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Acta Cryst. (2007). E63, m3007    [ doi:10.1107/S1600536807056991 ]

(2,2'-Bipyridine-[kappa]2N,N')(4'-ferrocenyl-2,2':6',2''-terpyridine-[kappa]3N,N',N'')copper(II) bis(tetrafluoridoborate)

S.-P. Tang and D.-Z. Kuang

Abstract top

In the title complex, [CuFe(C5H5)(C20H14N3)(C10H8N2)](BF4)2, the CuII atom is five-coordinated by a tridentate chelating 4'-ferrocenyl-2,2':6',2"-terpyridine (fctpy) ligand and a bidentate chelating 2,2'-bipyridine (bpy) ligand. The coordination polyhedron is distorted square-pyramidal with an N atom from the bipyridine ligand in the apical position at a Cu-N distance of 2.195 (3) Å. In the crystal structure, tetrafluoridoborate counter-ions are involved as acceptors in intermolecular C-H...F hydrogen-bonding interactions with both the bipyridyl and terpyridyl ligands, resulting in a three-dimensional supramolecular structure.

Comment top

The chemistry of 2,2':6',2"-terpyridine (tpy) ligand has been the subject of numerous studies because of its good chelating ability towards transition metal ions, and some of its complexes are promising materials for potential applications as luminescent devices (Andres & Schubert, 2004; Barigelletti & Flamigni, 2000; Licini & Williams, 1999). Especially, the central pyridyl ring can be easily functionalized to attain different aims, and much work has been done on functionalized terpyridine complexes (Hofmeier & and Schubert, 2004). For example, several studies have been carried out on the structure and electrochemical properties of 4'-ferrocenyl-2,2':6',2"-terpyridine (fctpy) and its AuI, RuII, CoII and FeII complexes (Aguado et al., 2005; Constable et al., 1994; Farlow et al., 1993). In this work, we represent a new mixed-ligand complex, incorporating fctpy and 2,2'-bipyridine (bpy) ligands.

In the title complex, (I), Fig. 1, the CuII atom is five-coordinated by three N atoms from the fctpy ligand and two N atoms from the bpy, ligand displaying a distorted square pyramidal geometry. The apex of the pyramid is occupied by the N5 from the bpy ligand with a Cu1—N5 distance of 2.195 (3) Å, which is somewhat longer than those in the basal plane [Cu—N distances in the range 1.928 (3)–2.062 (3) Å]. The angles subtended at Cu(1) by the tridentate terpyridyl ligand are 79.52 (12) and 80.08 (12) ° respectively. The two cyclopentadienyl rings of the ferrocenyl group are almost eclipsed and the dihedral angle between the two rings is 5.1 (2) °.

In the crystal structure, tetrafluoridoborate counterions are involved as acceptors in intermolecular C—H···F hydrogen-bonding interactions with both the bipyridyl and terpyridyl ligands, resulting a three-dimensional supramolecular structure, Table 1.

Related literature top

For general background, see: Andres & Schubert (2004); Barigelletti & Flamigni (2000); Licini & Williams (1999). For a functionalized terpyridine complex, see: Hofmeier & Schubert (2004). For 4'-ferrocenyl-2,2':6',2"-terpyridine metal complexes, see: Aguado et al. (2005); Constable et al. (1994); Farlow et al. (1993).

Experimental top

The ligand fctpy was synthesized according to the reported procedure (Farlow et al., 1993). A solution of copper fluoroborate hydrate (69.8 mg, 0.2 mmol), fctpy (82.5 mg, 0.2 mmol) and 2,2'-bipyridine (32.1 g, 0.2 mmol) in methanol (15 ml) was stirred for 4 h. The product was filtered off and dried. The precipitate were recrystallized from acetonitrile (10 ml) to give black block-shaped crystals of the title complex after one week. Yield: 105 mg (65%).

Refinement top

The carbon-bound H atoms were placed at calculated positions (C—H = 0.93 Å) and refined as riding, with U(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL (Bruker, 2002).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, with displacement ellipsoids drawn at the 30% probability level, and H atoms as spheres of arbitrary radius.
(2,2'-Bipyridine-κ2N,N')(4'-ferrocenyl-2,2':6',2''-terpyridine- κ3N,N',N'')copper(II) bis(tetrafluoridoborate) top
Crystal data top
[CuFe(C5H5)(C20H14N3)(C10H8N2)](BF4)2F000 = 1636
Mr = 810.63Dx = 1.596 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3768 reflections
a = 14.0780 (8) Åθ = 2.4–23.2º
b = 14.2074 (8) ŵ = 1.14 mm−1
c = 16.9442 (10) ÅT = 293 (2) K
β = 95.488 (1)ºBlock, orange
V = 3373.5 (3) Å30.20 × 0.18 × 0.10 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer		7656 independent reflections
Radiation source: fine-focus sealed tube5667 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 293(2) Kθmax = 27.5º
φ and ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −18→12
Tmin = 0.804, Tmax = 0.895k = −18→18
20780 measured reflectionsl = −19→21
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.163  w = 1/[σ2(Fo2) + (0.0922P)2 + 0.8536P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
7656 reflectionsΔρmax = 0.89 e Å−3
469 parametersΔρmin = −0.74 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[CuFe(C5H5)(C20H14N3)(C10H8N2)](BF4)2V = 3373.5 (3) Å3
Mr = 810.63Z = 4
Monoclinic, P21/nMo Kα
a = 14.0780 (8) ŵ = 1.14 mm−1
b = 14.2074 (8) ÅT = 293 (2) K
c = 16.9442 (10) Å0.20 × 0.18 × 0.10 mm
β = 95.488 (1)º
Data collection top
Bruker APEX area-detector
diffractometer		7656 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		5667 reflections with I > 2σ(I)
Tmin = 0.804, Tmax = 0.895Rint = 0.033
20780 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.059469 parameters
wR(F2) = 0.163H-atom parameters constrained
S = 1.05Δρmax = 0.89 e Å−3
7656 reflectionsΔρmin = −0.74 e Å−3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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 > σ(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
Cu1−0.10157 (3)0.23820 (3)0.12009 (3)0.03846 (15)
Fe10.38524 (4)0.01582 (4)0.12953 (3)0.03927 (17)
N1−0.0949 (2)0.2164 (2)0.00040 (18)0.0405 (7)
N20.0094 (2)0.1584 (2)0.12231 (16)0.0364 (6)
N3−0.0788 (2)0.2132 (2)0.23883 (18)0.0400 (7)
N4−0.2275 (2)0.3013 (2)0.11664 (18)0.0402 (7)
N5−0.0599 (2)0.3868 (2)0.11526 (18)0.0398 (7)
C1−0.1545 (3)0.2491 (3)−0.0600 (2)0.0467 (9)
H1−0.20700.2846−0.04870.056*
C2−0.1409 (3)0.2319 (3)−0.1378 (3)0.0554 (11)
H2−0.18400.2548−0.17830.066*
C3−0.0634 (4)0.1809 (3)−0.1554 (2)0.0555 (11)
H3−0.05320.1684−0.20780.067*
C4−0.0001 (3)0.1480 (3)−0.0937 (2)0.0498 (10)
H40.05390.1143−0.10410.060*
C5−0.0186 (3)0.1662 (2)−0.0169 (2)0.0388 (8)
C60.0418 (3)0.1303 (2)0.0539 (2)0.0388 (8)
C70.1199 (3)0.0721 (2)0.0536 (2)0.0390 (8)
H70.14230.05430.00600.047*
C80.1653 (3)0.0398 (2)0.1259 (2)0.0382 (8)
C90.1277 (3)0.0674 (2)0.1957 (2)0.0387 (8)
H90.15560.04630.24450.046*
C100.0495 (3)0.1260 (2)0.1922 (2)0.0363 (8)
C11−0.0021 (3)0.1583 (2)0.2599 (2)0.0382 (8)
C120.0236 (3)0.1346 (3)0.3378 (2)0.0456 (9)
H120.07730.09780.35140.055*
C13−0.0319 (3)0.1663 (3)0.3955 (2)0.0553 (11)
H13−0.01650.15040.44840.066*
C14−0.1094 (3)0.2212 (3)0.3739 (3)0.0570 (11)
H14−0.14750.24310.41200.068*
C15−0.1309 (3)0.2440 (3)0.2954 (3)0.0513 (10)
H15−0.18350.28210.28120.062*
C160.2469 (3)−0.0242 (2)0.1279 (2)0.0388 (8)
C170.2887 (3)−0.0628 (2)0.0609 (2)0.0433 (8)
H170.2680−0.05210.00790.052*
C180.3666 (3)−0.1198 (3)0.0895 (3)0.0477 (9)
H180.4058−0.15320.05830.057*
C190.3753 (3)−0.1178 (3)0.1735 (3)0.0521 (10)
H190.4215−0.14880.20690.062*
C200.3006 (3)−0.0597 (3)0.1976 (2)0.0448 (9)
H200.2889−0.04700.24970.054*
C210.3866 (4)0.1578 (3)0.1202 (4)0.0723 (14)
H210.33310.19650.11390.087*
C220.4337 (4)0.1174 (3)0.0592 (3)0.0668 (12)
H220.41660.12420.00510.080*
C230.5110 (3)0.0651 (3)0.0941 (3)0.0603 (11)
H230.55460.03160.06720.072*
C240.5112 (3)0.0721 (3)0.1762 (3)0.0637 (12)
H240.55460.04360.21360.076*
C250.4350 (4)0.1291 (3)0.1926 (3)0.0695 (13)
H250.41890.14540.24280.083*
C26−0.3100 (3)0.2553 (3)0.1214 (3)0.0530 (10)
H26−0.30880.19020.12720.064*
C27−0.3961 (3)0.3010 (3)0.1181 (3)0.0605 (12)
H27−0.45220.26740.12190.073*
C28−0.3986 (3)0.3955 (3)0.1091 (3)0.0597 (11)
H28−0.45650.42740.10660.072*
C29−0.3156 (3)0.4440 (3)0.1037 (3)0.0512 (10)
H29−0.31670.50900.09730.061*
C30−0.2305 (3)0.3962 (2)0.1079 (2)0.0370 (8)
C31−0.1365 (3)0.4431 (2)0.1060 (2)0.0380 (8)
C32−0.1273 (3)0.5395 (3)0.0946 (3)0.0538 (10)
H32−0.18100.57770.08720.065*
C33−0.0376 (4)0.5775 (3)0.0945 (3)0.0632 (12)
H33−0.03010.64210.08860.076*
C340.0409 (3)0.5200 (3)0.1030 (3)0.0568 (11)
H340.10200.54440.10180.068*
C350.0266 (3)0.4249 (3)0.1136 (2)0.0506 (10)
H350.07960.38560.11990.061*
B10.3098 (4)0.4133 (5)0.0985 (3)0.0656 (15)
B20.7926 (6)0.9894 (5)0.1737 (4)0.0788 (17)
F10.2382 (3)0.3522 (3)0.0919 (4)0.187 (3)
F20.2729 (3)0.5017 (2)0.1047 (2)0.0951 (10)
F30.3600 (4)0.4047 (4)0.0379 (2)0.171 (2)
F40.3677 (3)0.3941 (3)0.1634 (2)0.1181 (14)
F50.7456 (5)0.9235 (4)0.1292 (4)0.183 (2)
F60.7409 (3)1.0311 (4)0.2257 (2)0.156 (2)
F70.8184 (3)1.0528 (3)0.1205 (2)0.1159 (14)
F80.8733 (4)0.9568 (4)0.2117 (2)0.174 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0358 (3)0.0355 (3)0.0441 (3)0.00386 (18)0.00372 (19)0.00339 (18)
Fe10.0371 (3)0.0374 (3)0.0441 (3)0.0001 (2)0.0077 (2)−0.0013 (2)
N10.0397 (17)0.0382 (16)0.0429 (16)−0.0047 (14)0.0007 (14)0.0054 (13)
N20.0375 (16)0.0342 (15)0.0372 (15)0.0025 (12)0.0028 (12)0.0016 (12)
N30.0423 (17)0.0361 (16)0.0423 (16)0.0027 (14)0.0078 (14)0.0012 (12)
N40.0338 (16)0.0355 (16)0.0512 (18)−0.0028 (13)0.0042 (14)0.0011 (13)
N50.0326 (16)0.0387 (16)0.0473 (17)−0.0037 (13)−0.0001 (13)0.0009 (13)
C10.041 (2)0.046 (2)0.051 (2)−0.0065 (17)−0.0030 (18)0.0115 (17)
C20.054 (3)0.058 (3)0.051 (2)−0.016 (2)−0.011 (2)0.020 (2)
C30.073 (3)0.053 (2)0.040 (2)−0.012 (2)0.001 (2)0.0071 (18)
C40.064 (3)0.044 (2)0.041 (2)0.0012 (19)0.0055 (19)0.0037 (16)
C50.044 (2)0.0311 (17)0.0402 (18)−0.0035 (15)−0.0019 (16)0.0017 (14)
C60.044 (2)0.0347 (18)0.0382 (18)−0.0020 (15)0.0049 (16)0.0024 (14)
C70.044 (2)0.0346 (18)0.0393 (18)0.0037 (15)0.0106 (16)0.0007 (14)
C80.038 (2)0.0330 (17)0.0440 (19)−0.0044 (15)0.0083 (16)0.0048 (15)
C90.0369 (19)0.0389 (19)0.0403 (18)0.0001 (15)0.0033 (15)0.0049 (15)
C100.040 (2)0.0318 (17)0.0378 (18)−0.0022 (15)0.0058 (15)0.0011 (14)
C110.043 (2)0.0316 (17)0.0414 (19)−0.0042 (15)0.0088 (16)−0.0003 (14)
C120.051 (2)0.047 (2)0.0389 (19)−0.0004 (18)0.0037 (17)0.0033 (16)
C130.069 (3)0.061 (3)0.037 (2)−0.006 (2)0.009 (2)−0.0006 (18)
C140.064 (3)0.062 (3)0.049 (2)0.000 (2)0.023 (2)−0.009 (2)
C150.048 (2)0.050 (2)0.057 (2)0.0066 (18)0.013 (2)−0.0089 (18)
C160.037 (2)0.0329 (18)0.048 (2)0.0008 (15)0.0086 (16)0.0038 (15)
C170.044 (2)0.0376 (19)0.048 (2)−0.0005 (16)0.0051 (17)−0.0039 (16)
C180.048 (2)0.0355 (19)0.062 (2)0.0044 (17)0.0149 (19)−0.0024 (17)
C190.049 (2)0.042 (2)0.065 (3)0.0098 (18)0.010 (2)0.0145 (19)
C200.042 (2)0.044 (2)0.049 (2)0.0054 (17)0.0108 (17)0.0120 (17)
C210.053 (3)0.041 (2)0.124 (4)−0.005 (2)0.012 (3)−0.003 (2)
C220.072 (3)0.058 (3)0.070 (3)−0.022 (2)0.005 (2)0.009 (2)
C230.052 (3)0.058 (3)0.074 (3)−0.015 (2)0.022 (2)−0.008 (2)
C240.051 (3)0.071 (3)0.068 (3)−0.016 (2)−0.003 (2)−0.012 (2)
C250.069 (3)0.060 (3)0.082 (3)−0.017 (2)0.020 (3)−0.033 (2)
C260.044 (2)0.042 (2)0.074 (3)−0.0090 (18)0.008 (2)−0.0013 (19)
C270.036 (2)0.064 (3)0.082 (3)−0.014 (2)0.007 (2)−0.003 (2)
C280.034 (2)0.070 (3)0.075 (3)0.006 (2)0.002 (2)−0.006 (2)
C290.041 (2)0.043 (2)0.068 (3)0.0054 (18)0.001 (2)0.0006 (19)
C300.0360 (19)0.0361 (18)0.0386 (18)−0.0017 (15)0.0025 (15)0.0027 (14)
C310.0361 (19)0.0343 (18)0.0432 (18)−0.0001 (15)0.0020 (15)0.0064 (15)
C320.047 (2)0.036 (2)0.078 (3)0.0011 (18)0.008 (2)0.010 (2)
C330.061 (3)0.042 (2)0.086 (3)−0.017 (2)0.005 (3)0.007 (2)
C340.045 (3)0.058 (3)0.067 (3)−0.018 (2)0.005 (2)0.005 (2)
C350.034 (2)0.060 (3)0.058 (2)−0.0026 (18)0.0016 (18)0.0054 (19)
B10.044 (3)0.089 (4)0.064 (3)0.018 (3)0.005 (2)−0.015 (3)
B20.084 (4)0.090 (4)0.064 (3)0.015 (3)0.016 (3)0.011 (3)
F10.062 (2)0.101 (3)0.390 (8)−0.003 (2)−0.013 (4)−0.062 (4)
F20.077 (2)0.081 (2)0.126 (3)0.0149 (17)0.003 (2)−0.0155 (19)
F30.188 (5)0.254 (6)0.080 (2)0.114 (4)0.061 (3)0.028 (3)
F40.136 (4)0.135 (3)0.078 (2)0.035 (3)−0.021 (2)−0.007 (2)
F50.226 (6)0.130 (4)0.192 (5)−0.100 (4)0.013 (4)−0.006 (3)
F60.122 (4)0.258 (6)0.096 (3)0.089 (4)0.043 (3)0.024 (3)
F70.150 (4)0.114 (3)0.082 (2)−0.055 (3)0.002 (2)0.006 (2)
F80.177 (5)0.263 (6)0.085 (3)0.149 (4)0.026 (3)0.029 (3)
Geometric parameters (Å, °) top
Cu1—N21.928 (3)C14—C151.374 (6)
Cu1—N41.983 (3)C14—H140.9300
Cu1—N32.038 (3)C15—H150.9300
Cu1—N12.062 (3)C16—C201.432 (5)
Cu1—N52.195 (3)C16—C171.436 (5)
Fe1—C252.020 (4)C17—C181.410 (5)
Fe1—C212.023 (5)C17—H170.9300
Fe1—C162.026 (4)C18—C191.418 (6)
Fe1—C222.031 (5)C18—H180.9300
Fe1—C242.035 (4)C19—C201.427 (5)
Fe1—C172.036 (4)C19—H190.9300
Fe1—C202.040 (4)C20—H200.9300
Fe1—C232.047 (4)C21—C221.403 (7)
Fe1—C192.049 (4)C21—C251.406 (7)
Fe1—C182.051 (4)C21—H210.9300
N1—C11.342 (5)C22—C231.401 (7)
N1—C51.346 (5)C22—H220.9300
N2—C101.344 (4)C23—C241.396 (6)
N2—C61.345 (4)C23—H230.9300
N3—C151.335 (5)C24—C251.393 (7)
N3—C111.352 (5)C24—H240.9300
N4—C261.342 (5)C25—H250.9300
N4—C301.356 (4)C26—C271.371 (6)
N5—C351.336 (5)C26—H260.9300
N5—C311.339 (5)C27—C281.350 (6)
C1—C21.373 (6)C27—H270.9300
C1—H10.9300C28—C291.367 (6)
C2—C31.366 (7)C28—H280.9300
C2—H20.9300C29—C301.373 (5)
C3—C41.389 (6)C29—H290.9300
C3—H30.9300C30—C311.484 (5)
C4—C51.376 (5)C31—C321.392 (5)
C4—H40.9300C32—C331.374 (6)
C5—C61.493 (5)C32—H320.9300
C6—C71.376 (5)C33—C341.370 (7)
C7—C81.403 (5)C33—H330.9300
C7—H70.9300C34—C351.380 (6)
C8—C91.397 (5)C34—H340.9300
C8—C161.463 (5)C35—H350.9300
C9—C101.377 (5)B1—F31.306 (6)
C9—H90.9300B1—F11.326 (7)
C10—C111.487 (5)B1—F41.333 (7)
C11—C121.377 (5)B1—F21.367 (7)
C12—C131.385 (6)B2—F61.333 (8)
C12—H120.9300B2—F81.334 (8)
C13—C141.362 (6)B2—F51.336 (9)
C13—H130.9300B2—F71.348 (7)
N2—Cu1—N4170.84 (12)C13—C14—C15119.4 (4)
N2—Cu1—N380.08 (12)C13—C14—H14120.3
N4—Cu1—N399.41 (13)C15—C14—H14120.3
N2—Cu1—N179.52 (12)N3—C15—C14122.2 (4)
N4—Cu1—N199.40 (13)N3—C15—H15118.9
N3—Cu1—N1157.97 (12)C14—C15—H15118.9
N2—Cu1—N5110.34 (12)C20—C16—C17107.1 (3)
N4—Cu1—N578.78 (12)C20—C16—C8126.1 (3)
N3—Cu1—N5100.77 (11)C17—C16—C8126.8 (3)
N1—Cu1—N594.03 (11)C20—C16—Fe169.9 (2)
C25—Fe1—C2140.7 (2)C17—C16—Fe169.6 (2)
C25—Fe1—C16120.98 (18)C8—C16—Fe1125.3 (2)
C21—Fe1—C16107.16 (18)C18—C17—C16108.2 (3)
C25—Fe1—C2268.0 (2)C18—C17—Fe170.4 (2)
C21—Fe1—C2240.5 (2)C16—C17—Fe168.9 (2)
C16—Fe1—C22124.61 (18)C18—C17—H17125.9
C25—Fe1—C2440.2 (2)C16—C17—H17125.9
C21—Fe1—C2467.9 (2)Fe1—C17—H17126.3
C16—Fe1—C24156.34 (17)C17—C18—C19108.9 (3)
C22—Fe1—C2467.7 (2)C17—C18—Fe169.2 (2)
C25—Fe1—C17156.7 (2)C19—C18—Fe169.7 (2)
C21—Fe1—C17120.89 (19)C17—C18—H18125.6
C16—Fe1—C1741.42 (14)C19—C18—H18125.6
C22—Fe1—C17107.37 (18)Fe1—C18—H18127.1
C24—Fe1—C17161.26 (18)C18—C19—C20107.6 (4)
C25—Fe1—C20108.12 (19)C18—C19—Fe169.8 (2)
C21—Fe1—C20125.35 (19)C20—C19—Fe169.2 (2)
C16—Fe1—C2041.23 (15)C18—C19—H19126.2
C22—Fe1—C20162.26 (19)C20—C19—H19126.2
C24—Fe1—C20121.37 (19)Fe1—C19—H19126.3
C17—Fe1—C2068.93 (16)C19—C20—C16108.2 (3)
C25—Fe1—C2367.49 (19)C19—C20—Fe169.9 (2)
C21—Fe1—C2367.7 (2)C16—C20—Fe168.9 (2)
C16—Fe1—C23161.66 (18)C19—C20—H20125.9
C22—Fe1—C2340.2 (2)C16—C20—H20125.9
C24—Fe1—C2339.99 (18)Fe1—C20—H20126.9
C17—Fe1—C23124.69 (17)C22—C21—C25107.5 (5)
C20—Fe1—C23156.05 (18)C22—C21—Fe170.0 (3)
C25—Fe1—C19125.3 (2)C25—C21—Fe169.5 (3)
C21—Fe1—C19162.4 (2)C22—C21—H21126.2
C16—Fe1—C1969.28 (16)C25—C21—H21126.2
C22—Fe1—C19155.5 (2)Fe1—C21—H21125.8
C24—Fe1—C19108.0 (2)C23—C22—C21108.0 (5)
C17—Fe1—C1968.55 (17)C23—C22—Fe170.5 (3)
C20—Fe1—C1940.85 (15)C21—C22—Fe169.5 (3)
C23—Fe1—C19120.97 (19)C23—C22—H22126.0
C25—Fe1—C18161.9 (2)C21—C22—H22126.0
C21—Fe1—C18155.8 (2)Fe1—C22—H22125.6
C16—Fe1—C1868.86 (15)C24—C23—C22108.0 (4)
C22—Fe1—C18120.87 (19)C24—C23—Fe169.5 (3)
C24—Fe1—C18125.24 (19)C22—C23—Fe169.3 (3)
C17—Fe1—C1840.37 (16)C24—C23—H23126.0
C20—Fe1—C1868.30 (16)C22—C23—H23126.0
C23—Fe1—C18108.13 (18)Fe1—C23—H23126.8
C19—Fe1—C1840.46 (17)C25—C24—C23108.2 (5)
C1—N1—C5118.1 (3)C25—C24—Fe169.3 (3)
C1—N1—Cu1127.9 (3)C23—C24—Fe170.5 (3)
C5—N1—Cu1114.0 (2)C25—C24—H24125.9
C10—N2—C6120.6 (3)C23—C24—H24125.9
C10—N2—Cu1119.3 (2)Fe1—C24—H24125.9
C6—N2—Cu1119.9 (2)C24—C25—C21108.2 (5)
C15—N3—C11118.6 (3)C24—C25—Fe170.5 (2)
C15—N3—Cu1127.3 (3)C21—C25—Fe169.8 (3)
C11—N3—Cu1114.0 (2)C24—C25—H25125.9
C26—N4—C30118.2 (3)C21—C25—H25125.9
C26—N4—Cu1123.7 (3)Fe1—C25—H25125.4
C30—N4—Cu1118.1 (2)N4—C26—C27122.2 (4)
C35—N5—C31118.7 (3)N4—C26—H26118.9
C35—N5—Cu1129.7 (3)C27—C26—H26118.9
C31—N5—Cu1111.3 (2)C28—C27—C26119.2 (4)
N1—C1—C2122.5 (4)C28—C27—H27120.4
N1—C1—H1118.8C26—C27—H27120.4
C2—C1—H1118.8C27—C28—C29119.7 (4)
C3—C2—C1119.4 (4)C27—C28—H28120.1
C3—C2—H2120.3C29—C28—H28120.1
C1—C2—H2120.3C28—C29—C30119.6 (4)
C2—C3—C4118.9 (4)C28—C29—H29120.2
C2—C3—H3120.6C30—C29—H29120.2
C4—C3—H3120.6N4—C30—C29121.0 (3)
C5—C4—C3118.9 (4)N4—C30—C31115.5 (3)
C5—C4—H4120.6C29—C30—C31123.5 (3)
C3—C4—H4120.6N5—C31—C32121.3 (4)
N1—C5—C4122.2 (3)N5—C31—C30116.0 (3)
N1—C5—C6114.3 (3)C32—C31—C30122.7 (3)
C4—C5—C6123.5 (4)C33—C32—C31119.1 (4)
N2—C6—C7121.2 (3)C33—C32—H32120.5
N2—C6—C5112.2 (3)C31—C32—H32120.5
C7—C6—C5126.6 (3)C34—C33—C32119.8 (4)
C6—C7—C8119.4 (3)C34—C33—H33120.1
C6—C7—H7120.3C32—C33—H33120.1
C8—C7—H7120.3C33—C34—C35118.1 (4)
C9—C8—C7118.0 (3)C33—C34—H34120.9
C9—C8—C16121.0 (3)C35—C34—H34120.9
C7—C8—C16121.0 (3)N5—C35—C34123.0 (4)
C10—C9—C8120.0 (3)N5—C35—H35118.5
C10—C9—H9120.0C34—C35—H35118.5
C8—C9—H9120.0F3—B1—F1109.7 (6)
N2—C10—C9120.7 (3)F3—B1—F4107.2 (5)
N2—C10—C11112.2 (3)F1—B1—F4109.5 (6)
C9—C10—C11127.0 (3)F3—B1—F2112.6 (6)
N3—C11—C12121.6 (3)F1—B1—F2108.4 (4)
N3—C11—C10114.3 (3)F4—B1—F2109.3 (5)
C12—C11—C10124.0 (4)F6—B2—F8109.2 (5)
C11—C12—C13118.8 (4)F6—B2—F5114.3 (7)
C11—C12—H12120.6F8—B2—F5112.5 (7)
C13—C12—H12120.6F6—B2—F7110.1 (6)
C14—C13—C12119.3 (4)F8—B2—F7106.5 (6)
C14—C13—H13120.4F5—B2—F7103.9 (5)
C12—C13—H13120.4
N2—Cu1—N1—C1178.9 (3)C22—Fe1—C19—C18−48.1 (6)
N4—Cu1—N1—C18.1 (3)C24—Fe1—C19—C18−123.6 (3)
N3—Cu1—N1—C1156.5 (3)C17—Fe1—C19—C1836.8 (2)
N5—Cu1—N1—C1−71.2 (3)C20—Fe1—C19—C18119.0 (4)
N2—Cu1—N1—C5−4.0 (2)C23—Fe1—C19—C18−81.7 (3)
N4—Cu1—N1—C5−174.7 (2)C25—Fe1—C19—C2076.3 (3)
N3—Cu1—N1—C5−26.3 (5)C21—Fe1—C19—C2043.7 (7)
N5—Cu1—N1—C5106.0 (2)C16—Fe1—C19—C20−37.6 (2)
N3—Cu1—N2—C10−0.8 (3)C22—Fe1—C19—C20−167.1 (4)
N1—Cu1—N2—C10−172.5 (3)C24—Fe1—C19—C20117.4 (3)
N5—Cu1—N2—C1097.1 (3)C17—Fe1—C19—C20−82.2 (3)
N3—Cu1—N2—C6174.5 (3)C23—Fe1—C19—C20159.3 (2)
N1—Cu1—N2—C62.8 (3)C18—Fe1—C19—C20−119.0 (4)
N5—Cu1—N2—C6−87.6 (3)C18—C19—C20—C16−1.2 (4)
N2—Cu1—N3—C15−178.5 (3)Fe1—C19—C20—C1658.3 (3)
N4—Cu1—N3—C15−7.7 (3)C18—C19—C20—Fe1−59.5 (3)
N1—Cu1—N3—C15−156.1 (3)C17—C16—C20—C191.0 (4)
N5—Cu1—N3—C1572.5 (3)C8—C16—C20—C19−178.6 (3)
N2—Cu1—N3—C110.9 (2)Fe1—C16—C20—C19−59.0 (3)
N4—Cu1—N3—C11171.6 (2)C17—C16—C20—Fe160.0 (2)
N1—Cu1—N3—C1123.2 (5)C8—C16—C20—Fe1−119.6 (4)
N5—Cu1—N3—C11−108.1 (2)C25—Fe1—C20—C19−123.4 (3)
N3—Cu1—N4—C26−77.3 (3)C21—Fe1—C20—C19−165.2 (3)
N1—Cu1—N4—C2691.2 (3)C16—Fe1—C20—C19119.9 (3)
N5—Cu1—N4—C26−176.6 (3)C22—Fe1—C20—C19162.3 (6)
N3—Cu1—N4—C30103.6 (3)C24—Fe1—C20—C19−81.3 (3)
N1—Cu1—N4—C30−87.9 (3)C17—Fe1—C20—C1981.2 (3)
N5—Cu1—N4—C304.4 (3)C23—Fe1—C20—C19−48.3 (5)
N2—Cu1—N5—C350.2 (4)C18—Fe1—C20—C1937.7 (3)
N4—Cu1—N5—C35−178.9 (4)C25—Fe1—C20—C16116.6 (3)
N3—Cu1—N5—C3583.5 (3)C21—Fe1—C20—C1674.9 (3)
N1—Cu1—N5—C35−80.1 (3)C22—Fe1—C20—C1642.4 (7)
N2—Cu1—N5—C31174.1 (2)C24—Fe1—C20—C16158.7 (2)
N4—Cu1—N5—C31−5.0 (2)C17—Fe1—C20—C16−38.8 (2)
N3—Cu1—N5—C31−102.6 (3)C23—Fe1—C20—C16−168.2 (4)
N1—Cu1—N5—C3193.8 (3)C19—Fe1—C20—C16−119.9 (3)
C5—N1—C1—C21.0 (5)C18—Fe1—C20—C16−82.3 (2)
Cu1—N1—C1—C2178.0 (3)C25—Fe1—C21—C22118.5 (4)
N1—C1—C2—C3−0.9 (6)C16—Fe1—C21—C22−123.6 (3)
C1—C2—C3—C4−0.2 (6)C24—Fe1—C21—C2281.0 (3)
C2—C3—C4—C51.3 (6)C17—Fe1—C21—C22−80.5 (3)
C1—N1—C5—C40.2 (5)C20—Fe1—C21—C22−165.4 (3)
Cu1—N1—C5—C4−177.2 (3)C23—Fe1—C21—C2237.6 (3)
C1—N1—C5—C6−178.2 (3)C19—Fe1—C21—C22160.9 (6)
Cu1—N1—C5—C64.4 (4)C18—Fe1—C21—C22−47.1 (6)
C3—C4—C5—N1−1.4 (6)C16—Fe1—C21—C25117.8 (3)
C3—C4—C5—C6176.9 (4)C22—Fe1—C21—C25−118.5 (4)
C10—N2—C6—C7−3.6 (5)C24—Fe1—C21—C25−37.5 (3)
Cu1—N2—C6—C7−178.9 (3)C17—Fe1—C21—C25161.0 (3)
C10—N2—C6—C5173.9 (3)C20—Fe1—C21—C2576.1 (3)
Cu1—N2—C6—C5−1.3 (4)C23—Fe1—C21—C25−80.9 (3)
N1—C5—C6—N2−2.2 (4)C19—Fe1—C21—C2542.4 (8)
C4—C5—C6—N2179.5 (3)C18—Fe1—C21—C25−165.7 (4)
N1—C5—C6—C7175.2 (3)C25—C21—C22—C23−0.6 (5)
C4—C5—C6—C7−3.1 (6)Fe1—C21—C22—C23−60.3 (3)
N2—C6—C7—C81.4 (5)C25—C21—C22—Fe159.7 (3)
C5—C6—C7—C8−175.8 (3)C25—Fe1—C22—C2380.7 (3)
C6—C7—C8—C91.0 (5)C21—Fe1—C22—C23118.9 (4)
C6—C7—C8—C16178.4 (3)C16—Fe1—C22—C23−166.0 (3)
C7—C8—C9—C10−1.1 (5)C24—Fe1—C22—C2337.1 (3)
C16—C8—C9—C10−178.5 (3)C17—Fe1—C22—C23−123.6 (3)
C6—N2—C10—C93.5 (5)C20—Fe1—C22—C23161.4 (5)
Cu1—N2—C10—C9178.8 (3)C19—Fe1—C22—C23−47.4 (6)
C6—N2—C10—C11−174.7 (3)C18—Fe1—C22—C23−81.6 (3)
Cu1—N2—C10—C110.6 (4)C25—Fe1—C22—C21−38.2 (3)
C8—C9—C10—N2−1.1 (5)C16—Fe1—C22—C2175.2 (3)
C8—C9—C10—C11176.8 (3)C24—Fe1—C22—C21−81.7 (3)
C15—N3—C11—C12−0.6 (5)C17—Fe1—C22—C21117.5 (3)
Cu1—N3—C11—C12180.0 (3)C20—Fe1—C22—C2142.5 (7)
C15—N3—C11—C10178.6 (3)C23—Fe1—C22—C21−118.9 (4)
Cu1—N3—C11—C10−0.8 (4)C19—Fe1—C22—C21−166.2 (4)
N2—C10—C11—N30.2 (4)C18—Fe1—C22—C21159.5 (3)
C9—C10—C11—N3−177.8 (3)C21—C22—C23—C240.7 (5)
N2—C10—C11—C12179.4 (3)Fe1—C22—C23—C24−58.9 (3)
C9—C10—C11—C121.3 (6)C21—C22—C23—Fe159.6 (3)
N3—C11—C12—C131.3 (6)C25—Fe1—C23—C2437.6 (3)
C10—C11—C12—C13−177.8 (3)C21—Fe1—C23—C2481.7 (3)
C11—C12—C13—C14−1.0 (6)C16—Fe1—C23—C24158.9 (5)
C12—C13—C14—C150.0 (7)C22—Fe1—C23—C24119.6 (4)
C11—N3—C15—C14−0.4 (6)C17—Fe1—C23—C24−165.2 (3)
Cu1—N3—C15—C14178.9 (3)C20—Fe1—C23—C24−46.5 (5)
C13—C14—C15—N30.8 (7)C19—Fe1—C23—C24−81.2 (3)
C9—C8—C16—C20−4.6 (6)C18—Fe1—C23—C24−123.7 (3)
C7—C8—C16—C20178.1 (3)C25—Fe1—C23—C22−82.1 (3)
C9—C8—C16—C17175.8 (3)C21—Fe1—C23—C22−37.9 (3)
C7—C8—C16—C17−1.5 (6)C16—Fe1—C23—C2239.3 (7)
C9—C8—C16—Fe1−94.4 (4)C24—Fe1—C23—C22−119.6 (4)
C7—C8—C16—Fe188.3 (4)C17—Fe1—C23—C2275.1 (3)
C25—Fe1—C16—C20−82.3 (3)C20—Fe1—C23—C22−166.1 (4)
C21—Fe1—C16—C20−124.5 (3)C19—Fe1—C23—C22159.2 (3)
C22—Fe1—C16—C20−165.6 (3)C18—Fe1—C23—C22116.7 (3)
C24—Fe1—C16—C20−50.5 (5)C22—C23—C24—C25−0.5 (5)
C17—Fe1—C16—C20118.0 (3)Fe1—C23—C24—C25−59.3 (3)
C23—Fe1—C16—C20164.7 (5)C22—C23—C24—Fe158.8 (3)
C19—Fe1—C16—C2037.3 (2)C21—Fe1—C24—C2538.0 (3)
C18—Fe1—C16—C2080.8 (2)C16—Fe1—C24—C25−44.4 (6)
C25—Fe1—C16—C17159.8 (3)C22—Fe1—C24—C2581.9 (4)
C21—Fe1—C16—C17117.5 (3)C17—Fe1—C24—C25159.9 (5)
C22—Fe1—C16—C1776.5 (3)C20—Fe1—C24—C25−80.9 (4)
C24—Fe1—C16—C17−168.5 (4)C23—Fe1—C24—C25119.2 (5)
C20—Fe1—C16—C17−118.0 (3)C19—Fe1—C24—C25−123.8 (3)
C23—Fe1—C16—C1746.7 (6)C18—Fe1—C24—C25−165.2 (3)
C19—Fe1—C16—C17−80.7 (2)C25—Fe1—C24—C23−119.2 (5)
C18—Fe1—C16—C17−37.2 (2)C21—Fe1—C24—C23−81.2 (3)
C25—Fe1—C16—C838.4 (4)C16—Fe1—C24—C23−163.6 (4)
C21—Fe1—C16—C8−3.8 (4)C22—Fe1—C24—C23−37.3 (3)
C22—Fe1—C16—C8−44.9 (4)C17—Fe1—C24—C2340.7 (7)
C24—Fe1—C16—C870.2 (6)C20—Fe1—C24—C23159.8 (3)
C17—Fe1—C16—C8−121.3 (4)C19—Fe1—C24—C23117.0 (3)
C20—Fe1—C16—C8120.7 (4)C18—Fe1—C24—C2375.6 (3)
C23—Fe1—C16—C8−74.6 (6)C23—C24—C25—C210.2 (5)
C19—Fe1—C16—C8158.0 (4)Fe1—C24—C25—C21−59.8 (3)
C18—Fe1—C16—C8−158.5 (4)C23—C24—C25—Fe160.0 (3)
C20—C16—C17—C18−0.5 (4)C22—C21—C25—C240.3 (5)
C8—C16—C17—C18179.2 (3)Fe1—C21—C25—C2460.3 (3)
Fe1—C16—C17—C1859.7 (3)C22—C21—C25—Fe1−60.0 (3)
C20—C16—C17—Fe1−60.2 (3)C21—Fe1—C25—C24−118.9 (5)
C8—C16—C17—Fe1119.5 (4)C16—Fe1—C25—C24160.9 (3)
C25—Fe1—C17—C18−167.9 (5)C22—Fe1—C25—C24−81.0 (3)
C21—Fe1—C17—C18159.7 (3)C17—Fe1—C25—C24−163.8 (4)
C16—Fe1—C17—C18−119.5 (3)C20—Fe1—C25—C24117.5 (3)
C22—Fe1—C17—C18117.5 (3)C23—Fe1—C25—C24−37.4 (3)
C24—Fe1—C17—C1846.1 (6)C19—Fe1—C25—C2475.5 (4)
C20—Fe1—C17—C18−80.9 (2)C18—Fe1—C25—C2442.0 (7)
C23—Fe1—C17—C1876.7 (3)C16—Fe1—C25—C21−80.2 (3)
C19—Fe1—C17—C18−36.9 (2)C22—Fe1—C25—C2138.0 (3)
C25—Fe1—C17—C16−48.4 (6)C24—Fe1—C25—C21118.9 (5)
C21—Fe1—C17—C16−80.9 (3)C17—Fe1—C25—C21−44.9 (6)
C22—Fe1—C17—C16−123.0 (2)C20—Fe1—C25—C21−123.6 (3)
C24—Fe1—C17—C16165.5 (5)C23—Fe1—C25—C2181.5 (3)
C20—Fe1—C17—C1638.6 (2)C19—Fe1—C25—C21−165.6 (3)
C23—Fe1—C17—C16−163.8 (2)C18—Fe1—C25—C21161.0 (5)
C19—Fe1—C17—C1682.6 (2)C30—N4—C26—C27−0.3 (6)
C18—Fe1—C17—C16119.5 (3)Cu1—N4—C26—C27−179.3 (3)
C16—C17—C18—C19−0.3 (4)N4—C26—C27—C280.4 (7)
Fe1—C17—C18—C1958.5 (3)C26—C27—C28—C29−0.1 (7)
C16—C17—C18—Fe1−58.8 (2)C27—C28—C29—C30−0.3 (7)
C25—Fe1—C18—C17164.5 (6)C26—N4—C30—C29−0.2 (5)
C21—Fe1—C18—C17−46.8 (5)Cu1—N4—C30—C29178.9 (3)
C16—Fe1—C18—C1738.1 (2)C26—N4—C30—C31177.8 (3)
C22—Fe1—C18—C17−80.4 (3)Cu1—N4—C30—C31−3.1 (4)
C24—Fe1—C18—C17−163.5 (3)C28—C29—C30—N40.5 (6)
C20—Fe1—C18—C1782.6 (2)C28—C29—C30—C31−177.3 (4)
C23—Fe1—C18—C17−122.6 (3)C35—N5—C31—C320.2 (6)
C19—Fe1—C18—C17120.6 (3)Cu1—N5—C31—C32−174.4 (3)
C25—Fe1—C18—C1943.9 (7)C35—N5—C31—C30179.6 (3)
C21—Fe1—C18—C19−167.4 (4)Cu1—N5—C31—C304.9 (4)
C16—Fe1—C18—C19−82.5 (3)N4—C30—C31—N5−1.6 (5)
C22—Fe1—C18—C19159.0 (3)C29—C30—C31—N5176.3 (4)
C24—Fe1—C18—C1975.9 (3)N4—C30—C31—C32177.7 (4)
C17—Fe1—C18—C19−120.6 (3)C29—C30—C31—C32−4.4 (6)
C20—Fe1—C18—C19−38.0 (2)N5—C31—C32—C33−1.3 (6)
C23—Fe1—C18—C19116.8 (3)C30—C31—C32—C33179.4 (4)
C17—C18—C19—C200.9 (4)C31—C32—C33—C342.0 (7)
Fe1—C18—C19—C2059.1 (3)C32—C33—C34—C35−1.6 (7)
C17—C18—C19—Fe1−58.3 (3)C31—N5—C35—C340.2 (6)
C25—Fe1—C19—C18−164.7 (3)Cu1—N5—C35—C34173.7 (3)
C21—Fe1—C19—C18162.7 (6)C33—C34—C35—N50.5 (7)
C16—Fe1—C19—C1881.3 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···F4i0.932.513.306 (5)143
C4—H4···F8ii0.932.403.176 (6)141
C17—H17···F7ii0.932.393.296 (5)165
C13—H13···F3iii0.932.543.140 (6)123
C34—H34···F20.932.483.274 (6)144
C35—H35···F10.932.373.208 (6)149
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z; (iii) x−1/2, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···F4i0.932.513.306 (5)143
C4—H4···F8ii0.932.403.176 (6)141
C17—H17···F7ii0.932.393.296 (5)165
C13—H13···F3iii0.932.543.140 (6)123
C34—H34···F20.932.483.274 (6)144
C35—H35···F10.932.373.208 (6)149
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z; (iii) x−1/2, −y+1/2, z+1/2.
Acknowledgements top

We thank Hengyang Normal University for supporting this study.

references
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