O4ii—Co1—N4—C18 | 148.46 (13) |
C4—C5—C8—O4 | 92.8 (3) | O4—Co1—N4—C18 | −31.55 (13) |
C6—C5—C8—O4 | −87.8 (3) | O6—Co1—N4—C18ii | −122.04 (13) |
C4—C5—C8—O3 | −87.1 (3) | O6ii—Co1—N4—C18ii | 57.96 (13) |
C6—C5—C8—O3 | 92.3 (3) | O4ii—Co1—N4—C18ii | −31.54 (13) |
N1—C9—C10—C11 | −0.6 (4) | O4—Co1—N4—C18ii | 148.45 (13) |
C9—C10—C11—C10i | 0.30 (17) | O2—C1—O1—Co2 | −6.0 (4) |
N2—C12—C13—C14 | −2.6 (3) | C2—C1—O1—Co2 | 173.14 (15) |
C12—C13—C14—C13i | 1.23 (15) | O5i—Co2—O1—C1 | −1.5 (2) |
N3—C15—C16—C17 | 1.5 (4) | O5—Co2—O1—C1 | −179.5 (2) |
C15—C16—C17—C16ii | −0.68 (18) | N1—Co2—O1—C1 | −90.5 (2) |
N4—C18—C19—C20 | −0.5 (4) | N2—Co2—O1—C1 | 89.5 (2) |
C18—C19—C20—C19ii | 0.25 (17) | O3—C8—O4—Co1 | 8.8 (4) |
O8—C21—C22—O7 | −57.7 (3) | C5—C8—O4—Co1 | −171.12 (15) |
O7—C23—C24—O8 | 58.4 (3) | O6—Co1—O4—C8 | 171.8 (2) |
C10—C9—N1—C9i | 0.32 (18) | O6ii—Co1—O4—C8 | −13.8 (2) |
C10—C9—N1—Co2 | −179.68 (18) | N4—Co1—O4—C8 | −101.0 (2) |
O5i—Co2—N1—C9 | −154.24 (13) | N3—Co1—O4—C8 | 79.0 (2) |
O5—Co2—N1—C9 | 25.76 (13) | C24—C23—O7—C22 | −57.5 (3) |
O1i—Co2—N1—C9 | 116.52 (13) | C21—C22—O7—C23 | 57.5 (3) |
O1—Co2—N1—C9 | −63.48 (13) | C23—C24—O8—C21 | −58.3 (3) |
O5i—Co2—N1—C9i | 25.76 (13) | C22—C21—O8—C24 | 58.0 (3) |
Symmetry codes: (i) −x+3/2, −y+1, z; (ii) −x+1/2, −y+2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···O2i | 0.85 | 1.97 | 2.657 (3) | 137 |
O6—H6A···O3ii | 0.85 | 2.24 | 2.684 (2) | 113 |
O6—H6B···O9iii | 0.85 | 2.10 | 2.629 (2) | 120 |
O9—H9A···O3 | 0.85 | 2.09 | 2.829 (2) | 145 |
O9—H9B···O7 | 0.85 | 2.03 | 2.726 (3) | 138 |
O10—H10A···Cl1iv | 0.85 | 2.71 | 3.3714 (19) | 136 |
O11—H11A···O10 | 0.85 | 2.37 | 3.199 (3) | 164 |
C24—H24B···Cg1iv | 0.97 | 2.97 | 3.715 (3) | 135 |
Symmetry codes: (i) −x+3/2, −y+1, z; (ii) −x+1/2, −y+2, z; (iii) x, y+1, z; (iv) x, y−1, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Co(C8Cl4O4)(C5H5N)3(H2O)]·C5H5N | [Co(C8Cl4O4)(C5H5N)2(H2O)2]·C4H8O2·3H2O |
Mr | 695.23 | 697.19 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, Pcca |
Temperature (K) | 291 | 291 |
a, b, c (Å) | 8.7128 (10), 17.8408 (17), 21.227 (2) | 21.4257 (19), 8.6567 (8), 33.537 (3) |
α, β, γ (°) | 67.879 (1), 79.839 (2), 84.962 (1) | 90, 90, 90 |
V (Å3) | 3007.9 (5) | 6220.3 (10) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.97 | 0.95 |
Crystal size (mm) | 0.30 × 0.26 × 0.24 | 0.28 × 0.24 × 0.22 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.76, 0.79 | 0.77, 0.81 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23660, 11691, 8460 | 46466, 6133, 4296 |
Rint | 0.027 | 0.066 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.109, 1.01 | 0.043, 0.077, 1.02 |
No. of reflections | 11691 | 6133 |
No. of parameters | 757 | 366 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.62 | 0.48, −0.42 |
Selected bond lengths (Å) for (I) topCo1—O7 | 2.0619 (19) | Co2—O6 | 2.066 (2) |
Co1—O9 | 2.122 (2) | Co2—O3i | 2.127 (2) |
Co1—O2 | 2.126 (2) | Co2—O10 | 2.144 (2) |
Co1—N3 | 2.155 (3) | Co2—N5 | 2.167 (3) |
Co1—N1 | 2.158 (2) | Co2—N4 | 2.170 (2) |
Co1—N2 | 2.171 (3) | Co2—N6 | 2.190 (3) |
Symmetry code: (i) x−1, y−1, z+1. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9A···N8 | 0.85 | 1.91 | 2.718 (3) | 159.4 |
O9—H9B···O1 | 0.85 | 1.97 | 2.768 (3) | 157.0 |
O10—H10B···O4i | 0.85 | 1.85 | 2.686 (3) | 165.9 |
O10—H10A···N7ii | 0.85 | 1.98 | 2.814 (3) | 166.9 |
C40—H40···Cg1ii | 0.93 | 2.99 | 3.813 (4) | 149 |
C44—H44···Cg2iii | 0.93 | 2.94 | 3.638 (4) | 133 |
Symmetry codes: (i) x−1, y−1, z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1. |
Selected bond lengths (Å) for (II) topCo1—O6i | 2.0971 (15) | Co2—O5ii | 2.1043 (15) |
Co1—O6 | 2.0971 (15) | Co2—O5 | 2.1043 (15) |
Co1—N4 | 2.146 (3) | Co2—O1ii | 2.1302 (17) |
Co1—O4i | 2.1469 (17) | Co2—O1 | 2.1302 (17) |
Co1—O4 | 2.1469 (17) | Co2—N1 | 2.172 (3) |
Co1—N3 | 2.171 (3) | Co2—N2 | 2.177 (3) |
Symmetry codes: (i) −x+1/2, −y+2, z; (ii) −x+3/2, −y+1, z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···O2ii | 0.85 | 1.97 | 2.657 (3) | 136.8 |
O6—H6A···O3i | 0.85 | 2.24 | 2.684 (2) | 112.8 |
O6—H6B···O9iii | 0.85 | 2.10 | 2.629 (2) | 119.7 |
O9—H9A···O3 | 0.85 | 2.09 | 2.829 (2) | 145.0 |
O9—H9B···O7 | 0.85 | 2.03 | 2.726 (3) | 138.4 |
O10—H10A···Cl1iv | 0.85 | 2.71 | 3.3714 (19) | 136.3 |
O11—H11A···O10 | 0.85 | 2.37 | 3.199 (3) | 164.3 |
C24—H24B···Cg1iv | 0.97 | 2.97 | 3.715 (3) | 135 |
Symmetry codes: (i) −x+1/2, −y+2, z; (ii) −x+3/2, −y+1, z; (iii) x, y+1, z; (iv) x, y−1, z. |
The rapid development in crystal engineering of coordination polymers has afforded access to crystalline solid-state materials with potential applications in the desired areas of catalysis, magnetism, gas absorption, nonlinear optics and drug delivery (Férey, 2008; Wang et al., 2008). Currently, the aromatic bridging ligand 1,4-benzenedicarboxylate (BDC) has been widely utilized to fabricate coordination polymers based on paddle-wheel units with robust networks and attractive properties as conventional porous materials (Li et al., 1999; Serre et al., 2002; Xiao et al., 2005; Du et al., 2007). Derivatives of BDC with electron-donating or accepting substituents, such as 2,3,5,6-tetramethyl-1,4-benzenedicarboxylate (TBDC) and 2,3,5,6-tetrafluoro-1,4-benzenedicarboxylate (BDC-F4), have also received considerable attention in the design of porous materials with an efficient hydrogen-storage capacity (Kitaura et al., 2004; Chun et al., 2005). Few investigations of solvent effects have been carried out on crystalline compounds using substituted BDC building blocks (Chen et al., 2008). In the latter paper, solvent-regulated assemblies of manganese(II) coordination polymers with 2,3,5,6-tetrachloro-1,4-benzenedicarboxylic acid (H2BDC-Cl4) exhibit different binding modes and dimensionality in the final coordination networks with variable auxiliary solvent co-ligands. As part of our investigation of the coordination behavior of H2BDC-Cl4 and divalent transition metal ions, we report the solvent-directed assembly of two CoII coordination polymers, {[Co2(C8Cl4O4)2(C5H5N)6(H2O)2].2C5H5N}n, (I), and {[Co(C8Cl4O4)(C5H5N)2(H2O)2].C4H8O2.3H2O}n, (II).
The molecular unit of (I) contains two CoII atoms, two BDC-Cl4 ligands, six coordinated pyridine molecules and two water molecules, along with two pyridine molecules of crystallization (Fig. 1). The two CoII ions exhibit similar slightly distorted octahedral coordination geometries, with the N3O3 coordination environment made up from two BDC-Cl4 anions, one aqua ligand and three pyridine molecules. In the MnII–BDC-Cl4 polymer crystallized from similar pyridine–water media, the MnII ion is six-coordinated through two BDC-Cl4 anions, two aqua ligands and two pyridine molecules (Chen et al., 2008). Within the anionic unit, the rotation angles (ϕrot) of the tetrachlorinated phenyl ring relative to the carboxylate groups are 81.0 (2) and 86.2 (1)°, similar to the corresponding values of other polychlorinated carboxylate compounds (Maspoch et al., 2004). Each BDC-Cl4 ligand adopts a bis-monodentate coordination mode, bridging adjacent CoII centers into an infinite linear chain with pendent pyridine molecules, which runs along the [111] direction, as illustrated in Fig. 2.
There exist strong intramolecular O—H···O interactions (entries 2 and 3 in Table 2) between the carboxylate O atoms and the aqua ligands, which further stabilize the one-dimensional polymeric chain motif. Intermolecular O—H···N bonds (entries 1 and 4 in Table 2) join the uncoordinated pyridine molecules and the coordination chain together. Because there are a large number of coordinated and uncoordinated pyridine molecules in the structure, multiple weak π–π interactions are noted between the benzene and pyridine rings and between the pyridine rings (e.g. C10–C15, N7/C47–C51 and N8/C52–C56), with centroid-to-centroid distances in the range 3.508 (2)–3.641 (2) Å; these link the one-dimensional hydrogen-bonded chains into a two-dimensional supramolecular network (Fig. 2). The supramolecular architecture is further consolidated by multiple C—H···π interactions between CH groups and the centroids (Cg1 and Cg2, respectively) of the N3/C27–C31 pyridine and C2–C7 phenyl rings (Fig. 2 and Table 2).
The crystal structure of complex (II) also exhibits a one-dimensional coordination motif. In the asymmetric unit, two crystallographically independent centers, Co1 and Co2, lie on twofold rotation axes at (1/4, 1, y) and (3/4, 1/2, y), respectively. Each CoII center is coordinated by two carboxylate groups in a monodentate mode from two symmetry-related BDC-Cl4, two pyridine and two aqua ligands. The asymmetric unit also contains one dioxane and three water molecules as guests. The N2O4 coordination geometry, provided by two carboxylate O atoms, two pyridyl N atoms and two water molecules, can be described as an elongated octahedron with two pyridyl N atoms occupying the axial sites. Neighboring Co1 and Co2 atoms are bridged by the BDC-Cl4 dianion in a trans fashion (Fig. 3). Propagation of this arrangement generates a one-dimensional linear array, which is similar to that of complex (I) but with fewer coordinated pyridine molecules and more water molecules. Similarly to (I), the two carboxylate groups within each BDC-Cl4 group make ϕrot dihedral angles of 81.6 (1) and 87.7 (1)° with the central phenyl plane. Analogous intramolecular O—H···O bonds (entries 2 and 3 [or 1 and 2?] in Table 4) between uncoordinated carboxylate O atoms and aqua ligands consolidate the one-dimensional polymeric chain. Analysis of the crystal packing shows the existence of two main types of conventional hydrogen-bonding interactions (O—H···O and O—H···Cl; Table 4), which connect the polymeric chains, solvent water molecules and dioxane moelcules to form a two-dimensional network parallel to the ab plane (Fig. 4). Notably, one hydrogen-bonded pattern (entries 2–4, Table 4), denoted as R66(12) (Etter, 1990), is observed in this layer array. Additionally, the dioxane solvent has a C—H···π interaction with the phenyl ring (Cg1 denotes the centroid of the C2–C7 ring) of the BDC-Cl4 anion (Table 4). However, in contrast to (I), adjacent layers have no significant aromatic ring-based stacking interactions.