metal-organic compounds
Chloridobis(1,10-phenanthroline-κ2N,N′)copper(II) chlorido(1,10-phenanthroline-κ2N,N′)(pyridine-2,6-dicarboxylato-κ3O2,N,O6)manganate(II) methanol monosolvate
aTaras Shevchenko National University of Kyiv, Department of Inorganic Chemistry, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, bNational Taras Shevchenko University of Kyiv, Department of Chemistry, Volodymyrska str. 64, 01033 Kyiv, Ukraine, and cInstitute for Scintillation Materials, "Institute for Single Crystals", National Academy of Sciences of Ukraine, Lenina ave. 60, Kharkov 61001, Ukraine
*Correspondence e-mail: galina.goncharuck@mail.ru
The title complex, [CuCl(C12H8N2)2][Mn(C7H3NO4)Cl(C12H8N2)]·CH3OH, consists of discrete [CuCl(phen)2]+ cations (phen is 1,10-phenanthroline), [MnCl(pydc)(phen)]− anions (H2pydc is 2,6-pyridine-2,6-dicarboxylic acid) and one methanol solvent molecule of crystallization per It should be noted, that a solvent-masking procedure as implemented in OLEX2 [Dolomanov et al. (2009). J. Appl. Cryst. 42, 339–341] was used to remove the electronic contribution from one disordered solvent molecule, presumably methanol. Only the atoms used in the refined model are reported in chemical formula and related values. The CuII ion is five-coordinated by two phenanthroline ligands and one chloride ion in a distorted trigonal–bipyramidal geometry. The dihedral angle between the phen ligands is 65.21 (5)°. The MnII ion is six-coordinated by one Cl atom, two N atoms from a phen ligand, as well one N atom and two O atoms from pydc in a distorted octahedral coordination geometry, with cis angles ranging from 72.00 (8) to 122.07 (8)° and trans angles ranging from 143.98 (8) to 163.15 (6)°. In the crystal, C—H⋯O, O—H⋯O and C—H⋯Cl hydrogen bonds, cation–anion π–π interactions between the phen ring systems with centroid–centroid distances in the range 3.881 (34)–4.123 (36) Å, as well as cation–cation, anion–anion π–π interactions between the phen rings with centroid–centroid distances in the range 3.763 (4)–3.99 (5) Å and pydc rings with centroid–centroid distances 3.52 (5) Å link the various components.
CCDC reference: 993053
Related literature
For background to the direct synthesis of heterometallic complexes, see: Chygorin et al. (2012); Nesterov et al. (2012); Nesterova et al. (2013). For the structures of related complexes, see: Wei & Yang (2004); Lu et al. (2004); Murphy et al. (1997); Liu et al. (2006); Ma et al. (2002); Laine et al. (1995); Chatterjee et al. (1998).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009); molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
CCDC reference: 993053
10.1107/S1600536814006369/br2237sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814006369/br2237Isup2.hkl
Copper powder (0.08 g, 1.25 mmol), KMnO4 (0.2 g, 1.25 mmol), phen·H2O (0.50 g, 2.5 mmol) and NH4Cl (0.14 g, 2.5 mmol) in CH3OH (20 mL) were mechanically stirred at 323–333 K in air until total dissolution of copper was observed (3 h). The resulting green solution was filtered from the insignificant quantities of by-products and cooled to the room temperature. The PriOH was added dropwise within 2 days to obtain green crystals of the title complex. Yield 0.23 g (40% by copper).
All non-hydrogen atoms were refined isotropically. All hydrogen atoms were placed at calculated position and refined in a riding-model approximation. Idealised Me and tetrahedral OH refined as rotating groups.
without SQUEEZE procedure clearly shows severely disordered isolated solvent molecule, presumably methanol. However, we were unable to find acceptable model of disorder.Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of the title compound with hydrogen bonds with solvent molecule shown as dashed lines. | |
Fig. 2. Part of the crystal structure showing cation–anion and cation–cation, anion–anion π–π interactions. H atoms are omited for clarity. |
[CuCl(C12H8N2)2][MnCl(C7H3NO4)Cl(C12H8N2)]·CH4O | Z = 2 |
Mr = 927.14 | F(000) = 944 |
Triclinic, P1 | Dx = 1.491 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3680 (4) Å | Cell parameters from 6590 reflections |
b = 12.5332 (4) Å | θ = 2.4–27.2° |
c = 17.2709 (6) Å | µ = 1.01 mm−1 |
α = 72.966 (3)° | T = 293 K |
β = 74.709 (3)° | Block, clear light green |
γ = 89.262 (3)° | 0.25 × 0.19 × 0.11 mm |
V = 2064.78 (13) Å3 |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 9973 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 6764 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 16.1827 pixels mm-1 | θmax = 28.0°, θmin = 2.0° |
ω and π scans | h = −15→15 |
Absorption correction: analytical (Clark & Reid, 1995) | k = −18→18 |
Tmin = 0.837, Tmax = 0.918 | l = −26→24 |
35601 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0706P)2 + 0.2578P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
9973 reflections | Δρmax = 0.44 e Å−3 |
543 parameters | Δρmin = −0.51 e Å−3 |
[CuCl(C12H8N2)2][MnCl(C7H3NO4)Cl(C12H8N2)]·CH4O | γ = 89.262 (3)° |
Mr = 927.14 | V = 2064.78 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.3680 (4) Å | Mo Kα radiation |
b = 12.5332 (4) Å | µ = 1.01 mm−1 |
c = 17.2709 (6) Å | T = 293 K |
α = 72.966 (3)° | 0.25 × 0.19 × 0.11 mm |
β = 74.709 (3)° |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 9973 independent reflections |
Absorption correction: analytical (Clark & Reid, 1995) | 6764 reflections with I > 2σ(I) |
Tmin = 0.837, Tmax = 0.918 | Rint = 0.040 |
35601 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.44 e Å−3 |
9973 reflections | Δρmin = −0.51 e Å−3 |
543 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.20341 (4) | 0.29043 (3) | 0.50838 (3) | 0.03953 (12) | |
Cu1 | 0.72013 (3) | 0.78783 (3) | 0.01669 (2) | 0.04942 (12) | |
Cl1 | 0.61596 (9) | 0.88250 (8) | −0.08120 (6) | 0.0714 (3) | |
Cl2 | 0.00242 (8) | 0.27997 (7) | 0.62072 (5) | 0.0585 (2) | |
O1 | 0.2901 (2) | 0.15048 (16) | 0.59210 (13) | 0.0523 (5) | |
O2 | 0.3165 (3) | −0.03177 (19) | 0.62979 (16) | 0.0783 (8) | |
O3 | 0.1150 (2) | 0.33570 (17) | 0.39765 (12) | 0.0512 (5) | |
O4 | 0.0585 (3) | 0.2738 (2) | 0.30277 (17) | 0.0837 (8) | |
O5 | 0.4459 (4) | 0.0292 (4) | 0.7352 (3) | 0.1196 (12) | |
H5A | 0.3971 | 0.0297 | 0.7047 | 0.179* | |
N1 | 0.9021 (2) | 0.8129 (2) | −0.06475 (14) | 0.0462 (6) | |
N2 | 0.8308 (2) | 0.8280 (2) | 0.09067 (14) | 0.0448 (5) | |
N3 | 0.5495 (2) | 0.7495 (2) | 0.10901 (16) | 0.0520 (6) | |
N4 | 0.6926 (3) | 0.6098 (2) | 0.03421 (18) | 0.0630 (7) | |
N7 | 0.1860 (2) | 0.14053 (18) | 0.47194 (14) | 0.0408 (5) | |
N5 | 0.4197 (2) | 0.32798 (18) | 0.42308 (15) | 0.0430 (5) | |
N6 | 0.2590 (2) | 0.47013 (18) | 0.48676 (14) | 0.0423 (5) | |
C1 | 1.0019 (3) | 0.8371 (2) | −0.03370 (17) | 0.0403 (6) | |
C2 | 0.9630 (3) | 0.8457 (2) | 0.05011 (16) | 0.0397 (6) | |
C3 | 0.7928 (3) | 0.8376 (3) | 0.16789 (18) | 0.0533 (7) | |
H3 | 0.7021 | 0.8262 | 0.1963 | 0.064* | |
C4 | 0.8819 (4) | 0.8638 (3) | 0.2084 (2) | 0.0649 (9) | |
H4 | 0.8511 | 0.8698 | 0.2625 | 0.078* | |
C5 | 1.0152 (4) | 0.8804 (3) | 0.1673 (2) | 0.0593 (8) | |
H5 | 1.0763 | 0.8966 | 0.1940 | 0.071* | |
C6 | 1.0604 (3) | 0.8733 (2) | 0.08529 (18) | 0.0459 (7) | |
C7 | 1.1967 (3) | 0.8916 (3) | 0.0360 (2) | 0.0555 (8) | |
H7 | 1.2619 | 0.9103 | 0.0588 | 0.067* | |
C8 | 1.2337 (3) | 0.8827 (3) | −0.0427 (2) | 0.0526 (7) | |
H8 | 1.3236 | 0.8944 | −0.0729 | 0.063* | |
C9 | 1.1356 (3) | 0.8554 (2) | −0.08018 (18) | 0.0449 (6) | |
C10 | 1.1656 (3) | 0.8471 (3) | −0.1617 (2) | 0.0585 (8) | |
H10 | 1.2540 | 0.8575 | −0.1947 | 0.070* | |
C11 | 1.0657 (3) | 0.8237 (3) | −0.1927 (2) | 0.0636 (9) | |
H11 | 1.0852 | 0.8195 | −0.2474 | 0.076* | |
C12 | 0.9348 (3) | 0.8060 (3) | −0.1429 (2) | 0.0590 (8) | |
H12 | 0.8675 | 0.7888 | −0.1647 | 0.071* | |
C13 | 0.5034 (3) | 0.6408 (3) | 0.1362 (2) | 0.0540 (8) | |
C14 | 0.5776 (3) | 0.5656 (3) | 0.0954 (2) | 0.0566 (8) | |
C15 | 0.7615 (5) | 0.5422 (3) | −0.0057 (3) | 0.0823 (12) | |
H15 | 0.8415 | 0.5705 | −0.0466 | 0.099* | |
C16 | 0.7186 (6) | 0.4310 (4) | 0.0114 (3) | 0.1014 (15) | |
H16 | 0.7683 | 0.3868 | −0.0188 | 0.122* | |
C17 | 0.6042 (5) | 0.3875 (4) | 0.0722 (3) | 0.0942 (14) | |
H17 | 0.5753 | 0.3131 | 0.0839 | 0.113* | |
C18 | 0.5297 (4) | 0.4535 (3) | 0.1174 (3) | 0.0728 (10) | |
C19 | 0.4089 (4) | 0.4157 (4) | 0.1834 (3) | 0.0880 (14) | |
H19 | 0.3766 | 0.3414 | 0.1992 | 0.106* | |
C20 | 0.3403 (4) | 0.4854 (4) | 0.2233 (3) | 0.0819 (13) | |
H20 | 0.2625 | 0.4576 | 0.2665 | 0.098* | |
C21 | 0.3841 (3) | 0.6008 (3) | 0.2010 (2) | 0.0624 (9) | |
C22 | 0.3149 (3) | 0.6773 (4) | 0.2377 (2) | 0.0698 (10) | |
H22 | 0.2365 | 0.6541 | 0.2811 | 0.084* | |
C23 | 0.3627 (3) | 0.7868 (4) | 0.2095 (2) | 0.0712 (10) | |
H23 | 0.3172 | 0.8387 | 0.2336 | 0.085* | |
C24 | 0.4799 (3) | 0.8202 (3) | 0.1446 (2) | 0.0607 (8) | |
H24 | 0.5107 | 0.8952 | 0.1253 | 0.073* | |
C25 | 0.2817 (3) | 0.0541 (2) | 0.58579 (18) | 0.0488 (7) | |
C26 | 0.2221 (3) | 0.0444 (2) | 0.51651 (18) | 0.0453 (6) | |
C27 | 0.1351 (3) | 0.1451 (2) | 0.40829 (18) | 0.0471 (7) | |
C28 | 0.0989 (3) | 0.2606 (3) | 0.36521 (19) | 0.0500 (7) | |
C29 | 0.1164 (3) | 0.0505 (3) | 0.3861 (2) | 0.0616 (9) | |
H29 | 0.0815 | 0.0544 | 0.3410 | 0.074* | |
C30 | 0.1507 (4) | −0.0504 (3) | 0.4324 (2) | 0.0682 (10) | |
H30 | 0.1369 | −0.1156 | 0.4195 | 0.082* | |
C31 | 0.2059 (4) | −0.0542 (3) | 0.4980 (2) | 0.0605 (8) | |
H31 | 0.2314 | −0.1212 | 0.5288 | 0.073* | |
C32 | 0.4672 (3) | 0.4359 (2) | 0.39983 (16) | 0.0391 (6) | |
C33 | 0.3820 (3) | 0.5109 (2) | 0.43562 (16) | 0.0374 (6) | |
C34 | 0.1806 (3) | 0.5398 (3) | 0.5192 (2) | 0.0559 (8) | |
H34 | 0.0954 | 0.5130 | 0.5541 | 0.067* | |
C35 | 0.2213 (3) | 0.6513 (3) | 0.5028 (2) | 0.0601 (9) | |
H35 | 0.1634 | 0.6976 | 0.5265 | 0.072* | |
C36 | 0.3439 (3) | 0.6924 (2) | 0.4529 (2) | 0.0535 (8) | |
H36 | 0.3719 | 0.7666 | 0.4428 | 0.064* | |
C37 | 0.4295 (3) | 0.6222 (2) | 0.41604 (19) | 0.0440 (6) | |
C38 | 0.5602 (3) | 0.6602 (3) | 0.3616 (2) | 0.0535 (8) | |
H38 | 0.5915 | 0.7341 | 0.3494 | 0.064* | |
C39 | 0.6397 (3) | 0.5895 (2) | 0.3272 (2) | 0.0562 (8) | |
H39 | 0.7245 | 0.6157 | 0.2915 | 0.067* | |
C40 | 0.5944 (3) | 0.4756 (2) | 0.34522 (19) | 0.0497 (7) | |
C41 | 0.6731 (3) | 0.3983 (3) | 0.3127 (2) | 0.0627 (9) | |
H41 | 0.7574 | 0.4211 | 0.2751 | 0.075* | |
C42 | 0.6249 (3) | 0.2899 (3) | 0.3368 (2) | 0.0638 (9) | |
H42 | 0.6763 | 0.2376 | 0.3165 | 0.077* | |
C43 | 0.4988 (3) | 0.2581 (2) | 0.3919 (2) | 0.0537 (8) | |
H43 | 0.4677 | 0.1835 | 0.4079 | 0.064* | |
C44 | 0.5429 (6) | −0.0325 (7) | 0.7194 (4) | 0.148 (3) | |
H44A | 0.5849 | −0.0104 | 0.6599 | 0.221* | |
H44B | 0.5091 | −0.1093 | 0.7380 | 0.221* | |
H44C | 0.6074 | −0.0238 | 0.7484 | 0.221* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0478 (2) | 0.0291 (2) | 0.0440 (2) | −0.00048 (16) | −0.00924 (18) | −0.01727 (17) |
Cu1 | 0.03775 (19) | 0.0562 (2) | 0.0496 (2) | −0.00171 (15) | −0.00515 (15) | −0.01451 (17) |
Cl1 | 0.0576 (5) | 0.0819 (6) | 0.0751 (6) | 0.0079 (4) | −0.0284 (4) | −0.0149 (5) |
Cl2 | 0.0575 (4) | 0.0610 (5) | 0.0521 (4) | 0.0001 (4) | −0.0054 (3) | −0.0181 (4) |
O1 | 0.0729 (14) | 0.0371 (11) | 0.0513 (12) | 0.0012 (9) | −0.0191 (10) | −0.0178 (9) |
O2 | 0.126 (2) | 0.0424 (13) | 0.0748 (17) | 0.0173 (13) | −0.0472 (16) | −0.0138 (12) |
O3 | 0.0658 (13) | 0.0420 (11) | 0.0494 (12) | 0.0049 (9) | −0.0185 (10) | −0.0165 (9) |
O4 | 0.126 (2) | 0.0696 (17) | 0.0788 (18) | 0.0079 (15) | −0.0622 (18) | −0.0267 (14) |
O5 | 0.116 (3) | 0.146 (3) | 0.131 (3) | 0.036 (2) | −0.051 (2) | −0.078 (3) |
N1 | 0.0421 (12) | 0.0580 (15) | 0.0396 (13) | −0.0029 (11) | −0.0092 (10) | −0.0175 (11) |
N2 | 0.0468 (13) | 0.0479 (14) | 0.0378 (12) | 0.0068 (10) | −0.0078 (10) | −0.0137 (10) |
N3 | 0.0415 (13) | 0.0549 (16) | 0.0535 (15) | 0.0003 (11) | −0.0063 (11) | −0.0127 (12) |
N4 | 0.0590 (16) | 0.0509 (16) | 0.0680 (18) | 0.0048 (13) | −0.0024 (14) | −0.0145 (14) |
N7 | 0.0461 (12) | 0.0333 (12) | 0.0428 (13) | −0.0028 (9) | −0.0065 (10) | −0.0159 (10) |
N5 | 0.0486 (13) | 0.0301 (11) | 0.0484 (13) | 0.0012 (9) | −0.0036 (10) | −0.0172 (10) |
N6 | 0.0444 (13) | 0.0362 (12) | 0.0511 (14) | 0.0032 (10) | −0.0119 (11) | −0.0214 (10) |
C1 | 0.0395 (14) | 0.0398 (15) | 0.0412 (15) | 0.0024 (11) | −0.0097 (11) | −0.0124 (12) |
C2 | 0.0419 (14) | 0.0368 (14) | 0.0376 (14) | 0.0036 (11) | −0.0106 (11) | −0.0071 (11) |
C3 | 0.0567 (18) | 0.0568 (19) | 0.0394 (16) | 0.0072 (14) | −0.0054 (13) | −0.0107 (14) |
C4 | 0.083 (3) | 0.073 (2) | 0.0423 (18) | 0.0178 (19) | −0.0187 (17) | −0.0222 (16) |
C5 | 0.070 (2) | 0.067 (2) | 0.0500 (18) | 0.0124 (17) | −0.0298 (17) | −0.0186 (16) |
C6 | 0.0527 (16) | 0.0423 (16) | 0.0436 (16) | 0.0049 (12) | −0.0166 (13) | −0.0111 (12) |
C7 | 0.0500 (17) | 0.0566 (19) | 0.066 (2) | 0.0009 (14) | −0.0271 (15) | −0.0171 (16) |
C8 | 0.0407 (15) | 0.0582 (19) | 0.0575 (19) | −0.0012 (13) | −0.0098 (13) | −0.0184 (15) |
C9 | 0.0409 (14) | 0.0471 (16) | 0.0449 (16) | 0.0006 (12) | −0.0069 (12) | −0.0151 (13) |
C10 | 0.0427 (16) | 0.076 (2) | 0.0552 (19) | −0.0015 (15) | 0.0000 (14) | −0.0283 (17) |
C11 | 0.0574 (19) | 0.089 (3) | 0.0452 (18) | −0.0056 (17) | −0.0023 (15) | −0.0319 (18) |
C12 | 0.0514 (18) | 0.082 (2) | 0.0484 (18) | −0.0056 (16) | −0.0119 (14) | −0.0277 (17) |
C13 | 0.0430 (16) | 0.061 (2) | 0.0505 (18) | −0.0009 (14) | −0.0122 (13) | −0.0064 (15) |
C14 | 0.0525 (18) | 0.0520 (19) | 0.0580 (19) | −0.0057 (14) | −0.0134 (15) | −0.0066 (15) |
C15 | 0.089 (3) | 0.063 (3) | 0.082 (3) | 0.008 (2) | 0.001 (2) | −0.025 (2) |
C16 | 0.119 (4) | 0.062 (3) | 0.116 (4) | 0.016 (3) | −0.008 (3) | −0.038 (3) |
C17 | 0.117 (4) | 0.051 (2) | 0.113 (4) | 0.000 (2) | −0.033 (3) | −0.021 (2) |
C18 | 0.074 (2) | 0.057 (2) | 0.082 (3) | −0.0050 (18) | −0.028 (2) | −0.0056 (19) |
C19 | 0.074 (3) | 0.065 (3) | 0.103 (3) | −0.024 (2) | −0.023 (2) | 0.008 (2) |
C20 | 0.057 (2) | 0.084 (3) | 0.078 (3) | −0.021 (2) | −0.0114 (19) | 0.011 (2) |
C21 | 0.0422 (16) | 0.080 (3) | 0.0530 (19) | −0.0062 (16) | −0.0116 (14) | −0.0031 (17) |
C22 | 0.0420 (17) | 0.109 (3) | 0.0502 (19) | −0.0015 (19) | −0.0060 (14) | −0.017 (2) |
C23 | 0.0467 (18) | 0.105 (3) | 0.065 (2) | 0.0156 (19) | −0.0124 (16) | −0.033 (2) |
C24 | 0.0468 (17) | 0.068 (2) | 0.067 (2) | 0.0076 (15) | −0.0092 (15) | −0.0243 (18) |
C25 | 0.0603 (18) | 0.0370 (16) | 0.0460 (16) | −0.0001 (13) | −0.0102 (14) | −0.0113 (13) |
C26 | 0.0525 (16) | 0.0322 (14) | 0.0483 (16) | −0.0031 (12) | −0.0044 (13) | −0.0156 (12) |
C27 | 0.0487 (16) | 0.0457 (16) | 0.0505 (17) | −0.0043 (12) | −0.0094 (13) | −0.0233 (13) |
C28 | 0.0524 (17) | 0.0539 (19) | 0.0455 (17) | −0.0035 (13) | −0.0120 (14) | −0.0187 (14) |
C29 | 0.072 (2) | 0.061 (2) | 0.066 (2) | −0.0020 (17) | −0.0222 (17) | −0.0367 (17) |
C30 | 0.087 (3) | 0.048 (2) | 0.082 (3) | −0.0043 (17) | −0.020 (2) | −0.0406 (18) |
C31 | 0.075 (2) | 0.0398 (17) | 0.070 (2) | 0.0062 (15) | −0.0152 (18) | −0.0256 (16) |
C32 | 0.0427 (14) | 0.0333 (14) | 0.0412 (15) | 0.0030 (11) | −0.0101 (11) | −0.0123 (11) |
C33 | 0.0422 (14) | 0.0305 (13) | 0.0433 (15) | 0.0034 (10) | −0.0170 (12) | −0.0121 (11) |
C34 | 0.0482 (17) | 0.0492 (18) | 0.077 (2) | 0.0091 (14) | −0.0132 (15) | −0.0327 (16) |
C35 | 0.062 (2) | 0.0413 (17) | 0.087 (2) | 0.0153 (15) | −0.0195 (18) | −0.0363 (17) |
C36 | 0.065 (2) | 0.0319 (15) | 0.077 (2) | 0.0068 (13) | −0.0282 (17) | −0.0269 (15) |
C37 | 0.0508 (16) | 0.0335 (14) | 0.0558 (17) | 0.0045 (12) | −0.0239 (14) | −0.0171 (12) |
C38 | 0.0561 (18) | 0.0352 (15) | 0.068 (2) | −0.0071 (13) | −0.0190 (15) | −0.0113 (14) |
C39 | 0.0523 (17) | 0.0407 (17) | 0.066 (2) | −0.0086 (13) | −0.0045 (15) | −0.0110 (15) |
C40 | 0.0458 (16) | 0.0417 (16) | 0.0578 (18) | 0.0003 (12) | −0.0085 (13) | −0.0140 (14) |
C41 | 0.0529 (18) | 0.054 (2) | 0.068 (2) | 0.0017 (15) | 0.0075 (16) | −0.0197 (17) |
C42 | 0.060 (2) | 0.0488 (19) | 0.076 (2) | 0.0073 (15) | 0.0053 (17) | −0.0310 (17) |
C43 | 0.0583 (18) | 0.0336 (15) | 0.066 (2) | 0.0039 (13) | −0.0021 (15) | −0.0236 (14) |
C44 | 0.104 (5) | 0.229 (8) | 0.127 (5) | 0.018 (5) | −0.031 (4) | −0.080 (5) |
Mn1—Cl2 | 2.4185 (9) | C13—C21 | 1.411 (4) |
Mn1—O1 | 2.266 (2) | C14—C18 | 1.403 (5) |
Mn1—O3 | 2.257 (2) | C15—H15 | 0.9300 |
Mn1—N7 | 2.173 (2) | C15—C16 | 1.391 (6) |
Mn1—N5 | 2.302 (2) | C16—H16 | 0.9300 |
Mn1—N6 | 2.230 (2) | C16—C17 | 1.353 (6) |
Cu1—Cl1 | 2.2775 (9) | C17—H17 | 0.9300 |
Cu1—N1 | 1.998 (2) | C17—C18 | 1.391 (6) |
Cu1—N2 | 2.090 (2) | C18—C19 | 1.428 (6) |
Cu1—N3 | 1.997 (2) | C19—H19 | 0.9300 |
Cu1—N4 | 2.174 (3) | C19—C20 | 1.350 (6) |
O1—C25 | 1.250 (3) | C20—H20 | 0.9300 |
O2—C25 | 1.234 (3) | C20—C21 | 1.430 (6) |
O3—C28 | 1.261 (4) | C21—C22 | 1.391 (5) |
O4—C28 | 1.224 (4) | C22—H22 | 0.9300 |
O5—H5A | 0.8200 | C22—C23 | 1.366 (5) |
O5—C44 | 1.281 (6) | C23—H23 | 0.9300 |
N1—C1 | 1.359 (3) | C23—C24 | 1.388 (5) |
N1—C12 | 1.330 (4) | C24—H24 | 0.9300 |
N2—C2 | 1.353 (3) | C25—C26 | 1.518 (4) |
N2—C3 | 1.328 (4) | C26—C31 | 1.386 (4) |
N3—C13 | 1.352 (4) | C27—C28 | 1.513 (4) |
N3—C24 | 1.324 (4) | C27—C29 | 1.379 (4) |
N4—C14 | 1.362 (4) | C29—H29 | 0.9300 |
N4—C15 | 1.330 (5) | C29—C30 | 1.382 (5) |
N7—C26 | 1.335 (3) | C30—H30 | 0.9300 |
N7—C27 | 1.326 (4) | C30—C31 | 1.387 (5) |
N5—C32 | 1.352 (3) | C31—H31 | 0.9300 |
N5—C43 | 1.325 (3) | C32—C33 | 1.441 (4) |
N6—C33 | 1.351 (3) | C32—C40 | 1.400 (4) |
N6—C34 | 1.328 (4) | C33—C37 | 1.399 (4) |
C1—C2 | 1.432 (4) | C34—H34 | 0.9300 |
C1—C9 | 1.390 (4) | C34—C35 | 1.389 (4) |
C2—C6 | 1.402 (4) | C35—H35 | 0.9300 |
C3—H3 | 0.9300 | C35—C36 | 1.343 (5) |
C3—C4 | 1.390 (5) | C36—H36 | 0.9300 |
C4—H4 | 0.9300 | C36—C37 | 1.406 (4) |
C4—C5 | 1.364 (5) | C37—C38 | 1.425 (4) |
C5—H5 | 0.9300 | C38—H38 | 0.9300 |
C5—C6 | 1.399 (4) | C38—C39 | 1.359 (4) |
C6—C7 | 1.426 (4) | C39—H39 | 0.9300 |
C7—H7 | 0.9300 | C39—C40 | 1.427 (4) |
C7—C8 | 1.349 (4) | C40—C41 | 1.406 (4) |
C8—H8 | 0.9300 | C41—H41 | 0.9300 |
C8—C9 | 1.434 (4) | C41—C42 | 1.358 (5) |
C9—C10 | 1.394 (4) | C42—H42 | 0.9300 |
C10—H10 | 0.9300 | C42—C43 | 1.381 (4) |
C10—C11 | 1.355 (5) | C43—H43 | 0.9300 |
C11—H11 | 0.9300 | C44—H44A | 0.9600 |
C11—C12 | 1.383 (4) | C44—H44B | 0.9600 |
C12—H12 | 0.9300 | C44—H44C | 0.9600 |
C13—C14 | 1.436 (5) | ||
O1—Mn1—Cl2 | 91.88 (6) | N4—C15—C16 | 122.6 (4) |
O1—Mn1—N5 | 84.75 (8) | C16—C15—H15 | 118.7 |
O3—Mn1—Cl2 | 99.59 (6) | C15—C16—H16 | 120.2 |
O3—Mn1—O1 | 143.98 (7) | C17—C16—C15 | 119.6 (4) |
O3—Mn1—N5 | 92.69 (8) | C17—C16—H16 | 120.2 |
N7—Mn1—Cl2 | 104.76 (6) | C16—C17—H17 | 119.9 |
N7—Mn1—O1 | 72.07 (8) | C16—C17—C18 | 120.3 (4) |
N7—Mn1—O3 | 72.00 (8) | C18—C17—H17 | 119.9 |
N7—Mn1—N5 | 89.93 (8) | C14—C18—C19 | 118.3 (4) |
N7—Mn1—N6 | 155.48 (9) | C17—C18—C14 | 116.9 (4) |
N5—Mn1—Cl2 | 163.15 (6) | C17—C18—C19 | 124.8 (4) |
N6—Mn1—Cl2 | 95.19 (6) | C18—C19—H19 | 119.2 |
N6—Mn1—O1 | 122.07 (8) | C20—C19—C18 | 121.5 (4) |
N6—Mn1—O3 | 90.94 (8) | C20—C19—H19 | 119.2 |
N6—Mn1—N5 | 72.98 (8) | C19—C20—H20 | 119.1 |
N1—Cu1—Cl1 | 94.39 (7) | C19—C20—C21 | 121.7 (4) |
N1—Cu1—N2 | 80.86 (9) | C21—C20—H20 | 119.1 |
N1—Cu1—N4 | 96.83 (10) | C13—C21—C20 | 118.2 (4) |
N2—Cu1—Cl1 | 136.84 (7) | C22—C21—C13 | 117.6 (3) |
N2—Cu1—N4 | 114.64 (10) | C22—C21—C20 | 124.2 (3) |
N3—Cu1—Cl1 | 93.14 (8) | C21—C22—H22 | 120.2 |
N3—Cu1—N1 | 172.42 (10) | C23—C22—C21 | 119.6 (3) |
N3—Cu1—N2 | 94.28 (10) | C23—C22—H22 | 120.2 |
N3—Cu1—N4 | 79.84 (11) | C22—C23—H23 | 120.3 |
N4—Cu1—Cl1 | 108.52 (9) | C22—C23—C24 | 119.5 (4) |
C25—O1—Mn1 | 118.58 (19) | C24—C23—H23 | 120.3 |
C28—O3—Mn1 | 118.40 (19) | N3—C24—C23 | 122.6 (3) |
C44—O5—H5A | 109.5 | N3—C24—H24 | 118.7 |
C1—N1—Cu1 | 114.18 (18) | C23—C24—H24 | 118.7 |
C12—N1—Cu1 | 127.6 (2) | O1—C25—C26 | 115.4 (2) |
C12—N1—C1 | 118.2 (2) | O2—C25—O1 | 126.6 (3) |
C2—N2—Cu1 | 111.40 (17) | O2—C25—C26 | 118.0 (3) |
C3—N2—Cu1 | 131.1 (2) | N7—C26—C25 | 114.6 (2) |
C3—N2—C2 | 117.5 (3) | N7—C26—C31 | 120.7 (3) |
C13—N3—Cu1 | 115.5 (2) | C31—C26—C25 | 124.7 (3) |
C24—N3—Cu1 | 125.9 (2) | N7—C27—C28 | 114.2 (2) |
C24—N3—C13 | 118.6 (3) | N7—C27—C29 | 121.2 (3) |
C14—N4—Cu1 | 110.1 (2) | C29—C27—C28 | 124.6 (3) |
C15—N4—Cu1 | 132.3 (3) | O3—C28—C27 | 115.6 (3) |
C15—N4—C14 | 117.5 (3) | O4—C28—O3 | 125.8 (3) |
C26—N7—Mn1 | 118.99 (19) | O4—C28—C27 | 118.6 (3) |
C27—N7—Mn1 | 119.67 (18) | C27—C29—H29 | 120.7 |
C27—N7—C26 | 121.3 (2) | C27—C29—C30 | 118.5 (3) |
C32—N5—Mn1 | 114.83 (17) | C30—C29—H29 | 120.7 |
C43—N5—Mn1 | 127.8 (2) | C29—C30—H30 | 120.0 |
C43—N5—C32 | 117.3 (2) | C29—C30—C31 | 119.9 (3) |
C33—N6—Mn1 | 116.78 (16) | C31—C30—H30 | 120.0 |
C34—N6—Mn1 | 125.3 (2) | C26—C31—C30 | 118.4 (3) |
C34—N6—C33 | 117.9 (2) | C26—C31—H31 | 120.8 |
N1—C1—C2 | 116.7 (2) | C30—C31—H31 | 120.8 |
N1—C1—C9 | 122.8 (3) | N5—C32—C33 | 117.1 (2) |
C9—C1—C2 | 120.5 (2) | N5—C32—C40 | 123.0 (2) |
N2—C2—C1 | 116.7 (2) | C40—C32—C33 | 119.9 (2) |
N2—C2—C6 | 123.5 (3) | N6—C33—C32 | 118.2 (2) |
C6—C2—C1 | 119.8 (2) | N6—C33—C37 | 122.9 (2) |
N2—C3—H3 | 118.4 | C37—C33—C32 | 118.9 (2) |
N2—C3—C4 | 123.3 (3) | N6—C34—H34 | 118.8 |
C4—C3—H3 | 118.4 | N6—C34—C35 | 122.4 (3) |
C3—C4—H4 | 120.6 | C35—C34—H34 | 118.8 |
C5—C4—C3 | 118.9 (3) | C34—C35—H35 | 119.9 |
C5—C4—H4 | 120.6 | C36—C35—C34 | 120.3 (3) |
C4—C5—H5 | 119.9 | C36—C35—H35 | 119.9 |
C4—C5—C6 | 120.2 (3) | C35—C36—H36 | 120.3 |
C6—C5—H5 | 119.9 | C35—C36—C37 | 119.4 (3) |
C2—C6—C7 | 118.5 (3) | C37—C36—H36 | 120.3 |
C5—C6—C2 | 116.6 (3) | C33—C37—C36 | 117.2 (3) |
C5—C6—C7 | 124.9 (3) | C33—C37—C38 | 120.2 (3) |
C6—C7—H7 | 119.0 | C36—C37—C38 | 122.6 (3) |
C8—C7—C6 | 121.9 (3) | C37—C38—H38 | 119.7 |
C8—C7—H7 | 119.0 | C39—C38—C37 | 120.6 (3) |
C7—C8—H8 | 119.7 | C39—C38—H38 | 119.7 |
C7—C8—C9 | 120.6 (3) | C38—C39—H39 | 119.6 |
C9—C8—H8 | 119.7 | C38—C39—C40 | 120.8 (3) |
C1—C9—C8 | 118.9 (3) | C40—C39—H39 | 119.6 |
C1—C9—C10 | 117.2 (3) | C32—C40—C39 | 119.5 (3) |
C10—C9—C8 | 123.9 (3) | C32—C40—C41 | 117.2 (3) |
C9—C10—H10 | 120.1 | C41—C40—C39 | 123.2 (3) |
C11—C10—C9 | 119.8 (3) | C40—C41—H41 | 120.4 |
C11—C10—H10 | 120.1 | C42—C41—C40 | 119.3 (3) |
C10—C11—H11 | 120.0 | C42—C41—H41 | 120.4 |
C10—C11—C12 | 120.0 (3) | C41—C42—H42 | 120.3 |
C12—C11—H11 | 120.0 | C41—C42—C43 | 119.4 (3) |
N1—C12—C11 | 122.0 (3) | C43—C42—H42 | 120.3 |
N1—C12—H12 | 119.0 | N5—C43—C42 | 123.7 (3) |
C11—C12—H12 | 119.0 | N5—C43—H43 | 118.2 |
N3—C13—C14 | 118.0 (3) | C42—C43—H43 | 118.2 |
N3—C13—C21 | 122.1 (3) | O5—C44—H44A | 109.5 |
C21—C13—C14 | 119.8 (3) | O5—C44—H44B | 109.5 |
N4—C14—C13 | 116.5 (3) | O5—C44—H44C | 109.5 |
N4—C14—C18 | 123.1 (3) | H44A—C44—H44B | 109.5 |
C18—C14—C13 | 120.4 (3) | H44A—C44—H44C | 109.5 |
N4—C15—H15 | 118.7 | H44B—C44—H44C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···Cl2i | 0.93 | 2.87 | 3.683 (4) | 147 |
C34—H34···Cl2 | 0.93 | 2.88 | 3.492 (3) | 124 |
C30—H30···Cl2ii | 0.93 | 2.87 | 3.751 (3) | 158 |
C44—H44C···Cl1iii | 0.96 | 2.86 | 3.574 (6) | 132 |
O5—H5A···O2 | 0.82 | 2.03 | 2.798 (5) | 155 |
C20—H20···O3 | 0.93 | 2.45 | 3.337 (4) | 159 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) x, y−1, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···Cl2i | 0.93 | 2.87 | 3.683 (4) | 146.6 |
C34—H34···Cl2 | 0.93 | 2.88 | 3.492 (3) | 124.4 |
C30—H30···Cl2ii | 0.93 | 2.87 | 3.751 (3) | 157.9 |
C44—H44C···Cl1iii | 0.96 | 2.86 | 3.574 (6) | 132.4 |
O5—H5A···O2 | 0.82 | 2.03 | 2.798 (5) | 154.9 |
C20—H20···O3 | 0.93 | 2.45 | 3.337 (4) | 159.1 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) x, y−1, z+1. |
Acknowledgements
This work was partly supported by the State Fund for Fundamental Researches of Ukraine (project 54.3/005).
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
This work is a continuation of our research in the field of direct synthesis of heterometallic complexes (Chygorin et al., 2012; Nesterov et al., 2012; Nesterova et al., 2013). In this paper we present a novel Cu/Mn heterometallic ionic complex with pyridine-2,6-dicarboxylic acid in combination with 1,10-phenanthroline as a ligands selected to construct supramolecular heterometallic assemblies.
As is shown in Fig. 1. the unit of the title compound consists of [CuCl(phen)2]+ cations, [MnCl(2,6-pydc)(phen)]- anions and solvent (MeOH) molecule. The CuII ion adopts a distorted trigonal-bipyramidal environment by coordinating with four nitrogen atoms from two phen ligands and one Cl atom. The dihedral angle between the two phen ligands (114.79(0.05)°) as well as the range of Cu—N bond distances of 1.997 (2) - 2.174 (3) Å is in good agreement with the previously reported values for analagous complexes (Wei et al., 2004; Lu et al., 2004; Murphy et al., 1997; Liu et al., 2006). The MnII centre is surrounded by one bidentate phenanthroline ligand, one tridentate dipicolinate ligand and one chlorine atom and exhibits distorted octahedral geometry. The range of Mn—N and Mn—O bond distances of 2.173 (2) - 2.302 (2) Å and 2.257 (2) - 2.266 (2) Å respectively as well as cis angles ranging from 72.00 (8)° to 122.07 (8)° and trans angles ranging from 143.98 (8)° to 163.15 (6)° are in a good agreement with literature values (Ma et al., 2002; Laine et al., 1995; Chatterjee et al., 1998).
In the crystal anions are inolved in the formation of C—H···O hydrogen bonds with solvent molecules and O—H···O and C—H···Cl hydrogen bonds with cations with D···A distances ranging from 2.798 (5) to 3.751 (3) Å. In addition, cation–anion π–π interactions between the phen ring systems with centroid–centroid distances in the range 3.88 (3)-4.12 (4) Å and cation–cation, anion–anion π–π interactions between the phen rings with centroid–centroid distances in the range 3.76 (4)–3.99 (5) Å and pydc rings with centroid–centroid distances 3.52 (5) Å connect the various components together.