Literature DB >> 24454019

Bis[μ-3,5-bis-(pyridin-2-yl)-1H-pyrazole]-bis-[di-bromido-iron(III)].

Nagisa Katsuta1, Akio Mishima1, Akira Fuyuhiro2, Shinya Hayami3, Satoshi Kawata1.   

Abstract

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 octa-hedrally coordinated by four N atoms of two bpypz(-) ligands and two Br ions. π-π stacking inter-actions [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 mol-ecules.

Entities:  

Year:  2013        PMID： 24454019      PMCID： PMC3884243          DOI： 10.1107/S1600536813026573

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


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 = 873.79 Monoclinic, 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[F 2 > 2σ(F 2)] = 0.023 wR(F 2) = 0.060 S = 1.05 3246 reflections 181 parameters H-atom parameters constrained Δρmax = 0.70 e Å−3 Δρmin = −0.46 e Å−3 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. Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S1600536813026573/is5304sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026573/is5304Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[Fe2(C13H9N4)2Br4]F(000) = 1688.00
Mr = 873.79Dx = 2.047 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2ycCell parameters from 3978 reflections
a = 18.180 (4) Åθ = 3.1–27.5°
b = 14.857 (3) ŵ = 6.71 mm−1
c = 10.530 (3) ÅT = 110 K
β = 94.646 (3)°Block, black
V = 2834.7 (10) Å30.10 × 0.10 × 0.10 mm
Z = 4
Rigaku Saturn724 diffractometer2730 reflections with F2 > 2σ(F2)
Detector resolution: 7.111 pixels mm-1Rint = 0.031
ω scansθmax = 27.5°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)h = −23→23
Tmin = 0.408, Tmax = 0.511k = −19→18
16288 measured reflectionsl = −13→13
3246 independent reflections
Refinement on F2Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0344P)2] where P = (Fo2 + 2Fc2)/3
3246 reflections(Δ/σ)max = 0.001
181 parametersΔρmax = 0.70 e Å−3
0 restraintsΔρmin = −0.46 e Å−3
Primary atom site location: structure-invariant direct methods
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).
xyzUiso*/Ueq
Br10.443797 (14)0.261741 (15)0.48610 (2)0.01790 (7)
Br20.229060 (14)0.271406 (15)0.16980 (2)0.01985 (8)
Fe10.323234 (19)0.26281 (2)0.35150 (3)0.01290 (9)
N10.35940 (11)0.39427 (12)0.28651 (17)0.0132 (4)
N20.27110 (11)0.35166 (12)0.46615 (17)0.0127 (4)
N30.22342 (11)0.34385 (12)0.55761 (17)0.0129 (4)
N40.13421 (11)0.35514 (12)0.74213 (18)0.0142 (4)
C10.40369 (13)0.41136 (16)0.1936 (3)0.0170 (5)
C20.42317 (13)0.49806 (17)0.1611 (3)0.0189 (6)
C30.39704 (14)0.56992 (16)0.2285 (3)0.0183 (5)
C40.35166 (13)0.55314 (16)0.3250 (3)0.0162 (5)
C50.33295 (12)0.46438 (15)0.3509 (2)0.0125 (5)
C60.28327 (13)0.44061 (14)0.4473 (2)0.0115 (5)
C70.24257 (12)0.49193 (15)0.5276 (2)0.0133 (5)
C80.20575 (12)0.42818 (14)0.5948 (2)0.0116 (5)
C90.15481 (12)0.43495 (15)0.6951 (2)0.0122 (5)
C100.13052 (13)0.51621 (15)0.7420 (3)0.0149 (5)
C110.08420 (13)0.51551 (16)0.8403 (3)0.0181 (6)
C120.06344 (14)0.43331 (16)0.8892 (3)0.0186 (5)
C130.08932 (14)0.35518 (16)0.8374 (3)0.0186 (6)
H10.42240.36220.14840.0204*
H20.45390.50810.09360.0227*
H30.41020.62990.20870.0220*
H40.33350.60130.37290.0195*
H50.24060.55560.53470.0160*
H60.14550.57160.70700.0179*
H70.06700.57030.87370.0218*
H80.03200.43090.95690.0223*
H90.07480.29910.87060.0224*
U11U22U33U12U13U23
Br10.01636 (13)0.01757 (13)0.02030 (13)0.00300 (9)0.00476 (9)−0.00269 (9)
Br20.02435 (15)0.01322 (13)0.02169 (14)−0.00149 (10)0.00004 (10)0.00022 (9)
Fe10.01458 (18)0.00915 (17)0.01610 (17)−0.00004 (13)0.00820 (13)−0.00050 (12)
N10.0134 (10)0.0127 (10)0.0140 (10)−0.0010 (8)0.0045 (8)0.0016 (8)
N20.0145 (10)0.0101 (9)0.0147 (10)0.0001 (8)0.0079 (8)−0.0001 (8)
N30.0127 (10)0.0106 (10)0.0163 (10)0.0013 (8)0.0067 (8)−0.0006 (8)
N40.0158 (11)0.0105 (9)0.0172 (10)0.0010 (8)0.0066 (8)−0.0020 (8)
C10.0157 (13)0.0196 (13)0.0164 (12)−0.0010 (10)0.0055 (10)−0.0006 (10)
C20.0122 (12)0.0284 (14)0.0166 (12)−0.0046 (11)0.0033 (10)0.0067 (11)
C30.0185 (13)0.0155 (12)0.0210 (13)−0.0039 (10)0.0010 (11)0.0075 (10)
C40.0167 (13)0.0126 (12)0.0194 (13)−0.0008 (10)0.0013 (10)0.0021 (10)
C50.0121 (12)0.0124 (12)0.0132 (12)−0.0008 (9)0.0011 (9)0.0021 (9)
C60.0102 (12)0.0097 (11)0.0144 (11)−0.0002 (9)0.0005 (9)−0.0001 (9)
C70.0141 (12)0.0100 (11)0.0157 (12)0.0010 (9)0.0005 (10)−0.0003 (9)
C80.0105 (12)0.0095 (11)0.0148 (11)0.0016 (9)0.0022 (9)−0.0022 (9)
C90.0088 (11)0.0133 (11)0.0146 (11)−0.0010 (9)0.0016 (9)−0.0010 (9)
C100.0141 (12)0.0127 (11)0.0182 (12)−0.0007 (10)0.0026 (10)−0.0022 (9)
C110.0150 (13)0.0178 (13)0.0219 (13)0.0028 (10)0.0032 (10)−0.0070 (10)
C120.0159 (13)0.0223 (13)0.0189 (12)0.0017 (10)0.0092 (10)−0.0026 (10)
C130.0196 (13)0.0158 (12)0.0217 (13)−0.0011 (10)0.0089 (11)−0.0008 (10)
Br1—Fe12.5119 (6)C5—C61.456 (4)
Br2—Fe12.4652 (6)C6—C71.395 (4)
Fe1—N12.1882 (19)C7—C81.386 (4)
Fe1—N22.070 (2)C8—C91.464 (4)
Fe1—N3i2.0683 (19)C9—C101.390 (4)
Fe1—N4i2.183 (2)C10—C111.387 (4)
N1—C11.340 (4)C11—C121.389 (4)
N1—C51.352 (3)C12—C131.381 (4)
N2—N31.352 (3)C1—H10.950
N2—C61.357 (3)C2—H20.950
N3—C81.359 (3)C3—H30.950
N4—C91.350 (3)C4—H40.950
N4—C131.344 (4)C7—H50.950
C1—C21.386 (4)C10—H60.950
C2—C31.387 (4)C11—H70.950
C3—C41.382 (4)C12—H80.950
C4—C51.394 (4)C13—H90.950
N1···C32.778 (3)Br1···H7viii3.2176
N2···N2i3.211 (3)Br1···H8ix3.3070
N2···C93.555 (3)Br1···H9ix2.9039
N3···N3i3.221 (3)Br2···H4ii2.7927
N3···C53.552 (3)Br2···H5iii2.9531
N4···C112.779 (3)Br2···H6iii2.8284
C1···C42.731 (4)N1···H5iii3.3653
C2···C52.732 (4)N2···H3vi3.4557
C4···C73.162 (4)N2···H6iii3.5987
C7···C103.181 (4)N3···H7iii3.5460
C9···C122.736 (4)C1···H1iv3.5269
C10···C132.723 (4)C1···H2iv3.5841
Br2···C4ii3.562 (3)C1···H4iii3.5173
C1···C7iii3.587 (4)C1···H5iii3.3217
C2···C2iv3.235 (4)C2···H2iv3.2792
C2···C3iv3.544 (4)C2···H5iii3.5654
C2···C5iii3.578 (4)C3···H2iv3.2970
C2···C6iii3.382 (4)C4···H2vi3.3814
C2···C7iii3.468 (4)C5···H2vi3.2600
C3···C2iv3.544 (4)C6···H2vi3.4358
C3···C6iii3.476 (4)C6···H6iii3.4177
C3···C7iii3.499 (4)C7···H7iii3.5827
C4···Br2v3.562 (3)C8···H7iii3.2916
C4···C8iii3.456 (4)C10···H8iii3.4589
C5···C2vi3.578 (4)C11···H5vi3.5274
C6···C2vi3.382 (4)C11···H7vii3.5058
C6···C3vi3.476 (4)C11···H8x3.2231
C6···C10iii3.438 (4)C12···H5vi3.4559
C7···C1vi3.587 (4)C12···H6vi3.5530
C7···C2vi3.468 (4)C12···H7x3.5799
C7···C3vi3.499 (4)C12···H8x3.1884
C7···C10iii3.496 (4)C13···H5vi3.5645
C7···C11iii3.357 (4)H1···Br1iv3.2719
C8···C4vi3.456 (4)H1···C1iv3.5269
C8···C11iii3.436 (4)H1···H1iv3.3987
C10···C6vi3.438 (4)H1···H4iii3.2504
C10···C7vi3.496 (4)H2···C1iv3.5841
C11···C7vi3.357 (4)H2···C2iv3.2792
C11···C8vi3.436 (4)H2···C3iv3.2970
C11···C11vii3.471 (4)H2···C4iii3.3814
C12···C12vii3.580 (4)H2···C5iii3.2600
Fe1···H13.2605H2···C6iii3.4358
Fe1···H9i3.2336H2···H2iv3.5717
N1···H23.2407H2···H2xi2.7001
N1···H43.2527H2···H3iv3.5888
N1···H9i3.5694H2···H4iii3.4658
N2···H53.1742H3···Br1iii2.9480
N3···H53.1726H3···N2iii3.4557
N4···H63.2453H3···H2iv3.5888
N4···H83.2424H3···H3iv3.3113
C1···H33.2521H4···Br2v2.7927
C1···H9i3.2291H4···C1vi3.5173
C2···H43.2519H4···H1vi3.2504
C3···H13.2422H4···H2vi3.4658
C4···H23.2513H5···Br2vi2.9531
C4···H53.1113H5···N1vi3.3653
C5···H13.1713H5···C1vi3.3217
C5···H33.2556H5···C2vi3.5654
C5···H52.9888H5···C11iii3.5274
C6···H42.6951H5···C12iii3.4559
C7···H42.9097H5···C13iii3.5645
C7···H62.9367H6···Br2vi2.8284
C8···H62.7104H6···N2vi3.5987
C9···H52.9872H6···C6vi3.4177
C9···H73.2585H6···C12iii3.5530
C9···H93.1692H6···H8iii3.2113
C10···H53.1329H7···Br1xii3.2176
C10···H83.2546H7···N3vi3.5460
C11···H93.2375H7···C7vi3.5827
C12···H63.2537H7···C8vi3.2916
C13···H1i3.2409H7···C11vii3.5058
C13···H73.2484H7···C12x3.5799
H1···H22.3264H7···H7vii3.4188
H1···H9i2.4051H7···H8x2.6342
H2···H32.3513H8···Br1xiii3.3070
H3···H42.3459H8···C10vi3.4589
H4···H52.5858H8···C11x3.2231
H5···H62.6162H8···C12x3.1884
H6···H72.3505H8···H6vi3.2113
H7···H82.3563H8···H7x2.6342
H8···H92.3194H8···H8x2.5629
Br1···H1iv3.2719H9···Br1xiii2.9039
Br1···H3vi2.9480H9···H9vii3.5667
Br1—Fe1—Br2163.258 (18)C4—C5—C6122.7 (2)
Br1—Fe1—N184.93 (5)N2—C6—C5117.1 (2)
Br1—Fe1—N295.44 (6)N2—C6—C7110.0 (2)
Br1—Fe1—N3i96.08 (6)C5—C6—C7132.8 (2)
Br1—Fe1—N4i85.69 (6)C6—C7—C8103.8 (2)
Br2—Fe1—N185.32 (5)N3—C8—C7110.3 (2)
Br2—Fe1—N295.60 (6)N3—C8—C9116.7 (2)
Br2—Fe1—N3i96.53 (6)C7—C8—C9132.9 (2)
Br2—Fe1—N4i86.58 (6)N4—C9—C8114.5 (2)
N1—Fe1—N277.09 (8)N4—C9—C10121.8 (3)
N1—Fe1—N3i166.76 (8)C8—C9—C10123.6 (2)
N1—Fe1—N4i116.67 (8)C9—C10—C11119.2 (3)
N2—Fe1—N3i89.68 (8)C10—C11—C12118.9 (3)
N2—Fe1—N4i166.23 (8)C11—C12—C13118.8 (3)
N3i—Fe1—N4i76.56 (8)N4—C13—C12122.8 (3)
Fe1—N1—C1127.64 (16)N1—C1—H1118.756
Fe1—N1—C5113.76 (15)C2—C1—H1118.757
C1—N1—C5118.6 (2)C1—C2—H2120.548
Fe1—N2—N3135.33 (14)C3—C2—H2120.549
Fe1—N2—C6116.60 (16)C2—C3—H3120.420
N3—N2—C6108.03 (18)C4—C3—H3120.433
Fe1i—N3—N2134.91 (14)C3—C4—H4120.531
Fe1i—N3—C8117.24 (16)C5—C4—H4120.537
N2—N3—C8107.84 (18)C6—C7—H5128.129
Fe1i—N4—C9114.88 (16)C8—C7—H5128.117
Fe1i—N4—C13126.62 (16)C9—C10—H6120.378
C9—N4—C13118.5 (2)C11—C10—H6120.397
N1—C1—C2122.5 (3)C10—C11—H7120.565
C1—C2—C3118.9 (3)C12—C11—H7120.574
C2—C3—C4119.1 (3)C11—C12—H8120.618
C3—C4—C5118.9 (3)C13—C12—H8120.606
N1—C5—C4121.9 (2)N4—C13—H9118.594
N1—C5—C6115.4 (2)C12—C13—H9118.589
Br1—Fe1—N1—C184.08 (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—C7177.79 (11)
Br1—Fe1—N2—C683.63 (12)N3—N2—C6—C5−179.43 (16)
Br1—Fe1—N3i—N2i98.43 (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—C9i94.73 (12)C6—N2—N3—C80.4 (2)
Br1—Fe1—N4i—C13i−83.63 (14)Fe1i—N3—C8—C7178.53 (11)
Br2—Fe1—N1—C1−82.30 (14)Fe1i—N3—C8—C9−0.5 (3)
Br2—Fe1—N1—C598.13 (11)N2—N3—C8—C7−0.4 (3)
Br2—Fe1—N2—N393.51 (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—C10178.07 (13)
Br2—Fe1—N3i—C8i85.95 (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—C13i81.51 (14)C13—N4—C9—C8177.94 (18)
N1—Fe1—N2—N3177.39 (18)C13—N4—C9—C10−0.4 (3)
N1—Fe1—N2—C60.12 (12)N1—C1—C2—C31.2 (4)
N2—Fe1—N1—C1−179.14 (16)C1—C2—C3—C4−0.8 (4)
N2—Fe1—N1—C51.29 (11)C2—C3—C4—C5−0.6 (4)
N1—Fe1—N4i—C9i176.84 (11)C3—C4—C5—N11.7 (4)
N1—Fe1—N4i—C13i−1.51 (18)C3—C4—C5—C6−177.58 (19)
N4i—Fe1—N1—C11.50 (17)N1—C5—C6—N22.6 (3)
N4i—Fe1—N1—C5−178.07 (10)N1—C5—C6—C7−176.4 (2)
N2—Fe1—N3i—N2i3.00 (17)C4—C5—C6—N2−178.08 (19)
N2—Fe1—N3i—C8i−178.45 (13)C4—C5—C6—C72.9 (4)
N3i—Fe1—N2—N3−3.02 (17)N2—C6—C7—C8−0.0 (3)
N3i—Fe1—N2—C6179.70 (13)C5—C6—C7—C8179.0 (3)
N3i—Fe1—N4i—C9i−2.58 (12)C6—C7—C8—N30.3 (3)
N3i—Fe1—N4i—C13i179.07 (16)C6—C7—C8—C9179.0 (2)
N4i—Fe1—N3i—N2i−177.49 (18)N3—C8—C9—N42.7 (3)
N4i—Fe1—N3i—C8i1.06 (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—C4178.28 (13)C7—C8—C9—C102.3 (4)
Fe1—N1—C5—C6−2.4 (2)N4—C9—C10—C110.4 (4)
C1—N1—C5—C4−1.3 (3)C8—C9—C10—C11−177.79 (18)
C1—N1—C5—C6177.99 (17)C9—C10—C11—C120.0 (4)
C5—N1—C1—C2−0.2 (3)C10—C11—C12—C13−0.4 (4)
Fe1—N2—N3—Fe1i4.3 (4)C11—C12—C13—N40.4 (4)
Table 1

Selected bond lengths (Å)

Br1—Fe12.5119 (6)
Br2—Fe12.4652 (6)
Fe1—N12.1882 (19)
Fe1—N22.070 (2)
Fe1—N3i 2.0683 (19)
Fe1—N4i 2.183 (2)

Symmetry code: (i) .

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4.  An [Fe(II) (3)O](4+) core wrapped by two [Fe(II)L(3)](-) units.

Authors:  Ko Yoneda; Keiichi Adachi; Kyonosuke Nishio; Mikio Yamasaki; Akira Fuyuhiro; Motomi Katada; Sumio Kaizaki; Satoshi Kawata
Journal:  Angew Chem Int Ed Engl       Date:  2006-08-18       Impact factor: 15.336

5.  Bis[μ-3,5-bis-(2-pyrid-yl)pyrazolato]bis-(hydrogensulfato)-dicopper(II) methanol disolvate.

Authors:  Akio Mishima; Akira Fuyuhiro; Hitoshi Kumagai; Satoshi Kawata
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2011-10-12
  5 in total

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