Bis(4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxyl-ato-κO)bis-(3,5-dimethyl-1H-pyrazole-κN(2))manganese(II).

In the title compound, [Mn(C(19)H(11)F(2)O(2))(2)(C(5)H(8)N(2))(2)], the Mn(2+) cation is coordinated by the N atoms of two 3,5-dimethyl-pyrazole ligands and carboxyl-ate O atoms from two 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxyl-ato ligands, forming an MnN(2)O(2) polyhedron with a slightly distorted tetra-hedral coordination geometry. Two intra-molecular hydrogen bonds are observed between the carboxyl-ate and pyrazole ligands. The combined influence of the sterically hindered carboxyl-ate ligands and the intra-molecular hydrogen-bonding inter-actions 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 = 865.76

Triclinic,

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[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 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

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014201/sj5226sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[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

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

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⋯F4iv	0.95	2.64	3.239 (3)	121
C45—H30⋯F3v	0.95	2.67	3.560 (4)	156

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .