Bis(4,4′-bipyridinium) di-μ-bromo-bis­[tetra­bromo­bismuthate(III)]

The crystal structure of the title complex, (C₁₀H₁₀N₂)₂[BiBr₁₀] or (bipyH₂)₂[Bi₂Br₁₀], where bipyH₂ is 4,4′-bipyridinium, is built of bipyH₂ dications and deca­bromo­dibismuthate tetra­anions; the latter occupy special positions at inversion centres. The Bi atom in the anion has a distorted octa­hedral environment. N—H...Br hydrogen bonds link the ions into infinite chains running along the [1] direction.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.015 Å
• R factor = 0.038
• wR factor = 0.099
• Data-to-parameter ratio = 18.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Bi1    -   Br5_a   ..      13.86 su

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
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.81
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.41
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         15

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.405
            Tmax scaled      0.072 Tmin scaled      0.066

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

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

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Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Bis(4,4'-bipyridinium) di-µ-bromo-bis[tetrabromobismuthate(III)]

Crystal data

(C10H10N2)2[Bi2Br10]	Z = 1
Mr = 1533.4	F(000) = 684
Triclinic, P1	Dx = 2.968 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5435 (18) Å	Cell parameters from 1654 reflections
b = 10.191 (2) Å	θ = 2.5–27.9°
c = 11.344 (2) Å	µ = 21.91 mm^−1
α = 113.609 (3)°	T = 298 K
β = 100.661 (3)°	Block, yellow
γ = 99.411 (3)°	0.13 × 0.13 × 0.12 mm
V = 857.9 (3) Å^3

Data collection

Siemens SMART CCD area-detector diffractometer	2991 independent reflections
Radiation source: fine-focus sealed tube	2364 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 0 pixels mm^-1	θmax = 25.0°, θmin = 2.0°
φ and ω scans	h = −9→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→12
Tmin = 0.163, Tmax = 0.178	l = −13→11
4547 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0514P)^2] where P = (Fo^2 + 2Fc^2)/3
2991 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 2.56 e Å^−3
0 restraints	Δρmin = −1.96 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Bi1	0.43787 (4)	0.93890 (4)	0.65820 (3)	0.02939 (14)
Br1	0.61601 (13)	0.88285 (13)	0.84863 (11)	0.0503 (3)
Br2	0.49942 (12)	1.25104 (11)	0.84319 (10)	0.0401 (3)
Br3	0.14385 (12)	0.88318 (12)	0.71812 (10)	0.0447 (3)
Br4	0.37707 (13)	0.64386 (12)	0.47247 (10)	0.0426 (3)
Br5	0.74091 (11)	1.00672 (11)	0.57434 (9)	0.0356 (2)
N1	0.7345 (11)	0.6375 (11)	0.3728 (8)	0.048 (2)
H1	0.6843	0.6874	0.4270	0.058*
N2	1.1509 (10)	0.2308 (10)	−0.0507 (7)	0.040 (2)
H2	1.2042	0.1797	−0.1010	0.048*
C1	0.6638 (13)	0.4968 (12)	0.2930 (10)	0.044 (3)
H1A	0.5600	0.4529	0.2939	0.053*
C2	0.7425 (13)	0.4160 (13)	0.2095 (11)	0.047 (3)
H2A	0.6916	0.3162	0.1530	0.057*
C3	0.8982 (11)	0.4785 (11)	0.2056 (8)	0.032 (2)
C4	0.9639 (12)	0.6279 (12)	0.2910 (10)	0.049 (3)
H4	1.0671	0.6757	0.2922	0.058*
C5	0.8813 (14)	0.7059 (13)	0.3729 (11)	0.058 (3)
H5	0.9267	0.8067	0.4290	0.070*
C6	1.2253 (12)	0.3740 (13)	0.0353 (10)	0.044 (3)
H6	1.3306	0.4175	0.0368	0.052*
C7	1.1466 (12)	0.4546 (11)	0.1197 (10)	0.040 (3)
H7	1.1992	0.5528	0.1807	0.048*
C8	0.9876 (11)	0.3913 (10)	0.1156 (8)	0.030 (2)
C9	0.9160 (12)	0.2467 (11)	0.0225 (10)	0.040 (3)
H9	0.8085	0.2019	0.0154	0.048*
C10	0.9994 (13)	0.1666 (12)	−0.0604 (10)	0.044 (3)
H10	0.9495	0.0683	−0.1224	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0321 (2)	0.0286 (2)	0.0297 (2)	0.01360 (16)	0.01202 (15)	0.01150 (16)
Br1	0.0485 (6)	0.0457 (7)	0.0525 (6)	0.0033 (5)	−0.0043 (5)	0.0290 (6)
Br2	0.0430 (6)	0.0303 (6)	0.0435 (6)	0.0105 (5)	0.0169 (4)	0.0106 (5)
Br3	0.0385 (5)	0.0441 (7)	0.0506 (6)	0.0132 (5)	0.0223 (5)	0.0148 (5)
Br4	0.0508 (6)	0.0326 (6)	0.0416 (6)	0.0176 (5)	0.0169 (5)	0.0094 (5)
Br5	0.0316 (5)	0.0354 (6)	0.0413 (5)	0.0134 (4)	0.0124 (4)	0.0158 (5)
N1	0.053 (6)	0.054 (7)	0.034 (5)	0.028 (5)	0.016 (4)	0.009 (5)
N2	0.046 (5)	0.042 (6)	0.035 (4)	0.020 (4)	0.021 (4)	0.015 (4)
C1	0.050 (6)	0.047 (7)	0.048 (6)	0.028 (6)	0.027 (5)	0.022 (6)
C2	0.043 (6)	0.050 (7)	0.058 (7)	0.017 (5)	0.028 (5)	0.025 (6)
C3	0.041 (5)	0.028 (5)	0.028 (5)	0.018 (5)	0.006 (4)	0.009 (4)
C4	0.031 (5)	0.036 (7)	0.054 (6)	0.009 (5)	0.015 (5)	−0.005 (5)
C5	0.050 (7)	0.038 (7)	0.051 (7)	0.012 (6)	0.002 (5)	−0.010 (6)
C6	0.027 (5)	0.052 (7)	0.053 (6)	0.011 (5)	0.016 (5)	0.022 (6)
C7	0.039 (5)	0.025 (6)	0.051 (6)	0.007 (5)	0.021 (5)	0.008 (5)
C8	0.033 (5)	0.030 (6)	0.030 (5)	0.016 (4)	0.006 (4)	0.015 (4)
C9	0.032 (5)	0.030 (6)	0.045 (6)	0.005 (4)	0.016 (4)	0.003 (5)
C10	0.044 (6)	0.036 (6)	0.049 (6)	0.011 (5)	0.016 (5)	0.015 (5)

Geometric parameters (Å, º)

Bi1—Br1	2.7140 (12)	C2—C3	1.394 (13)
Bi1—Br2	2.9149 (12)	C2—H2A	0.9300
Bi1—Br3	2.7512 (11)	C3—C4	1.382 (13)
Bi1—Br4	2.7856 (12)	C3—C8	1.483 (13)
Bi1—Br5	2.9897 (11)	C4—C5	1.353 (14)
Bi1—Br5^i	3.0912 (11)	C4—H4	0.9300
Br5—Bi1^i	3.0912 (11)	C5—H5	0.9300
N1—C1	1.309 (13)	C6—C7	1.353 (13)
N1—C5	1.330 (14)	C6—H6	0.9300
N1—H1	0.8600	C7—C8	1.389 (12)
N2—C10	1.315 (12)	C7—H7	0.9300
N2—C6	1.347 (13)	C8—C9	1.371 (13)
N2—H2	0.8600	C9—C10	1.372 (14)
C1—C2	1.349 (14)	C9—H9	0.9300
C1—H1A	0.9300	C10—H10	0.9300
Br1—Bi1—Br3	95.10 (4)	C1—C2—H2A	119.2
Br1—Bi1—Br4	90.04 (4)	C3—C2—H2A	119.2
Br3—Bi1—Br4	92.08 (3)	C4—C3—C2	115.5 (9)
Br1—Bi1—Br2	92.16 (4)	C4—C3—C8	122.0 (9)
Br3—Bi1—Br2	88.75 (3)	C2—C3—C8	122.5 (9)
Br4—Bi1—Br2	177.58 (3)	C5—C4—C3	121.3 (10)
Br1—Bi1—Br5	90.16 (4)	C5—C4—H4	119.3
Br3—Bi1—Br5	174.73 (3)	C3—C4—H4	119.3
Br4—Bi1—Br5	88.15 (3)	N1—C5—C4	119.5 (10)
Br2—Bi1—Br5	90.82 (3)	N1—C5—H5	120.2
Br1—Bi1—Br5^i	174.45 (3)	C4—C5—H5	120.2
Br3—Bi1—Br5^i	89.80 (3)	N2—C6—C7	119.9 (9)
Br4—Bi1—Br5^i	87.18 (3)	N2—C6—H6	120.0
Br2—Bi1—Br5^i	90.54 (3)	C7—C6—H6	120.0
Br5—Bi1—Br5^i	84.96 (3)	C6—C7—C8	120.3 (9)
Bi1—Br5—Bi1^i	95.04 (3)	C6—C7—H7	119.9
C1—N1—C5	122.3 (9)	C8—C7—H7	119.9
C1—N1—H1	118.8	C9—C8—C7	117.1 (9)
C5—N1—H1	118.8	C9—C8—C3	121.8 (8)
C10—N2—C6	122.1 (9)	C7—C8—C3	121.1 (8)
C10—N2—H2	118.9	C8—C9—C10	121.5 (9)
C6—N2—H2	118.9	C8—C9—H9	119.3
N1—C1—C2	119.6 (10)	C10—C9—H9	119.3
N1—C1—H1A	120.2	N2—C10—C9	119.0 (10)
C2—C1—H1A	120.2	N2—C10—H10	120.5
C1—C2—C3	121.6 (11)	C9—C10—H10	120.5

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br4	0.86	2.77	3.449 (9)	137
N1—H1···Br5	0.86	2.91	3.519 (9)	130
N2—H2···Br2^ii	0.86	2.77	3.418 (8)	134
N2—H2···Br3^ii	0.86	2.78	3.444 (9)	135

Symmetry code: (ii) x+1, y−1, z−1.