Bis(4,4′′-difluoro-1,1′:3′,1′′-terphenyl-2′-carboxyl­ato-κO)bis­(3,5-dimethyl-1H-pyrazole-κN2)manganese(II)

Dharmalingam, S.; Jeon, Y.; Yoon, S.

doi:10.1107/S1600536812014201

metal-organic compounds

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ISSN: 2056-9890

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

doi:10.1107/S1600536812014201

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Bis(4,4′′-difluoro-1,1′:3′,1′′-terphenyl-2′-carboxylato-κO)bis(3,5-dimethyl-1H-pyrazole-κN²)manganese(II)

Sivanesan Dharmalingam,^a Yeojin Jeon ^a and Sungho Yoon ^a ^*

^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 ); 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

[Mn(C₁₉H₁₁F₂O₂)₂(C₅H₈N₂)₂]
M_r = 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 ) T_min = 0.469, T_max = 1.0
15553 measured reflections
7378 independent reflections
6578 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.67 e Å⁻³
Δρ_min = −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	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⋯F4^iv	0.95	2.64	3.239 (3)	121
C45—H30⋯F3^v	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); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812014201/sj5226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014201/sj5226Isup2.hkl

checkCIF report

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).

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

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
M_r = 865.76	F(000) = 894
Triclinic, P1	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	7378 independent reflections
Radiation source: fine-focus sealed tube	6578 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→12
T_min = 0.469, T_max = 1.0	k = −16→16
15553 measured reflections	l = −18→18

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)] = 0.047	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(F_o²) + (0.0504P)² + 1.1718P] where P = (F_o² + 2F_c²)/3
7378 reflections	(Δ/σ)_max = 0.001
562 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Mn(C₁₉H₁₁F₂O₂)₂(C₅H₈N₂)₂]	γ = 77.476 (2)°
M_r = 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)°

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)
T_min = 0.469, T_max = 1.0	R_int = 0.032
15553 measured reflections

Refinement top

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	Δρ_max = 0.67 e Å⁻³
7378 reflections	Δρ_min = −0.37 e Å⁻³
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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···F4^iv	0.95	2.64	3.239 (3)	121
C45—H30···F3^v	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]
M_r	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)
T_min, T_max	0.469, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	15553, 7378, 6578
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	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—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)

Hydrogen-bond geometry (Å, º) top

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···F4^iv	0.95	2.64	3.239 (3)	121.4
C45—H30···F3^v	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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