metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 68| Part 5| May 2012| Pages m582-m583

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

(Received 27 March 2012; accepted 2 April 2012; online 13 April 2012)

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 coordination number 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[Saednya, A. & Hart, H. (1996). Synthesis. pp. 1455-1458.]); Du et al. (1986[Du, C. J. F., Hart, H. & Ng, K. K. D. (1986). J. Org. Chem. 51, 3162-3165.]); Chen & Siegel (1994[Chen, C. T. & Siegel, J. S. (1994). J. Am. Chem. Soc. 116, 5959-5960.]). For background to metal complexes with terphenyl-based carboxyl­ate ligands, see: Kannan et al. (2011[Kannan, S., Venkatachalam, G., Lee, H. J., Min, B. K., Kim, W., Koo, E., Do, Y. R. & Yoon, S. (2011). Polyhedron. 30, 340-346.]); Yoon & Lippard (2004a[Yoon, S. & Lippard, S. J. (2004a). J. Am. Chem. Soc. 126, 2666-2667.],b[Yoon, S. & Lippard, S. J. (2004b). J. Am. Chem. Soc. 126, 16692-16693.]); Lee & Lippard (1998[Lee, D. & Lippard, S. J. (1998). J. Am. Chem. Soc. 120, 12153-12154.], 2001[Lee, D. & Lippard, S. J. (2001). J. Am. Chem. Soc. 123, 4611-4612.], 2002[Lee, D. & Lippard, S. J. (2002). Inorg. Chem. 41, 827-837.]) and for those with 3,5-dimethyl­pyrazole ligands, see: Zhang et al. (2007[Zhang, X.-J., Han, J., Wang, C.-G. & Xing, Y.-H. (2007). Acta Cryst. E63, m2620-m2621.]); Cheng et al. (1990[Cheng, C.-H., Lain, J.-S., Wu, Y.-J. & Wang, S.-L. (1990). Acta Cryst. C46, 208-210.]).

[Scheme 1]

Experimental

Crystal data
  • [Mn(C19H11F2O2)2(C5H8N2)2]

  • Mr = 865.76

  • Triclinic, [P \overline 1]

  • a = 10.9310 (16) Å

  • b = 13.668 (2) Å

  • c = 15.541 (2) Å

  • α = 69.283 (2)°

  • β = 88.854 (2)°

  • γ = 77.476 (2)°

  • V = 2115.9 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.38 mm−1

  • T = 173 K

  • 0.10 × 0.10 × 0.05 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.469, Tmax = 1.0

  • 15553 measured reflections

  • 7378 independent reflections

  • 6578 reflections with I > 2σ(I)

  • Rint = 0.032

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.118

  • S = 1.08

  • 7378 reflections

  • 562 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.67 e Å−3

  • Δρmin = −0.37 e Å−3

Table 1
Selected geometric parameters (Å, °)

Mn1—O3 2.0636 (15)
Mn1—O1 2.0805 (16)
Mn1—N1 2.1292 (19)
Mn1—N3 2.1591 (19)
O3—Mn1—O1 107.39 (7)
O3—Mn1—N1 105.08 (7)
O1—Mn1—N1 105.31 (7)
O3—Mn1—N3 101.78 (7)
O1—Mn1—N3 123.66 (7)
N1—Mn1—N3 112.13 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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.

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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.

Related literature top

For the synthesis of substituted terphenyl-based carboxylate ligands, see: Saednya et al. (1996); Du et al. (1986); Chen et al. (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 top

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).

Refinement top

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)].

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: 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).

Figures top
[Figure 1] 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.
Bis(4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylato-κO)bis(3,5- dimethyl-1H-pyrazole-κN2)manganese(II) top
Crystal data top
[Mn(C19H11F2O2)2(C5H8N2)2]Z = 2
Mr = 865.76F(000) = 894
Triclinic, P1Dx = 1.359 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.9310 (16) ÅCell parameters from 1018 reflections
b = 13.668 (2) Åθ = 2.5–27.2°
c = 15.541 (2) ŵ = 0.38 mm1
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
Data collection top
Bruker SMART CCD area-detector
diffractometer
7378 independent reflections
Radiation source: fine-focus sealed tube6578 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ϕ and ω scansθmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1212
Tmin = 0.469, Tmax = 1.0k = 1616
15553 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H 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 parametersΔρmax = 0.67 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
[Mn(C19H11F2O2)2(C5H8N2)2]γ = 77.476 (2)°
Mr = 865.76V = 2115.9 (5) Å3
Triclinic, P1Z = 2
a = 10.9310 (16) ÅMo Kα radiation
b = 13.668 (2) ŵ = 0.38 mm1
c = 15.541 (2) ÅT = 173 K
α = 69.283 (2)°0.10 × 0.10 × 0.05 mm
β = 88.854 (2)°
Data collection top
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 = 1.0Rint = 0.032
15553 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.67 e Å3
7378 reflectionsΔρmin = 0.37 e Å3
562 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C11.0866 (2)0.5295 (3)0.7746 (2)0.0513 (8)
H1A1.13750.55220.72160.077*
H2B1.13990.47420.82660.077*
H3C1.04900.59130.79180.077*
C20.9853 (2)0.4851 (2)0.74983 (16)0.0314 (5)
C30.9922 (3)0.3873 (2)0.73963 (18)0.0407 (6)
H31.06580.33270.74620.049*
C40.8721 (3)0.3847 (2)0.71824 (18)0.0422 (6)
C50.8188 (4)0.3015 (2)0.7006 (3)0.0709 (11)
H5A0.78480.25950.75710.106*
H6B0.88510.25380.68160.106*
H7C0.75160.33640.65170.106*
C60.9539 (3)0.8351 (2)0.56558 (18)0.0461 (7)
H8A0.93060.76680.57550.069*
H9B1.03980.83130.54550.069*
H10C0.89600.89320.51810.069*
C70.9467 (2)0.85669 (19)0.65348 (16)0.0314 (5)
C80.9967 (2)0.9287 (2)0.67876 (18)0.0376 (6)
H41.04450.97680.64190.045*
C90.9638 (2)0.91730 (19)0.76706 (17)0.0338 (6)
C100.9886 (3)0.9709 (2)0.8309 (2)0.0507 (7)
H12A0.91750.97580.86970.076*
H13B0.99971.04320.79510.076*
H14C1.06500.92910.86990.076*
C110.7265 (2)0.64209 (16)0.92263 (15)0.0249 (5)
C120.67639 (19)0.60871 (16)1.01669 (14)0.0185 (4)
C170.63182 (19)0.68616 (17)1.05611 (14)0.0212 (4)
C160.5773 (2)0.65568 (18)1.14060 (14)0.0264 (5)
H150.54980.70691.16930.032*
C150.5629 (2)0.55161 (19)1.18310 (15)0.0284 (5)
H160.52200.53251.23920.034*
C140.6080 (2)0.47540 (17)1.14401 (15)0.0260 (5)
H170.59740.40421.17350.031*
C130.66876 (19)0.50138 (17)1.06224 (14)0.0211 (4)
C240.7289 (2)0.41609 (16)1.02611 (14)0.0223 (5)
C290.8558 (2)0.40187 (18)1.00785 (16)0.0278 (5)
H180.90310.44871.01650.033*
C280.9137 (2)0.3206 (2)0.97736 (17)0.0342 (6)
H191.00010.31100.96520.041*
C270.8434 (3)0.25472 (19)0.96519 (17)0.0359 (6)
C260.7184 (2)0.26476 (19)0.98273 (18)0.0373 (6)
H200.67230.21730.97390.045*
C250.6619 (2)0.34618 (17)1.01366 (16)0.0298 (5)
H210.57570.35431.02660.036*
C180.6370 (2)0.80062 (17)1.00680 (14)0.0223 (5)
C190.7005 (3)0.85289 (19)1.04621 (16)0.0338 (6)
H220.74080.81571.10610.041*
C200.7060 (3)0.9594 (2)0.99926 (18)0.0407 (6)
H230.75020.99531.02610.049*
C210.6463 (2)1.01103 (17)0.91372 (16)0.0306 (5)
C220.5818 (2)0.96331 (19)0.87257 (16)0.0318 (5)
H240.54061.00180.81310.038*
C230.5775 (2)0.85704 (18)0.91944 (16)0.0282 (5)
H250.53340.82220.89150.034*
C300.57304 (19)0.71049 (17)0.60758 (14)0.0232 (5)
C310.4892 (2)0.77015 (17)0.52004 (14)0.0227 (5)
C360.3932 (2)0.85918 (18)0.51369 (15)0.0263 (5)
C350.3179 (2)0.9123 (2)0.43246 (16)0.0361 (6)
H260.25270.97290.42780.043*
C340.3364 (3)0.8786 (2)0.35867 (17)0.0406 (6)
H270.28370.91530.30380.049*
C330.4312 (2)0.7916 (2)0.36461 (16)0.0349 (6)
H280.44440.76940.31310.042*
C320.5081 (2)0.73568 (18)0.44486 (15)0.0263 (5)
C430.6113 (2)0.64322 (19)0.44768 (15)0.0286 (5)
C440.7327 (2)0.6363 (2)0.47775 (19)0.0412 (6)
H290.75060.69210.49500.049*
C450.8276 (3)0.5491 (3)0.4828 (2)0.0598 (9)
H300.91070.54400.50370.072*
C460.7997 (3)0.4703 (3)0.4571 (2)0.0541 (8)
C470.6825 (3)0.4741 (2)0.42535 (19)0.0458 (7)
H310.66630.41840.40720.055*
C480.5882 (2)0.5621 (2)0.42059 (16)0.0348 (6)
H320.50590.56710.39830.042*
C370.3671 (2)0.89838 (18)0.59182 (15)0.0251 (5)
C380.3556 (2)1.0065 (2)0.57712 (17)0.0343 (6)
H330.36661.05460.51760.041*
C390.3282 (2)1.0448 (2)0.64837 (19)0.0406 (6)
H340.32141.11840.63870.049*
C400.3111 (2)0.9740 (2)0.73290 (18)0.0378 (6)
C410.3204 (2)0.8674 (2)0.75057 (17)0.0387 (6)
H350.30760.82040.81010.046*
C420.3490 (2)0.8299 (2)0.67922 (16)0.0321 (5)
H360.35630.75590.69010.039*
F10.90001 (16)0.17383 (12)0.93543 (12)0.0536 (4)
F20.65221 (16)1.11511 (11)0.86681 (10)0.0464 (4)
F30.89370 (19)0.38355 (17)0.46375 (17)0.0866 (7)
F40.28254 (16)1.01216 (16)0.80295 (12)0.0579 (5)
Mn10.76676 (3)0.68954 (3)0.74376 (2)0.02314 (11)
N10.86659 (17)0.54142 (15)0.73521 (13)0.0271 (4)
N20.7995 (2)0.47746 (16)0.71690 (15)0.0362 (5)
N30.88491 (18)0.80274 (15)0.72287 (13)0.0286 (4)
N40.89665 (19)0.84149 (17)0.79094 (15)0.0324 (5)
O10.65725 (16)0.64746 (13)0.85637 (10)0.0349 (4)
O20.83122 (17)0.66487 (14)0.91176 (13)0.0421 (5)
O30.64655 (14)0.76094 (12)0.62699 (10)0.0274 (4)
O40.56667 (15)0.61680 (12)0.65369 (11)0.0307 (4)
H10.721 (3)0.507 (2)0.699 (2)0.045 (8)*
H20.875 (3)0.808 (2)0.842 (2)0.039 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0296 (14)0.064 (2)0.0631 (19)0.0012 (13)0.0081 (13)0.0312 (16)
C20.0282 (12)0.0352 (14)0.0268 (12)0.0010 (10)0.0019 (10)0.0108 (10)
C30.0394 (14)0.0352 (15)0.0405 (14)0.0093 (12)0.0051 (12)0.0151 (12)
C40.0536 (17)0.0254 (14)0.0418 (15)0.0035 (12)0.0111 (13)0.0074 (11)
C50.092 (3)0.0313 (17)0.086 (3)0.0122 (17)0.025 (2)0.0165 (17)
C60.0505 (16)0.0426 (16)0.0366 (14)0.0090 (13)0.0153 (13)0.0054 (12)
C70.0254 (12)0.0264 (12)0.0298 (12)0.0028 (10)0.0039 (10)0.0030 (10)
C80.0332 (13)0.0286 (13)0.0403 (14)0.0142 (11)0.0042 (11)0.0046 (11)
C90.0278 (12)0.0278 (13)0.0391 (14)0.0094 (10)0.0036 (11)0.0018 (11)
C100.0547 (18)0.0441 (17)0.0580 (18)0.0266 (14)0.0036 (14)0.0147 (14)
C110.0342 (13)0.0116 (10)0.0271 (12)0.0057 (9)0.0090 (10)0.0049 (9)
C120.0201 (10)0.0164 (10)0.0197 (10)0.0088 (8)0.0003 (8)0.0043 (8)
C170.0238 (11)0.0188 (11)0.0219 (10)0.0081 (9)0.0006 (9)0.0063 (9)
C160.0318 (12)0.0263 (12)0.0223 (11)0.0076 (10)0.0041 (9)0.0099 (9)
C150.0324 (12)0.0302 (13)0.0196 (11)0.0104 (10)0.0071 (9)0.0035 (9)
C140.0300 (12)0.0181 (11)0.0249 (11)0.0101 (9)0.0006 (9)0.0011 (9)
C130.0210 (10)0.0190 (11)0.0223 (10)0.0084 (9)0.0010 (9)0.0035 (9)
C240.0303 (12)0.0144 (10)0.0191 (10)0.0074 (9)0.0020 (9)0.0010 (8)
C290.0332 (12)0.0225 (12)0.0312 (12)0.0128 (10)0.0045 (10)0.0100 (10)
C280.0362 (13)0.0310 (13)0.0347 (13)0.0053 (11)0.0054 (11)0.0122 (11)
C270.0523 (16)0.0206 (12)0.0327 (13)0.0016 (11)0.0031 (12)0.0123 (10)
C260.0471 (15)0.0206 (12)0.0468 (15)0.0092 (11)0.0104 (12)0.0135 (11)
C250.0318 (12)0.0186 (11)0.0368 (13)0.0077 (10)0.0056 (10)0.0058 (10)
C180.0264 (11)0.0176 (11)0.0243 (11)0.0057 (9)0.0068 (9)0.0091 (9)
C190.0551 (16)0.0243 (12)0.0246 (11)0.0147 (11)0.0021 (11)0.0080 (10)
C200.0689 (19)0.0279 (13)0.0364 (14)0.0245 (13)0.0007 (13)0.0166 (11)
C210.0475 (15)0.0136 (11)0.0325 (12)0.0099 (10)0.0093 (11)0.0089 (10)
C220.0367 (13)0.0224 (12)0.0309 (12)0.0065 (10)0.0016 (10)0.0031 (10)
C230.0314 (12)0.0210 (12)0.0329 (12)0.0105 (10)0.0016 (10)0.0077 (10)
C300.0205 (10)0.0248 (12)0.0216 (11)0.0022 (9)0.0043 (9)0.0069 (9)
C310.0240 (11)0.0200 (11)0.0213 (10)0.0084 (9)0.0024 (9)0.0023 (9)
C360.0283 (12)0.0229 (12)0.0229 (11)0.0065 (9)0.0015 (9)0.0021 (9)
C350.0368 (14)0.0308 (14)0.0304 (13)0.0042 (11)0.0035 (11)0.0052 (11)
C340.0454 (15)0.0421 (16)0.0240 (12)0.0006 (12)0.0097 (11)0.0050 (11)
C330.0423 (14)0.0397 (15)0.0228 (11)0.0099 (12)0.0010 (10)0.0110 (11)
C320.0287 (12)0.0260 (12)0.0236 (11)0.0107 (10)0.0036 (9)0.0057 (9)
C430.0314 (12)0.0315 (13)0.0232 (11)0.0097 (10)0.0075 (9)0.0087 (10)
C440.0329 (14)0.0460 (16)0.0538 (16)0.0088 (12)0.0096 (12)0.0291 (14)
C450.0311 (14)0.076 (2)0.082 (2)0.0030 (15)0.0018 (15)0.049 (2)
C460.0492 (18)0.0503 (18)0.0619 (19)0.0108 (14)0.0078 (15)0.0324 (16)
C470.0600 (18)0.0408 (16)0.0425 (15)0.0116 (14)0.0129 (14)0.0223 (13)
C480.0396 (14)0.0377 (14)0.0297 (12)0.0099 (12)0.0076 (11)0.0147 (11)
C370.0213 (11)0.0246 (12)0.0257 (11)0.0025 (9)0.0006 (9)0.0060 (9)
C380.0378 (14)0.0293 (13)0.0349 (13)0.0113 (11)0.0059 (11)0.0083 (11)
C390.0427 (15)0.0352 (15)0.0531 (16)0.0162 (12)0.0076 (13)0.0227 (13)
C400.0298 (13)0.0550 (17)0.0383 (14)0.0087 (12)0.0034 (11)0.0287 (13)
C410.0371 (14)0.0458 (16)0.0248 (12)0.0029 (12)0.0042 (11)0.0062 (11)
C420.0330 (13)0.0264 (13)0.0293 (12)0.0015 (10)0.0022 (10)0.0038 (10)
F10.0702 (11)0.0338 (9)0.0608 (10)0.0030 (8)0.0018 (9)0.0298 (8)
F20.0813 (12)0.0172 (7)0.0421 (8)0.0208 (7)0.0021 (8)0.0067 (6)
F30.0693 (13)0.0766 (14)0.1162 (18)0.0258 (11)0.0018 (12)0.0617 (14)
F40.0544 (10)0.0866 (13)0.0533 (10)0.0181 (9)0.0114 (8)0.0488 (10)
Mn10.02515 (19)0.01969 (19)0.02176 (18)0.00732 (14)0.00321 (13)0.00279 (14)
N10.0261 (10)0.0254 (10)0.0291 (10)0.0053 (8)0.0003 (8)0.0094 (8)
N20.0303 (11)0.0240 (11)0.0487 (13)0.0055 (9)0.0096 (10)0.0062 (10)
N30.0305 (10)0.0273 (11)0.0254 (10)0.0126 (9)0.0033 (8)0.0030 (8)
N40.0365 (11)0.0351 (12)0.0279 (11)0.0208 (10)0.0053 (9)0.0068 (9)
O10.0490 (10)0.0341 (10)0.0195 (8)0.0078 (8)0.0050 (7)0.0081 (7)
O20.0407 (10)0.0342 (10)0.0510 (11)0.0208 (8)0.0231 (9)0.0086 (9)
O30.0287 (8)0.0275 (9)0.0252 (8)0.0083 (7)0.0018 (7)0.0071 (7)
O40.0306 (9)0.0218 (8)0.0299 (8)0.0063 (7)0.0002 (7)0.0029 (7)
Geometric parameters (Å, º) top
C1—C21.489 (4)C19—C201.393 (3)
C1—H1A0.9800C19—H220.9500
C1—H2B0.9800C20—C211.365 (4)
C1—H3C0.9800C20—H230.9500
C2—N11.335 (3)C21—C221.358 (3)
C2—C31.387 (4)C21—F21.365 (3)
C3—C41.371 (4)C22—C231.386 (3)
C3—H30.9500C22—H240.9500
C4—N21.335 (3)C23—H250.9500
C4—C51.491 (4)C30—O41.243 (3)
C5—H5A0.9800C30—O31.269 (3)
C5—H6B0.9800C30—C311.516 (3)
C5—H7C0.9800C31—C361.399 (3)
C6—C71.493 (4)C31—C321.403 (3)
C6—H8A0.9800C36—C351.390 (3)
C6—H9B0.9800C36—C371.491 (3)
C6—H10C0.9800C35—C341.376 (4)
C7—N31.337 (3)C35—H260.9500
C7—C81.393 (4)C34—C331.374 (4)
C8—C91.375 (4)C34—H270.9500
C8—H40.9500C33—C321.391 (3)
C9—N41.341 (3)C33—H280.9500
C9—C101.485 (4)C32—C431.488 (3)
C10—H12A0.9800C43—C481.387 (3)
C10—H13B0.9800C43—C441.389 (3)
C10—H14C0.9800C44—C451.379 (4)
C11—O21.243 (3)C44—H290.9500
C11—O11.262 (3)C45—C461.366 (4)
C11—C121.500 (3)C45—H300.9500
C12—C171.399 (3)C46—F31.365 (3)
C12—C131.406 (3)C46—C471.366 (4)
C17—C161.393 (3)C47—C481.385 (4)
C17—C181.492 (3)C47—H310.9500
C16—C151.383 (3)C48—H320.9500
C16—H150.9500C37—C421.389 (3)
C15—C141.382 (3)C37—C381.391 (3)
C15—H160.9500C38—C391.385 (4)
C14—C131.390 (3)C38—H330.9500
C14—H170.9500C39—C401.366 (4)
C13—C241.491 (3)C39—H340.9500
C24—C251.388 (3)C40—C411.365 (4)
C24—C291.396 (3)C40—F41.368 (3)
C29—C281.383 (3)C41—C421.382 (3)
C29—H180.9500C41—H350.9500
C28—C271.365 (4)C42—H360.9500
C28—H190.9500Mn1—O32.0636 (15)
C27—F11.368 (3)Mn1—O12.0805 (16)
C27—C261.375 (4)Mn1—N12.1292 (19)
C26—C251.386 (3)Mn1—N32.1591 (19)
C26—H200.9500N1—N21.358 (3)
C25—H210.9500N2—H10.87 (3)
C18—C191.381 (3)N3—N41.359 (3)
C18—C231.392 (3)N4—H20.82 (3)
C2—C1—H1A109.5C21—C20—H23120.8
C2—C1—H2B109.5C19—C20—H23120.8
H1A—C1—H2B109.5C22—C21—C20123.0 (2)
C2—C1—H3C109.5C22—C21—F2118.3 (2)
H1A—C1—H3C109.5C20—C21—F2118.7 (2)
H2B—C1—H3C109.5C21—C22—C23118.3 (2)
N1—C2—C3110.1 (2)C21—C22—H24120.8
N1—C2—C1120.2 (2)C23—C22—H24120.8
C3—C2—C1129.7 (2)C22—C23—C18121.0 (2)
C4—C3—C2106.6 (2)C22—C23—H25119.5
C4—C3—H3126.7C18—C23—H25119.5
C2—C3—H3126.7O4—C30—O3125.1 (2)
N2—C4—C3106.1 (2)O4—C30—C31118.58 (19)
N2—C4—C5121.8 (3)O3—C30—C31116.30 (18)
C3—C4—C5132.1 (3)C36—C31—C32119.83 (19)
C4—C5—H5A109.5C36—C31—C30120.54 (19)
C4—C5—H6B109.5C32—C31—C30119.63 (19)
H5A—C5—H6B109.5C35—C36—C31119.2 (2)
C4—C5—H7C109.5C35—C36—C37118.5 (2)
H5A—C5—H7C109.5C31—C36—C37122.26 (19)
H6B—C5—H7C109.5C34—C35—C36121.0 (2)
C7—C6—H8A109.5C34—C35—H26119.5
C7—C6—H9B109.5C36—C35—H26119.5
H8A—C6—H9B109.5C33—C34—C35119.8 (2)
C7—C6—H10C109.5C33—C34—H27120.1
H8A—C6—H10C109.5C35—C34—H27120.1
H9B—C6—H10C109.5C34—C33—C32121.0 (2)
N3—C7—C8109.6 (2)C34—C33—H28119.5
N3—C7—C6120.6 (2)C32—C33—H28119.5
C8—C7—C6129.9 (2)C33—C32—C31119.1 (2)
C9—C8—C7107.1 (2)C33—C32—C43119.2 (2)
C9—C8—H4126.5C31—C32—C43121.63 (19)
C7—C8—H4126.5C48—C43—C44118.6 (2)
N4—C9—C8105.6 (2)C48—C43—C32120.8 (2)
N4—C9—C10121.8 (2)C44—C43—C32120.6 (2)
C8—C9—C10132.7 (2)C45—C44—C43120.6 (3)
C9—C10—H12A109.5C45—C44—H29119.7
C9—C10—H13B109.5C43—C44—H29119.7
H12A—C10—H13B109.5C46—C45—C44118.6 (3)
C9—C10—H14C109.5C46—C45—H30120.7
H12A—C10—H14C109.5C44—C45—H30120.7
H13B—C10—H14C109.5F3—C46—C47118.6 (3)
O2—C11—O1122.4 (2)F3—C46—C45118.2 (3)
O2—C11—C12120.4 (2)C47—C46—C45123.2 (3)
O1—C11—C12117.16 (19)C46—C47—C48117.5 (3)
C17—C12—C13120.69 (19)C46—C47—H31121.2
C17—C12—C11119.38 (18)C48—C47—H31121.2
C13—C12—C11119.85 (18)C47—C48—C43121.4 (2)
C16—C17—C12118.90 (19)C47—C48—H32119.3
C16—C17—C18120.29 (19)C43—C48—H32119.3
C12—C17—C18120.74 (18)C42—C37—C38118.6 (2)
C15—C16—C17120.6 (2)C42—C37—C36121.5 (2)
C15—C16—H15119.7C38—C37—C36119.9 (2)
C17—C16—H15119.7C39—C38—C37120.7 (2)
C14—C15—C16120.0 (2)C39—C38—H33119.7
C14—C15—H16120.0C37—C38—H33119.7
C16—C15—H16120.0C40—C39—C38118.4 (2)
C15—C14—C13121.0 (2)C40—C39—H34120.8
C15—C14—H17119.5C38—C39—H34120.8
C13—C14—H17119.5C41—C40—C39123.1 (2)
C14—C13—C12118.6 (2)C41—C40—F4118.5 (2)
C14—C13—C24120.40 (19)C39—C40—F4118.3 (3)
C12—C13—C24121.00 (19)C40—C41—C42118.0 (2)
C25—C24—C29118.5 (2)C40—C41—H35121.0
C25—C24—C13121.0 (2)C42—C41—H35121.0
C29—C24—C13120.49 (19)C41—C42—C37121.2 (2)
C28—C29—C24121.0 (2)C41—C42—H36119.4
C28—C29—H18119.5C37—C42—H36119.4
C24—C29—H18119.5O3—Mn1—O1107.39 (7)
C27—C28—C29118.3 (2)O3—Mn1—N1105.08 (7)
C27—C28—H19120.9O1—Mn1—N1105.31 (7)
C29—C28—H19120.9O3—Mn1—N3101.78 (7)
C28—C27—F1118.7 (2)O1—Mn1—N3123.66 (7)
C28—C27—C26123.0 (2)N1—Mn1—N3112.13 (7)
F1—C27—C26118.2 (2)C2—N1—N2105.00 (19)
C27—C26—C25118.0 (2)C2—N1—Mn1136.67 (16)
C27—C26—H20121.0N2—N1—Mn1118.13 (14)
C25—C26—H20121.0C4—N2—N1112.3 (2)
C26—C25—C24121.1 (2)C4—N2—H1131.1 (19)
C26—C25—H21119.4N1—N2—H1115.9 (19)
C24—C25—H21119.4C7—N3—N4105.33 (19)
C19—C18—C23118.6 (2)C7—N3—Mn1136.36 (17)
C19—C18—C17121.18 (19)N4—N3—Mn1118.01 (14)
C23—C18—C17120.26 (19)C9—N4—N3112.5 (2)
C18—C19—C20120.8 (2)C9—N4—H2130 (2)
C18—C19—H22119.6N3—N4—H2117 (2)
C20—C19—H22119.6C11—O1—Mn1103.42 (14)
C21—C20—C19118.3 (2)C30—O3—Mn1120.59 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H2···O20.82 (3)2.03 (3)2.712 (3)140 (3)
N2—H1···O40.87 (3)1.95 (3)2.783 (3)160 (3)
C26—H20···F2i0.952.563.355 (3)141
C15—H16···O4ii0.952.503.298 (3)141
C38—H33···O3iii0.952.703.606 (3)160
C20—H23···F4iv0.952.643.239 (3)121
C45—H30···F3v0.952.673.560 (4)156
Symmetry codes: (i) x, y1, 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]
Mr865.76
Crystal system, space groupTriclinic, 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)
V3)2115.9 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.10 × 0.10 × 0.05
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.469, 1.0
No. of measured, independent and
observed [I > 2σ(I)] reflections
15553, 7378, 6578
Rint0.032
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.118, 1.08
No. of reflections7378
No. of parameters562
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.67, 0.37

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Mn1—O32.0636 (15)Mn1—N12.1292 (19)
Mn1—O12.0805 (16)Mn1—N32.1591 (19)
O3—Mn1—O1107.39 (7)O3—Mn1—N3101.78 (7)
O3—Mn1—N1105.08 (7)O1—Mn1—N3123.66 (7)
O1—Mn1—N1105.31 (7)N1—Mn1—N3112.13 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H2···O20.82 (3)2.03 (3)2.712 (3)140 (3)
N2—H1···O40.87 (3)1.95 (3)2.783 (3)160 (3)
C26—H20···F2i0.952.563.355 (3)141.2
C15—H16···O4ii0.952.503.298 (3)141.3
C38—H33···O3iii0.952.703.606 (3)160.4
C20—H23···F4iv0.952.643.239 (3)121.4
C45—H30···F3v0.952.673.560 (4)156.4
Symmetry codes: (i) x, y1, 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).

References

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Volume 68| Part 5| May 2012| Pages m582-m583
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