metal-organic compounds
Bis(4,4′′-difluoro-1,1′:3′,1′′-terphenyl-2′-carboxylato-κO)bis(3,5-dimethyl-1H-pyrazole-κN2)manganese(II)
aDepartment of Bio & Nano Chemistry, College of Natural Sciences, Kookmin University, 861-1 Jeongneung-dong, Seongbuk-gu, Seoul 136-702, Republic of Korea
*Correspondence e-mail: yoona@kookmin.ac.kr
In the title compound, [Mn(C19H11F2O2)2(C5H8N2)2], the Mn2+ cation is coordinated by the N atoms of two 3,5-dimethylpyrazole ligands and carboxylate O atoms from two 4,4′′-difluoro-1,1′:3′,1′′-terphenyl-2′-carboxylato ligands, forming an MnN2O2 polyhedron with a slightly distorted tetrahedral coordination geometry. Two intramolecular hydrogen bonds are observed between the carboxylate and pyrazole ligands. The combined influence of the sterically hindered carboxylate ligands and the intramolecular hydrogen-bonding interactions stabilizes the title compound with a low of four. In the crystal, weak C—H⋯F and C—H⋯O hydrogen bonds are observed.
Related literature
For the synthesis of substituted terphenyl-based carboxylate ligands, see: Saednya & Hart (1996); Du et al. (1986); Chen & Siegel (1994). For background to metal complexes with terphenyl-based carboxylate ligands, see: Kannan et al. (2011); Yoon & Lippard (2004a,b); Lee & Lippard (1998, 2001, 2002) and for those with 3,5-dimethylpyrazole ligands, see: Zhang et al. (2007); Cheng et al. (1990).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812014201/sj5226sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812014201/sj5226Isup2.hkl
A portion of sodium [4,4''-difluoro-[1,1':3',1''-terphenyl]-2'-carboxylate] (0.110 g, 0.331 mmol) was mixed with Mn(OTf)2.2CH3CN (0.0720 g, 0.165 mmol) in 10 mL of tetrahydrofuran at room temperature. After 6 hours stirring, 3,5-dimethylpyrazole (0.0317g, 0.331 mmol) was added. After a further three hours, the tetrahydrofuran was removed under reduced pressure and colorless block-like crystals were collected using a dichloromethane and pentane layering system. Yield = 89%, (0.1268 g).
Hydrogen atoms bound to N were located in the difference Fourier map and refined isotropically. Other H atoms were placed in calculated positions and refined as riding with C—H (aromatic) = 0.95 Å, C—H(CH3) = 0.98 Å with [Uiso(H) = 1.2 (1.5 for CH3 groups) Ueq(C)].
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, showing the atom-numbering and with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are omitted for the clarity. |
[Mn(C19H11F2O2)2(C5H8N2)2] | Z = 2 |
Mr = 865.76 | F(000) = 894 |
Triclinic, P1 | Dx = 1.359 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.9310 (16) Å | Cell parameters from 1018 reflections |
b = 13.668 (2) Å | θ = 2.5–27.2° |
c = 15.541 (2) Å | µ = 0.38 mm−1 |
α = 69.283 (2)° | T = 173 K |
β = 88.854 (2)° | Block, colorless |
γ = 77.476 (2)° | 0.10 × 0.10 × 0.05 mm |
V = 2115.9 (5) Å3 |
Bruker SMART CCD area-detector diffractometer | 7378 independent reflections |
Radiation source: fine-focus sealed tube | 6578 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −12→12 |
Tmin = 0.469, Tmax = 1.0 | k = −16→16 |
15553 measured reflections | l = −18→18 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0504P)2 + 1.1718P] where P = (Fo2 + 2Fc2)/3 |
7378 reflections | (Δ/σ)max = 0.001 |
562 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Mn(C19H11F2O2)2(C5H8N2)2] | γ = 77.476 (2)° |
Mr = 865.76 | V = 2115.9 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.9310 (16) Å | Mo Kα radiation |
b = 13.668 (2) Å | µ = 0.38 mm−1 |
c = 15.541 (2) Å | T = 173 K |
α = 69.283 (2)° | 0.10 × 0.10 × 0.05 mm |
β = 88.854 (2)° |
Bruker SMART CCD area-detector diffractometer | 7378 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 6578 reflections with I > 2σ(I) |
Tmin = 0.469, Tmax = 1.0 | Rint = 0.032 |
15553 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.67 e Å−3 |
7378 reflections | Δρmin = −0.37 e Å−3 |
562 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.0866 (2) | 0.5295 (3) | 0.7746 (2) | 0.0513 (8) | |
H1A | 1.1375 | 0.5522 | 0.7216 | 0.077* | |
H2B | 1.1399 | 0.4742 | 0.8266 | 0.077* | |
H3C | 1.0490 | 0.5913 | 0.7918 | 0.077* | |
C2 | 0.9853 (2) | 0.4851 (2) | 0.74983 (16) | 0.0314 (5) | |
C3 | 0.9922 (3) | 0.3873 (2) | 0.73963 (18) | 0.0407 (6) | |
H3 | 1.0658 | 0.3327 | 0.7462 | 0.049* | |
C4 | 0.8721 (3) | 0.3847 (2) | 0.71824 (18) | 0.0422 (6) | |
C5 | 0.8188 (4) | 0.3015 (2) | 0.7006 (3) | 0.0709 (11) | |
H5A | 0.7848 | 0.2595 | 0.7571 | 0.106* | |
H6B | 0.8851 | 0.2538 | 0.6816 | 0.106* | |
H7C | 0.7516 | 0.3364 | 0.6517 | 0.106* | |
C6 | 0.9539 (3) | 0.8351 (2) | 0.56558 (18) | 0.0461 (7) | |
H8A | 0.9306 | 0.7668 | 0.5755 | 0.069* | |
H9B | 1.0398 | 0.8313 | 0.5455 | 0.069* | |
H10C | 0.8960 | 0.8932 | 0.5181 | 0.069* | |
C7 | 0.9467 (2) | 0.85669 (19) | 0.65348 (16) | 0.0314 (5) | |
C8 | 0.9967 (2) | 0.9287 (2) | 0.67876 (18) | 0.0376 (6) | |
H4 | 1.0445 | 0.9768 | 0.6419 | 0.045* | |
C9 | 0.9638 (2) | 0.91730 (19) | 0.76706 (17) | 0.0338 (6) | |
C10 | 0.9886 (3) | 0.9709 (2) | 0.8309 (2) | 0.0507 (7) | |
H12A | 0.9175 | 0.9758 | 0.8697 | 0.076* | |
H13B | 0.9997 | 1.0432 | 0.7951 | 0.076* | |
H14C | 1.0650 | 0.9291 | 0.8699 | 0.076* | |
C11 | 0.7265 (2) | 0.64209 (16) | 0.92263 (15) | 0.0249 (5) | |
C12 | 0.67639 (19) | 0.60871 (16) | 1.01669 (14) | 0.0185 (4) | |
C17 | 0.63182 (19) | 0.68616 (17) | 1.05611 (14) | 0.0212 (4) | |
C16 | 0.5773 (2) | 0.65568 (18) | 1.14060 (14) | 0.0264 (5) | |
H15 | 0.5498 | 0.7069 | 1.1693 | 0.032* | |
C15 | 0.5629 (2) | 0.55161 (19) | 1.18310 (15) | 0.0284 (5) | |
H16 | 0.5220 | 0.5325 | 1.2392 | 0.034* | |
C14 | 0.6080 (2) | 0.47540 (17) | 1.14401 (15) | 0.0260 (5) | |
H17 | 0.5974 | 0.4042 | 1.1735 | 0.031* | |
C13 | 0.66876 (19) | 0.50138 (17) | 1.06224 (14) | 0.0211 (4) | |
C24 | 0.7289 (2) | 0.41609 (16) | 1.02611 (14) | 0.0223 (5) | |
C29 | 0.8558 (2) | 0.40187 (18) | 1.00785 (16) | 0.0278 (5) | |
H18 | 0.9031 | 0.4487 | 1.0165 | 0.033* | |
C28 | 0.9137 (2) | 0.3206 (2) | 0.97736 (17) | 0.0342 (6) | |
H19 | 1.0001 | 0.3110 | 0.9652 | 0.041* | |
C27 | 0.8434 (3) | 0.25472 (19) | 0.96519 (17) | 0.0359 (6) | |
C26 | 0.7184 (2) | 0.26476 (19) | 0.98273 (18) | 0.0373 (6) | |
H20 | 0.6723 | 0.2173 | 0.9739 | 0.045* | |
C25 | 0.6619 (2) | 0.34618 (17) | 1.01366 (16) | 0.0298 (5) | |
H21 | 0.5757 | 0.3543 | 1.0266 | 0.036* | |
C18 | 0.6370 (2) | 0.80062 (17) | 1.00680 (14) | 0.0223 (5) | |
C19 | 0.7005 (3) | 0.85289 (19) | 1.04621 (16) | 0.0338 (6) | |
H22 | 0.7408 | 0.8157 | 1.1061 | 0.041* | |
C20 | 0.7060 (3) | 0.9594 (2) | 0.99926 (18) | 0.0407 (6) | |
H23 | 0.7502 | 0.9953 | 1.0261 | 0.049* | |
C21 | 0.6463 (2) | 1.01103 (17) | 0.91372 (16) | 0.0306 (5) | |
C22 | 0.5818 (2) | 0.96331 (19) | 0.87257 (16) | 0.0318 (5) | |
H24 | 0.5406 | 1.0018 | 0.8131 | 0.038* | |
C23 | 0.5775 (2) | 0.85704 (18) | 0.91944 (16) | 0.0282 (5) | |
H25 | 0.5334 | 0.8222 | 0.8915 | 0.034* | |
C30 | 0.57304 (19) | 0.71049 (17) | 0.60758 (14) | 0.0232 (5) | |
C31 | 0.4892 (2) | 0.77015 (17) | 0.52004 (14) | 0.0227 (5) | |
C36 | 0.3932 (2) | 0.85918 (18) | 0.51369 (15) | 0.0263 (5) | |
C35 | 0.3179 (2) | 0.9123 (2) | 0.43246 (16) | 0.0361 (6) | |
H26 | 0.2527 | 0.9729 | 0.4278 | 0.043* | |
C34 | 0.3364 (3) | 0.8786 (2) | 0.35867 (17) | 0.0406 (6) | |
H27 | 0.2837 | 0.9153 | 0.3038 | 0.049* | |
C33 | 0.4312 (2) | 0.7916 (2) | 0.36461 (16) | 0.0349 (6) | |
H28 | 0.4444 | 0.7694 | 0.3131 | 0.042* | |
C32 | 0.5081 (2) | 0.73568 (18) | 0.44486 (15) | 0.0263 (5) | |
C43 | 0.6113 (2) | 0.64322 (19) | 0.44768 (15) | 0.0286 (5) | |
C44 | 0.7327 (2) | 0.6363 (2) | 0.47775 (19) | 0.0412 (6) | |
H29 | 0.7506 | 0.6921 | 0.4950 | 0.049* | |
C45 | 0.8276 (3) | 0.5491 (3) | 0.4828 (2) | 0.0598 (9) | |
H30 | 0.9107 | 0.5440 | 0.5037 | 0.072* | |
C46 | 0.7997 (3) | 0.4703 (3) | 0.4571 (2) | 0.0541 (8) | |
C47 | 0.6825 (3) | 0.4741 (2) | 0.42535 (19) | 0.0458 (7) | |
H31 | 0.6663 | 0.4184 | 0.4072 | 0.055* | |
C48 | 0.5882 (2) | 0.5621 (2) | 0.42059 (16) | 0.0348 (6) | |
H32 | 0.5059 | 0.5671 | 0.3983 | 0.042* | |
C37 | 0.3671 (2) | 0.89838 (18) | 0.59182 (15) | 0.0251 (5) | |
C38 | 0.3556 (2) | 1.0065 (2) | 0.57712 (17) | 0.0343 (6) | |
H33 | 0.3666 | 1.0546 | 0.5176 | 0.041* | |
C39 | 0.3282 (2) | 1.0448 (2) | 0.64837 (19) | 0.0406 (6) | |
H34 | 0.3214 | 1.1184 | 0.6387 | 0.049* | |
C40 | 0.3111 (2) | 0.9740 (2) | 0.73290 (18) | 0.0378 (6) | |
C41 | 0.3204 (2) | 0.8674 (2) | 0.75057 (17) | 0.0387 (6) | |
H35 | 0.3076 | 0.8204 | 0.8101 | 0.046* | |
C42 | 0.3490 (2) | 0.8299 (2) | 0.67922 (16) | 0.0321 (5) | |
H36 | 0.3563 | 0.7559 | 0.6901 | 0.039* | |
F1 | 0.90001 (16) | 0.17383 (12) | 0.93543 (12) | 0.0536 (4) | |
F2 | 0.65221 (16) | 1.11511 (11) | 0.86681 (10) | 0.0464 (4) | |
F3 | 0.89370 (19) | 0.38355 (17) | 0.46375 (17) | 0.0866 (7) | |
F4 | 0.28254 (16) | 1.01216 (16) | 0.80295 (12) | 0.0579 (5) | |
Mn1 | 0.76676 (3) | 0.68954 (3) | 0.74376 (2) | 0.02314 (11) | |
N1 | 0.86659 (17) | 0.54142 (15) | 0.73521 (13) | 0.0271 (4) | |
N2 | 0.7995 (2) | 0.47746 (16) | 0.71690 (15) | 0.0362 (5) | |
N3 | 0.88491 (18) | 0.80274 (15) | 0.72287 (13) | 0.0286 (4) | |
N4 | 0.89665 (19) | 0.84149 (17) | 0.79094 (15) | 0.0324 (5) | |
O1 | 0.65725 (16) | 0.64746 (13) | 0.85637 (10) | 0.0349 (4) | |
O2 | 0.83122 (17) | 0.66487 (14) | 0.91176 (13) | 0.0421 (5) | |
O3 | 0.64655 (14) | 0.76094 (12) | 0.62699 (10) | 0.0274 (4) | |
O4 | 0.56667 (15) | 0.61680 (12) | 0.65369 (11) | 0.0307 (4) | |
H1 | 0.721 (3) | 0.507 (2) | 0.699 (2) | 0.045 (8)* | |
H2 | 0.875 (3) | 0.808 (2) | 0.842 (2) | 0.039 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0296 (14) | 0.064 (2) | 0.0631 (19) | −0.0012 (13) | −0.0081 (13) | −0.0312 (16) |
C2 | 0.0282 (12) | 0.0352 (14) | 0.0268 (12) | 0.0010 (10) | −0.0019 (10) | −0.0108 (10) |
C3 | 0.0394 (14) | 0.0352 (15) | 0.0405 (14) | 0.0093 (12) | −0.0051 (12) | −0.0151 (12) |
C4 | 0.0536 (17) | 0.0254 (14) | 0.0418 (15) | −0.0035 (12) | −0.0111 (13) | −0.0074 (11) |
C5 | 0.092 (3) | 0.0313 (17) | 0.086 (3) | −0.0122 (17) | −0.025 (2) | −0.0165 (17) |
C6 | 0.0505 (16) | 0.0426 (16) | 0.0366 (14) | −0.0090 (13) | 0.0153 (13) | −0.0054 (12) |
C7 | 0.0254 (12) | 0.0264 (12) | 0.0298 (12) | −0.0028 (10) | 0.0039 (10) | 0.0030 (10) |
C8 | 0.0332 (13) | 0.0286 (13) | 0.0403 (14) | −0.0142 (11) | 0.0042 (11) | 0.0046 (11) |
C9 | 0.0278 (12) | 0.0278 (13) | 0.0391 (14) | −0.0094 (10) | −0.0036 (11) | −0.0018 (11) |
C10 | 0.0547 (18) | 0.0441 (17) | 0.0580 (18) | −0.0266 (14) | −0.0036 (14) | −0.0147 (14) |
C11 | 0.0342 (13) | 0.0116 (10) | 0.0271 (12) | −0.0057 (9) | 0.0090 (10) | −0.0049 (9) |
C12 | 0.0201 (10) | 0.0164 (10) | 0.0197 (10) | −0.0088 (8) | 0.0003 (8) | −0.0043 (8) |
C17 | 0.0238 (11) | 0.0188 (11) | 0.0219 (10) | −0.0081 (9) | 0.0006 (9) | −0.0063 (9) |
C16 | 0.0318 (12) | 0.0263 (12) | 0.0223 (11) | −0.0076 (10) | 0.0041 (9) | −0.0099 (9) |
C15 | 0.0324 (12) | 0.0302 (13) | 0.0196 (11) | −0.0104 (10) | 0.0071 (9) | −0.0035 (9) |
C14 | 0.0300 (12) | 0.0181 (11) | 0.0249 (11) | −0.0101 (9) | 0.0006 (9) | 0.0011 (9) |
C13 | 0.0210 (10) | 0.0190 (11) | 0.0223 (10) | −0.0084 (9) | −0.0010 (9) | −0.0035 (9) |
C24 | 0.0303 (12) | 0.0144 (10) | 0.0191 (10) | −0.0074 (9) | −0.0020 (9) | −0.0010 (8) |
C29 | 0.0332 (12) | 0.0225 (12) | 0.0312 (12) | −0.0128 (10) | 0.0045 (10) | −0.0100 (10) |
C28 | 0.0362 (13) | 0.0310 (13) | 0.0347 (13) | −0.0053 (11) | 0.0054 (11) | −0.0122 (11) |
C27 | 0.0523 (16) | 0.0206 (12) | 0.0327 (13) | 0.0016 (11) | −0.0031 (12) | −0.0123 (10) |
C26 | 0.0471 (15) | 0.0206 (12) | 0.0468 (15) | −0.0092 (11) | −0.0104 (12) | −0.0135 (11) |
C25 | 0.0318 (12) | 0.0186 (11) | 0.0368 (13) | −0.0077 (10) | −0.0056 (10) | −0.0058 (10) |
C18 | 0.0264 (11) | 0.0176 (11) | 0.0243 (11) | −0.0057 (9) | 0.0068 (9) | −0.0091 (9) |
C19 | 0.0551 (16) | 0.0243 (12) | 0.0246 (11) | −0.0147 (11) | −0.0021 (11) | −0.0080 (10) |
C20 | 0.0689 (19) | 0.0279 (13) | 0.0364 (14) | −0.0245 (13) | −0.0007 (13) | −0.0166 (11) |
C21 | 0.0475 (15) | 0.0136 (11) | 0.0325 (12) | −0.0099 (10) | 0.0093 (11) | −0.0089 (10) |
C22 | 0.0367 (13) | 0.0224 (12) | 0.0309 (12) | −0.0065 (10) | −0.0016 (10) | −0.0031 (10) |
C23 | 0.0314 (12) | 0.0210 (12) | 0.0329 (12) | −0.0105 (10) | −0.0016 (10) | −0.0077 (10) |
C30 | 0.0205 (10) | 0.0248 (12) | 0.0216 (11) | −0.0022 (9) | 0.0043 (9) | −0.0069 (9) |
C31 | 0.0240 (11) | 0.0200 (11) | 0.0213 (10) | −0.0084 (9) | 0.0024 (9) | −0.0023 (9) |
C36 | 0.0283 (12) | 0.0229 (12) | 0.0229 (11) | −0.0065 (9) | 0.0015 (9) | −0.0021 (9) |
C35 | 0.0368 (14) | 0.0308 (14) | 0.0304 (13) | 0.0042 (11) | −0.0035 (11) | −0.0052 (11) |
C34 | 0.0454 (15) | 0.0421 (16) | 0.0240 (12) | 0.0006 (12) | −0.0097 (11) | −0.0050 (11) |
C33 | 0.0423 (14) | 0.0397 (15) | 0.0228 (11) | −0.0099 (12) | 0.0010 (10) | −0.0110 (11) |
C32 | 0.0287 (12) | 0.0260 (12) | 0.0236 (11) | −0.0107 (10) | 0.0036 (9) | −0.0057 (9) |
C43 | 0.0314 (12) | 0.0315 (13) | 0.0232 (11) | −0.0097 (10) | 0.0075 (9) | −0.0087 (10) |
C44 | 0.0329 (14) | 0.0460 (16) | 0.0538 (16) | −0.0088 (12) | 0.0096 (12) | −0.0291 (14) |
C45 | 0.0311 (14) | 0.076 (2) | 0.082 (2) | 0.0030 (15) | 0.0018 (15) | −0.049 (2) |
C46 | 0.0492 (18) | 0.0503 (18) | 0.0619 (19) | 0.0108 (14) | 0.0078 (15) | −0.0324 (16) |
C47 | 0.0600 (18) | 0.0408 (16) | 0.0425 (15) | −0.0116 (14) | 0.0129 (14) | −0.0223 (13) |
C48 | 0.0396 (14) | 0.0377 (14) | 0.0297 (12) | −0.0099 (12) | 0.0076 (11) | −0.0147 (11) |
C37 | 0.0213 (11) | 0.0246 (12) | 0.0257 (11) | −0.0025 (9) | 0.0006 (9) | −0.0060 (9) |
C38 | 0.0378 (14) | 0.0293 (13) | 0.0349 (13) | −0.0113 (11) | 0.0059 (11) | −0.0083 (11) |
C39 | 0.0427 (15) | 0.0352 (15) | 0.0531 (16) | −0.0162 (12) | 0.0076 (13) | −0.0227 (13) |
C40 | 0.0298 (13) | 0.0550 (17) | 0.0383 (14) | −0.0087 (12) | 0.0034 (11) | −0.0287 (13) |
C41 | 0.0371 (14) | 0.0458 (16) | 0.0248 (12) | −0.0029 (12) | 0.0042 (11) | −0.0062 (11) |
C42 | 0.0330 (13) | 0.0264 (13) | 0.0293 (12) | −0.0015 (10) | 0.0022 (10) | −0.0038 (10) |
F1 | 0.0702 (11) | 0.0338 (9) | 0.0608 (10) | 0.0030 (8) | −0.0018 (9) | −0.0298 (8) |
F2 | 0.0813 (12) | 0.0172 (7) | 0.0421 (8) | −0.0208 (7) | 0.0021 (8) | −0.0067 (6) |
F3 | 0.0693 (13) | 0.0766 (14) | 0.1162 (18) | 0.0258 (11) | −0.0018 (12) | −0.0617 (14) |
F4 | 0.0544 (10) | 0.0866 (13) | 0.0533 (10) | −0.0181 (9) | 0.0114 (8) | −0.0488 (10) |
Mn1 | 0.02515 (19) | 0.01969 (19) | 0.02176 (18) | −0.00732 (14) | 0.00321 (13) | −0.00279 (14) |
N1 | 0.0261 (10) | 0.0254 (10) | 0.0291 (10) | −0.0053 (8) | 0.0003 (8) | −0.0094 (8) |
N2 | 0.0303 (11) | 0.0240 (11) | 0.0487 (13) | −0.0055 (9) | −0.0096 (10) | −0.0062 (10) |
N3 | 0.0305 (10) | 0.0273 (11) | 0.0254 (10) | −0.0126 (9) | 0.0033 (8) | −0.0030 (8) |
N4 | 0.0365 (11) | 0.0351 (12) | 0.0279 (11) | −0.0208 (10) | 0.0053 (9) | −0.0068 (9) |
O1 | 0.0490 (10) | 0.0341 (10) | 0.0195 (8) | −0.0078 (8) | 0.0050 (7) | −0.0081 (7) |
O2 | 0.0407 (10) | 0.0342 (10) | 0.0510 (11) | −0.0208 (8) | 0.0231 (9) | −0.0086 (9) |
O3 | 0.0287 (8) | 0.0275 (9) | 0.0252 (8) | −0.0083 (7) | −0.0018 (7) | −0.0071 (7) |
O4 | 0.0306 (9) | 0.0218 (8) | 0.0299 (8) | −0.0063 (7) | 0.0002 (7) | 0.0029 (7) |
C1—C2 | 1.489 (4) | C19—C20 | 1.393 (3) |
C1—H1A | 0.9800 | C19—H22 | 0.9500 |
C1—H2B | 0.9800 | C20—C21 | 1.365 (4) |
C1—H3C | 0.9800 | C20—H23 | 0.9500 |
C2—N1 | 1.335 (3) | C21—C22 | 1.358 (3) |
C2—C3 | 1.387 (4) | C21—F2 | 1.365 (3) |
C3—C4 | 1.371 (4) | C22—C23 | 1.386 (3) |
C3—H3 | 0.9500 | C22—H24 | 0.9500 |
C4—N2 | 1.335 (3) | C23—H25 | 0.9500 |
C4—C5 | 1.491 (4) | C30—O4 | 1.243 (3) |
C5—H5A | 0.9800 | C30—O3 | 1.269 (3) |
C5—H6B | 0.9800 | C30—C31 | 1.516 (3) |
C5—H7C | 0.9800 | C31—C36 | 1.399 (3) |
C6—C7 | 1.493 (4) | C31—C32 | 1.403 (3) |
C6—H8A | 0.9800 | C36—C35 | 1.390 (3) |
C6—H9B | 0.9800 | C36—C37 | 1.491 (3) |
C6—H10C | 0.9800 | C35—C34 | 1.376 (4) |
C7—N3 | 1.337 (3) | C35—H26 | 0.9500 |
C7—C8 | 1.393 (4) | C34—C33 | 1.374 (4) |
C8—C9 | 1.375 (4) | C34—H27 | 0.9500 |
C8—H4 | 0.9500 | C33—C32 | 1.391 (3) |
C9—N4 | 1.341 (3) | C33—H28 | 0.9500 |
C9—C10 | 1.485 (4) | C32—C43 | 1.488 (3) |
C10—H12A | 0.9800 | C43—C48 | 1.387 (3) |
C10—H13B | 0.9800 | C43—C44 | 1.389 (3) |
C10—H14C | 0.9800 | C44—C45 | 1.379 (4) |
C11—O2 | 1.243 (3) | C44—H29 | 0.9500 |
C11—O1 | 1.262 (3) | C45—C46 | 1.366 (4) |
C11—C12 | 1.500 (3) | C45—H30 | 0.9500 |
C12—C17 | 1.399 (3) | C46—F3 | 1.365 (3) |
C12—C13 | 1.406 (3) | C46—C47 | 1.366 (4) |
C17—C16 | 1.393 (3) | C47—C48 | 1.385 (4) |
C17—C18 | 1.492 (3) | C47—H31 | 0.9500 |
C16—C15 | 1.383 (3) | C48—H32 | 0.9500 |
C16—H15 | 0.9500 | C37—C42 | 1.389 (3) |
C15—C14 | 1.382 (3) | C37—C38 | 1.391 (3) |
C15—H16 | 0.9500 | C38—C39 | 1.385 (4) |
C14—C13 | 1.390 (3) | C38—H33 | 0.9500 |
C14—H17 | 0.9500 | C39—C40 | 1.366 (4) |
C13—C24 | 1.491 (3) | C39—H34 | 0.9500 |
C24—C25 | 1.388 (3) | C40—C41 | 1.365 (4) |
C24—C29 | 1.396 (3) | C40—F4 | 1.368 (3) |
C29—C28 | 1.383 (3) | C41—C42 | 1.382 (3) |
C29—H18 | 0.9500 | C41—H35 | 0.9500 |
C28—C27 | 1.365 (4) | C42—H36 | 0.9500 |
C28—H19 | 0.9500 | Mn1—O3 | 2.0636 (15) |
C27—F1 | 1.368 (3) | Mn1—O1 | 2.0805 (16) |
C27—C26 | 1.375 (4) | Mn1—N1 | 2.1292 (19) |
C26—C25 | 1.386 (3) | Mn1—N3 | 2.1591 (19) |
C26—H20 | 0.9500 | N1—N2 | 1.358 (3) |
C25—H21 | 0.9500 | N2—H1 | 0.87 (3) |
C18—C19 | 1.381 (3) | N3—N4 | 1.359 (3) |
C18—C23 | 1.392 (3) | N4—H2 | 0.82 (3) |
C2—C1—H1A | 109.5 | C21—C20—H23 | 120.8 |
C2—C1—H2B | 109.5 | C19—C20—H23 | 120.8 |
H1A—C1—H2B | 109.5 | C22—C21—C20 | 123.0 (2) |
C2—C1—H3C | 109.5 | C22—C21—F2 | 118.3 (2) |
H1A—C1—H3C | 109.5 | C20—C21—F2 | 118.7 (2) |
H2B—C1—H3C | 109.5 | C21—C22—C23 | 118.3 (2) |
N1—C2—C3 | 110.1 (2) | C21—C22—H24 | 120.8 |
N1—C2—C1 | 120.2 (2) | C23—C22—H24 | 120.8 |
C3—C2—C1 | 129.7 (2) | C22—C23—C18 | 121.0 (2) |
C4—C3—C2 | 106.6 (2) | C22—C23—H25 | 119.5 |
C4—C3—H3 | 126.7 | C18—C23—H25 | 119.5 |
C2—C3—H3 | 126.7 | O4—C30—O3 | 125.1 (2) |
N2—C4—C3 | 106.1 (2) | O4—C30—C31 | 118.58 (19) |
N2—C4—C5 | 121.8 (3) | O3—C30—C31 | 116.30 (18) |
C3—C4—C5 | 132.1 (3) | C36—C31—C32 | 119.83 (19) |
C4—C5—H5A | 109.5 | C36—C31—C30 | 120.54 (19) |
C4—C5—H6B | 109.5 | C32—C31—C30 | 119.63 (19) |
H5A—C5—H6B | 109.5 | C35—C36—C31 | 119.2 (2) |
C4—C5—H7C | 109.5 | C35—C36—C37 | 118.5 (2) |
H5A—C5—H7C | 109.5 | C31—C36—C37 | 122.26 (19) |
H6B—C5—H7C | 109.5 | C34—C35—C36 | 121.0 (2) |
C7—C6—H8A | 109.5 | C34—C35—H26 | 119.5 |
C7—C6—H9B | 109.5 | C36—C35—H26 | 119.5 |
H8A—C6—H9B | 109.5 | C33—C34—C35 | 119.8 (2) |
C7—C6—H10C | 109.5 | C33—C34—H27 | 120.1 |
H8A—C6—H10C | 109.5 | C35—C34—H27 | 120.1 |
H9B—C6—H10C | 109.5 | C34—C33—C32 | 121.0 (2) |
N3—C7—C8 | 109.6 (2) | C34—C33—H28 | 119.5 |
N3—C7—C6 | 120.6 (2) | C32—C33—H28 | 119.5 |
C8—C7—C6 | 129.9 (2) | C33—C32—C31 | 119.1 (2) |
C9—C8—C7 | 107.1 (2) | C33—C32—C43 | 119.2 (2) |
C9—C8—H4 | 126.5 | C31—C32—C43 | 121.63 (19) |
C7—C8—H4 | 126.5 | C48—C43—C44 | 118.6 (2) |
N4—C9—C8 | 105.6 (2) | C48—C43—C32 | 120.8 (2) |
N4—C9—C10 | 121.8 (2) | C44—C43—C32 | 120.6 (2) |
C8—C9—C10 | 132.7 (2) | C45—C44—C43 | 120.6 (3) |
C9—C10—H12A | 109.5 | C45—C44—H29 | 119.7 |
C9—C10—H13B | 109.5 | C43—C44—H29 | 119.7 |
H12A—C10—H13B | 109.5 | C46—C45—C44 | 118.6 (3) |
C9—C10—H14C | 109.5 | C46—C45—H30 | 120.7 |
H12A—C10—H14C | 109.5 | C44—C45—H30 | 120.7 |
H13B—C10—H14C | 109.5 | F3—C46—C47 | 118.6 (3) |
O2—C11—O1 | 122.4 (2) | F3—C46—C45 | 118.2 (3) |
O2—C11—C12 | 120.4 (2) | C47—C46—C45 | 123.2 (3) |
O1—C11—C12 | 117.16 (19) | C46—C47—C48 | 117.5 (3) |
C17—C12—C13 | 120.69 (19) | C46—C47—H31 | 121.2 |
C17—C12—C11 | 119.38 (18) | C48—C47—H31 | 121.2 |
C13—C12—C11 | 119.85 (18) | C47—C48—C43 | 121.4 (2) |
C16—C17—C12 | 118.90 (19) | C47—C48—H32 | 119.3 |
C16—C17—C18 | 120.29 (19) | C43—C48—H32 | 119.3 |
C12—C17—C18 | 120.74 (18) | C42—C37—C38 | 118.6 (2) |
C15—C16—C17 | 120.6 (2) | C42—C37—C36 | 121.5 (2) |
C15—C16—H15 | 119.7 | C38—C37—C36 | 119.9 (2) |
C17—C16—H15 | 119.7 | C39—C38—C37 | 120.7 (2) |
C14—C15—C16 | 120.0 (2) | C39—C38—H33 | 119.7 |
C14—C15—H16 | 120.0 | C37—C38—H33 | 119.7 |
C16—C15—H16 | 120.0 | C40—C39—C38 | 118.4 (2) |
C15—C14—C13 | 121.0 (2) | C40—C39—H34 | 120.8 |
C15—C14—H17 | 119.5 | C38—C39—H34 | 120.8 |
C13—C14—H17 | 119.5 | C41—C40—C39 | 123.1 (2) |
C14—C13—C12 | 118.6 (2) | C41—C40—F4 | 118.5 (2) |
C14—C13—C24 | 120.40 (19) | C39—C40—F4 | 118.3 (3) |
C12—C13—C24 | 121.00 (19) | C40—C41—C42 | 118.0 (2) |
C25—C24—C29 | 118.5 (2) | C40—C41—H35 | 121.0 |
C25—C24—C13 | 121.0 (2) | C42—C41—H35 | 121.0 |
C29—C24—C13 | 120.49 (19) | C41—C42—C37 | 121.2 (2) |
C28—C29—C24 | 121.0 (2) | C41—C42—H36 | 119.4 |
C28—C29—H18 | 119.5 | C37—C42—H36 | 119.4 |
C24—C29—H18 | 119.5 | O3—Mn1—O1 | 107.39 (7) |
C27—C28—C29 | 118.3 (2) | O3—Mn1—N1 | 105.08 (7) |
C27—C28—H19 | 120.9 | O1—Mn1—N1 | 105.31 (7) |
C29—C28—H19 | 120.9 | O3—Mn1—N3 | 101.78 (7) |
C28—C27—F1 | 118.7 (2) | O1—Mn1—N3 | 123.66 (7) |
C28—C27—C26 | 123.0 (2) | N1—Mn1—N3 | 112.13 (7) |
F1—C27—C26 | 118.2 (2) | C2—N1—N2 | 105.00 (19) |
C27—C26—C25 | 118.0 (2) | C2—N1—Mn1 | 136.67 (16) |
C27—C26—H20 | 121.0 | N2—N1—Mn1 | 118.13 (14) |
C25—C26—H20 | 121.0 | C4—N2—N1 | 112.3 (2) |
C26—C25—C24 | 121.1 (2) | C4—N2—H1 | 131.1 (19) |
C26—C25—H21 | 119.4 | N1—N2—H1 | 115.9 (19) |
C24—C25—H21 | 119.4 | C7—N3—N4 | 105.33 (19) |
C19—C18—C23 | 118.6 (2) | C7—N3—Mn1 | 136.36 (17) |
C19—C18—C17 | 121.18 (19) | N4—N3—Mn1 | 118.01 (14) |
C23—C18—C17 | 120.26 (19) | C9—N4—N3 | 112.5 (2) |
C18—C19—C20 | 120.8 (2) | C9—N4—H2 | 130 (2) |
C18—C19—H22 | 119.6 | N3—N4—H2 | 117 (2) |
C20—C19—H22 | 119.6 | C11—O1—Mn1 | 103.42 (14) |
C21—C20—C19 | 118.3 (2) | C30—O3—Mn1 | 120.59 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H2···O2 | 0.82 (3) | 2.03 (3) | 2.712 (3) | 140 (3) |
N2—H1···O4 | 0.87 (3) | 1.95 (3) | 2.783 (3) | 160 (3) |
C26—H20···F2i | 0.95 | 2.56 | 3.355 (3) | 141 |
C15—H16···O4ii | 0.95 | 2.50 | 3.298 (3) | 141 |
C38—H33···O3iii | 0.95 | 2.70 | 3.606 (3) | 160 |
C20—H23···F4iv | 0.95 | 2.64 | 3.239 (3) | 121 |
C45—H30···F3v | 0.95 | 2.67 | 3.560 (4) | 156 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+2, −z+1; (iv) −x+1, −y+2, −z+2; (v) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C19H11F2O2)2(C5H8N2)2] |
Mr | 865.76 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 10.9310 (16), 13.668 (2), 15.541 (2) |
α, β, γ (°) | 69.283 (2), 88.854 (2), 77.476 (2) |
V (Å3) | 2115.9 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.10 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.469, 1.0 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15553, 7378, 6578 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.118, 1.08 |
No. of reflections | 7378 |
No. of parameters | 562 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.67, −0.37 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Mn1—O3 | 2.0636 (15) | Mn1—N1 | 2.1292 (19) |
Mn1—O1 | 2.0805 (16) | Mn1—N3 | 2.1591 (19) |
O3—Mn1—O1 | 107.39 (7) | O3—Mn1—N3 | 101.78 (7) |
O3—Mn1—N1 | 105.08 (7) | O1—Mn1—N3 | 123.66 (7) |
O1—Mn1—N1 | 105.31 (7) | N1—Mn1—N3 | 112.13 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H2···O2 | 0.82 (3) | 2.03 (3) | 2.712 (3) | 140 (3) |
N2—H1···O4 | 0.87 (3) | 1.95 (3) | 2.783 (3) | 160 (3) |
C26—H20···F2i | 0.95 | 2.56 | 3.355 (3) | 141.2 |
C15—H16···O4ii | 0.95 | 2.50 | 3.298 (3) | 141.3 |
C38—H33···O3iii | 0.95 | 2.70 | 3.606 (3) | 160.4 |
C20—H23···F4iv | 0.95 | 2.64 | 3.239 (3) | 121.4 |
C45—H30···F3v | 0.95 | 2.67 | 3.560 (4) | 156.4 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+2, −z+1; (iv) −x+1, −y+2, −z+2; (v) −x+2, −y+1, −z+1. |
Acknowledgements
This research was supported by the Basic Science Research program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (MEST) (KRF-2008-C00146).
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4,4''-difluoro-[1,1':3',1''-terphenyl]-2'-carboxylato coordinated Fe2+ complexes are well known for their reactivity with dioxygen (Yoon & Lippard, 2004a,b; Lee & Lippard, 1998, 2001, 2002). The synthesis of terphenyl-based carboxylate ligands has been reported (Saednya et al., 1996; Du et al., 1986; Chen et al., 1994). Also four coordinate Fe2+, Co2+, and Ni2+ metal complexes with a slightly distorted tetrahedral coordination geometry have also been reported with two 3,5-dimethylpyrazole and two 4,4''-difluoro-[1,1':3',1''-terphenyl]-2'-carboxylato ligands (Kannan et al. 2011; Yoon & Lippard, 2004a). Complexes with 3,5-dimethylpyrazole ligands have also been reported (Zhang et al., 2007; Cheng et al., 1990).
Here, we report the structure of a tetrahedrally coordinated Mn2+ complex which crystallizes in the triclinic space group P -1. Bond distances and bond angles to the metal are given in Table 1 with the structure of the molecule shown in Fig 1. In the crystal structure, weak intermolecular C—H···F and C—H···O hydrogen bonds, Table 2, stabilise the packing.