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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): m402.
Published online 2009 March 14. doi:  10.1107/S1600536809007090
PMCID: PMC2968881

Low-temperature rerefinement of non­merohedrally twinned tripyridinium bis­[tetra­bromidoferrate(III)] bromide

Abstract

The asymmetric unit of the title double salt, (C5H6N)3[FeBr4]2Br, consists of three pyridinium cations, two tetra­hedral bromidoferrate(III) anions and a bromide anion. The three cations each form one N—H(...)Br hydrogen bond to the bromide anion. The crystal under investigation was a non-merohedral twin, with a portion of 22% for the minor twin component.

Related literature

The authors of the original room-temperature study noted twinning but the refinement program then could not take this into consideration; see: Lowe et al. (1994 [triangle]).

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Object name is e-65-0m402-scheme1.jpg

Experimental

Crystal data

  • (C5H6N)3[FeBr4]2Br
  • M r = 1071.21
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m402-efi1.jpg
  • a = 7.5602 (1) Å
  • b = 14.0125 (2) Å
  • c = 13.5609 (2) Å
  • β = 95.172 (1)°
  • V = 1430.76 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 13.59 mm−1
  • T = 123 K
  • 0.30 × 0.25 × 0.20 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.098, T max = 0.154
  • 13428 measured reflections
  • 6460 independent reflections
  • 6006 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.106
  • S = 1.07
  • 6460 reflections
  • 263 parameters
  • 109 restraints
  • H-atom parameters constrained
  • Δρmax = 1.29 e Å−3
  • Δρmin = −1.71 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 3046 Friedel pairs
  • Flack parameter: 0.10 (2)

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]) and PLATON (Spek, 2009 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007090/tk2380sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007090/tk2380Isup2.hkl

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

Acknowledgments

The author thanks the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

The crystals were provided by Dr. Nasser Safari of Shahid Beheshti University. Pyridine (2.2 ml, 25 mmol) was added to a solution of ferric bromide (1.25 g, 4.23 mmol) dissolved in a mixture of 1.2 M hydrobromic acid and 2.4 M acetic acid (20 ml). The red solution was set aside for two weeks, after which crystals separated out.

Refinement

The refinement initally converged to an R1 value of 0.088, but there were large peaks/deep holes. The crystal is in fact a nonmerohedral twin. The law, as given by PLATON (Spek, 2003), is (-1 0 0, 0 - 1 0, 0.323 0 1). The refinement, with an approximate twin component of 22%, halved the R1 index. The twinning affected the anisotropic temperature factors of the carbon and nitrogen atoms; these were restrained to be nearly isotropic.

Carbon- and nitrogen-bound H-atoms were placed in calculated positions (C–H 0.95, N–H 0.88 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C,N).

The final difference Fourier map had large peaks/holes in the vicinity of the bromide atoms.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of [C5H6N]3[FeBr4]2[Br].

Crystal data

(C5H6N)3[FeBr4]2BrF(000) = 992
Mr = 1071.21Dx = 2.487 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 8983 reflections
a = 7.5602 (1) Åθ = 2.7–28.3°
b = 14.0125 (2) ŵ = 13.59 mm1
c = 13.5609 (2) ÅT = 123 K
β = 95.172 (1)°Irregular block, brown
V = 1430.76 (3) Å30.30 × 0.25 × 0.20 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer6460 independent reflections
Radiation source: fine-focus sealed tube6006 reflections with I > 2σ(I)
graphiteRint = 0.038
ω scansθmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.098, Tmax = 0.154k = −18→18
13428 measured reflectionsl = −17→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.106w = 1/[σ2(Fo2) + (0.0502P)2 + 4.7139P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
6460 reflectionsΔρmax = 1.29 e Å3
263 parametersΔρmin = −1.71 e Å3
109 restraintsAbsolute structure: Flack (1983), 3046 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.10 (2)

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

xyzUiso*/Ueq
Br10.27784 (12)0.49992 (6)0.74070 (6)0.02428 (19)
Br20.27108 (13)0.35971 (6)0.50468 (7)0.0250 (2)
Br30.02833 (11)0.60181 (6)0.50814 (7)0.02457 (19)
Br40.52742 (11)0.59765 (7)0.52624 (7)0.0268 (2)
Br50.52708 (11)0.89250 (6)0.95876 (7)0.02335 (19)
Br60.75284 (12)1.00789 (7)0.74713 (6)0.02522 (19)
Br71.02585 (12)0.91096 (8)0.97548 (8)0.0356 (3)
Br80.74006 (15)1.13935 (7)0.98802 (7)0.0350 (2)
Br90.74762 (11)0.65558 (7)0.83903 (6)0.02359 (19)
Fe10.27879 (15)0.51483 (9)0.56879 (9)0.0177 (2)
Fe20.76356 (16)0.98860 (9)0.91855 (9)0.0197 (3)
N10.7426 (11)0.4395 (6)0.7619 (7)0.038 (2)
H10.74270.49310.79590.045*
N20.7876 (12)0.7029 (7)1.0778 (6)0.0343 (19)
H20.79930.72331.01730.041*
N30.3634 (10)0.7457 (5)0.7543 (5)0.0203 (15)
H30.43240.70320.78630.024*
C10.8048 (15)0.4412 (10)0.6741 (9)0.047 (3)
H1A0.84570.49880.64700.056*
C20.8080 (17)0.3569 (11)0.6239 (9)0.054 (3)
H2A0.85820.35490.56220.065*
C30.7408 (16)0.2758 (9)0.6606 (10)0.048 (3)
H3A0.73630.21820.62340.058*
C40.6797 (14)0.2790 (8)0.7523 (9)0.038 (2)
H40.63710.22260.78100.046*
C50.6802 (15)0.3618 (9)0.8016 (7)0.038 (2)
H50.63570.36470.86490.046*
C60.7428 (14)0.6150 (8)1.0919 (7)0.035 (2)
H60.72460.57381.03630.042*
C70.7210 (16)0.5797 (8)1.1832 (9)0.041 (3)
H70.68730.51511.19190.049*
C80.7500 (12)0.6418 (8)1.2642 (7)0.032 (2)
H80.73610.61991.32940.039*
C90.7984 (14)0.7340 (8)1.2482 (7)0.035 (2)
H90.81920.77711.30210.042*
C100.8163 (16)0.7633 (7)1.1548 (8)0.039 (2)
H100.84970.82741.14330.047*
C110.1903 (12)0.7447 (6)0.7669 (6)0.0208 (17)
H110.14350.69890.80920.025*
C120.0815 (12)0.8104 (7)0.7182 (6)0.0260 (18)
H12−0.04200.81020.72620.031*
C130.1503 (13)0.8766 (6)0.6576 (7)0.0256 (19)
H130.07570.92310.62410.031*
C140.3330 (13)0.8744 (6)0.6459 (7)0.0260 (19)
H140.38310.91900.60350.031*
C150.4375 (12)0.8082 (7)0.6956 (7)0.0269 (19)
H150.56140.80620.68880.032*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0313 (4)0.0211 (4)0.0195 (4)−0.0010 (4)−0.0025 (3)−0.0005 (3)
Br20.0325 (5)0.0188 (4)0.0241 (4)−0.0009 (4)0.0039 (4)−0.0032 (3)
Br30.0164 (4)0.0285 (5)0.0285 (4)0.0046 (4)0.0009 (3)0.0077 (4)
Br40.0168 (4)0.0268 (5)0.0369 (5)−0.0041 (4)0.0030 (3)0.0016 (4)
Br50.0181 (4)0.0236 (4)0.0286 (4)−0.0015 (3)0.0038 (3)0.0022 (3)
Br60.0311 (4)0.0272 (4)0.0175 (4)0.0014 (4)0.0031 (3)0.0012 (4)
Br70.0186 (4)0.0520 (7)0.0356 (5)0.0033 (4)−0.0007 (4)0.0137 (5)
Br80.0507 (6)0.0292 (6)0.0246 (5)−0.0099 (5)0.0008 (4)−0.0090 (4)
Br90.0204 (4)0.0272 (5)0.0225 (4)0.0047 (4)−0.0019 (3)−0.0033 (3)
Fe10.0153 (5)0.0167 (6)0.0206 (6)0.0002 (5)−0.0005 (4)−0.0003 (5)
Fe20.0186 (5)0.0230 (6)0.0173 (6)−0.0020 (5)0.0003 (4)0.0008 (5)
N10.025 (4)0.030 (4)0.056 (5)0.003 (3)−0.013 (4)−0.012 (4)
N20.038 (4)0.043 (5)0.023 (4)0.011 (4)0.010 (3)0.009 (3)
N30.020 (3)0.019 (3)0.021 (3)−0.002 (3)−0.006 (3)0.002 (3)
C10.030 (5)0.055 (6)0.055 (6)−0.009 (5)−0.004 (4)0.028 (5)
C20.042 (6)0.083 (8)0.038 (5)0.003 (6)0.009 (5)0.000 (6)
C30.040 (5)0.047 (6)0.056 (6)0.008 (5)−0.005 (5)−0.021 (5)
C40.028 (5)0.028 (5)0.055 (6)−0.007 (4)−0.013 (4)0.016 (4)
C50.036 (5)0.058 (6)0.021 (4)0.001 (5)0.005 (4)−0.002 (4)
C60.043 (5)0.035 (5)0.024 (4)0.013 (4)−0.011 (4)−0.005 (4)
C70.044 (5)0.026 (5)0.051 (6)−0.013 (4)−0.009 (5)0.005 (4)
C80.028 (4)0.045 (5)0.024 (4)0.000 (4)−0.001 (3)0.010 (4)
C90.037 (5)0.039 (5)0.029 (5)−0.002 (4)0.004 (4)−0.013 (4)
C100.049 (5)0.022 (4)0.048 (5)0.002 (4)0.010 (5)0.001 (4)
C110.023 (4)0.019 (4)0.021 (4)−0.002 (3)0.004 (3)−0.001 (3)
C120.023 (4)0.031 (4)0.025 (4)0.001 (4)0.004 (3)−0.004 (3)
C130.027 (4)0.020 (4)0.029 (4)0.008 (4)0.001 (3)0.005 (3)
C140.028 (4)0.020 (4)0.031 (4)−0.010 (3)0.008 (4)0.005 (3)
C150.021 (4)0.032 (4)0.028 (4)−0.007 (4)−0.003 (3)−0.003 (4)

Geometric parameters (Å, °)

Br1—Fe12.341 (2)C3—H3A0.9500
Br2—Fe12.340 (2)C4—C51.340 (16)
Br3—Fe12.338 (1)C4—H40.9500
Br4—Fe12.326 (1)C5—H50.9500
Br5—Fe22.342 (1)C6—C71.357 (15)
Br6—Fe22.335 (1)C6—H60.9500
Br7—Fe22.331 (2)C7—C81.404 (15)
Br8—Fe22.326 (2)C7—H70.9500
N1—C11.319 (15)C8—C91.366 (15)
N1—C51.320 (15)C8—H80.9500
N1—H10.8800C9—C101.349 (15)
N2—C61.296 (14)C9—H90.9500
N2—C101.347 (14)C10—H100.9500
N2—H20.8800C11—C121.364 (13)
N3—C111.335 (11)C11—H110.9500
N3—C151.340 (12)C12—C131.372 (13)
N3—H30.8800C12—H120.9500
C1—C21.36 (2)C13—C141.405 (13)
C1—H1A0.9500C13—H130.9500
C2—C31.357 (19)C14—C151.358 (13)
C2—H2A0.9500C14—H140.9500
C3—C41.366 (17)C15—H150.9500
Br4—Fe1—Br3107.44 (6)N1—C5—C4119.7 (9)
Br4—Fe1—Br2111.41 (6)N1—C5—H5120.2
Br3—Fe1—Br2111.18 (6)C4—C5—H5120.2
Br4—Fe1—Br1111.51 (6)N2—C6—C7122.4 (10)
Br3—Fe1—Br1108.77 (6)N2—C6—H6118.8
Br2—Fe1—Br1106.55 (6)C7—C6—H6118.8
Br8—Fe2—Br7112.54 (6)C6—C7—C8117.7 (10)
Br8—Fe2—Br6107.52 (6)C6—C7—H7121.1
Br7—Fe2—Br6109.63 (6)C8—C7—H7121.1
Br8—Fe2—Br5109.89 (6)C9—C8—C7119.1 (9)
Br7—Fe2—Br5107.40 (6)C9—C8—H8120.4
Br6—Fe2—Br5109.86 (6)C7—C8—H8120.4
C1—N1—C5123.5 (10)C10—C9—C8119.2 (10)
C1—N1—H1118.2C10—C9—H9120.4
C5—N1—H1118.2C8—C9—H9120.4
C6—N2—C10120.6 (9)N2—C10—C9121.0 (10)
C6—N2—H2119.7N2—C10—H10119.5
C10—N2—H2119.7C9—C10—H10119.5
C11—N3—C15123.4 (8)N3—C11—C12119.1 (8)
C11—N3—H3118.3N3—C11—H11120.4
C15—N3—H3118.3C12—C11—H11120.4
N1—C1—C2117.3 (11)C11—C12—C13120.1 (8)
N1—C1—H1A121.4C11—C12—H12120.0
C2—C1—H1A121.4C13—C12—H12120.0
C3—C2—C1121.2 (11)C12—C13—C14118.9 (8)
C3—C2—H2A119.4C12—C13—H13120.6
C1—C2—H2A119.4C14—C13—H13120.6
C2—C3—C4118.3 (11)C15—C14—C13119.5 (8)
C2—C3—H3A120.8C15—C14—H14120.3
C4—C3—H3A120.8C13—C14—H14120.3
C5—C4—C3119.8 (10)N3—C15—C14119.1 (8)
C5—C4—H4120.1N3—C15—H15120.5
C3—C4—H4120.1C14—C15—H15120.5
C5—N1—C1—C2−1.8 (17)C7—C8—C9—C100.3 (17)
N1—C1—C2—C33.5 (19)C6—N2—C10—C9−0.3 (17)
C1—C2—C3—C4−4.1 (19)C8—C9—C10—N2−0.2 (17)
C2—C3—C4—C52.9 (18)C15—N3—C11—C12−0.2 (13)
C1—N1—C5—C40.6 (17)N3—C11—C12—C13−0.3 (13)
C3—C4—C5—N1−1.2 (17)C11—C12—C13—C140.9 (14)
C10—N2—C6—C70.7 (16)C12—C13—C14—C15−1.0 (14)
N2—C6—C7—C8−0.5 (17)C11—N3—C15—C140.1 (13)
C6—C7—C8—C90.0 (16)C13—C14—C15—N30.5 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···Br90.882.353.202 (9)163
N2—H2···Br90.882.593.292 (8)137
N3—H3···Br90.882.523.279 (7)146

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2380).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Lowe, C. B., Schultz, A. J., Shaviv, R. & Carlin, R. L. (1994). Inorg. Chem.33, 3051–3054.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.

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