Bis[μ-3,5-bis­(pyridin-2-yl)-1H-pyrazole]­bis­[di­bromido­iron(III)]

Katsuta, N.; Mishima, A.; Fuyuhiro, A.; Hayami, S.; Kawata, S.

doi:10.1107/S1600536813026573

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page m574

doi:10.1107/S1600536813026573

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Bis[μ-3,5-bis(pyridin-2-yl)-1H-pyrazole]bis[dibromidoiron(III)]

Nagisa Katsuta,^a Akio Mishima,^a Akira Fuyuhiro,^b Shinya Hayami ^c and Satoshi Kawata ^a ^*

^aDepartment of Chemistry, Faculty of Science, Fukuoka University, Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan, ^bDepartment of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, and ^cDepartment of Chemistry, Graduate School of Science and Technology, Kumamoto University, Kurokami, Kumamoto 860-8555, Japan
^*Correspondence e-mail: kawata@fukuoka-u.ac.jp

(Received 9 September 2013; accepted 26 September 2013; online 2 October 2013)

The title dinuclear complex, [Fe₂Br₄(C₁₃H₉N₄)₂], which lies on an inversion center, features two approximately planar bis(pyridin-2-yl)pyrazole (bpypz⁻) ligands [maximum deviation = 0.082 (3) Å] and four bromide ions. Each Fe^III ion is octahedrally coordinated by four N atoms of two bpypz⁻ ligands and two Br ions. π–π stacking interactions [centroid–centroid distances = 3.7004 (17)–4.0123 (18) Å] are observed between pyridyl and pyrazole rings, and between pyridyl and pyridyl rings of adjacent complex molecules.

CCDC reference: 963325

Related literature

For metal complexes of 3,5-bis(pyridin-2-yl)pyrazole, see: Yoneda, Adachi, Hayami et al. (2006 ); Yoneda, Adachi, Nishio et al. (2006 ); Ishikawa et al. (2010 ); Mishima et al. (2011 ); Washizaki et al. (2012 ).

Experimental

Crystal data

[Fe₂(C₁₃H₉N₄)₂Br₄]
M_r = 873.79
Monoclinic, C 2/c
a = 18.180 (4) Å
b = 14.857 (3) Å
c = 10.530 (3) Å
β = 94.646 (3)°
V = 2834.7 (10) Å³
Z = 4
Mo Kα radiation
μ = 6.71 mm⁻¹
T = 110 K
0.10 × 0.10 × 0.10 mm

Data collection

Rigaku Saturn724 diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ) T_min = 0.408, T_max = 0.511
16288 measured reflections
3246 independent reflections
2730 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.060
S = 1.05
3246 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Selected bond lengths (Å)

Br1—Fe1	2.5119 (6)
Br2—Fe1	2.4652 (6)
Fe1—N1	2.1882 (19)
Fe1—N2	2.070 (2)
Fe1—N3ⁱ	2.0683 (19)
Fe1—N4ⁱ	2.183 (2)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010 ); software used to prepare material for publication: CrystalStructure.

Supporting information

CCDC reference: 963325

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536813026573/is5304sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026573/is5304Isup2.hkl

checkCIF report

Comment top

3,5-Bis(pyridin-2-yl)pyrazole[Hbpypz] is a versatile ligand in the construction of a series of mononuclear, dinuclear and polynuclear complexes (Yoneda, Adachi, Hayami et al., 2006; Yoneda, Adachi, Nishio et al., 2006; Ishikawa et al., 2010). The dinuclear complexes show the structure where two bpypz^- ions are bridging two metal ions with the axial coordination sites. This kind of dinuclear complexes with transition metal ions were reported previously (Mishima et al., 2011; Washizaki et al., 2012). We have succeeded in synthesizing the title compound that contains iron(III) ion for the first time. To the best of our knowledge, similar compounds with the only iron(II) ions in it (Yoneda, Adachi, Hayami et al., 2006; Yoneda, Adachi, Nishio et al., 2006). In the dinuclear complex, four N donors from two deprotonated tetrahedral bridging bpypz^- ligands make an equatorial plane (Table 1). The iron(III) ions are six-coordinated and the axial positions are occupied by bromide ions. From the Mössbauer measurement, the valence of all iron ions is trivalent. There are π–π stacking interactions between pyridyl and pyrazole rings and between pyridyl and pyridyl rings [centroid-centroid distances 3.7004 (17) Å, 4.0123 (18) Å and 4.0022 (18) Å] to form a three-dimensional structure.

Related literature top

For metal complexes of 3,5-bis(pyridin-2-yl)pyrazole, see: Yoneda, Adachi, Hayami et al. (2006); Yoneda, Adachi, Nishio et al. (2006); Ishikawa et al. (2010); Mishima et al. (2011); Washizaki et al. (2012).

Experimental top

A methanolic solution of FeBr₃ (5 ml, 5 mmolL^-1) was transferred to a glass tube, and methanolic solution of Hbpypz (5 ml, 5 mmolL^-1) was poured into the glass tube without mixing the solutions. Black crystals began to form at ambient temperature within one week (yield 58%). Element analysis: calcd (%) for C₂₆H₁₈Fe₂N₈Br₄: C 35.74, H 2.08, N 12.83; found; C 35.97, H 2.26, N 12.67.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures top

	Fig. 1. An ORTEP drawing of the title complex, showing 50% probability displacement elipsoids.
	Fig. 2. A packing diagram of the title compound, viewed along the b axis.

Bis[µ-3,5-bis(pyridin-2-yl)-1H-pyrazole]bis[dibromidoiron(III)] top

Crystal data top

[Fe₂(C₁₃H₉N₄)₂Br₄]	F(000) = 1688.00
M_r = 873.79	D_x = 2.047 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2yc	Cell parameters from 3978 reflections
a = 18.180 (4) Å	θ = 3.1–27.5°
b = 14.857 (3) Å	µ = 6.71 mm⁻¹
c = 10.530 (3) Å	T = 110 K
β = 94.646 (3)°	Block, black
V = 2834.7 (10) Å³	0.10 × 0.10 × 0.10 mm
Z = 4

Data collection top

Rigaku Saturn724 diffractometer	2730 reflections with F² > 2σ(F²)
Detector resolution: 7.111 pixels mm^-1	R_int = 0.031
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −23→23
T_min = 0.408, T_max = 0.511	k = −19→18
16288 measured reflections	l = −13→13
3246 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0344P)²] where P = (F_o² + 2F_c²)/3
3246 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

[Fe₂(C₁₃H₉N₄)₂Br₄]	V = 2834.7 (10) Å³
M_r = 873.79	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.180 (4) Å	µ = 6.71 mm⁻¹
b = 14.857 (3) Å	T = 110 K
c = 10.530 (3) Å	0.10 × 0.10 × 0.10 mm
β = 94.646 (3)°

Data collection top

Rigaku Saturn724 diffractometer	3246 independent reflections
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	2730 reflections with F² > 2σ(F²)
T_min = 0.408, T_max = 0.511	R_int = 0.031
16288 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.05	Δρ_max = 0.70 e Å⁻³
3246 reflections	Δρ_min = −0.46 e Å⁻³
181 parameters

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.443797 (14)	0.261741 (15)	0.48610 (2)	0.01790 (7)
Br2	0.229060 (14)	0.271406 (15)	0.16980 (2)	0.01985 (8)
Fe1	0.323234 (19)	0.26281 (2)	0.35150 (3)	0.01290 (9)
N1	0.35940 (11)	0.39427 (12)	0.28651 (17)	0.0132 (4)
N2	0.27110 (11)	0.35166 (12)	0.46615 (17)	0.0127 (4)
N3	0.22342 (11)	0.34385 (12)	0.55761 (17)	0.0129 (4)
N4	0.13421 (11)	0.35514 (12)	0.74213 (18)	0.0142 (4)
C1	0.40369 (13)	0.41136 (16)	0.1936 (3)	0.0170 (5)
C2	0.42317 (13)	0.49806 (17)	0.1611 (3)	0.0189 (6)
C3	0.39704 (14)	0.56992 (16)	0.2285 (3)	0.0183 (5)
C4	0.35166 (13)	0.55314 (16)	0.3250 (3)	0.0162 (5)
C5	0.33295 (12)	0.46438 (15)	0.3509 (2)	0.0125 (5)
C6	0.28327 (13)	0.44061 (14)	0.4473 (2)	0.0115 (5)
C7	0.24257 (12)	0.49193 (15)	0.5276 (2)	0.0133 (5)
C8	0.20575 (12)	0.42818 (14)	0.5948 (2)	0.0116 (5)
C9	0.15481 (12)	0.43495 (15)	0.6951 (2)	0.0122 (5)
C10	0.13052 (13)	0.51621 (15)	0.7420 (3)	0.0149 (5)
C11	0.08420 (13)	0.51551 (16)	0.8403 (3)	0.0181 (6)
C12	0.06344 (14)	0.43331 (16)	0.8892 (3)	0.0186 (5)
C13	0.08932 (14)	0.35518 (16)	0.8374 (3)	0.0186 (6)
H1	0.4224	0.3622	0.1484	0.0204*
H2	0.4539	0.5081	0.0936	0.0227*
H3	0.4102	0.6299	0.2087	0.0220*
H4	0.3335	0.6013	0.3729	0.0195*
H5	0.2406	0.5556	0.5347	0.0160*
H6	0.1455	0.5716	0.7070	0.0179*
H7	0.0670	0.5703	0.8737	0.0218*
H8	0.0320	0.4309	0.9569	0.0223*
H9	0.0748	0.2991	0.8706	0.0224*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01636 (13)	0.01757 (13)	0.02030 (13)	0.00300 (9)	0.00476 (9)	−0.00269 (9)
Br2	0.02435 (15)	0.01322 (13)	0.02169 (14)	−0.00149 (10)	0.00004 (10)	0.00022 (9)
Fe1	0.01458 (18)	0.00915 (17)	0.01610 (17)	−0.00004 (13)	0.00820 (13)	−0.00050 (12)
N1	0.0134 (10)	0.0127 (10)	0.0140 (10)	−0.0010 (8)	0.0045 (8)	0.0016 (8)
N2	0.0145 (10)	0.0101 (9)	0.0147 (10)	0.0001 (8)	0.0079 (8)	−0.0001 (8)
N3	0.0127 (10)	0.0106 (10)	0.0163 (10)	0.0013 (8)	0.0067 (8)	−0.0006 (8)
N4	0.0158 (11)	0.0105 (9)	0.0172 (10)	0.0010 (8)	0.0066 (8)	−0.0020 (8)
C1	0.0157 (13)	0.0196 (13)	0.0164 (12)	−0.0010 (10)	0.0055 (10)	−0.0006 (10)
C2	0.0122 (12)	0.0284 (14)	0.0166 (12)	−0.0046 (11)	0.0033 (10)	0.0067 (11)
C3	0.0185 (13)	0.0155 (12)	0.0210 (13)	−0.0039 (10)	0.0010 (11)	0.0075 (10)
C4	0.0167 (13)	0.0126 (12)	0.0194 (13)	−0.0008 (10)	0.0013 (10)	0.0021 (10)
C5	0.0121 (12)	0.0124 (12)	0.0132 (12)	−0.0008 (9)	0.0011 (9)	0.0021 (9)
C6	0.0102 (12)	0.0097 (11)	0.0144 (11)	−0.0002 (9)	0.0005 (9)	−0.0001 (9)
C7	0.0141 (12)	0.0100 (11)	0.0157 (12)	0.0010 (9)	0.0005 (10)	−0.0003 (9)
C8	0.0105 (12)	0.0095 (11)	0.0148 (11)	0.0016 (9)	0.0022 (9)	−0.0022 (9)
C9	0.0088 (11)	0.0133 (11)	0.0146 (11)	−0.0010 (9)	0.0016 (9)	−0.0010 (9)
C10	0.0141 (12)	0.0127 (11)	0.0182 (12)	−0.0007 (10)	0.0026 (10)	−0.0022 (9)
C11	0.0150 (13)	0.0178 (13)	0.0219 (13)	0.0028 (10)	0.0032 (10)	−0.0070 (10)
C12	0.0159 (13)	0.0223 (13)	0.0189 (12)	0.0017 (10)	0.0092 (10)	−0.0026 (10)
C13	0.0196 (13)	0.0158 (12)	0.0217 (13)	−0.0011 (10)	0.0089 (11)	−0.0008 (10)

Geometric parameters (Å, º) top

Br1—Fe1	2.5119 (6)	C5—C6	1.456 (4)
Br2—Fe1	2.4652 (6)	C6—C7	1.395 (4)
Fe1—N1	2.1882 (19)	C7—C8	1.386 (4)
Fe1—N2	2.070 (2)	C8—C9	1.464 (4)
Fe1—N3ⁱ	2.0683 (19)	C9—C10	1.390 (4)
Fe1—N4ⁱ	2.183 (2)	C10—C11	1.387 (4)
N1—C1	1.340 (4)	C11—C12	1.389 (4)
N1—C5	1.352 (3)	C12—C13	1.381 (4)
N2—N3	1.352 (3)	C1—H1	0.950
N2—C6	1.357 (3)	C2—H2	0.950
N3—C8	1.359 (3)	C3—H3	0.950
N4—C9	1.350 (3)	C4—H4	0.950
N4—C13	1.344 (4)	C7—H5	0.950
C1—C2	1.386 (4)	C10—H6	0.950
C2—C3	1.387 (4)	C11—H7	0.950
C3—C4	1.382 (4)	C12—H8	0.950
C4—C5	1.394 (4)	C13—H9	0.950

N1···C3	2.778 (3)	Br1···H7^viii	3.2176
N2···N2ⁱ	3.211 (3)	Br1···H8^ix	3.3070
N2···C9	3.555 (3)	Br1···H9^ix	2.9039
N3···N3ⁱ	3.221 (3)	Br2···H4ⁱⁱ	2.7927
N3···C5	3.552 (3)	Br2···H5ⁱⁱⁱ	2.9531
N4···C11	2.779 (3)	Br2···H6ⁱⁱⁱ	2.8284
C1···C4	2.731 (4)	N1···H5ⁱⁱⁱ	3.3653
C2···C5	2.732 (4)	N2···H3^vi	3.4557
C4···C7	3.162 (4)	N2···H6ⁱⁱⁱ	3.5987
C7···C10	3.181 (4)	N3···H7ⁱⁱⁱ	3.5460
C9···C12	2.736 (4)	C1···H1^iv	3.5269
C10···C13	2.723 (4)	C1···H2^iv	3.5841
Br2···C4ⁱⁱ	3.562 (3)	C1···H4ⁱⁱⁱ	3.5173
C1···C7ⁱⁱⁱ	3.587 (4)	C1···H5ⁱⁱⁱ	3.3217
C2···C2^iv	3.235 (4)	C2···H2^iv	3.2792
C2···C3^iv	3.544 (4)	C2···H5ⁱⁱⁱ	3.5654
C2···C5ⁱⁱⁱ	3.578 (4)	C3···H2^iv	3.2970
C2···C6ⁱⁱⁱ	3.382 (4)	C4···H2^vi	3.3814
C2···C7ⁱⁱⁱ	3.468 (4)	C5···H2^vi	3.2600
C3···C2^iv	3.544 (4)	C6···H2^vi	3.4358
C3···C6ⁱⁱⁱ	3.476 (4)	C6···H6ⁱⁱⁱ	3.4177
C3···C7ⁱⁱⁱ	3.499 (4)	C7···H7ⁱⁱⁱ	3.5827
C4···Br2^v	3.562 (3)	C8···H7ⁱⁱⁱ	3.2916
C4···C8ⁱⁱⁱ	3.456 (4)	C10···H8ⁱⁱⁱ	3.4589
C5···C2^vi	3.578 (4)	C11···H5^vi	3.5274
C6···C2^vi	3.382 (4)	C11···H7^vii	3.5058
C6···C3^vi	3.476 (4)	C11···H8^x	3.2231
C6···C10ⁱⁱⁱ	3.438 (4)	C12···H5^vi	3.4559
C7···C1^vi	3.587 (4)	C12···H6^vi	3.5530
C7···C2^vi	3.468 (4)	C12···H7^x	3.5799
C7···C3^vi	3.499 (4)	C12···H8^x	3.1884
C7···C10ⁱⁱⁱ	3.496 (4)	C13···H5^vi	3.5645
C7···C11ⁱⁱⁱ	3.357 (4)	H1···Br1^iv	3.2719
C8···C4^vi	3.456 (4)	H1···C1^iv	3.5269
C8···C11ⁱⁱⁱ	3.436 (4)	H1···H1^iv	3.3987
C10···C6^vi	3.438 (4)	H1···H4ⁱⁱⁱ	3.2504
C10···C7^vi	3.496 (4)	H2···C1^iv	3.5841
C11···C7^vi	3.357 (4)	H2···C2^iv	3.2792
C11···C8^vi	3.436 (4)	H2···C3^iv	3.2970
C11···C11^vii	3.471 (4)	H2···C4ⁱⁱⁱ	3.3814
C12···C12^vii	3.580 (4)	H2···C5ⁱⁱⁱ	3.2600
Fe1···H1	3.2605	H2···C6ⁱⁱⁱ	3.4358
Fe1···H9ⁱ	3.2336	H2···H2^iv	3.5717
N1···H2	3.2407	H2···H2^xi	2.7001
N1···H4	3.2527	H2···H3^iv	3.5888
N1···H9ⁱ	3.5694	H2···H4ⁱⁱⁱ	3.4658
N2···H5	3.1742	H3···Br1ⁱⁱⁱ	2.9480
N3···H5	3.1726	H3···N2ⁱⁱⁱ	3.4557
N4···H6	3.2453	H3···H2^iv	3.5888
N4···H8	3.2424	H3···H3^iv	3.3113
C1···H3	3.2521	H4···Br2^v	2.7927
C1···H9ⁱ	3.2291	H4···C1^vi	3.5173
C2···H4	3.2519	H4···H1^vi	3.2504
C3···H1	3.2422	H4···H2^vi	3.4658
C4···H2	3.2513	H5···Br2^vi	2.9531
C4···H5	3.1113	H5···N1^vi	3.3653
C5···H1	3.1713	H5···C1^vi	3.3217
C5···H3	3.2556	H5···C2^vi	3.5654
C5···H5	2.9888	H5···C11ⁱⁱⁱ	3.5274
C6···H4	2.6951	H5···C12ⁱⁱⁱ	3.4559
C7···H4	2.9097	H5···C13ⁱⁱⁱ	3.5645
C7···H6	2.9367	H6···Br2^vi	2.8284
C8···H6	2.7104	H6···N2^vi	3.5987
C9···H5	2.9872	H6···C6^vi	3.4177
C9···H7	3.2585	H6···C12ⁱⁱⁱ	3.5530
C9···H9	3.1692	H6···H8ⁱⁱⁱ	3.2113
C10···H5	3.1329	H7···Br1^xii	3.2176
C10···H8	3.2546	H7···N3^vi	3.5460
C11···H9	3.2375	H7···C7^vi	3.5827
C12···H6	3.2537	H7···C8^vi	3.2916
C13···H1ⁱ	3.2409	H7···C11^vii	3.5058
C13···H7	3.2484	H7···C12^x	3.5799
H1···H2	2.3264	H7···H7^vii	3.4188
H1···H9ⁱ	2.4051	H7···H8^x	2.6342
H2···H3	2.3513	H8···Br1^xiii	3.3070
H3···H4	2.3459	H8···C10^vi	3.4589
H4···H5	2.5858	H8···C11^x	3.2231
H5···H6	2.6162	H8···C12^x	3.1884
H6···H7	2.3505	H8···H6^vi	3.2113
H7···H8	2.3563	H8···H7^x	2.6342
H8···H9	2.3194	H8···H8^x	2.5629
Br1···H1^iv	3.2719	H9···Br1^xiii	2.9039
Br1···H3^vi	2.9480	H9···H9^vii	3.5667

Br1—Fe1—Br2	163.258 (18)	C4—C5—C6	122.7 (2)
Br1—Fe1—N1	84.93 (5)	N2—C6—C5	117.1 (2)
Br1—Fe1—N2	95.44 (6)	N2—C6—C7	110.0 (2)
Br1—Fe1—N3ⁱ	96.08 (6)	C5—C6—C7	132.8 (2)
Br1—Fe1—N4ⁱ	85.69 (6)	C6—C7—C8	103.8 (2)
Br2—Fe1—N1	85.32 (5)	N3—C8—C7	110.3 (2)
Br2—Fe1—N2	95.60 (6)	N3—C8—C9	116.7 (2)
Br2—Fe1—N3ⁱ	96.53 (6)	C7—C8—C9	132.9 (2)
Br2—Fe1—N4ⁱ	86.58 (6)	N4—C9—C8	114.5 (2)
N1—Fe1—N2	77.09 (8)	N4—C9—C10	121.8 (3)
N1—Fe1—N3ⁱ	166.76 (8)	C8—C9—C10	123.6 (2)
N1—Fe1—N4ⁱ	116.67 (8)	C9—C10—C11	119.2 (3)
N2—Fe1—N3ⁱ	89.68 (8)	C10—C11—C12	118.9 (3)
N2—Fe1—N4ⁱ	166.23 (8)	C11—C12—C13	118.8 (3)
N3ⁱ—Fe1—N4ⁱ	76.56 (8)	N4—C13—C12	122.8 (3)
Fe1—N1—C1	127.64 (16)	N1—C1—H1	118.756
Fe1—N1—C5	113.76 (15)	C2—C1—H1	118.757
C1—N1—C5	118.6 (2)	C1—C2—H2	120.548
Fe1—N2—N3	135.33 (14)	C3—C2—H2	120.549
Fe1—N2—C6	116.60 (16)	C2—C3—H3	120.420
N3—N2—C6	108.03 (18)	C4—C3—H3	120.433
Fe1ⁱ—N3—N2	134.91 (14)	C3—C4—H4	120.531
Fe1ⁱ—N3—C8	117.24 (16)	C5—C4—H4	120.537
N2—N3—C8	107.84 (18)	C6—C7—H5	128.129
Fe1ⁱ—N4—C9	114.88 (16)	C8—C7—H5	128.117
Fe1ⁱ—N4—C13	126.62 (16)	C9—C10—H6	120.378
C9—N4—C13	118.5 (2)	C11—C10—H6	120.397
N1—C1—C2	122.5 (3)	C10—C11—H7	120.565
C1—C2—C3	118.9 (3)	C12—C11—H7	120.574
C2—C3—C4	119.1 (3)	C11—C12—H8	120.618
C3—C4—C5	118.9 (3)	C13—C12—H8	120.606
N1—C5—C4	121.9 (2)	N4—C13—H9	118.594
N1—C5—C6	115.4 (2)	C12—C13—H9	118.589

Br1—Fe1—N1—C1	84.08 (14)	Fe1—N2—N3—C8	−177.09 (13)
Br1—Fe1—N1—C5	−95.49 (11)	Fe1—N2—C6—C5	−1.4 (3)
Br1—Fe1—N2—N3	−99.09 (17)	Fe1—N2—C6—C7	177.79 (11)
Br1—Fe1—N2—C6	83.63 (12)	N3—N2—C6—C5	−179.43 (16)
Br1—Fe1—N3ⁱ—N2ⁱ	98.43 (16)	N3—N2—C6—C7	−0.2 (3)
Br1—Fe1—N3ⁱ—C8ⁱ	−83.02 (12)	C6—N2—N3—Fe1ⁱ	−178.29 (16)
Br1—Fe1—N4ⁱ—C9ⁱ	94.73 (12)	C6—N2—N3—C8	0.4 (2)
Br1—Fe1—N4ⁱ—C13ⁱ	−83.63 (14)	Fe1ⁱ—N3—C8—C7	178.53 (11)
Br2—Fe1—N1—C1	−82.30 (14)	Fe1ⁱ—N3—C8—C9	−0.5 (3)
Br2—Fe1—N1—C5	98.13 (11)	N2—N3—C8—C7	−0.4 (3)
Br2—Fe1—N2—N3	93.51 (17)	N2—N3—C8—C9	−179.40 (16)
Br2—Fe1—N2—C6	−83.77 (12)	Fe1ⁱ—N4—C9—C8	−3.6 (3)
Br2—Fe1—N3ⁱ—N2ⁱ	−92.60 (16)	Fe1ⁱ—N4—C9—C10	178.07 (13)
Br2—Fe1—N3ⁱ—C8ⁱ	85.95 (12)	Fe1ⁱ—N4—C13—C12	−178.31 (13)
Br2—Fe1—N4ⁱ—C9ⁱ	−100.13 (12)	C9—N4—C13—C12	−0.0 (4)
Br2—Fe1—N4ⁱ—C13ⁱ	81.51 (14)	C13—N4—C9—C8	177.94 (18)
N1—Fe1—N2—N3	177.39 (18)	C13—N4—C9—C10	−0.4 (3)
N1—Fe1—N2—C6	0.12 (12)	N1—C1—C2—C3	1.2 (4)
N2—Fe1—N1—C1	−179.14 (16)	C1—C2—C3—C4	−0.8 (4)
N2—Fe1—N1—C5	1.29 (11)	C2—C3—C4—C5	−0.6 (4)
N1—Fe1—N4ⁱ—C9ⁱ	176.84 (11)	C3—C4—C5—N1	1.7 (4)
N1—Fe1—N4ⁱ—C13ⁱ	−1.51 (18)	C3—C4—C5—C6	−177.58 (19)
N4ⁱ—Fe1—N1—C1	1.50 (17)	N1—C5—C6—N2	2.6 (3)
N4ⁱ—Fe1—N1—C5	−178.07 (10)	N1—C5—C6—C7	−176.4 (2)
N2—Fe1—N3ⁱ—N2ⁱ	3.00 (17)	C4—C5—C6—N2	−178.08 (19)
N2—Fe1—N3ⁱ—C8ⁱ	−178.45 (13)	C4—C5—C6—C7	2.9 (4)
N3ⁱ—Fe1—N2—N3	−3.02 (17)	N2—C6—C7—C8	−0.0 (3)
N3ⁱ—Fe1—N2—C6	179.70 (13)	C5—C6—C7—C8	179.0 (3)
N3ⁱ—Fe1—N4ⁱ—C9ⁱ	−2.58 (12)	C6—C7—C8—N3	0.3 (3)
N3ⁱ—Fe1—N4ⁱ—C13ⁱ	179.07 (16)	C6—C7—C8—C9	179.0 (2)
N4ⁱ—Fe1—N3ⁱ—N2ⁱ	−177.49 (18)	N3—C8—C9—N4	2.7 (3)
N4ⁱ—Fe1—N3ⁱ—C8ⁱ	1.06 (12)	N3—C8—C9—C10	−178.92 (17)
Fe1—N1—C1—C2	−179.70 (13)	C7—C8—C9—N4	−176.0 (2)
Fe1—N1—C5—C4	178.28 (13)	C7—C8—C9—C10	2.3 (4)
Fe1—N1—C5—C6	−2.4 (2)	N4—C9—C10—C11	0.4 (4)
C1—N1—C5—C4	−1.3 (3)	C8—C9—C10—C11	−177.79 (18)
C1—N1—C5—C6	177.99 (17)	C9—C10—C11—C12	0.0 (4)
C5—N1—C1—C2	−0.2 (3)	C10—C11—C12—C13	−0.4 (4)
Fe1—N2—N3—Fe1ⁱ	4.3 (4)	C11—C12—C13—N4	0.4 (4)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x, −y+1, z−1/2; (iv) −x+1, y, −z+1/2; (v) −x+1/2, y+1/2, −z+1/2; (vi) x, −y+1, z+1/2; (vii) −x, y, −z+3/2; (viii) −x+1/2, y−1/2, −z+3/2; (ix) x+1/2, −y+1/2, z−1/2; (x) −x, −y+1, −z+2; (xi) −x+1, −y+1, −z; (xii) −x+1/2, y+1/2, −z+3/2; (xiii) x−1/2, −y+1/2, z+1/2.

Selected bond lengths (Å) top

Br1—Fe1	2.5119 (6)	Fe1—N2	2.070 (2)
Br2—Fe1	2.4652 (6)	Fe1—N3ⁱ	2.0683 (19)
Fe1—N1	2.1882 (19)	Fe1—N4ⁱ	2.183 (2)

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Acknowledgements

This work was supported by the fund Grant-in-Aids for Science Research (No. 25410078) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

References

Ishikawa, R., Nakano, M., Fuyuhiro, A., Takeuchi, T., Kimura, S., Kashiwagi, T., Hagiwara, M., Kindo, K., Kaizaki, S. & Kawata, S. (2010). Chem. Eur. J. 16, 11139–11144. Web of Science CSD CrossRef CAS PubMed Google Scholar
Mishima, A., Fuyuhiro, A., Kumagai, H. & Kawata, S. (2011). Acta Cryst. E67, m1523–m1524. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Washizaki, T., Ishikawa, R., Yoneda, K., Kitagawa, S., Kaizaki, S., Fuyuhiro, A. & Kawata, S. (2012). RSC Adv. 2, 12169–12172. Web of Science CSD CrossRef CAS Google Scholar
Yoneda, K., Adachi, K., Hayami, S., Maeda, Y., Katada, M., Fuyuhiro, A., Kawata, S. & Kaizaki, S. (2006). Chem. Commun. pp. 45–47. Web of Science CSD CrossRef Google Scholar
Yoneda, K., Adachi, K., Nishio, K., Yamasaki, M., Fuyuhiro, A., Kaizaki, S. & Kawata, S. (2006). Angew. Chem. Int. Ed. 45, 5459–5461. Web of Science CSD CrossRef CAS Google Scholar