Understanding distortions of inorganic sub­structures in chlor­ido­bis­mu­thates(III)

The molar ratio variations of organic and inorganic reactants of chlor­ido­bis­mu­thates(III) with N,N-di­methyl­ethane-1,2-di­ammonium, [(CH₃)₂NH(CH₂)₂NH₃]²⁺, and N,N,N′,N′-tetra­methyl­guanidinium, [NH₂C{N(CH₃)₂}₂]⁺, cations lead to the formation of four different products, namely, tris(N,N-di­methyl­ethane-1,2-di­ammonium) bis[hexachlor­ido­bis­mu­thate(III)], [(CH₃)₂NH(CH₂)₂NH₃]₃[BiCl₆]₂ (1), catena-poly[N,N-di­methyl­ethane-1,2-di­ammonium [[tetra­chlor­ido­bis­mu­thate(III)]-μ-chlorido]], {[(CH₃)₂NH(CH₂)₂NH₃][BiCl₅]}_n (2), tris(N,N,N′,N′-tetra­methyl­guanidinium) tri-μ-chlorido-bis[trichlor­ido­bis­mu­thate(III)], [NH₂C{N(CH₃)₂}₂]₃[Bi₂Cl₉] (3), and catena-poly[N,N,N′,N′-tetra­methyl­guanidinium [[dichlor­ido­bis­mu­thate(III)]-di-μ-chlorido]], {[NH₂C{N(CH₃)₂}₂][BiCl₄]}_n (4). The hybrid crystals 1–4, containing relatively large but different organic cations, are com­posed of four distinct anionic substructures. They are built up from isolated [BiCl₆]³⁻ octahedra in 1, from face-sharing bioctahedral [Bi₂Cl₉]³⁻ units in 3, from polymeric corner-sharing {[BiCl₅]²⁻}_n chains in 2 and from edge-sharing {[BiCl₄]⁻}_n chains in 4. The distortions shown by the single [BiCl₆]³⁻ polyhedra in 1–4 are associated with intrinsic interactions within the anionic substructures and the organic...inorganic substructures interactions, namely, N/C—H...Cl hydrogen bonds. The first factor is the stronger, which is evident in com­parison of the experimentally determined geometrical and calculated distortion parameters for the isolated octahedron in 1 to the more com­plex inorganic substructures in 2–4. The formation of N—H...Cl hydrogen bonds, in terms of their number and strength, is favoured for 1 and 3 containing relatively easily accessed hydrogen-bond acceptors of isolated [BiCl₆]³⁻ and [Bi₂Cl₉]³⁻ units. The studies of the deviations from regularity of the [BiCl₆]³⁻ octahedra within inorganic substructures were supported by a survey of the Cambridge Structural Database, which confirmed the role played by different factors in the variations in geometry of the inorganic anions.

Computing details

For all structures, data collection: CrysAlis CCD 1.171.29.10 (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO 1.171.40.56a (Rigaku Oxford Diffraction, 2019); data reduction: CrysAlis PRO 1.171.40.56a (Rigaku Oxford Diffraction, 2019); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014); molecular graphics: Mercury (Macrae at al., 2020); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2014).

Tris(N,N-dimethylethane-1,2-diammonium) bis[hexachloridobismuthate(III)] (NNBiCl_1_295K)

Crystal data

(C4H14N2)3[BiCl6]2	F(000) = 2104
Mr = 1113.88	Dx = 2.144 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.8842 (4) Å	Cell parameters from 8308 reflections
b = 10.19431 (13) Å	θ = 3.2–29.5°
c = 12.45639 (17) Å	µ = 11.13 mm^−1
β = 102.9110 (14)°	T = 295 K
V = 3451.34 (8) Å^3	Plate, colourless
Z = 4	0.25 × 0.16 × 0.09 mm

Data collection

Xcalibur diffractometer	3130 reflections with I > 2σ(I)
ω–scan	Rint = 0.017
Absorption correction: multi-scan CrysAlisPro 1.171.40.56a (Rigaku Oxford Diffraction, 2019) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θmax = 26.0°, θmin = 3.0°
Tmin = 0.30, Tmax = 1.00	h = −34→34
11329 measured reflections	k = −9→12
3386 independent reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.016	H-atom parameters constrained
wR(F^2) = 0.037	w = 1/[σ^2(Fo^2) + (0.0163P)^2 + 4.6776P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.003
3386 reflections	Δρmax = 0.63 e Å^−3
189 parameters	Δρmin = −0.45 e Å^−3
18 restraints	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00068 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0.12880 (2)	0.19413 (2)	0.59479 (2)	0.03268 (5)
Cl1	0.14239 (4)	0.07948 (9)	0.79109 (7)	0.0631 (3)
Cl2	0.12098 (3)	0.31871 (8)	0.39393 (7)	0.04733 (19)
Cl3	0.18255 (3)	0.40206 (7)	0.68834 (6)	0.04779 (19)
Cl4	0.07140 (3)	−0.00882 (8)	0.50912 (7)	0.0525 (2)
Cl5	0.21238 (3)	0.08005 (9)	0.56471 (7)	0.0559 (2)
Cl6	0.04708 (4)	0.31178 (11)	0.63193 (11)	0.0798 (3)
N21	0.20715 (11)	0.8141 (3)	0.8035 (2)	0.0542 (7)
H211	0.2383	0.8247	0.8392	0.081*
H212	0.1922	0.7596	0.8412	0.081*
H213	0.1919	0.8914	0.7966	0.081*
C21	0.20558 (13)	0.7592 (4)	0.6935 (3)	0.0528 (8)
H214	0.2235	0.6769	0.7012	0.063*
H215	0.2218	0.8191	0.6526	0.063*
C22	0.15403 (12)	0.7362 (3)	0.6307 (3)	0.0454 (7)
H223	0.1417	0.6578	0.6595	0.054*
H224	0.1339	0.8091	0.6446	0.054*
N221	0.14721 (17)	0.7210 (5)	0.5098 (4)	0.0482 (12)	0.660 (8)
H221	0.1472	0.8091	0.4783	0.058*	0.660 (8)
N222	0.1510 (3)	0.6437 (10)	0.5384 (7)	0.0428 (19)	0.340 (8)
H222	0.1516	0.5557	0.5703	0.051*	0.340 (8)
C23	0.09882 (15)	0.6601 (4)	0.4610 (3)	0.0663 (11)
H231	0.0940	0.6583	0.3822	0.099*
H232	0.0731	0.7106	0.4810	0.099*
H233	0.0981	0.5722	0.4882	0.099*
C24	0.18779 (16)	0.6442 (4)	0.4764 (3)	0.0671 (11)
H241	0.2183	0.6910	0.4987	0.101*
H242	0.1802	0.6331	0.3979	0.101*
H243	0.1907	0.5598	0.5114	0.101*
N11	−0.0090 (4)	−0.0775 (5)	0.2653 (10)	0.058 (2)	0.5
H111	−0.0090	−0.0789	0.3367	0.086*	0.5
H112	0.0078	−0.1461	0.2490	0.086*	0.5
H113	−0.0398	−0.0814	0.2259	0.086*	0.5
C11	0.0142 (2)	0.0444 (6)	0.2391 (5)	0.0393 (14)	0.5
H114	0.0119	0.0498	0.1603	0.047*	0.5
H115	0.0487	0.0450	0.2760	0.047*	0.5
C12	−0.0117 (2)	0.1610 (6)	0.2767 (5)	0.0408 (14)	0.5
H122	−0.0456	0.1635	0.2354	0.049*	0.5
H123	−0.0119	0.1507	0.3540	0.049*	0.5
N12	0.01278 (16)	0.2863 (5)	0.2610 (6)	0.0428 (14)	0.5
H121	0.0478	0.2758	0.2950	0.051*	0.5
C13	0.0084 (3)	0.3990 (8)	0.1891 (7)	0.060 (2)	0.5
H131	−0.0047	0.3720	0.1144	0.090*	0.5
H132	0.0402	0.4378	0.1947	0.090*	0.5
H133	−0.0133	0.4621	0.2104	0.090*	0.5
C14	−0.0138 (3)	0.3143 (8)	0.3549 (7)	0.0554 (18)	0.5
H141	0.0100	0.3358	0.4210	0.083*	0.5
H142	−0.0319	0.2380	0.3676	0.083*	0.5
H143	−0.0361	0.3866	0.3346	0.083*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.03254 (7)	0.03421 (7)	0.03032 (7)	0.00249 (4)	0.00497 (4)	0.00204 (4)
Cl1	0.1046 (8)	0.0494 (5)	0.0396 (4)	0.0095 (5)	0.0250 (5)	0.0098 (4)
Cl2	0.0458 (4)	0.0540 (5)	0.0396 (4)	−0.0010 (3)	0.0040 (3)	0.0097 (3)
Cl3	0.0573 (5)	0.0402 (4)	0.0406 (4)	−0.0056 (3)	−0.0002 (4)	0.0021 (3)
Cl4	0.0532 (5)	0.0522 (5)	0.0479 (4)	−0.0114 (4)	0.0024 (4)	−0.0035 (4)
Cl5	0.0420 (4)	0.0650 (5)	0.0597 (5)	0.0116 (4)	0.0093 (4)	−0.0031 (4)
Cl6	0.0629 (6)	0.0810 (7)	0.0960 (8)	0.0308 (5)	0.0188 (6)	−0.0121 (6)
N21	0.0446 (17)	0.068 (2)	0.0472 (17)	0.0034 (14)	0.0034 (13)	−0.0123 (14)
C21	0.048 (2)	0.062 (2)	0.0460 (19)	−0.0005 (17)	0.0071 (16)	−0.0123 (17)
C22	0.0490 (19)	0.0435 (17)	0.0393 (17)	0.0097 (15)	0.0008 (14)	−0.0025 (14)
N221	0.061 (2)	0.045 (3)	0.035 (2)	0.000 (2)	0.0030 (18)	0.0036 (18)
N222	0.051 (3)	0.040 (3)	0.034 (3)	0.002 (3)	0.003 (3)	0.003 (3)
C23	0.069 (3)	0.063 (2)	0.055 (2)	0.000 (2)	−0.0121 (19)	−0.0109 (19)
C24	0.083 (3)	0.081 (3)	0.043 (2)	−0.002 (2)	0.026 (2)	−0.0013 (19)
N11	0.065 (7)	0.045 (3)	0.064 (7)	−0.003 (3)	0.018 (4)	−0.002 (3)
C11	0.035 (4)	0.048 (4)	0.034 (3)	0.001 (2)	0.007 (3)	0.001 (3)
C12	0.033 (3)	0.052 (4)	0.038 (4)	0.006 (3)	0.009 (2)	0.003 (3)
N12	0.030 (4)	0.046 (3)	0.050 (4)	0.0008 (19)	0.004 (4)	−0.008 (3)
C13	0.050 (4)	0.063 (5)	0.066 (5)	−0.006 (4)	0.009 (4)	0.019 (4)
C14	0.056 (5)	0.055 (5)	0.055 (5)	0.002 (4)	0.013 (4)	−0.005 (4)

Geometric parameters (Å, º)

Bi1—Cl1	2.6597 (8)	C23—H233	0.9600
Bi1—Cl4	2.6866 (8)	C24—H241	0.9600
Bi1—Cl5	2.7045 (8)	C24—H242	0.9600
Bi1—Cl6	2.7047 (10)	C24—H243	0.9600
Bi1—Cl3	2.7049 (8)	N11—C11	1.471 (7)
Bi1—Cl2	2.7707 (8)	N11—H111	0.8900
N21—C21	1.471 (4)	N11—H112	0.8900
N21—H211	0.8900	N11—H113	0.8900
N21—H212	0.8900	C11—C12	1.518 (8)
N21—H213	0.8900	C11—H114	0.9700
C21—C22	1.494 (5)	C11—H115	0.9700
C21—H214	0.9700	C12—N12	1.481 (8)
C21—H215	0.9700	C12—C14	1.850 (9)
C22—N222	1.475 (8)	C12—H122	0.9700
C22—N221	1.483 (5)	C12—H123	0.9700
C22—H223	0.9700	N12—C13	1.445 (9)
C22—H224	0.9700	N12—C14	1.547 (11)
N221—C23	1.486 (6)	N12—H121	0.9800
N221—C24	1.508 (6)	C13—H131	0.9600
N221—H221	0.9800	C13—H132	0.9600
N222—C24	1.415 (9)	C13—H133	0.9600
N222—C23	1.565 (9)	C14—H141	0.9600
N222—H222	0.9800	C14—H142	0.9600
C23—H231	0.9600	C14—H143	0.9600
C23—H232	0.9600
Cl1—Bi1—Cl4	88.66 (3)	H232—C23—H233	109.5
Cl1—Bi1—Cl5	89.33 (3)	N221—C24—H241	109.5
Cl4—Bi1—Cl5	93.97 (3)	N221—C24—H242	109.5
Cl1—Bi1—Cl6	89.43 (4)	H241—C24—H242	109.5
Cl4—Bi1—Cl6	87.68 (3)	N221—C24—H243	109.5
Cl5—Bi1—Cl6	177.91 (3)	H241—C24—H243	109.5
Cl1—Bi1—Cl3	89.82 (3)	H242—C24—H243	109.5
Cl4—Bi1—Cl3	176.53 (3)	C11—N11—H111	109.5
Cl5—Bi1—Cl3	89.14 (3)	C11—N11—H112	109.5
Cl6—Bi1—Cl3	89.18 (3)	H111—N11—H112	109.5
Cl1—Bi1—Cl2	176.27 (3)	C11—N11—H113	109.5
Cl4—Bi1—Cl2	94.28 (2)	H111—N11—H113	109.5
Cl5—Bi1—Cl2	88.19 (3)	H112—N11—H113	109.5
Cl6—Bi1—Cl2	92.97 (3)	N11—C11—C12	109.3 (5)
Cl3—Bi1—Cl2	87.37 (2)	N11—C11—H114	109.8
C21—N21—H211	109.5	C12—C11—H114	109.8
C21—N21—H212	109.5	N11—C11—H115	109.8
H211—N21—H212	109.5	C12—C11—H115	109.8
C21—N21—H213	109.5	H114—C11—H115	108.3
H211—N21—H213	109.5	N12—C12—C11	111.6 (5)
H212—N21—H213	109.5	N12—C12—C14	54.0 (4)
N21—C21—C22	111.9 (3)	C11—C12—C14	153.9 (5)
N21—C21—H214	109.2	N12—C12—H122	109.3
C22—C21—H214	109.2	C11—C12—H122	109.3
N21—C21—H215	109.2	C14—C12—H122	96.6
C22—C21—H215	109.2	N12—C12—H123	109.3
H214—C21—H215	107.9	C11—C12—H123	109.3
N222—C22—C21	112.9 (4)	C14—C12—H123	63.9
N221—C22—C21	116.0 (3)	H122—C12—H123	108.0
N221—C22—H223	108.3	C13—N12—C12	142.2 (6)
C21—C22—H223	108.3	C13—N12—C14	109.5 (6)
N221—C22—H224	108.3	C12—N12—C14	75.3 (5)
C21—C22—H224	108.3	C13—N12—H121	107.0
H223—C22—H224	107.4	C12—N12—H121	107.0
C22—N221—C23	111.0 (4)	C14—N12—H121	107.0
C22—N221—C24	113.6 (4)	N12—C13—H131	109.5
C23—N221—C24	109.8 (4)	N12—C13—H132	109.5
C22—N221—H221	107.4	H131—C13—H132	109.5
C23—N221—H221	107.4	N12—C13—H133	109.5
C24—N221—H221	107.4	H131—C13—H133	109.5
C24—N222—C22	120.0 (7)	H132—C13—H133	109.5
C24—N222—C23	110.6 (6)	N12—C14—C12	50.8 (3)
C22—N222—C23	107.2 (6)	N12—C14—H141	109.5
C24—N222—H222	106.0	C12—C14—H141	123.1
C22—N222—H222	106.0	N12—C14—H142	109.5
C23—N222—H222	106.0	C12—C14—H142	58.8
N221—C23—H231	109.5	H141—C14—H142	109.5
N221—C23—H232	109.5	N12—C14—H143	109.5
H231—C23—H232	109.5	C12—C14—H143	127.2
N221—C23—H233	109.5	H141—C14—H143	109.5
H231—C23—H233	109.5	H142—C14—H143	109.5
N21—C21—C22—N222	−161.1 (5)	N11—C11—C12—C14	124.1 (12)
N21—C21—C22—N221	161.7 (4)	C11—C12—N12—C13	102.2 (10)
C21—C22—N221—C23	163.0 (4)	C14—C12—N12—C13	−102.9 (11)
C21—C22—N221—C24	38.6 (5)	C11—C12—N12—C14	−154.9 (6)
C21—C22—N222—C24	−36.6 (9)	C13—N12—C14—C12	140.6 (6)
C21—C22—N222—C23	−163.7 (5)	C11—C12—C14—N12	63.5 (12)
N11—C11—C12—N12	175.2 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H113···Cl1^i	0.89	2.82	3.628 (11)	152
N11—H111···Cl4	0.89	2.83	3.421 (14)	125
N11—H111···Cl6^i	0.89	2.66	3.013 (6)	105
N11—H112···Cl6^ii	0.89	2.63	3.474 (6)	160
N12—H121···Cl2	0.98	2.18	3.118 (5)	160
N21—H213···Cl1^iii	0.89	2.35	3.237 (3)	171
N21—H212···Cl2^iv	0.89	2.36	3.176 (3)	152
N21—H211···Cl3^v	0.89	2.44	3.183 (3)	142
N221—H221···Cl1^vi	0.98	2.57	3.379 (5)	140
N221—H221···Cl4^iii	0.98	2.90	3.471 (5)	118
N222—H222···Cl3	0.98	2.19	3.098 (11)	154
C11—H114···Cl4^ii	0.97	2.81	3.595 (6)	139
C11—H114···Cl4^vii	0.97	2.83	3.500 (7)	127
C11—H115···Cl4	0.97	2.88	3.429 (7)	117
C12—H122···Cl2^vii	0.97	2.83	3.673 (6)	146
C13—H132···Cl6^vi	0.96	2.69	3.272 (8)	120
C14—H141···Cl6	0.96	2.61	3.489 (8)	152
C21—H215···Cl5^iii	0.97	2.87	3.667 (4)	141
C22—H223···Cl3	0.97	2.84	3.535 (3)	130
C22—H224···Cl4^iii	0.97	2.83	3.577 (3)	134
C23—H232···Cl4^iii	0.96	2.88	3.541 (4)	127
C24—H242···Cl3^vi	0.96	2.65	3.590 (4)	166
C24—H243···Cl3	0.96	2.78	3.641 (4)	150

Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y, z−1/2; (iii) x, y+1, z; (iv) x, −y+1, z+1/2; (v) −x+1/2, y+1/2, −z+3/2; (vi) x, −y+1, z−1/2; (vii) −x, y, −z+1/2.

Tris(N,N-dimethylethane-1,2-diammonium) bis[hexachloridobismuthate(III)] (NNBiCl_1_100K)

Crystal data

(C4H14N2)3[BiCl6]2	F(000) = 2104
Mr = 1113.88	Dx = 2.194 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.5447 (3) Å	Cell parameters from 9666 reflections
b = 10.14187 (11) Å	θ = 3.1–29.5°
c = 12.38379 (14) Å	µ = 11.39 mm^−1
β = 102.9055 (12)°	T = 100 K
V = 3372.08 (7) Å^3	Plate, colourless
Z = 4	0.25 × 0.16 × 0.09 mm

Data collection

Xcalibur diffractometer	3182 reflections with I > 2σ(I)
ω–scan	Rint = 0.014
Absorption correction: multi-scan CrysAlisPro 1.171.40.56a (Rigaku Oxford Diffraction, 2019) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θmax = 26.0°, θmin = 3.0°
Tmin = 0.25, Tmax = 1.00	h = −33→33
10977 measured reflections	k = −8→12
3301 independent reflections	l = −15→15

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)] = 0.016	Hydrogen site location: difference Fourier map
wR(F^2) = 0.037	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0171P)^2 + 9.7374P] where P = (Fo^2 + 2Fc^2)/3
3301 reflections	(Δ/σ)max = 0.004
188 parameters	Δρmax = 0.92 e Å^−3
18 restraints	Δρmin = −0.88 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0.12889 (2)	0.19747 (2)	0.59449 (2)	0.01351 (4)
Cl1	0.14238 (3)	0.08234 (7)	0.79430 (6)	0.02641 (17)
Cl2	0.12157 (3)	0.32433 (7)	0.39517 (6)	0.02001 (14)
Cl3	0.18234 (3)	0.40586 (7)	0.68923 (5)	0.01988 (14)
Cl4	0.07098 (3)	−0.00762 (7)	0.50787 (6)	0.02230 (15)
Cl5	0.21344 (3)	0.08319 (7)	0.56496 (6)	0.02164 (15)
Cl6	0.04548 (4)	0.31386 (11)	0.63160 (10)	0.0507 (3)
N21	0.20711 (10)	0.8168 (3)	0.8057 (2)	0.0224 (6)
H211	0.2386	0.8298	0.8410	0.034*
H212	0.1930	0.7586	0.8431	0.034*
H213	0.1906	0.8927	0.8007	0.034*
C21	0.20562 (12)	0.7652 (3)	0.6924 (2)	0.0219 (6)
H214	0.2250	0.6846	0.6976	0.026*
H215	0.2203	0.8292	0.6511	0.026*
C22	0.15256 (12)	0.7379 (3)	0.6325 (2)	0.0211 (6)
H223	0.1413	0.6579	0.6622	0.025*
H224	0.1316	0.8097	0.6469	0.025*
N221	0.14607 (13)	0.7228 (4)	0.5100 (3)	0.0239 (9)	0.813 (7)
H221	0.1467	0.8114	0.4788	0.029*	0.813 (7)
N222	0.1501 (5)	0.6447 (16)	0.5366 (11)	0.019 (2)	0.187 (7)
H222	0.1502	0.5558	0.5677	0.023*	0.187 (7)
C23	0.09665 (13)	0.6636 (3)	0.4595 (3)	0.0291 (7)
H231	0.0923	0.6608	0.3804	0.044*
H232	0.0707	0.7162	0.4782	0.044*
H233	0.0951	0.5757	0.4873	0.044*
C24	0.18666 (13)	0.6445 (3)	0.4768 (3)	0.0283 (7)
H241	0.2183	0.6846	0.5074	0.042*
H242	0.1812	0.6428	0.3974	0.042*
H243	0.1864	0.5560	0.5042	0.042*
N11	−0.0105 (2)	−0.0788 (5)	0.2663 (5)	0.0209 (12)	0.5
H111	−0.0081	−0.0832	0.3391	0.031*	0.5
H112	0.0043	−0.1486	0.2444	0.031*	0.5
H113	−0.0425	−0.0779	0.2316	0.031*	0.5
C11	0.0139 (2)	0.0429 (5)	0.2395 (5)	0.0150 (12)	0.5
H114	0.0118	0.0477	0.1604	0.018*	0.5
H115	0.0488	0.0427	0.2772	0.018*	0.5
C12	−0.0123 (2)	0.1610 (6)	0.2767 (5)	0.0157 (11)	0.5
H122	−0.0465	0.1643	0.2347	0.019*	0.5
H123	−0.0127	0.1514	0.3544	0.019*	0.5
N12	0.01358 (16)	0.2863 (4)	0.2603 (5)	0.0165 (12)	0.5
H121	0.0491	0.2752	0.2933	0.020*	0.5
C13	0.0079 (2)	0.4019 (6)	0.1910 (5)	0.0229 (13)	0.5
H131	−0.0035	0.3764	0.1149	0.034*	0.5
H132	0.0394	0.4461	0.2003	0.034*	0.5
H133	−0.0159	0.4603	0.2117	0.034*	0.5
C14	−0.0143 (2)	0.3129 (6)	0.3582 (5)	0.0205 (13)	0.5
H141	0.0099	0.3307	0.4254	0.031*	0.5
H142	−0.0334	0.2367	0.3682	0.031*	0.5
H143	−0.0360	0.3875	0.3397	0.031*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01258 (6)	0.01472 (6)	0.01197 (6)	0.00171 (4)	0.00004 (4)	0.00031 (4)
Cl1	0.0470 (5)	0.0187 (3)	0.0164 (3)	0.0031 (3)	0.0132 (3)	0.0028 (3)
Cl2	0.0195 (4)	0.0206 (3)	0.0173 (3)	−0.0019 (3)	−0.0015 (3)	0.0037 (3)
Cl3	0.0263 (4)	0.0170 (3)	0.0140 (3)	−0.0029 (3)	−0.0003 (3)	0.0009 (3)
Cl4	0.0234 (4)	0.0242 (4)	0.0166 (3)	−0.0058 (3)	−0.0015 (3)	0.0007 (3)
Cl5	0.0169 (3)	0.0256 (4)	0.0214 (3)	0.0031 (3)	0.0022 (3)	−0.0008 (3)
Cl6	0.0305 (5)	0.0552 (6)	0.0601 (7)	0.0248 (4)	−0.0031 (5)	−0.0199 (5)
N21	0.0212 (14)	0.0259 (14)	0.0172 (13)	0.0045 (11)	−0.0019 (11)	−0.0050 (10)
C21	0.0238 (16)	0.0254 (16)	0.0155 (14)	−0.0024 (13)	0.0022 (12)	−0.0069 (12)
C22	0.0262 (17)	0.0186 (14)	0.0148 (14)	0.0049 (12)	−0.0031 (12)	−0.0027 (12)
N221	0.0330 (18)	0.0205 (19)	0.0147 (15)	−0.0024 (14)	−0.0019 (13)	0.0017 (13)
N222	0.023 (4)	0.018 (4)	0.014 (4)	−0.001 (3)	−0.001 (3)	0.000 (3)
C23	0.034 (2)	0.0240 (16)	0.0223 (16)	−0.0019 (14)	−0.0087 (14)	−0.0028 (13)
C24	0.038 (2)	0.0319 (18)	0.0145 (15)	−0.0022 (15)	0.0062 (14)	−0.0010 (13)
N11	0.019 (4)	0.019 (2)	0.025 (4)	0.002 (2)	0.003 (2)	0.001 (2)
C11	0.017 (3)	0.018 (3)	0.010 (3)	0.001 (2)	0.003 (2)	0.001 (2)
C12	0.012 (3)	0.019 (3)	0.015 (3)	0.003 (2)	0.003 (2)	0.002 (2)
N12	0.013 (3)	0.018 (2)	0.017 (3)	0.0012 (16)	0.002 (3)	−0.004 (2)
C13	0.020 (3)	0.023 (3)	0.025 (3)	−0.005 (3)	0.003 (3)	0.005 (3)
C14	0.024 (3)	0.020 (3)	0.016 (3)	0.000 (2)	0.004 (2)	0.000 (2)

Geometric parameters (Å, º)

Bi1—Cl1	2.6858 (7)	C23—H233	0.9600
Bi1—Cl3	2.6906 (7)	C24—H241	0.9600
Bi1—Cl4	2.6939 (7)	C24—H242	0.9600
Bi1—Cl5	2.6985 (7)	C24—H243	0.9600
Bi1—Cl6	2.7120 (9)	N11—C11	1.478 (7)
Bi1—Cl2	2.7507 (7)	N11—H111	0.8900
N21—C21	1.489 (4)	N11—H112	0.8900
N21—H211	0.8900	N11—H113	0.8900
N21—H212	0.8900	C11—C12	1.521 (7)
N21—H213	0.8900	C11—H114	0.9700
C21—C22	1.510 (4)	C11—H115	0.9700
C21—H214	0.9700	C12—N12	1.494 (7)
C21—H215	0.9700	C12—C14	1.849 (8)
C22—N221	1.495 (4)	C12—H122	0.9700
C22—N222	1.508 (13)	C12—H123	0.9700
C22—H223	0.9700	N12—C13	1.440 (8)
C22—H224	0.9700	N12—C14	1.596 (8)
N221—C23	1.491 (5)	N12—H121	0.9800
N221—C24	1.502 (5)	C13—H131	0.9600
N221—H221	0.9800	C13—H132	0.9600
N222—C24	1.377 (14)	C13—H133	0.9600
N222—C23	1.577 (14)	C14—H141	0.9600
N222—H222	0.9800	C14—H142	0.9600
C23—H231	0.9600	C14—H143	0.9600
C23—H232	0.9600
Cl1—Bi1—Cl3	89.43 (2)	H232—C23—H233	109.5
Cl1—Bi1—Cl4	88.79 (2)	N221—C24—H241	109.5
Cl3—Bi1—Cl4	176.20 (2)	N221—C24—H242	109.5
Cl1—Bi1—Cl5	89.55 (2)	H241—C24—H242	109.5
Cl3—Bi1—Cl5	89.53 (2)	N221—C24—H243	109.5
Cl4—Bi1—Cl5	93.82 (2)	H241—C24—H243	109.5
Cl1—Bi1—Cl6	88.92 (3)	H242—C24—H243	109.5
Cl3—Bi1—Cl6	89.19 (3)	C11—N11—H111	109.5
Cl4—Bi1—Cl6	87.41 (3)	C11—N11—H112	109.5
Cl5—Bi1—Cl6	178.02 (3)	H111—N11—H112	109.5
Cl1—Bi1—Cl2	175.87 (2)	C11—N11—H113	109.5
Cl3—Bi1—Cl2	86.97 (2)	H111—N11—H113	109.5
Cl4—Bi1—Cl2	94.91 (2)	H112—N11—H113	109.5
Cl5—Bi1—Cl2	88.38 (2)	N11—C11—C12	108.7 (4)
Cl6—Bi1—Cl2	93.06 (3)	N11—C11—H114	110.0
C21—N21—H211	109.5	C12—C11—H114	110.0
C21—N21—H212	109.5	N11—C11—H115	110.0
H211—N21—H212	109.5	C12—C11—H115	110.0
C21—N21—H213	109.5	H114—C11—H115	108.3
H211—N21—H213	109.5	N12—C12—C11	110.9 (4)
H212—N21—H213	109.5	N12—C12—C14	55.8 (3)
N21—C21—C22	110.3 (3)	C11—C12—C14	153.5 (5)
N21—C21—H214	109.6	N12—C12—H122	109.5
C22—C21—H214	109.6	C11—C12—H122	109.5
N21—C21—H215	109.6	C14—C12—H122	96.9
C22—C21—H215	109.6	N12—C12—H123	109.5
H214—C21—H215	108.1	C11—C12—H123	109.5
N221—C22—C21	113.7 (3)	C14—C12—H123	62.3
N222—C22—C21	111.7 (6)	H122—C12—H123	108.1
N221—C22—H223	108.8	C13—N12—C12	141.5 (5)
C21—C22—H223	108.8	C13—N12—C14	107.9 (4)
N221—C22—H224	108.8	C12—N12—C14	73.5 (4)
C21—C22—H224	108.8	C13—N12—H121	107.9
H223—C22—H224	107.7	C12—N12—H121	107.9
C23—N221—C22	111.0 (3)	C14—N12—H121	107.9
C23—N221—C24	109.7 (3)	N12—C13—H131	109.5
C22—N221—C24	113.9 (3)	N12—C13—H132	109.5
C23—N221—H221	107.3	H131—C13—H132	109.5
C22—N221—H221	107.3	N12—C13—H133	109.5
C24—N221—H221	107.3	H131—C13—H133	109.5
C24—N222—C22	121.0 (10)	H132—C13—H133	109.5
C24—N222—C23	111.7 (9)	N12—C14—C12	50.7 (3)
C22—N222—C23	105.8 (9)	N12—C14—H141	109.5
C24—N222—H222	105.7	C12—C14—H141	122.0
C22—N222—H222	105.7	N12—C14—H142	109.5
C23—N222—H222	105.7	C12—C14—H142	58.9
N221—C23—H231	109.5	H141—C14—H142	109.5
N221—C23—H232	109.5	N12—C14—H143	109.5
H231—C23—H232	109.5	C12—C14—H143	128.3
N221—C23—H233	109.5	H141—C14—H143	109.5
H231—C23—H233	109.5	H142—C14—H143	109.5
N21—C21—C22—N221	163.7 (3)	N11—C11—C12—C14	120.9 (10)
N21—C21—C22—N222	−160.4 (7)	C11—C12—N12—C13	107.8 (8)
C21—C22—N221—C23	165.8 (3)	C14—C12—N12—C13	−98.2 (8)
C21—C22—N221—C24	41.3 (4)	C11—C12—N12—C14	−154.0 (5)
C21—C22—N222—C24	−32.7 (14)	C13—N12—C14—C12	139.6 (5)
C21—C22—N222—C23	−160.9 (6)	C11—C12—C14—N12	66.6 (10)
N11—C11—C12—N12	175.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H113···Cl1^i	0.89	2.70	3.541 (5)	159
N11—H111···Cl4	0.89	2.77	3.392 (7)	128
N11—H111···Cl6^i	0.89	2.61	2.959 (5)	104
N11—H112···Cl6^ii	0.89	2.60	3.463 (5)	164
N12—H121···Cl2	0.98	2.17	3.093 (4)	157
N21—H213···Cl1^iii	0.89	2.33	3.216 (3)	175
N21—H212···Cl2^iv	0.89	2.36	3.161 (3)	150
N21—H211···Cl3^v	0.89	2.42	3.163 (3)	142
N221—H221···Cl1^vi	0.98	2.51	3.307 (4)	139
N221—H221···Cl4^iii	0.98	2.86	3.425 (4)	118
N222—H222···Cl3	0.98	2.18	3.079 (17)	151
C11—H114···Cl4^ii	0.97	2.79	3.584 (5)	140
C11—H114···Cl4^vii	0.97	2.78	3.451 (6)	127
C11—H115···Cl4	0.97	2.83	3.383 (6)	117
C12—H122···Cl2^vii	0.97	2.83	3.671 (6)	145
C13—H132···Cl6^vi	0.96	2.60	3.203 (6)	121
C14—H141···Cl6	0.96	2.53	3.419 (6)	154
C21—H215···Cl5^iii	0.97	2.78	3.619 (3)	145
C22—H223···Cl3	0.97	2.78	3.500 (3)	131
C22—H224···Cl4^iii	0.97	2.81	3.542 (3)	133
C23—H232···Cl4^iii	0.96	2.82	3.488 (3)	127
C24—H242···Cl3^vi	0.96	2.63	3.573 (3)	166
C24—H243···Cl3	0.96	2.77	3.596 (3)	144

Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y, z−1/2; (iii) x, y+1, z; (iv) x, −y+1, z+1/2; (v) −x+1/2, y+1/2, −z+3/2; (vi) x, −y+1, z−1/2; (vii) −x, y, −z+1/2.

catena-Poly[N,N-dimethylethane-1,2-diammonium [[tetrachloridobismuthate(III)]-µ-chlorido]] (NNBiCl_2_295K)

Crystal data

(C4H14N2)[BiCl5]	Dx = 2.442 Mg m^−3
Mr = 476.40	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 8285 reflections
a = 7.60312 (9) Å	θ = 3.1–29.7°
b = 12.50404 (14) Å	µ = 14.60 mm^−1
c = 13.63023 (15) Å	T = 295 K
V = 1295.82 (3) Å^3	Pillar, colourless
Z = 4	0.35 × 0.23 × 0.13 mm
F(000) = 880

Data collection

Xcalibur diffractometer	2514 reflections with I > 2σ(I)
ω–scan	Rint = 0.012
Absorption correction: analytical CrysAlisPro 1.171.40.56a (Rigaku Oxford Diffraction, 2019) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θmax = 26.0°, θmin = 3.1°
Tmin = 0.06, Tmax = 0.22	h = −9→5
8742 measured reflections	k = −15→15
2545 independent reflections	l = −16→16

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.010	w = 1/[σ^2(Fo^2) + (0.0097P)^2 + 0.4838P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.024	(Δ/σ)max = 0.001
S = 1.14	Δρmax = 0.46 e Å^−3
2545 reflections	Δρmin = −0.31 e Å^−3
113 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00133 (10)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 1035 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.031 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Bi1	0.18597 (2)	0.39389 (2)	0.06540 (2)	0.02607 (5)
Cl1	0.48961 (14)	0.47531 (10)	0.10365 (9)	0.0464 (3)
Cl2	−0.13638 (14)	0.29292 (10)	0.00821 (9)	0.0482 (3)
Cl3	0.02510 (16)	0.56208 (9)	0.12695 (8)	0.0448 (3)
Cl4	0.19903 (16)	0.48399 (9)	−0.11328 (8)	0.0456 (3)
Cl5	0.15790 (18)	0.29450 (9)	0.24127 (8)	0.0482 (3)
N1	0.8915 (5)	0.5624 (3)	0.3614 (3)	0.0459 (10)
H11	0.9031	0.6206	0.3244	0.069*
H12	0.9936	0.5278	0.3641	0.069*
H13	0.8591	0.5814	0.4217	0.069*
N2	0.5883 (5)	0.3251 (3)	0.3396 (3)	0.0430 (9)
H21	0.4903	0.3708	0.3192	0.052*
C1	0.7568 (6)	0.4921 (5)	0.3186 (4)	0.0530 (12)
H14	0.7936	0.4696	0.2537	0.064*
H15	0.6471	0.5311	0.3121	0.064*
C2	0.7293 (6)	0.3968 (4)	0.3816 (4)	0.0494 (11)
H22	0.6952	0.4196	0.4469	0.059*
H23	0.8385	0.3572	0.3869	0.059*
C3	0.6432 (8)	0.2614 (5)	0.2529 (4)	0.0603 (15)
H31	0.6803	0.3087	0.2014	0.090*
H32	0.5459	0.2191	0.2304	0.090*
H33	0.7388	0.2152	0.2707	0.090*
C4	0.5220 (9)	0.2529 (4)	0.4179 (4)	0.0667 (16)
H41	0.4759	0.2948	0.4710	0.100*
H42	0.6166	0.2090	0.4415	0.100*
H43	0.4307	0.2081	0.3918	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.02598 (7)	0.02497 (7)	0.02727 (7)	−0.00014 (6)	0.00064 (6)	−0.00007 (6)
Cl1	0.0341 (5)	0.0450 (6)	0.0601 (7)	−0.0077 (5)	−0.0095 (5)	−0.0042 (5)
Cl2	0.0390 (6)	0.0489 (7)	0.0568 (7)	−0.0115 (5)	−0.0036 (5)	−0.0088 (5)
Cl3	0.0535 (7)	0.0391 (6)	0.0418 (6)	0.0107 (5)	0.0081 (5)	−0.0064 (5)
Cl4	0.0427 (6)	0.0550 (6)	0.0390 (5)	0.0119 (6)	0.0061 (5)	0.0150 (5)
Cl5	0.0643 (8)	0.0461 (6)	0.0342 (5)	−0.0105 (6)	0.0002 (5)	0.0062 (4)
N1	0.040 (2)	0.050 (2)	0.048 (2)	−0.0048 (18)	−0.0029 (18)	0.0072 (19)
N2	0.040 (2)	0.0320 (19)	0.057 (2)	0.0057 (16)	−0.0008 (18)	−0.0030 (18)
C1	0.038 (2)	0.062 (3)	0.060 (3)	−0.009 (2)	−0.007 (2)	0.012 (3)
C2	0.047 (3)	0.049 (3)	0.052 (3)	0.002 (2)	−0.003 (2)	0.005 (3)
C3	0.064 (4)	0.066 (4)	0.051 (3)	0.018 (3)	0.002 (3)	−0.011 (3)
C4	0.089 (4)	0.047 (3)	0.064 (4)	−0.004 (3)	0.014 (3)	−0.002 (3)

Geometric parameters (Å, º)

Bi1—Cl3	2.5735 (11)	N2—C2	1.510 (6)
Bi1—Cl1	2.5764 (11)	N2—H21	0.9800
Bi1—Cl4	2.6853 (10)	C1—C2	1.483 (7)
Bi1—Cl5	2.7085 (11)	C1—H14	0.9700
Bi1—Cl2	2.8650 (11)	C1—H15	0.9700
Bi1—Cl2^i	2.8788 (11)	C2—H22	0.9700
Cl2—Bi1^ii	2.8787 (11)	C2—H23	0.9700
N1—C1	1.470 (6)	C3—H31	0.9600
N1—H11	0.8900	C3—H32	0.9600
N1—H12	0.8900	C3—H33	0.9600
N1—H13	0.8900	C4—H41	0.9600
N2—C3	1.485 (6)	C4—H42	0.9600
N2—C4	1.486 (6)	C4—H43	0.9600
Cl3—Bi1—Cl1	92.12 (4)	C4—N2—H21	107.5
Cl3—Bi1—Cl4	88.30 (4)	C2—N2—H21	107.5
Cl1—Bi1—Cl4	89.12 (4)	N1—C1—C2	110.4 (4)
Cl3—Bi1—Cl5	92.81 (4)	N1—C1—H14	109.6
Cl1—Bi1—Cl5	94.18 (4)	C2—C1—H14	109.6
Cl4—Bi1—Cl5	176.48 (4)	N1—C1—H15	109.6
Cl3—Bi1—Cl2	92.42 (4)	C2—C1—H15	109.6
Cl1—Bi1—Cl2	174.69 (4)	H14—C1—H15	108.1
Cl4—Bi1—Cl2	88.27 (4)	C1—C2—N2	111.0 (4)
Cl5—Bi1—Cl2	88.35 (4)	C1—C2—H22	109.4
Cl3—Bi1—Cl2^i	178.62 (4)	N2—C2—H22	109.4
Cl1—Bi1—Cl2^i	88.33 (4)	C1—C2—H23	109.4
Cl4—Bi1—Cl2^i	90.40 (4)	N2—C2—H23	109.4
Cl5—Bi1—Cl2^i	88.46 (4)	H22—C2—H23	108.0
Cl2—Bi1—Cl2^i	87.077 (12)	N2—C3—H31	109.5
Bi1—Cl2—Bi1^ii	148.62 (5)	N2—C3—H32	109.5
C1—N1—H11	109.5	H31—C3—H32	109.5
C1—N1—H12	109.5	N2—C3—H33	109.5
H11—N1—H12	109.5	H31—C3—H33	109.5
C1—N1—H13	109.5	H32—C3—H33	109.5
H11—N1—H13	109.5	N2—C4—H41	109.5
H12—N1—H13	109.5	N2—C4—H42	109.5
C3—N2—C4	109.9 (4)	H41—C4—H42	109.5
C3—N2—C2	114.9 (4)	N2—C4—H43	109.5
C4—N2—C2	109.2 (4)	H41—C4—H43	109.5
C3—N2—H21	107.5	H42—C4—H43	109.5
N1—C1—C2—N2	178.8 (4)	C4—N2—C2—C1	−161.0 (4)
C3—N2—C2—C1	74.9 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H13···Cl1^iii	0.89	2.82	3.455 (4)	129
N1—H13···Cl2^iv	0.89	2.59	3.322 (4)	140
N1—H12···Cl4^iii	0.89	2.36	3.186 (4)	154
N1—H11···Cl5^v	0.89	2.40	3.243 (4)	159
N2—H21···Cl4^iv	0.98	2.49	3.299 (4)	139
N2—H21···Cl5	0.98	2.90	3.557 (4)	125
C1—H14···Cl3^vi	0.97	2.72	3.428 (6)	130
C1—H15···Cl4^iv	0.97	2.83	3.600 (5)	137
C4—H41···Cl3^iv	0.96	2.78	3.688 (6)	158

Symmetry codes: (iii) −x+3/2, −y+1, z+1/2; (iv) −x+1/2, −y+1, z+1/2; (v) −x+1, y+1/2, −z+1/2; (vi) x+1, y, z.

Tris(N,N,N',N'-tetramethylguanidinium) tri-µ-chlorido-bis[trichloridobismuthate(III)] (TmgBiCl_3_295K)

Crystal data

(C5H14N3)3[Bi2Cl9]	F(000) = 2056
Mr = 1085.59	Dx = 2.024 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.57031 (17) Å	Cell parameters from 12505 reflections
b = 29.2063 (4) Å	θ = 3.0–29.5°
c = 12.04367 (19) Å	µ = 10.56 mm^−1
β = 106.6342 (17)°	T = 295 K
V = 3562.52 (10) Å^3	Pillar, colourless
Z = 4	0.22 × 0.20 × 0.19 mm

Data collection

Xcalibur diffractometer	6102 reflections with I > 2σ(I)
ω–scan	Rint = 0.023
Absorption correction: analytical CrysAlisPro 1.171.40.56a (Rigaku Oxford Diffraction, 2019) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θmax = 26.0°, θmin = 3.1°
Tmin = 0.21, Tmax = 0.27	h = −13→13
23916 measured reflections	k = −36→36
6979 independent reflections	l = −14→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.018	H-atom parameters constrained
wR(F^2) = 0.037	w = 1/[σ^2(Fo^2) + (0.0127P)^2 + 1.928P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.003
6979 reflections	Δρmax = 0.70 e Å^−3
329 parameters	Δρmin = −0.63 e Å^−3
12 restraints	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00220 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Bi1	0.17900 (2)	0.40340 (2)	0.29526 (2)	0.03424 (4)
Bi2	0.25329 (2)	0.34809 (2)	0.60555 (2)	0.03534 (4)
Cl1	−0.05278 (9)	0.39190 (4)	0.16377 (8)	0.0602 (2)
Cl2	0.42743 (8)	0.40316 (3)	0.50121 (8)	0.0504 (2)
Cl3	0.08193 (9)	0.30002 (4)	0.66543 (9)	0.0613 (3)
Cl4	0.29023 (10)	0.38508 (3)	0.13968 (8)	0.0580 (2)
Cl5	0.06958 (8)	0.41757 (3)	0.49445 (7)	0.0459 (2)
Cl6	0.42799 (9)	0.28379 (3)	0.68143 (8)	0.0512 (2)
Cl7	0.16839 (10)	0.49020 (3)	0.24346 (9)	0.0576 (2)
Cl8	0.18885 (10)	0.31149 (3)	0.37320 (8)	0.0530 (2)
Cl9	0.33459 (9)	0.39077 (3)	0.79966 (8)	0.0556 (2)
N11	0.5794 (3)	0.30533 (12)	0.4881 (3)	0.0741 (11)
H111	0.5318	0.3272	0.4501	0.089*
H112	0.5606	0.2934	0.5467	0.089*
C11	0.6817 (4)	0.29006 (12)	0.4566 (3)	0.0488 (9)
N12	0.7070 (3)	0.30919 (11)	0.3668 (3)	0.0576 (8)
C12	0.8468 (4)	0.31255 (15)	0.3587 (4)	0.0720 (12)
H121	0.9072	0.3023	0.4300	0.108*
H122	0.8661	0.3438	0.3447	0.108*
H123	0.8559	0.2937	0.2961	0.108*
C13	0.6082 (6)	0.33624 (19)	0.2834 (4)	0.1047 (19)
H131	0.5216	0.3273	0.2858	0.157*
H132	0.6162	0.3311	0.2070	0.157*
H133	0.6217	0.3681	0.3023	0.157*
N13	0.7567 (3)	0.25636 (9)	0.5145 (2)	0.0476 (7)
C14	0.8263 (4)	0.22276 (14)	0.4633 (3)	0.0680 (11)
H141	0.8018	0.2268	0.3808	0.102*
H142	0.8030	0.1924	0.4810	0.102*
H143	0.9199	0.2270	0.4946	0.102*
C15	0.7549 (4)	0.24619 (15)	0.6314 (3)	0.0672 (11)
H151	0.7441	0.2741	0.6700	0.101*
H152	0.8366	0.2319	0.6727	0.101*
H153	0.6828	0.2259	0.6294	0.101*
N21	0.6443 (3)	0.37057 (14)	0.7702 (3)	0.0802 (11)
H211	0.5818	0.3592	0.7944	0.096*
H212	0.6261	0.3897	0.7135	0.096*
C21	0.7679 (3)	0.35864 (11)	0.8202 (3)	0.0419 (8)
N22	0.8632 (3)	0.37592 (10)	0.7807 (2)	0.0446 (7)
C22	0.9892 (4)	0.38961 (15)	0.8581 (4)	0.0671 (11)
H221	0.9888	0.3849	0.9368	0.101*
H222	1.0043	0.4214	0.8463	0.101*
H223	1.0582	0.3716	0.8424	0.101*
C23	0.8335 (4)	0.39353 (13)	0.6624 (3)	0.0611 (10)
H231	0.7636	0.3758	0.6125	0.092*
H232	0.9108	0.3914	0.6361	0.092*
H233	0.8065	0.4250	0.6611	0.092*
N23	0.7935 (3)	0.32924 (10)	0.9072 (2)	0.0478 (7)
C24	0.9098 (4)	0.29955 (14)	0.9337 (4)	0.0715 (12)
H241	0.9525	0.3023	0.8735	0.107*
H242	0.8832	0.2684	0.9385	0.107*
H243	0.9700	0.3085	1.0064	0.107*
C25	0.6966 (4)	0.31749 (15)	0.9673 (4)	0.0714 (12)
H251	0.6401	0.3433	0.9664	0.107*
H252	0.7412	0.3094	1.0461	0.107*
H253	0.6446	0.2920	0.9292	0.107*
N31	0.1341 (3)	0.49680 (10)	0.7121 (2)	0.0484 (7)
H311	0.1071	0.4920	0.6387	0.058*
H312	0.0814	0.4927	0.7540	0.058*
C31	0.2564 (3)	0.51056 (11)	0.7607 (3)	0.0392 (8)
N32	0.2977 (3)	0.51754 (9)	0.8753 (2)	0.0452 (7)
C32	0.3894 (4)	0.55436 (13)	0.9254 (3)	0.0640 (11)
H321	0.4101	0.5713	0.8645	0.096*
H322	0.4688	0.5416	0.9758	0.096*
H323	0.3496	0.5745	0.9688	0.096*
C33	0.2250 (4)	0.49829 (14)	0.9508 (3)	0.0634 (11)
H331	0.1917	0.4686	0.9227	0.095*
H332	0.1527	0.5181	0.9513	0.095*
H333	0.2830	0.4955	1.0281	0.095*
N33	0.3376 (3)	0.51693 (10)	0.6959 (2)	0.0458 (7)
C34	0.4786 (3)	0.50633 (14)	0.7376 (4)	0.0624 (11)
H341	0.4975	0.4918	0.8121	0.094*
H342	0.5287	0.5341	0.7443	0.094*
H343	0.5021	0.4861	0.6839	0.094*
C35	0.2861 (4)	0.52309 (14)	0.5701 (3)	0.0621 (11)
H351	0.2019	0.5381	0.5523	0.093*
H352	0.2762	0.4937	0.5328	0.093*
H353	0.3465	0.5415	0.5430	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.03585 (7)	0.03608 (7)	0.03089 (7)	0.00278 (5)	0.00970 (5)	0.00190 (5)
Bi2	0.03480 (7)	0.03907 (7)	0.03305 (7)	0.00171 (5)	0.01113 (5)	0.00272 (5)
Cl1	0.0462 (5)	0.0757 (7)	0.0509 (5)	−0.0061 (5)	0.0014 (4)	−0.0017 (5)
Cl2	0.0390 (5)	0.0501 (5)	0.0618 (6)	−0.0023 (4)	0.0140 (4)	0.0013 (4)
Cl3	0.0496 (5)	0.0743 (7)	0.0621 (6)	−0.0163 (5)	0.0198 (5)	0.0056 (5)
Cl4	0.0716 (6)	0.0575 (6)	0.0559 (6)	0.0088 (5)	0.0360 (5)	−0.0016 (4)
Cl5	0.0429 (5)	0.0522 (5)	0.0447 (5)	0.0077 (4)	0.0155 (4)	−0.0008 (4)
Cl6	0.0536 (5)	0.0510 (5)	0.0525 (5)	0.0146 (4)	0.0209 (4)	0.0092 (4)
Cl7	0.0610 (6)	0.0413 (5)	0.0782 (7)	0.0058 (4)	0.0323 (5)	0.0063 (4)
Cl8	0.0672 (6)	0.0410 (5)	0.0512 (5)	−0.0001 (4)	0.0177 (5)	−0.0050 (4)
Cl9	0.0560 (6)	0.0610 (6)	0.0507 (5)	−0.0012 (4)	0.0168 (4)	−0.0142 (4)
N11	0.063 (2)	0.073 (2)	0.101 (3)	0.0215 (18)	0.049 (2)	0.019 (2)
C11	0.0487 (12)	0.0488 (12)	0.0495 (12)	−0.0004 (9)	0.0147 (9)	−0.0021 (9)
N12	0.060 (2)	0.063 (2)	0.0490 (18)	−0.0119 (16)	0.0153 (16)	0.0133 (15)
C12	0.073 (3)	0.089 (3)	0.065 (3)	−0.024 (2)	0.039 (2)	0.000 (2)
C13	0.114 (5)	0.123 (5)	0.079 (3)	0.049 (4)	0.029 (3)	0.045 (3)
N13	0.0480 (10)	0.0447 (10)	0.0481 (10)	0.0028 (8)	0.0103 (8)	0.0005 (8)
C14	0.088 (3)	0.064 (3)	0.056 (2)	0.010 (2)	0.027 (2)	−0.003 (2)
C15	0.079 (3)	0.068 (3)	0.060 (3)	0.009 (2)	0.027 (2)	0.002 (2)
N21	0.041 (2)	0.119 (3)	0.079 (3)	0.004 (2)	0.0136 (18)	0.032 (2)
C21	0.0398 (19)	0.0417 (19)	0.0435 (19)	−0.0026 (15)	0.0108 (16)	−0.0045 (15)
N22	0.0409 (16)	0.0491 (17)	0.0452 (17)	−0.0046 (13)	0.0145 (14)	0.0043 (13)
C22	0.047 (2)	0.083 (3)	0.071 (3)	−0.020 (2)	0.016 (2)	0.001 (2)
C23	0.080 (3)	0.056 (2)	0.053 (2)	0.000 (2)	0.029 (2)	0.0093 (18)
N23	0.0530 (19)	0.0476 (17)	0.0430 (17)	−0.0081 (14)	0.0141 (14)	0.0014 (13)
C24	0.088 (3)	0.057 (3)	0.069 (3)	0.015 (2)	0.022 (2)	0.016 (2)
C25	0.083 (3)	0.080 (3)	0.060 (3)	−0.027 (2)	0.034 (2)	0.000 (2)
N31	0.0399 (17)	0.0632 (19)	0.0425 (16)	−0.0012 (14)	0.0123 (14)	−0.0007 (14)
C31	0.0389 (19)	0.0356 (18)	0.0404 (19)	0.0046 (14)	0.0068 (15)	0.0051 (14)
N32	0.0491 (17)	0.0466 (17)	0.0378 (16)	−0.0035 (13)	0.0091 (13)	0.0034 (13)
C32	0.071 (3)	0.057 (2)	0.054 (2)	−0.012 (2)	0.003 (2)	−0.0072 (19)
C33	0.068 (3)	0.077 (3)	0.045 (2)	0.000 (2)	0.015 (2)	0.011 (2)
N33	0.0382 (16)	0.0564 (18)	0.0418 (16)	−0.0016 (13)	0.0101 (13)	0.0071 (13)
C34	0.036 (2)	0.082 (3)	0.069 (3)	0.0007 (19)	0.0138 (19)	0.005 (2)
C35	0.061 (3)	0.080 (3)	0.046 (2)	−0.007 (2)	0.0171 (19)	0.013 (2)

Geometric parameters (Å, º)

Bi1—Cl1	2.5301 (9)	N22—C22	1.446 (4)
Bi1—Cl4	2.5378 (9)	N22—C23	1.461 (4)
Bi1—Cl7	2.6055 (9)	C22—H221	0.9600
Bi1—Cl8	2.8357 (9)	C22—H222	0.9600
Bi1—Cl5	2.9754 (8)	C22—H223	0.9600
Bi1—Cl2	3.0527 (9)	C23—H231	0.9600
Bi2—Cl3	2.5534 (9)	C23—H232	0.9600
Bi2—Cl9	2.5704 (9)	C23—H233	0.9600
Bi2—Cl6	2.6088 (8)	N23—C25	1.455 (4)
Bi2—Cl5	2.8621 (8)	N23—C24	1.462 (5)
Bi2—Cl8	2.8890 (9)	C24—H241	0.9600
Bi2—Cl2	2.9797 (9)	C24—H242	0.9600
N11—C11	1.322 (4)	C24—H243	0.9600
N11—H111	0.8600	C25—H251	0.9600
N11—H112	0.8600	C25—H252	0.9600
C11—N12	1.310 (4)	C25—H253	0.9600
C11—N13	1.329 (4)	N31—C31	1.320 (4)
N12—C13	1.457 (5)	N31—H311	0.8600
N12—C12	1.512 (5)	N31—H312	0.8600
C12—H121	0.9600	C31—N33	1.327 (4)
C12—H122	0.9600	C31—N32	1.339 (4)
C12—H123	0.9600	N32—C32	1.458 (4)
C13—H131	0.9600	N32—C33	1.461 (4)
C13—H132	0.9600	C32—H321	0.9600
C13—H133	0.9600	C32—H322	0.9600
N13—C15	1.445 (4)	C32—H323	0.9600
N13—C14	1.464 (5)	C33—H331	0.9600
C14—H141	0.9600	C33—H332	0.9600
C14—H142	0.9600	C33—H333	0.9600
C14—H143	0.9600	N33—C34	1.463 (4)
C15—H151	0.9600	N33—C35	1.467 (4)
C15—H152	0.9600	C34—H341	0.9600
C15—H153	0.9600	C34—H342	0.9600
N21—C21	1.320 (4)	C34—H343	0.9600
N21—H211	0.8600	C35—H351	0.9600
N21—H212	0.8600	C35—H352	0.9600
C21—N23	1.322 (4)	C35—H353	0.9600
C21—N22	1.331 (4)
Cl1—Bi1—Cl4	94.60 (3)	H211—N21—H212	120.0
Cl1—Bi1—Cl7	90.67 (3)	N21—C21—N23	119.0 (3)
Cl4—Bi1—Cl7	91.47 (3)	N21—C21—N22	119.3 (3)
Cl1—Bi1—Cl8	91.08 (3)	N23—C21—N22	121.7 (3)
Cl4—Bi1—Cl8	93.67 (3)	C21—N22—C22	121.7 (3)
Cl7—Bi1—Cl8	174.42 (3)	C21—N22—C23	120.5 (3)
Cl1—Bi1—Cl5	89.59 (3)	C22—N22—C23	115.6 (3)
Cl4—Bi1—Cl5	173.61 (3)	N22—C22—H221	109.5
Cl7—Bi1—Cl5	93.31 (3)	N22—C22—H222	109.5
Cl8—Bi1—Cl5	81.41 (2)	H221—C22—H222	109.5
Cl1—Bi1—Cl2	164.13 (3)	N22—C22—H223	109.5
Cl4—Bi1—Cl2	97.29 (3)	H221—C22—H223	109.5
Cl7—Bi1—Cl2	99.48 (3)	H222—C22—H223	109.5
Cl8—Bi1—Cl2	77.73 (3)	N22—C23—H231	109.5
Cl5—Bi1—Cl2	77.74 (2)	N22—C23—H232	109.5
Cl3—Bi2—Cl9	95.12 (3)	H231—C23—H232	109.5
Cl3—Bi2—Cl6	89.63 (3)	N22—C23—H233	109.5
Cl9—Bi2—Cl6	90.67 (3)	H231—C23—H233	109.5
Cl3—Bi2—Cl5	94.62 (3)	H232—C23—H233	109.5
Cl9—Bi2—Cl5	94.98 (3)	C21—N23—C25	122.3 (3)
Cl6—Bi2—Cl5	172.59 (3)	C21—N23—C24	121.8 (3)
Cl3—Bi2—Cl8	94.62 (3)	C25—N23—C24	114.8 (3)
Cl9—Bi2—Cl8	170.11 (3)	N23—C24—H241	109.5
Cl6—Bi2—Cl8	91.14 (3)	N23—C24—H242	109.5
Cl5—Bi2—Cl8	82.48 (2)	H241—C24—H242	109.5
Cl3—Bi2—Cl2	171.77 (3)	N23—C24—H243	109.5
Cl9—Bi2—Cl2	92.05 (3)	H241—C24—H243	109.5
Cl6—Bi2—Cl2	94.33 (3)	H242—C24—H243	109.5
Cl5—Bi2—Cl2	80.70 (2)	N23—C25—H251	109.5
Cl8—Bi2—Cl2	78.12 (3)	N23—C25—H252	109.5
Bi2—Cl2—Bi1	81.51 (2)	H251—C25—H252	109.5
Bi2—Cl5—Bi1	84.84 (2)	N23—C25—H253	109.5
Bi1—Cl8—Bi2	86.94 (2)	H251—C25—H253	109.5
C11—N11—H111	120.0	H252—C25—H253	109.5
C11—N11—H112	120.0	C31—N31—H311	120.0
H111—N11—H112	120.0	C31—N31—H312	120.0
N12—C11—N11	118.1 (4)	H311—N31—H312	120.0
N12—C11—N13	121.1 (3)	N31—C31—N33	119.9 (3)
N11—C11—N13	120.9 (3)	N31—C31—N32	119.4 (3)
C11—N12—C13	121.7 (4)	N33—C31—N32	120.7 (3)
C11—N12—C12	121.0 (3)	C31—N32—C32	121.4 (3)
C13—N12—C12	116.1 (3)	C31—N32—C33	120.7 (3)
N12—C12—H121	109.5	C32—N32—C33	115.6 (3)
N12—C12—H122	109.5	N32—C32—H321	109.5
H121—C12—H122	109.5	N32—C32—H322	109.5
N12—C12—H123	109.5	H321—C32—H322	109.5
H121—C12—H123	109.5	N32—C32—H323	109.5
H122—C12—H123	109.5	H321—C32—H323	109.5
N12—C13—H131	109.5	H322—C32—H323	109.5
N12—C13—H132	109.5	N32—C33—H331	109.5
H131—C13—H132	109.5	N32—C33—H332	109.5
N12—C13—H133	109.5	H331—C33—H332	109.5
H131—C13—H133	109.5	N32—C33—H333	109.5
H132—C13—H133	109.5	H331—C33—H333	109.5
C11—N13—C15	119.4 (3)	H332—C33—H333	109.5
C11—N13—C14	124.9 (3)	C31—N33—C34	122.3 (3)
C15—N13—C14	114.9 (3)	C31—N33—C35	120.8 (3)
N13—C14—H141	109.5	C34—N33—C35	114.9 (3)
N13—C14—H142	109.5	N33—C34—H341	109.5
H141—C14—H142	109.5	N33—C34—H342	109.5
N13—C14—H143	109.5	H341—C34—H342	109.5
H141—C14—H143	109.5	N33—C34—H343	109.5
H142—C14—H143	109.5	H341—C34—H343	109.5
N13—C15—H151	109.5	H342—C34—H343	109.5
N13—C15—H152	109.5	N33—C35—H351	109.5
H151—C15—H152	109.5	N33—C35—H352	109.5
N13—C15—H153	109.5	H351—C35—H352	109.5
H151—C15—H153	109.5	N33—C35—H353	109.5
H152—C15—H153	109.5	H351—C35—H353	109.5
C21—N21—H211	120.0	H352—C35—H353	109.5
C21—N21—H212	120.0
N11—C11—N12—C13	−17.9 (6)	N21—C21—N23—C25	−14.4 (5)
N13—C11—N12—C13	162.2 (4)	N22—C21—N23—C25	166.7 (3)
N11—C11—N12—C12	149.2 (4)	N21—C21—N23—C24	152.8 (4)
N13—C11—N12—C12	−30.7 (5)	N22—C21—N23—C24	−26.1 (5)
N12—C11—N13—C15	159.9 (3)	N31—C31—N32—C32	−144.2 (3)
N11—C11—N13—C15	−19.9 (5)	N33—C31—N32—C32	36.4 (5)
N12—C11—N13—C14	−31.0 (6)	N31—C31—N32—C33	17.5 (5)
N11—C11—N13—C14	149.2 (4)	N33—C31—N32—C33	−161.9 (3)
N21—C21—N22—C22	140.5 (4)	N31—C31—N33—C34	−144.1 (3)
N23—C21—N22—C22	−40.5 (5)	N32—C31—N33—C34	35.3 (5)
N21—C21—N22—C23	−22.3 (5)	N31—C31—N33—C35	19.3 (5)
N23—C21—N22—C23	156.6 (3)	N32—C31—N33—C35	−161.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H111···Cl2	0.86	2.63	3.304 (3)	136
N11—H112···Cl6	0.86	2.44	3.242 (3)	155
N21—H212···Cl2	0.86	2.83	3.522 (4)	138
N21—H211···Cl6	0.86	2.84	3.376 (4)	122
N21—H211···Cl9	0.86	2.79	3.443 (3)	134
N31—H311···Cl5	0.86	2.74	3.416 (3)	137
N31—H312···Cl7^i	0.86	2.70	3.411 (3)	141
C23—H232···Cl5^ii	0.96	2.82	3.702 (4)	153
C23—H233···Cl7^iii	0.96	2.71	3.582 (4)	151
C12—H121···N13	0.96	2.51	2.854 (5)	101
C14—H141···N12	0.96	2.59	2.911 (5)	100
C22—H221···N23	0.96	2.57	2.905 (5)	101
C24—H241···N22	0.96	2.48	2.845 (5)	102
C32—H321···N33	0.96	2.52	2.875 (5)	102
C34—H341···N32	0.96	2.55	2.886 (5)	100

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

catena-Poly[N,N,N',N'-Tetramethylguanidinium [[dichloridobismuthate(III)]-di-µ-chlorido]] (TmgBiCl_4_295K)

Crystal data

(C5H14N3)[BiCl4]	Z = 4
Mr = 466.97	F(000) = 864
Triclinic, P1	Dx = 2.273 Mg m^−3
a = 7.7179 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5660 (5) Å	Cell parameters from 5942 reflections
c = 18.0362 (7) Å	θ = 3.2–29.3°
α = 95.585 (3)°	µ = 13.67 mm^−1
β = 91.008 (3)°	T = 295 K
γ = 110.965 (4)°	Pillar, colourless
V = 1364.74 (11) Å^3	0.31 × 0.22 × 0.06 mm

Data collection

Xcalibur diffractometer	4631 reflections with I > 2σ(I)
ω–scan	Rint = 0.030
Absorption correction: analytical CrysAlisPro 1.171.40.56a (Rigaku Oxford Diffraction, 2019) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θmax = 26.0°, θmin = 3.0°
Tmin = 0.09, Tmax = 0.49	h = −9→6
9281 measured reflections	k = −13→13
5286 independent reflections	l = −22→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.0208P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
5286 reflections	Δρmax = 0.69 e Å^−3
244 parameters	Δρmin = −0.76 e Å^−3
0 restraints	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00533 (17)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Bi1	−0.03098 (2)	0.21386 (2)	0.31887 (2)	0.03733 (7)
Cl1	−0.0051 (2)	0.05740 (15)	0.40971 (9)	0.0644 (4)
Cl2	−0.16017 (18)	0.38086 (15)	0.21434 (9)	0.0623 (4)
Cl3	−0.0778 (2)	0.37333 (17)	0.42162 (9)	0.0700 (4)
Cl4	0.10690 (19)	0.06298 (16)	0.19700 (10)	0.0691 (5)
Cl5	0.33920 (18)	0.35196 (14)	0.34011 (9)	0.0565 (4)
Cl6	−0.4051 (2)	0.06421 (18)	0.30445 (12)	0.0830 (6)
Bi2	0.47181 (2)	0.22420 (2)	0.20850 (2)	0.03656 (7)
Cl7	0.5155 (2)	0.08178 (16)	0.09500 (9)	0.0664 (4)
Cl8	0.4005 (2)	0.39216 (15)	0.13139 (10)	0.0666 (4)
N11	0.5139 (7)	0.7670 (6)	0.5078 (3)	0.0822 (18)
H111	0.4380	0.7970	0.5314	0.099*
H112	0.6012	0.7532	0.5321	0.099*
C11	0.4963 (7)	0.7422 (5)	0.4339 (3)	0.0498 (13)
N12	0.6132 (6)	0.6947 (4)	0.3984 (3)	0.0499 (11)
C12	0.6680 (9)	0.7244 (7)	0.3235 (4)	0.080 (2)
H121	0.6130	0.7858	0.3069	0.120*
H122	0.6262	0.6412	0.2903	0.120*
H123	0.8009	0.7657	0.3238	0.120*
C13	0.7216 (8)	0.6319 (7)	0.4384 (4)	0.075 (2)
H131	0.8387	0.7002	0.4566	0.112*
H132	0.7430	0.5629	0.4052	0.112*
H133	0.6546	0.5913	0.4796	0.112*
N13	0.3615 (6)	0.7641 (5)	0.3976 (3)	0.0556 (12)
C14	0.2655 (10)	0.6826 (7)	0.3302 (4)	0.088 (2)
H141	0.3165	0.6136	0.3165	0.132*
H142	0.2802	0.7399	0.2907	0.132*
H143	0.1358	0.6402	0.3383	0.132*
C15	0.2735 (9)	0.8558 (8)	0.4307 (4)	0.082 (2)
H151	0.3587	0.9222	0.4671	0.123*
H152	0.1640	0.8042	0.4543	0.123*
H153	0.2400	0.9012	0.3924	0.123*
N21	0.0315 (7)	0.7625 (6)	−0.0444 (3)	0.0752 (17)
H211	0.1136	0.7457	−0.0711	0.090*
H212	−0.0462	0.7928	−0.0640	0.090*
C21	0.0247 (7)	0.7417 (5)	0.0272 (3)	0.0486 (13)
N22	0.1447 (6)	0.6952 (5)	0.0565 (3)	0.0518 (11)
C22	0.2214 (10)	0.7360 (7)	0.1328 (4)	0.083 (2)
H221	0.1660	0.7957	0.1573	0.125*
H222	0.3534	0.7828	0.1328	0.125*
H223	0.1956	0.6566	0.1587	0.125*
C23	0.2413 (8)	0.6230 (6)	0.0084 (4)	0.0693 (18)
H231	0.1627	0.5762	−0.0351	0.104*
H232	0.2690	0.5582	0.0356	0.104*
H233	0.3547	0.6878	−0.0064	0.104*
N23	−0.1047 (6)	0.7679 (5)	0.0671 (3)	0.0569 (12)
C24	−0.1815 (11)	0.6964 (7)	0.1312 (4)	0.092 (2)
H241	−0.1291	0.6279	0.1371	0.139*
H242	−0.3141	0.6540	0.1233	0.139*
H243	−0.1520	0.7603	0.1754	0.139*
C25	−0.2012 (8)	0.8532 (8)	0.0420 (5)	0.083 (2)
H251	−0.1230	0.9164	0.0109	0.124*
H252	−0.2303	0.9025	0.0844	0.124*
H253	−0.3140	0.7968	0.0140	0.124*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.03750 (11)	0.04648 (12)	0.03575 (12)	0.02369 (9)	0.00246 (8)	0.00779 (8)
Cl1	0.0806 (10)	0.0680 (9)	0.0623 (10)	0.0437 (8)	0.0002 (8)	0.0250 (8)
Cl2	0.0445 (7)	0.0640 (9)	0.0737 (11)	0.0077 (7)	−0.0059 (7)	0.0337 (8)
Cl3	0.0968 (12)	0.0769 (10)	0.0585 (10)	0.0591 (9)	0.0153 (9)	0.0013 (8)
Cl4	0.0445 (7)	0.0649 (9)	0.0800 (12)	0.0073 (7)	0.0055 (7)	−0.0286 (8)
Cl5	0.0485 (7)	0.0573 (8)	0.0557 (9)	0.0145 (6)	−0.0020 (6)	−0.0134 (7)
Cl6	0.0474 (8)	0.0795 (11)	0.1264 (17)	0.0150 (8)	0.0001 (9)	0.0632 (11)
Bi2	0.03232 (11)	0.04369 (12)	0.03724 (12)	0.01759 (8)	0.00117 (8)	0.00645 (8)
Cl7	0.0768 (10)	0.0673 (9)	0.0596 (10)	0.0331 (8)	0.0202 (8)	−0.0017 (8)
Cl8	0.0656 (9)	0.0618 (9)	0.0790 (11)	0.0280 (7)	−0.0140 (8)	0.0234 (8)
N11	0.081 (4)	0.140 (5)	0.053 (4)	0.073 (4)	0.005 (3)	0.010 (3)
C11	0.041 (3)	0.054 (3)	0.054 (4)	0.015 (2)	0.003 (3)	0.017 (3)
N12	0.045 (2)	0.048 (2)	0.058 (3)	0.020 (2)	0.000 (2)	0.002 (2)
C12	0.095 (5)	0.080 (5)	0.066 (5)	0.033 (4)	0.030 (4)	0.003 (4)
C13	0.058 (4)	0.081 (5)	0.095 (6)	0.038 (4)	−0.009 (4)	0.000 (4)
N13	0.051 (3)	0.057 (3)	0.064 (3)	0.023 (2)	−0.002 (2)	0.021 (2)
C14	0.088 (5)	0.077 (5)	0.094 (6)	0.026 (4)	−0.044 (4)	0.007 (4)
C15	0.063 (4)	0.100 (5)	0.101 (6)	0.047 (4)	0.013 (4)	0.023 (5)
N21	0.061 (3)	0.134 (5)	0.054 (3)	0.057 (3)	0.013 (3)	0.037 (3)
C21	0.040 (3)	0.051 (3)	0.047 (3)	0.007 (2)	0.001 (2)	0.004 (3)
N22	0.052 (3)	0.057 (3)	0.047 (3)	0.018 (2)	0.000 (2)	0.012 (2)
C22	0.107 (6)	0.079 (5)	0.062 (5)	0.033 (4)	−0.027 (4)	0.006 (4)
C23	0.067 (4)	0.068 (4)	0.081 (5)	0.032 (3)	0.004 (3)	0.016 (4)
N23	0.052 (3)	0.056 (3)	0.057 (3)	0.014 (2)	0.009 (2)	−0.001 (2)
C24	0.115 (6)	0.066 (4)	0.084 (6)	0.015 (4)	0.053 (5)	0.014 (4)
C25	0.046 (4)	0.094 (5)	0.113 (7)	0.031 (4)	0.002 (4)	0.007 (5)

Geometric parameters (Å, º)

Bi1—Cl1	2.4917 (13)	N13—C15	1.458 (8)
Bi1—Cl3	2.5011 (15)	C14—H141	0.9600
Bi1—Cl5	2.7033 (13)	C14—H142	0.9600
Bi1—Cl6	2.7441 (15)	C14—H143	0.9600
Bi1—Cl4	3.0199 (15)	C15—H151	0.9600
Bi1—Cl2	3.0826 (14)	C15—H152	0.9600
Cl2—Bi2^i	2.7220 (13)	C15—H153	0.9600
Cl4—Bi2	2.7119 (14)	N21—C21	1.330 (7)
Cl5—Bi2	2.9925 (14)	N21—H211	0.8600
Cl6—Bi2^i	2.9011 (15)	N21—H212	0.8600
Bi2—Cl7	2.5212 (15)	C21—N22	1.318 (7)
Bi2—Cl8	2.5572 (14)	C21—N23	1.333 (7)
Bi2—Cl2^ii	2.7220 (13)	N22—C22	1.450 (8)
Bi2—Cl6^ii	2.9010 (15)	N22—C23	1.479 (7)
N11—C11	1.329 (7)	C22—H221	0.9600
N11—H111	0.8600	C22—H222	0.9600
N11—H112	0.8600	C22—H223	0.9600
C11—N13	1.319 (6)	C23—H231	0.9600
C11—N12	1.326 (7)	C23—H232	0.9600
N12—C12	1.453 (8)	C23—H233	0.9600
N12—C13	1.460 (7)	N23—C25	1.456 (8)
C12—H121	0.9600	N23—C24	1.461 (8)
C12—H122	0.9600	C24—H241	0.9600
C12—H123	0.9600	C24—H242	0.9600
C13—H131	0.9600	C24—H243	0.9600
C13—H132	0.9600	C25—H251	0.9600
C13—H133	0.9600	C25—H252	0.9600
N13—C14	1.442 (8)	C25—H253	0.9600
Cl1—Bi1—Cl3	91.12 (5)	H131—C13—H133	109.5
Cl1—Bi1—Cl5	89.01 (5)	H132—C13—H133	109.5
Cl3—Bi1—Cl5	88.43 (5)	C11—N13—C14	123.5 (5)
Cl1—Bi1—Cl6	87.39 (5)	C11—N13—C15	121.6 (6)
Cl3—Bi1—Cl6	91.22 (6)	C14—N13—C15	113.9 (5)
Cl5—Bi1—Cl6	176.37 (5)	N13—C14—H141	109.5
Cl1—Bi1—Cl4	91.01 (5)	N13—C14—H142	109.5
Cl3—Bi1—Cl4	168.17 (5)	H141—C14—H142	109.5
Cl5—Bi1—Cl4	79.98 (4)	N13—C14—H143	109.5
Cl6—Bi1—Cl4	100.50 (6)	H141—C14—H143	109.5
Cl1—Bi1—Cl2	166.53 (5)	H142—C14—H143	109.5
Cl3—Bi1—Cl2	84.94 (5)	N13—C15—H151	109.5
Cl5—Bi1—Cl2	103.72 (4)	N13—C15—H152	109.5
Cl6—Bi1—Cl2	79.84 (4)	H151—C15—H152	109.5
Cl4—Bi1—Cl2	95.48 (5)	N13—C15—H153	109.5
Bi2^i—Cl2—Bi1	96.37 (4)	H151—C15—H153	109.5
Bi2—Cl4—Bi1	99.03 (4)	H152—C15—H153	109.5
Bi1—Cl5—Bi2	99.90 (4)	C21—N21—H211	120.0
Bi1—Cl6—Bi2^i	100.22 (5)	C21—N21—H212	120.0
Cl7—Bi2—Cl8	93.38 (6)	H211—N21—H212	120.0
Cl7—Bi2—Cl4	87.84 (5)	N22—C21—N21	119.3 (5)
Cl8—Bi2—Cl4	89.98 (5)	N22—C21—N23	122.0 (5)
Cl7—Bi2—Cl2^ii	89.77 (5)	N21—C21—N23	118.7 (5)
Cl8—Bi2—Cl2^ii	89.78 (5)	C21—N22—C22	122.9 (5)
Cl4—Bi2—Cl2^ii	177.58 (5)	C21—N22—C23	120.7 (5)
Cl7—Bi2—Cl6^ii	90.17 (6)	C22—N22—C23	115.0 (5)
Cl8—Bi2—Cl6^ii	172.42 (5)	N22—C22—H221	109.5
Cl4—Bi2—Cl6^ii	96.85 (5)	N22—C22—H222	109.5
Cl2^ii—Bi2—Cl6^ii	83.54 (4)	H221—C22—H222	109.5
Cl7—Bi2—Cl5	168.16 (5)	N22—C22—H223	109.5
Cl8—Bi2—Cl5	87.43 (5)	H221—C22—H223	109.5
Cl4—Bi2—Cl5	80.34 (4)	H222—C22—H223	109.5
Cl2^ii—Bi2—Cl5	102.06 (5)	N22—C23—H231	109.5
Cl6^ii—Bi2—Cl5	90.46 (6)	N22—C23—H232	109.5
C11—N11—H111	120.0	H231—C23—H232	109.5
C11—N11—H112	120.0	N22—C23—H233	109.5
H111—N11—H112	120.0	H231—C23—H233	109.5
N13—C11—N12	121.6 (6)	H232—C23—H233	109.5
N13—C11—N11	119.1 (5)	C21—N23—C25	121.5 (5)
N12—C11—N11	119.2 (5)	C21—N23—C24	122.8 (5)
C11—N12—C12	122.8 (5)	C25—N23—C24	115.0 (5)
C11—N12—C13	120.5 (5)	N23—C24—H241	109.5
C12—N12—C13	115.6 (5)	N23—C24—H242	109.5
N12—C12—H121	109.5	H241—C24—H242	109.5
N12—C12—H122	109.5	N23—C24—H243	109.5
H121—C12—H122	109.5	H241—C24—H243	109.5
N12—C12—H123	109.5	H242—C24—H243	109.5
H121—C12—H123	109.5	N23—C25—H251	109.5
H122—C12—H123	109.5	N23—C25—H252	109.5
N12—C13—H131	109.5	H251—C25—H252	109.5
N12—C13—H132	109.5	N23—C25—H253	109.5
H131—C13—H132	109.5	H251—C25—H253	109.5
N12—C13—H133	109.5	H252—C25—H253	109.5
N13—C11—N12—C12	31.3 (8)	N21—C21—N22—C22	145.0 (6)
N11—C11—N12—C12	−149.4 (6)	N23—C21—N22—C22	−35.5 (8)
N13—C11—N12—C13	−160.9 (5)	N21—C21—N22—C23	−20.9 (8)
N11—C11—N12—C13	18.4 (8)	N23—C21—N22—C23	158.7 (5)
N12—C11—N13—C14	33.1 (8)	N22—C21—N23—C25	162.6 (5)
N11—C11—N13—C14	−146.2 (7)	N21—C21—N23—C25	−17.9 (8)
N12—C11—N13—C15	−159.3 (5)	N22—C21—N23—C24	−28.0 (8)
N11—C11—N13—C15	21.4 (8)	N21—C21—N23—C24	151.5 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H112···Cl5^iii	0.86	2.75	3.460 (6)	140
C12—H121···N13	0.96	2.52	2.876 (8)	102
C14—H141···N12	0.96	2.53	2.888 (8)	102
C22—H221···N23	0.96	2.54	2.903 (8)	103
C24—H241···N22	0.96	2.51	2.881 (9)	103

Symmetry code: (iii) −x+1, −y+1, −z+1.