Crystal structure of the new hybrid material bis­(1,4-diazo­niabi­cyclo­[2.2.2]octa­ne) di-μ-chlorido-bis­[tetra­chlorido­bis­muthate(III)] dihydrate

The title salt, (C₆H₁₄N₂)₂[Bi₂Cl₁₀]·2H₂O, bears a close resemblance to its homologous anti­monate structure. The crystal structure is formed by an alternating packing of organic and inorganic layers along [001] and contains isolated (Bi₂Cl₁₀)⁴⁻ bi­octa­hedra.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.036
• wR factor = 0.102
• Data-to-parameter ratio = 22.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT971_ALERT_2_B Check Calcd Residual Density  0.88A From      Bi       3.18 eA-3
PLAT971_ALERT_2_B Check Calcd Residual Density  0.91A From      Bi       3.06 eA-3
PLAT972_ALERT_2_B Check Calcd Residual Density  0.83A From      Bi      -2.53 eA-3

Alert level C
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         Bi Check
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0120 Ang.
PLAT934_ALERT_3_C Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          1 Check
PLAT971_ALERT_2_C Check Calcd Residual Density  0.85A From      Bi       2.30 eA-3
PLAT971_ALERT_2_C Check Calcd Residual Density  0.82A From      Bi       2.03 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.82A From      Bi      -2.47 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.83A From      Bi      -2.24 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.85A From      Bi      -2.12 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  1.53A From      Bi      -1.62 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  1.54A From      Bi      -1.53 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Bi     --  Cl1     ..       10.9 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Bi     --  Cl4     ..        5.4 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Bi     --  Cl1_a   ..        9.7 su
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3 Note
PLAT794_ALERT_5_G Tentative Bond Valency for Bi      (III)   .....       3.32 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   3 ALERT level B = A potentially serious problem, consider carefully
  10 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  15 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(1,4-diazoniabicyclo[2.2.2]octane) di-µ-chlorido-bis[tetrachloridobismuthate(III)] dihydrate

Crystal data

(C6H14N2)2[Bi2Cl10]·2H2O	F(000) = 968
Mr = 1036.88	Dx = 2.369 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.875 (3) Å	Cell parameters from 3158 reflections
b = 18.379 (5) Å	θ = 2.2–2.7°
c = 10.444 (4) Å	µ = 13.03 mm^−1
β = 105.95 (3)°	T = 293 K
V = 1453.4 (9) Å^3	Prism, colourless
Z = 2	0.5 × 0.3 × 0.2 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	2681 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 27.0°, θmin = 2.2°
ω/2θ scans	h = −10→1
Absorption correction: ψ scan North et al. (1968). Number of ψ scan sets used was 5 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.	k = −1→23
Tmin = 0.013, Tmax = 0.074	l = −12→13
3159 measured reflections	2 standard reflections every 120 min
3159 independent reflections	intensity decay: 10%

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0625P)^2 + 4.4831P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3159 reflections	Δρmax = 3.48 e Å^−3
142 parameters	Δρmin = −2.57 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.

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

	x	y	z	Uiso*/Ueq
Bi	0.42097 (3)	0.42073 (2)	0.34670 (2)	0.02518 (11)
Cl1	0.2576 (2)	0.50934 (10)	0.50438 (18)	0.0329 (4)
Cl2	0.4635 (3)	0.32483 (10)	0.54389 (18)	0.0361 (4)
Cl3	0.1117 (3)	0.36755 (11)	0.2279 (2)	0.0441 (5)
Cl4	0.3821 (3)	0.52442 (12)	0.1571 (2)	0.0438 (5)
Cl5	0.5941 (4)	0.33648 (14)	0.2288 (3)	0.0635 (7)
OW	0.7852 (9)	0.2151 (4)	0.4798 (8)	0.0609 (18)
HW1	0.701 (11)	0.194 (6)	0.501 (12)	0.070*
HW2	0.732 (14)	0.251 (4)	0.434 (10)	0.070*
N1	0.0157 (8)	0.3538 (3)	0.8660 (6)	0.0291 (12)
H1	−0.0668	0.3405	0.9173	0.035*
N2	0.2250 (8)	0.3886 (3)	0.7369 (6)	0.0319 (13)
H2	0.3082	0.4026	0.6866	0.038*
C1	0.1780 (10)	0.3089 (4)	0.9111 (8)	0.0340 (16)
H1A	0.1513	0.2584	0.8867	0.041*
H1B	0.2238	0.3117	1.0072	0.041*
C6	0.0703 (11)	0.3511 (5)	0.6456 (7)	0.0403 (19)
H6A	0.1062	0.3045	0.6179	0.048*
H6B	0.0224	0.3805	0.5668	0.048*
C3	0.0613 (10)	0.4331 (4)	0.8868 (8)	0.0344 (16)
H3A	−0.0457	0.4618	0.8708	0.041*
H3B	0.1310	0.4413	0.9778	0.041*
C4	0.1641 (11)	0.4551 (4)	0.7924 (8)	0.0385 (17)
H4A	0.0904	0.4841	0.7209	0.046*
H4B	0.2650	0.4843	0.8386	0.046*
C5	−0.0695 (11)	0.3398 (5)	0.7206 (7)	0.0386 (17)
H5A	−0.1673	0.3731	0.6874	0.046*
H5B	−0.1147	0.2905	0.7078	0.046*
C2	0.3144 (11)	0.3374 (4)	0.8454 (8)	0.0385 (17)
H2A	0.4078	0.3625	0.9105	0.046*
H2B	0.3663	0.2973	0.8090	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi	0.02361 (17)	0.02675 (16)	0.02414 (16)	−0.00230 (9)	0.00482 (11)	−0.00228 (8)
Cl1	0.0253 (8)	0.0374 (9)	0.0354 (9)	0.0006 (7)	0.0073 (7)	0.0026 (7)
Cl2	0.0343 (9)	0.0360 (9)	0.0374 (9)	0.0016 (7)	0.0087 (7)	0.0066 (7)
Cl3	0.0352 (10)	0.0522 (11)	0.0396 (10)	−0.0140 (9)	0.0011 (8)	0.0003 (8)
Cl4	0.0282 (9)	0.0570 (12)	0.0434 (10)	−0.0072 (8)	0.0052 (8)	0.0165 (9)
Cl5	0.0703 (16)	0.0640 (15)	0.0643 (15)	0.0110 (12)	0.0319 (13)	−0.0197 (12)
OW	0.045 (4)	0.073 (5)	0.067 (5)	0.017 (3)	0.019 (3)	−0.016 (4)
N1	0.024 (3)	0.037 (3)	0.030 (3)	−0.001 (2)	0.013 (2)	−0.002 (2)
N2	0.027 (3)	0.035 (3)	0.037 (3)	0.003 (2)	0.016 (3)	0.005 (3)
C1	0.032 (4)	0.034 (4)	0.036 (4)	0.010 (3)	0.009 (3)	0.011 (3)
C6	0.044 (5)	0.054 (5)	0.021 (3)	0.002 (4)	0.005 (3)	−0.003 (3)
C3	0.032 (4)	0.030 (3)	0.043 (4)	0.002 (3)	0.012 (3)	−0.007 (3)
C4	0.038 (4)	0.030 (4)	0.050 (5)	−0.003 (3)	0.017 (4)	0.001 (3)
C5	0.033 (4)	0.050 (4)	0.028 (4)	−0.005 (3)	−0.001 (3)	−0.005 (3)
C2	0.034 (4)	0.041 (4)	0.040 (4)	0.012 (3)	0.010 (3)	0.014 (3)

Geometric parameters (Å, º)

Bi—Cl5	2.588 (2)	N2—H2	0.9800
Bi—Cl3	2.601 (2)	C1—C2	1.517 (11)
Bi—Cl2	2.6611 (19)	C1—H1A	0.9700
Bi—Cl4	2.704 (2)	C1—H1B	0.9700
Bi—Cl1	2.8610 (19)	C6—C5	1.531 (11)
Bi—Cl1^i	2.884 (2)	C6—H6A	0.9700
Cl1—Bi^i	2.884 (2)	C6—H6B	0.9700
OW—HW1	0.850 (10)	C3—C4	1.493 (11)
OW—HW2	0.850 (10)	C3—H3A	0.9700
N1—C1	1.485 (9)	C3—H3B	0.9700
N1—C3	1.503 (9)	C4—H4A	0.9700
N1—C5	1.504 (9)	C4—H4B	0.9700
N1—H1	0.9800	C5—H5A	0.9700
N2—C4	1.489 (10)	C5—H5B	0.9700
N2—C2	1.492 (9)	C2—H2A	0.9700
N2—C6	1.494 (10)	C2—H2B	0.9700
Cl5—Bi—Cl3	95.45 (9)	C2—C1—H1B	110.0
Cl5—Bi—Cl2	90.07 (8)	H1A—C1—H1B	108.4
Cl3—Bi—Cl2	91.28 (7)	N2—C6—C5	108.1 (6)
Cl5—Bi—Cl4	92.39 (9)	N2—C6—H6A	110.1
Cl3—Bi—Cl4	90.73 (7)	C5—C6—H6A	110.1
Cl2—Bi—Cl4	176.66 (6)	N2—C6—H6B	110.1
Cl5—Bi—Cl1	173.58 (7)	C5—C6—H6B	110.1
Cl3—Bi—Cl1	88.74 (7)	H6A—C6—H6B	108.4
Cl2—Bi—Cl1	84.97 (6)	C4—C3—N1	108.6 (6)
Cl4—Bi—Cl1	92.41 (7)	C4—C3—H3A	110.0
Cl5—Bi—Cl1^i	91.38 (8)	N1—C3—H3A	110.0
Cl3—Bi—Cl1^i	173.16 (6)	C4—C3—H3B	110.0
Cl2—Bi—Cl1^i	88.44 (6)	N1—C3—H3B	110.0
Cl4—Bi—Cl1^i	89.25 (6)	H3A—C3—H3B	108.4
Cl1—Bi—Cl1^i	84.43 (6)	N2—C4—C3	109.0 (6)
Bi—Cl1—Bi^i	95.57 (6)	N2—C4—H4A	109.9
HW1—OW—HW2	102 (10)	C3—C4—H4A	109.9
C1—N1—C3	110.0 (6)	N2—C4—H4B	109.9
C1—N1—C5	109.4 (6)	C3—C4—H4B	109.9
C3—N1—C5	109.5 (6)	H4A—C4—H4B	108.3
C1—N1—H1	109.3	N1—C5—C6	108.0 (6)
C3—N1—H1	109.3	N1—C5—H5A	110.1
C5—N1—H1	109.3	C6—C5—H5A	110.1
C4—N2—C2	110.9 (6)	N1—C5—H5B	110.1
C4—N2—C6	109.5 (6)	C6—C5—H5B	110.1
C2—N2—C6	109.1 (6)	H5A—C5—H5B	108.4
C4—N2—H2	109.1	N2—C2—C1	108.5 (6)
C2—N2—H2	109.1	N2—C2—H2A	110.0
C6—N2—H2	109.1	C1—C2—H2A	110.0
N1—C1—C2	108.6 (5)	N2—C2—H2B	110.0
N1—C1—H1A	110.0	C1—C2—H2B	110.0
C2—C1—H1A	110.0	H2A—C2—H2B	108.4
N1—C1—H1B	110.0

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
Ow—Hw2···Cl5	0.91	2.63	3.458 (8)	163
N1—H1···Ow^ii	0.91	1.87	2.739 (10)	159
Ow—Hw1···Cl5^iii	0.91	2.80	3.475 (9)	138
N2—H2···Cl1	0.91	2.73	3.352 (6)	127
N2—H2···Cl2	0.91	2.65	3.325 (7)	132

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