4,4′-Bipyridyl adduct of an iodo­bismuthate anion linked by a 4,4′-bipyridinium cation

Charmant, J.P.H.; Norman, N.C.; Orpen, A.G.; Starbuck, J.

doi:10.1107/S1600536803022359

4,4′-Bipyridyl adduct of an iodobismuthate anion linked by a 4,4′-bipyridinium cation

J. P. H. Charmant, N. C. Norman, A. G. Orpen and J. Starbuck

The crystal structure of the title iodobismuthate complex, 4,4′-bipyridinium(2+) di-μ-iodo-bis[(4,4′-bipyridyl)triiodobismuth(III)], formulated as [4,4′-H₂bipy]²⁺[Bi₂I₈(4,4′-bipy)₂]²⁻ or (C₁₀H₁₀N₂)[Bi₂I₈(C₁₀H₈N₂)₂], has been determined. The compound is isostructural with its antimony analogue, each containing layers of hydrogen-bonded ribbon polymers in which anionic dinuclear complexes are linked through hydrogen bonding with 4,4′-H₂bipy cations.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803022359/br6119sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803022359/br6119Isup2.hkl Contains datablock I

CCDC reference: 226648

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.025 Å
R factor = 0.072
wR factor = 0.212
Data-to-parameter ratio = 41.6

checkCIF/PLATON results

No syntax errors found



Alert level A
ABSTM02_ALERT_3_A  The ratio of Tmax/Tmin expected RT(exp) is > 1.30
            An absorption correction should be applied.
            Tmin and Tmax expected:      0.212     0.510
            RT(exp) =      2.408

Author Response: At the time that this experiment was performed no integration software and absorption correction program existed for dealing with the non-merohedrally twinned data collected.

REFLT03_ALERT_3_A  Reflection count > 15% excess reflns - sys abs data present?
           From the CIF: _diffrn_reflns_theta_max           24.00
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total              10596
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         3492
           Completeness (_total/calc)            303.44%

Author Response: The data were not merged as the structure in non-merohedrally twinned.

PLAT021_ALERT_1_A Ratio Unique / Expected Reflections too High ...       3.03

Author Response: The merging of symmetry equivalent data would not be wise as the data are non-merohedral twinned.

PLAT027_ALERT_3_A _diffrn_reflns_theta_full too Low ..............      24.00 Deg.

Author Response: Data were very weak with nothing but noise produced beyond this resolution limit.

PLAT057_ALERT_3_A Correction for Absorption Required   RT(exp)   =       2.36

Author Response: At the time that this experiment was performed no integration software and absorption correction program existed for dealing with the non-merohedrally twinned data collected.


Alert level B
THETM01_ALERT_3_B  The value of sine(theta_max)/wavelength is less than 0.575
            Calculated sin(theta_max)/wavelength =    0.5723
PLAT023_ALERT_3_B Resolution (too) Low [sin(th)/Lambda < 0.6].....      24.00 Deg.
PLAT213_ALERT_2_B Atom C15     has ADP max/min Ratio .............       4.20 oblate
PLAT342_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ...         25

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT142_ALERT_4_C su on b - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT213_ALERT_2_C Atom C3      has ADP max/min Ratio .............       4.00 prolat
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....         C6
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....        C1'
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....        C5'
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         N1
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         N2
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....         C8
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        N1'
PLAT250_ALERT_2_C Large U3/U1 ratio for average U(i,j) tensor ....       3.85
PLAT301_ALERT_3_C Main Residue  Disorder .........................      13.00 Perc.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C1'    ..  C2'      =       3.14 Ang.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      37.70 Deg.
              C4'  -C3   -C4      1.555   1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C10 H10 N2

   5 ALERT level A = In general: serious problem
   4 ALERT level B = Potentially serious problem
  17 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  12 ALERT type 2 Indicator that the structure model may be wrong or deficient
   8 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SHELXTL (Siemens, 1996); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

4,4'-bipyridinium(2+) di-µ-iodo-bis[(4,4'-bipyridyl)triiodobismuth(III)] top

Crystal data top

(C₁₀H₈N₂)[Bi₂I₈(C₁₀H₈N₂)₂]	F(000) = 1676
M_r = 1903.72	D_x = 2.842 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7961 reflections
a = 9.6366 (2) Å	θ = 2–27°
b = 12.7506 (1) Å	µ = 13.48 mm⁻¹
c = 18.1728 (3) Å	T = 173 K
β = 95.013 (1)°	Block, orange
V = 2224.39 (6) Å³	0.20 × 0.10 × 0.05 mm
Z = 2

Data collection top

Siemens SMART CCD area-detector diffractometer	10596 independent reflections
Radiation source: fine-focus sealed tube	7484 reflections with I > 2σ(I)
Graphite monochromator	θ_max = 24.0°, θ_min = 2.0°
Detector resolution: 8.192 pixels mm^-1	h = −11→9
Frames, each covering 0.3 ° in ω scans	k = −14→14
10596 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.212	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1215P)²] where P = (F_o² + 2F_c²)/3
10596 reflections	(Δ/σ)_max = 0.001
255 parameters	Δρ_max = 2.08 e Å⁻³
60 restraints	Δρ_min = −4.26 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Bi1	0.98100 (7)	0.37867 (5)	−0.09766 (3)	0.0314 (2)
I1	0.73080 (13)	0.27596 (9)	−0.16863 (6)	0.0415 (3)
I2	0.76732 (12)	0.51422 (9)	−0.00661 (6)	0.0394 (3)
I3	1.17959 (12)	0.23779 (9)	−0.16374 (6)	0.0424 (3)
I4	1.00116 (13)	0.54725 (10)	−0.20967 (6)	0.0489 (4)
N1	0.996 (3)	0.2431 (18)	0.0146 (13)	0.022 (6)	0.61 (2)
C1	1.109 (3)	0.2137 (19)	0.0487 (14)	0.033 (7)	0.61 (2)
H1	1.1915	0.2406	0.0308	0.040*	0.61 (2)
C2	1.126 (3)	0.150 (2)	0.1062 (15)	0.041 (8)	0.61 (2)
H2	1.2161	0.1298	0.1272	0.049*	0.61 (2)
C4	0.864 (3)	0.147 (2)	0.0987 (16)	0.039 (7)	0.61 (2)
H4	0.7776	0.1209	0.1122	0.047*	0.61 (2)
C5	0.871 (3)	0.215 (2)	0.0452 (17)	0.042 (8)	0.61 (2)
H5	0.7874	0.2481	0.0259	0.050*	0.61 (2)
N1'	0.961 (4)	0.219 (3)	0.006 (2)	0.021 (10)	0.39 (2)
C1'	1.029 (5)	0.137 (4)	0.015 (3)	0.054 (14)	0.39 (2)
H1'	1.0713	0.1169	−0.0280	0.065*	0.39 (2)
C2'	1.059 (5)	0.066 (4)	0.075 (3)	0.044 (12)	0.39 (2)
H2'	1.1102	0.0026	0.0747	0.053*	0.39 (2)
C4'	0.915 (5)	0.194 (3)	0.126 (2)	0.034 (11)	0.39 (2)
H4'	0.8511	0.2057	0.1626	0.040*	0.39 (2)
C5'	0.911 (5)	0.259 (4)	0.073 (3)	0.047 (12)	0.39 (2)
H5'	0.8790	0.3289	0.0776	0.056*	0.39 (2)
N2	1.0089 (15)	−0.0781 (10)	0.3298 (8)	0.036 (3)
C3	0.995 (2)	0.1128 (13)	0.1360 (9)	0.049 (6)
C6	1.108 (2)	−0.0776 (14)	0.2882 (13)	0.060 (6)
H6	1.1878	−0.1198	0.3020	0.072*
C7	1.1077 (19)	−0.0183 (11)	0.2232 (9)	0.037 (4)
H7	1.1835	−0.0223	0.1932	0.044*
C8	0.9972 (15)	0.0448 (12)	0.2036 (8)	0.028 (4)
C9	0.8900 (18)	0.0458 (17)	0.2498 (9)	0.053 (5)
H9	0.8135	0.0921	0.2396	0.064*
C10	0.893 (2)	−0.0194 (14)	0.3101 (9)	0.049 (5)
H10	0.8144	−0.0237	0.3382	0.059*
N3	1.0065 (18)	−0.2467 (11)	0.4184 (8)	0.053 (5)
H3	1.0061	−0.1850	0.3967	0.063*
C12	1.0037 (19)	−0.3566 (11)	0.5280 (9)	0.039 (4)
H12	1.0036	−0.3622	0.5801	0.047*
C13	1.0004 (18)	−0.4478 (14)	0.4825 (10)	0.046 (5)
C15	1.006 (2)	−0.3349 (16)	0.3818 (9)	0.053 (5)
H15	1.0133	−0.3302	0.3301	0.063*
C11	1.007 (2)	−0.2584 (16)	0.4936 (10)	0.055 (5)
H11	1.0102	−0.1972	0.5235	0.066*
C14	0.997 (2)	−0.4297 (14)	0.4099 (10)	0.065 (7)
H14	0.9886	−0.4878	0.3771	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi1	0.0452 (4)	0.0360 (4)	0.0124 (3)	0.0000 (3)	−0.0007 (3)	−0.0002 (3)
I1	0.0516 (8)	0.0410 (6)	0.0305 (6)	−0.0067 (6)	−0.0045 (5)	−0.0053 (5)
I2	0.0486 (7)	0.0457 (7)	0.0226 (6)	0.0056 (6)	−0.0048 (5)	−0.0108 (5)
I3	0.0506 (8)	0.0452 (7)	0.0312 (7)	0.0022 (6)	0.0021 (5)	−0.0082 (5)
I4	0.0529 (8)	0.0688 (8)	0.0241 (6)	−0.0048 (6)	−0.0007 (5)	0.0208 (6)
N1	0.022 (7)	0.022 (7)	0.022 (7)	−0.0002 (10)	0.0020 (11)	0.0002 (10)
C1	0.033 (7)	0.033 (7)	0.033 (7)	−0.0001 (10)	0.0031 (12)	0.0003 (10)
C2	0.041 (8)	0.041 (8)	0.041 (8)	0.0001 (10)	0.0033 (12)	0.0002 (10)
C4	0.039 (7)	0.039 (7)	0.039 (7)	0.0001 (10)	0.0033 (12)	0.0001 (10)
C5	0.042 (8)	0.042 (8)	0.042 (8)	0.0000 (10)	0.0036 (12)	0.0001 (10)
N1'	0.021 (10)	0.021 (10)	0.021 (10)	0.0000 (10)	0.0019 (13)	0.0000 (10)
C1'	0.054 (14)	0.054 (14)	0.054 (14)	0.0001 (10)	0.0048 (16)	0.0000 (10)
C2'	0.044 (12)	0.044 (12)	0.044 (12)	0.0001 (10)	0.0040 (15)	0.0001 (10)
C4'	0.034 (11)	0.033 (11)	0.034 (11)	0.0000 (10)	0.0029 (14)	0.0001 (10)
C5'	0.047 (12)	0.047 (12)	0.046 (12)	−0.0001 (10)	0.0041 (15)	0.0001 (10)
N2	0.029 (9)	0.033 (8)	0.043 (9)	0.000 (7)	−0.010 (7)	0.000 (7)
C3	0.069 (14)	0.056 (12)	0.016 (9)	0.045 (11)	−0.022 (8)	−0.016 (8)
C6	0.063 (15)	0.035 (10)	0.081 (16)	0.024 (10)	0.002 (13)	0.007 (11)
C7	0.066 (13)	0.020 (8)	0.023 (9)	0.007 (8)	0.006 (9)	0.009 (7)
C8	0.022 (9)	0.034 (9)	0.029 (9)	−0.011 (7)	0.014 (7)	−0.009 (7)
C9	0.039 (11)	0.097 (16)	0.025 (10)	0.025 (11)	0.011 (8)	0.018 (10)
C10	0.067 (14)	0.065 (12)	0.013 (9)	−0.007 (11)	−0.005 (9)	0.003 (9)
N3	0.098 (14)	0.032 (8)	0.027 (9)	−0.004 (9)	−0.005 (8)	0.013 (7)
C12	0.072 (13)	0.025 (8)	0.017 (8)	0.000 (9)	−0.015 (8)	0.000 (7)
C13	0.043 (11)	0.059 (12)	0.034 (11)	0.005 (10)	−0.010 (9)	0.013 (9)
C15	0.079 (15)	0.071 (14)	0.010 (8)	−0.007 (12)	0.009 (9)	0.016 (9)
C11	0.062 (14)	0.070 (14)	0.032 (11)	−0.005 (11)	−0.002 (10)	0.003 (10)
C14	0.13 (2)	0.034 (10)	0.028 (11)	−0.019 (12)	−0.013 (12)	−0.003 (9)

Geometric parameters (Å, º) top

Bi1—N1	2.67 (2)	C4'—H4'	0.9500
Bi1—N1'	2.80 (4)	C5'—H5'	0.9500
Bi1—I1	2.9408 (12)	N2—C6	1.27 (2)
Bi1—I3	2.9551 (13)	N2—C10	1.37 (2)
Bi1—I4	2.9782 (13)	C3—C8	1.50 (2)
Bi1—I2ⁱ	3.2458 (12)	C6—C7	1.40 (2)
Bi1—I2	3.2497 (13)	C6—H6	0.9500
I2—Bi1ⁱ	3.2457 (12)	C7—C8	1.36 (2)
N1—C1	1.26 (3)	C7—H7	0.9500
N1—C5	1.41 (4)	C8—C9	1.39 (2)
C1—C2	1.32 (4)	C9—C10	1.37 (2)
C1—H1	0.9500	C9—H9	0.9500
C2—C3	1.50 (3)	C10—H10	0.9500
C2—H2	0.9500	N3—C15	1.31 (2)
C4—C5	1.31 (4)	N3—C11	1.37 (2)
C4—C3	1.44 (3)	N3—H3	0.8800
C4—H4	0.9500	C12—C11	1.40 (2)
C5—H5	0.9500	C12—C13	1.43 (2)
N1'—C1'	1.23 (6)	C12—H12	0.9500
N1'—C5'	1.44 (7)	C13—C14	1.34 (2)
C1'—C2'	1.42 (6)	C13—C13ⁱⁱ	1.47 (3)
C1'—H1'	0.9500	C15—C14	1.32 (2)
C2'—C3	1.45 (5)	C15—H15	0.9500
C2'—H2'	0.9500	C11—H11	0.9500
C4'—C5'	1.27 (6)	C14—H14	0.9500
C4'—C3	1.29 (4)

N1—Bi1—N1'	9.6 (9)	C3—C4'—H4'	116.5
N1—Bi1—I1	92.0 (6)	C4'—C5'—N1'	115 (4)
N1'—Bi1—I1	82.5 (8)	C4'—C5'—H5'	122.6
N1—Bi1—I3	85.6 (5)	N1'—C5'—H5'	122.6
N1'—Bi1—I3	85.3 (8)	C6—N2—C10	119.0 (16)
I1—Bi1—I3	94.95 (4)	C4'—C3—C4	37.7 (18)
N1—Bi1—I4	171.0 (6)	C4'—C3—C2'	121 (3)
N1'—Bi1—I4	179.4 (8)	C4—C3—C2'	100 (2)
I1—Bi1—I4	96.98 (4)	C4'—C3—C2	102 (3)
I3—Bi1—I4	94.46 (4)	C4—C3—C2	118 (2)
N1—Bi1—I2ⁱ	80.7 (6)	C2'—C3—C2	55 (2)
N1'—Bi1—I2ⁱ	90.3 (8)	C4'—C3—C8	123 (2)
I1—Bi1—I2ⁱ	170.26 (4)	C4—C3—C8	121 (2)
I3—Bi1—I2ⁱ	90.90 (3)	C2'—C3—C8	115 (2)
I4—Bi1—I2ⁱ	90.30 (3)	C2—C3—C8	121.8 (16)
N1—Bi1—I2	87.1 (5)	N2—C6—C7	123.6 (17)
N1'—Bi1—I2	87.7 (8)	N2—C6—H6	118.2
I1—Bi1—I2	85.90 (3)	C7—C6—H6	118.2
I3—Bi1—I2	172.68 (4)	C8—C7—C6	119.2 (17)
I4—Bi1—I2	92.65 (4)	C8—C7—H7	120.4
I2ⁱ—Bi1—I2	87.33 (3)	C6—C7—H7	120.4
Bi1ⁱ—I2—Bi1	92.67 (3)	C7—C8—C9	117.1 (16)
C1—N1—C5	117 (2)	C7—C8—C3	120.8 (14)
C1—N1—Bi1	124 (2)	C9—C8—C3	122.1 (15)
C5—N1—Bi1	118.2 (17)	C10—C9—C8	120.8 (17)
N1—C1—C2	128 (3)	C10—C9—H9	119.6
N1—C1—H1	116.0	C8—C9—H9	119.6
C2—C1—H1	116.0	N2—C10—C9	120.0 (18)
C1—C2—C3	115 (2)	N2—C10—H10	120.0
C1—C2—H2	122.4	C9—C10—H10	120.0
C3—C2—H2	122.4	C15—N3—C11	114.4 (15)
C5—C4—C3	117 (3)	C15—N3—H3	122.8
C5—C4—H4	121.7	C11—N3—H3	122.8
C3—C4—H4	121.7	C11—C12—C13	118.1 (15)
C4—C5—N1	124 (3)	C11—C12—H12	121.0
C4—C5—H5	118.0	C13—C12—H12	121.0
N1—C5—H5	118.0	C14—C13—C12	115.4 (16)
C1'—N1'—C5'	114 (4)	C14—C13—C13ⁱⁱ	126 (2)
C1'—N1'—Bi1	129 (4)	C12—C13—C13ⁱⁱ	119 (2)
C5'—N1'—Bi1	111 (3)	N3—C15—C14	126.2 (16)
N1'—C1'—C2'	135 (5)	N3—C15—H15	116.9
N1'—C1'—H1'	112.6	C14—C15—H15	116.9
C2'—C1'—H1'	112.6	N3—C11—C12	122.9 (17)
C1'—C2'—C3	105 (4)	N3—C11—H11	118.6
C1'—C2'—H2'	127.7	C12—C11—H11	118.6
C3—C2'—H2'	127.7	C15—C14—C13	123.0 (18)
C5'—C4'—C3	127 (4)	C15—C14—H14	118.5
C5'—C4'—H4'	116.5	C13—C14—H14	118.5

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y−1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N2	0.88	1.83	2.69 (4)	165

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4,4′-Bipyridyl adduct of an iodo­bismuthate anion linked by a 4,4′-bipyridinium cation

Supporting information

Key indicators

checkCIF/PLATON results

4,4′-Bipyridyl adduct of an iodobismuthate anion linked by a 4,4′-bipyridinium cation