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

Ng, S.W.

doi:10.1107/S1600536809007090

metal-organic compounds

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Volume 65| Part 4| April 2009| Page m402

doi:10.1107/S1600536809007090

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

Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 25 February 2009; accepted 26 February 2009; online 14 March 2009)

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 ).

Experimental

Crystal data

(C₅H₆N)₃[FeBr₄]₂Br
M_r = 1071.21
Monoclinic, P 2₁
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 ) 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[F² > 2σ(F²)] = 0.043
wR(F²) = 0.106
S = 1.07
6460 reflections
263 parameters
109 restraints
H-atom parameters constrained
Δρ_max = 1.29 e Å⁻³
Δρ_min = −1.71 e Å⁻³
Absolute structure: Flack (1983 ), 3046 Friedel pairs
Flack parameter: 0.10 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br9	0.88	2.35	3.202 (9)	163
N2—H2⋯Br9	0.88	2.59	3.292 (8)	137
N3—H3⋯Br9	0.88	2.52	3.279 (7)	146

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

Supporting information

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

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

checkCIF report

Related literature top

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).

Experimental top

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.

Computing details top

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

Figures top

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

tripyridinium bis[tetrabromidoferrate(III)] bromide top

Crystal data top

(C₅H₆N)₃[FeBr₄]₂Br	F(000) = 992
M_r = 1071.21	D_x = 2.487 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 8983 reflections
a = 7.5602 (1) Å	θ = 2.7–28.3°
b = 14.0125 (2) Å	µ = 13.59 mm⁻¹
c = 13.5609 (2) Å	T = 123 K
β = 95.172 (1)°	Irregular block, brown
V = 1430.76 (3) Å³	0.30 × 0.25 × 0.20 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	6460 independent reflections
Radiation source: fine-focus sealed tube	6006 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.098, T_max = 0.154	k = −18→18
13428 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0502P)² + 4.7139P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
6460 reflections	Δρ_max = 1.29 e Å⁻³
263 parameters	Δρ_min = −1.71 e Å⁻³
109 restraints	Absolute structure: Flack (1983), 3046 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.10 (2)

Crystal data top

(C₅H₆N)₃[FeBr₄]₂Br	V = 1430.76 (3) Å³
M_r = 1071.21	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.5602 (1) Å	µ = 13.59 mm⁻¹
b = 14.0125 (2) Å	T = 123 K
c = 13.5609 (2) Å	0.30 × 0.25 × 0.20 mm
β = 95.172 (1)°

Data collection top

Bruker SMART APEX diffractometer	6460 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	6006 reflections with I > 2σ(I)
T_min = 0.098, T_max = 0.154	R_int = 0.038
13428 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.106	Δρ_max = 1.29 e Å⁻³
S = 1.07	Δρ_min = −1.71 e Å⁻³
6460 reflections	Absolute structure: Flack (1983), 3046 Friedel pairs
263 parameters	Absolute structure parameter: 0.10 (2)
109 restraints

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

	x	y	z	U_iso*/U_eq
Br1	0.27784 (12)	0.49992 (6)	0.74070 (6)	0.02428 (19)
Br2	0.27108 (13)	0.35971 (6)	0.50468 (7)	0.0250 (2)
Br3	0.02833 (11)	0.60181 (6)	0.50814 (7)	0.02457 (19)
Br4	0.52742 (11)	0.59765 (7)	0.52624 (7)	0.0268 (2)
Br5	0.52708 (11)	0.89250 (6)	0.95876 (7)	0.02335 (19)
Br6	0.75284 (12)	1.00789 (7)	0.74713 (6)	0.02522 (19)
Br7	1.02585 (12)	0.91096 (8)	0.97548 (8)	0.0356 (3)
Br8	0.74006 (15)	1.13935 (7)	0.98802 (7)	0.0350 (2)
Br9	0.74762 (11)	0.65558 (7)	0.83903 (6)	0.02359 (19)
Fe1	0.27879 (15)	0.51483 (9)	0.56879 (9)	0.0177 (2)
Fe2	0.76356 (16)	0.98860 (9)	0.91855 (9)	0.0197 (3)
N1	0.7426 (11)	0.4395 (6)	0.7619 (7)	0.038 (2)
H1	0.7427	0.4931	0.7959	0.045*
N2	0.7876 (12)	0.7029 (7)	1.0778 (6)	0.0343 (19)
H2	0.7993	0.7233	1.0173	0.041*
N3	0.3634 (10)	0.7457 (5)	0.7543 (5)	0.0203 (15)
H3	0.4324	0.7032	0.7863	0.024*
C1	0.8048 (15)	0.4412 (10)	0.6741 (9)	0.047 (3)
H1A	0.8457	0.4988	0.6470	0.056*
C2	0.8080 (17)	0.3569 (11)	0.6239 (9)	0.054 (3)
H2A	0.8582	0.3549	0.5622	0.065*
C3	0.7408 (16)	0.2758 (9)	0.6606 (10)	0.048 (3)
H3A	0.7363	0.2182	0.6234	0.058*
C4	0.6797 (14)	0.2790 (8)	0.7523 (9)	0.038 (2)
H4	0.6371	0.2226	0.7810	0.046*
C5	0.6802 (15)	0.3618 (9)	0.8016 (7)	0.038 (2)
H5	0.6357	0.3647	0.8649	0.046*
C6	0.7428 (14)	0.6150 (8)	1.0919 (7)	0.035 (2)
H6	0.7246	0.5738	1.0363	0.042*
C7	0.7210 (16)	0.5797 (8)	1.1832 (9)	0.041 (3)
H7	0.6873	0.5151	1.1919	0.049*
C8	0.7500 (12)	0.6418 (8)	1.2642 (7)	0.032 (2)
H8	0.7361	0.6199	1.3294	0.039*
C9	0.7984 (14)	0.7340 (8)	1.2482 (7)	0.035 (2)
H9	0.8192	0.7771	1.3021	0.042*
C10	0.8163 (16)	0.7633 (7)	1.1548 (8)	0.039 (2)
H10	0.8497	0.8274	1.1433	0.047*
C11	0.1903 (12)	0.7447 (6)	0.7669 (6)	0.0208 (17)
H11	0.1435	0.6989	0.8092	0.025*
C12	0.0815 (12)	0.8104 (7)	0.7182 (6)	0.0260 (18)
H12	−0.0420	0.8102	0.7262	0.031*
C13	0.1503 (13)	0.8766 (6)	0.6576 (7)	0.0256 (19)
H13	0.0757	0.9231	0.6241	0.031*
C14	0.3330 (13)	0.8744 (6)	0.6459 (7)	0.0260 (19)
H14	0.3831	0.9190	0.6035	0.031*
C15	0.4375 (12)	0.8082 (7)	0.6956 (7)	0.0269 (19)
H15	0.5614	0.8062	0.6888	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0313 (4)	0.0211 (4)	0.0195 (4)	−0.0010 (4)	−0.0025 (3)	−0.0005 (3)
Br2	0.0325 (5)	0.0188 (4)	0.0241 (4)	−0.0009 (4)	0.0039 (4)	−0.0032 (3)
Br3	0.0164 (4)	0.0285 (5)	0.0285 (4)	0.0046 (4)	0.0009 (3)	0.0077 (4)
Br4	0.0168 (4)	0.0268 (5)	0.0369 (5)	−0.0041 (4)	0.0030 (3)	0.0016 (4)
Br5	0.0181 (4)	0.0236 (4)	0.0286 (4)	−0.0015 (3)	0.0038 (3)	0.0022 (3)
Br6	0.0311 (4)	0.0272 (4)	0.0175 (4)	0.0014 (4)	0.0031 (3)	0.0012 (4)
Br7	0.0186 (4)	0.0520 (7)	0.0356 (5)	0.0033 (4)	−0.0007 (4)	0.0137 (5)
Br8	0.0507 (6)	0.0292 (6)	0.0246 (5)	−0.0099 (5)	0.0008 (4)	−0.0090 (4)
Br9	0.0204 (4)	0.0272 (5)	0.0225 (4)	0.0047 (4)	−0.0019 (3)	−0.0033 (3)
Fe1	0.0153 (5)	0.0167 (6)	0.0206 (6)	0.0002 (5)	−0.0005 (4)	−0.0003 (5)
Fe2	0.0186 (5)	0.0230 (6)	0.0173 (6)	−0.0020 (5)	0.0003 (4)	0.0008 (5)
N1	0.025 (4)	0.030 (4)	0.056 (5)	0.003 (3)	−0.013 (4)	−0.012 (4)
N2	0.038 (4)	0.043 (5)	0.023 (4)	0.011 (4)	0.010 (3)	0.009 (3)
N3	0.020 (3)	0.019 (3)	0.021 (3)	−0.002 (3)	−0.006 (3)	0.002 (3)
C1	0.030 (5)	0.055 (6)	0.055 (6)	−0.009 (5)	−0.004 (4)	0.028 (5)
C2	0.042 (6)	0.083 (8)	0.038 (5)	0.003 (6)	0.009 (5)	0.000 (6)
C3	0.040 (5)	0.047 (6)	0.056 (6)	0.008 (5)	−0.005 (5)	−0.021 (5)
C4	0.028 (5)	0.028 (5)	0.055 (6)	−0.007 (4)	−0.013 (4)	0.016 (4)
C5	0.036 (5)	0.058 (6)	0.021 (4)	0.001 (5)	0.005 (4)	−0.002 (4)
C6	0.043 (5)	0.035 (5)	0.024 (4)	0.013 (4)	−0.011 (4)	−0.005 (4)
C7	0.044 (5)	0.026 (5)	0.051 (6)	−0.013 (4)	−0.009 (5)	0.005 (4)
C8	0.028 (4)	0.045 (5)	0.024 (4)	0.000 (4)	−0.001 (3)	0.010 (4)
C9	0.037 (5)	0.039 (5)	0.029 (5)	−0.002 (4)	0.004 (4)	−0.013 (4)
C10	0.049 (5)	0.022 (4)	0.048 (5)	0.002 (4)	0.010 (5)	0.001 (4)
C11	0.023 (4)	0.019 (4)	0.021 (4)	−0.002 (3)	0.004 (3)	−0.001 (3)
C12	0.023 (4)	0.031 (4)	0.025 (4)	0.001 (4)	0.004 (3)	−0.004 (3)
C13	0.027 (4)	0.020 (4)	0.029 (4)	0.008 (4)	0.001 (3)	0.005 (3)
C14	0.028 (4)	0.020 (4)	0.031 (4)	−0.010 (3)	0.008 (4)	0.005 (3)
C15	0.021 (4)	0.032 (4)	0.028 (4)	−0.007 (4)	−0.003 (3)	−0.003 (4)

Geometric parameters (Å, º) top

Br1—Fe1	2.341 (2)	C3—H3A	0.9500
Br2—Fe1	2.340 (2)	C4—C5	1.340 (16)
Br3—Fe1	2.338 (1)	C4—H4	0.9500
Br4—Fe1	2.326 (1)	C5—H5	0.9500
Br5—Fe2	2.342 (1)	C6—C7	1.357 (15)
Br6—Fe2	2.335 (1)	C6—H6	0.9500
Br7—Fe2	2.331 (2)	C7—C8	1.404 (15)
Br8—Fe2	2.326 (2)	C7—H7	0.9500
N1—C1	1.319 (15)	C8—C9	1.366 (15)
N1—C5	1.320 (15)	C8—H8	0.9500
N1—H1	0.8800	C9—C10	1.349 (15)
N2—C6	1.296 (14)	C9—H9	0.9500
N2—C10	1.347 (14)	C10—H10	0.9500
N2—H2	0.8800	C11—C12	1.364 (13)
N3—C11	1.335 (11)	C11—H11	0.9500
N3—C15	1.340 (12)	C12—C13	1.372 (13)
N3—H3	0.8800	C12—H12	0.9500
C1—C2	1.36 (2)	C13—C14	1.405 (13)
C1—H1A	0.9500	C13—H13	0.9500
C2—C3	1.357 (19)	C14—C15	1.358 (13)
C2—H2A	0.9500	C14—H14	0.9500
C3—C4	1.366 (17)	C15—H15	0.9500

Br4—Fe1—Br3	107.44 (6)	N1—C5—C4	119.7 (9)
Br4—Fe1—Br2	111.41 (6)	N1—C5—H5	120.2
Br3—Fe1—Br2	111.18 (6)	C4—C5—H5	120.2
Br4—Fe1—Br1	111.51 (6)	N2—C6—C7	122.4 (10)
Br3—Fe1—Br1	108.77 (6)	N2—C6—H6	118.8
Br2—Fe1—Br1	106.55 (6)	C7—C6—H6	118.8
Br8—Fe2—Br7	112.54 (6)	C6—C7—C8	117.7 (10)
Br8—Fe2—Br6	107.52 (6)	C6—C7—H7	121.1
Br7—Fe2—Br6	109.63 (6)	C8—C7—H7	121.1
Br8—Fe2—Br5	109.89 (6)	C9—C8—C7	119.1 (9)
Br7—Fe2—Br5	107.40 (6)	C9—C8—H8	120.4
Br6—Fe2—Br5	109.86 (6)	C7—C8—H8	120.4
C1—N1—C5	123.5 (10)	C10—C9—C8	119.2 (10)
C1—N1—H1	118.2	C10—C9—H9	120.4
C5—N1—H1	118.2	C8—C9—H9	120.4
C6—N2—C10	120.6 (9)	N2—C10—C9	121.0 (10)
C6—N2—H2	119.7	N2—C10—H10	119.5
C10—N2—H2	119.7	C9—C10—H10	119.5
C11—N3—C15	123.4 (8)	N3—C11—C12	119.1 (8)
C11—N3—H3	118.3	N3—C11—H11	120.4
C15—N3—H3	118.3	C12—C11—H11	120.4
N1—C1—C2	117.3 (11)	C11—C12—C13	120.1 (8)
N1—C1—H1A	121.4	C11—C12—H12	120.0
C2—C1—H1A	121.4	C13—C12—H12	120.0
C3—C2—C1	121.2 (11)	C12—C13—C14	118.9 (8)
C3—C2—H2A	119.4	C12—C13—H13	120.6
C1—C2—H2A	119.4	C14—C13—H13	120.6
C2—C3—C4	118.3 (11)	C15—C14—C13	119.5 (8)
C2—C3—H3A	120.8	C15—C14—H14	120.3
C4—C3—H3A	120.8	C13—C14—H14	120.3
C5—C4—C3	119.8 (10)	N3—C15—C14	119.1 (8)
C5—C4—H4	120.1	N3—C15—H15	120.5
C3—C4—H4	120.1	C14—C15—H15	120.5

C5—N1—C1—C2	−1.8 (17)	C7—C8—C9—C10	0.3 (17)
N1—C1—C2—C3	3.5 (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—C5	2.9 (18)	C15—N3—C11—C12	−0.2 (13)
C1—N1—C5—C4	0.6 (17)	N3—C11—C12—C13	−0.3 (13)
C3—C4—C5—N1	−1.2 (17)	C11—C12—C13—C14	0.9 (14)
C10—N2—C6—C7	0.7 (16)	C12—C13—C14—C15	−1.0 (14)
N2—C6—C7—C8	−0.5 (17)	C11—N3—C15—C14	0.1 (13)
C6—C7—C8—C9	0.0 (16)	C13—C14—C15—N3	0.5 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br9	0.88	2.35	3.202 (9)	163
N2—H2···Br9	0.88	2.59	3.292 (8)	137
N3—H3···Br9	0.88	2.52	3.279 (7)	146

Experimental details

Crystal data
Chemical formula	(C₅H₆N)₃[FeBr₄]₂Br
M_r	1071.21
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	123
a, b, c (Å)	7.5602 (1), 14.0125 (2), 13.5609 (2)
β (°)	95.172 (1)
V (Å³)	1430.76 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	13.59
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.098, 0.154
No. of measured, independent and observed [I > 2σ(I)] reflections	13428, 6460, 6006
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.106, 1.07
No. of reflections	6460
No. of parameters	263
No. of restraints	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.29, −1.71
Absolute structure	Flack (1983), 3046 Friedel pairs
Absolute structure parameter	0.10 (2)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br9	0.88	2.35	3.202 (9)	163
N2—H2···Br9	0.88	2.59	3.292 (8)	137
N3—H3···Br9	0.88	2.52	3.279 (7)	146

Acknowledgements

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

References

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Volume 65| Part 4| April 2009| Page m402

doi:10.1107/S1600536809007090

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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