Low-dimensional bis­muth(III) iodide hybrid material with high activity for the fast removal of rhodamine B

Organic–inorganic hybrid lead-based perovskite crystal materials have been widely studied due to their excellent optical–electronic properties. However, the toxicity of lead limits their widespread use. Here, a lead-free perovskite-type compound, tetra­kis­(1,2,3-tri­methyl­imidazolium) di-μ₃-iodido-tetra-μ₂-iodido-deca­iodido­tetra­bis­muth(III), (C₆H₁₁N₂)₄[Bi₄I₁₆], has been successfully synthesized by a simple solvothermal method. It exhibits a zero-dimensional (0D) tetra­meric structure, including edge-sharing [Bi₄I₁₆]⁴⁻ distorted octa­hedra. The band gap of 2.0 eV is close to that of (NH₄)₃[Bi₂I₉]. Degradation ability measurements were performed to examine the potential application of this material as an alternative for waste-water treatment.

Computing details

Data collection: APEX2 (Bruker, 2015); cell refinement: APEX2 (Bruker, 2015); data reduction: APEX2 (Bruker, 2015); program(s) used to solve structure: SHELXT2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: ?; software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).

Tetrakis(3,4,5-trimethylimidazolium) di-µ₃-iodido-tetra-µ₂-iodido-decaiodidotetrabismuth(III)

Crystal data

(C6H11N2)4[Bi4I16]	F(000) = 2848
Mr = 3310.99	Dx = 3.290 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.1008 (8) Å	Cell parameters from 9569 reflections
b = 13.2084 (8) Å	θ = 3.0–27.1°
c = 19.3147 (12) Å	µ = 17.91 mm^−1
β = 90.701 (2)°	T = 298 K
V = 3342.0 (4) Å^3	Needle, red
Z = 2	0.10 × 0.08 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer	6286 reflections with I > 2σ(I)
w scans	Rint = 0.046
Absorption correction: multi-scan (SADABS; Bruker, 2015)	θmax = 27.2°, θmin = 3.0°
Tmin = 0.267, Tmax = 0.468	h = −15→16
77016 measured reflections	k = −16→16
7377 independent reflections	l = −24→24

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0206P)^2 + 21.5758P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
7377 reflections	Δρmax = 1.05 e Å^−3
237 parameters	Δρmin = −1.23 e Å^−3
7 restraints	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00055 (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.

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 > 2sigma(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	0.64031 (2)	0.94829 (2)	0.07923 (2)	0.03945 (8)
Bi2	0.33458 (2)	0.75331 (2)	0.05698 (2)	0.03808 (7)
I3	0.38659 (3)	0.99509 (3)	0.08522 (2)	0.04178 (11)
I4	0.66542 (4)	1.18360 (4)	0.10551 (2)	0.05504 (13)
I5	0.65888 (5)	0.90145 (5)	0.22733 (3)	0.06238 (15)
I6	0.58832 (4)	0.73191 (4)	0.04223 (3)	0.05620 (14)
I7	0.33180 (5)	0.53611 (4)	0.03390 (3)	0.06554 (16)
I8	0.11392 (4)	0.77402 (5)	0.05034 (3)	0.05972 (14)
I9	0.34114 (5)	0.73376 (5)	0.20890 (3)	0.06408 (15)
I10	0.85364 (4)	0.91076 (5)	0.05462 (3)	0.07074 (17)
N4	0.5052 (8)	0.4696 (7)	0.2132 (5)	0.089 (3)
N2	0.4996 (7)	0.9699 (9)	0.3873 (5)	0.094 (3)
N3	0.4406 (9)	0.5145 (9)	0.3075 (5)	0.099 (3)
N1	0.5655 (9)	1.1041 (8)	0.3484 (5)	0.099 (3)
C13	0.5180 (7)	0.5327 (7)	0.2647 (6)	0.071 (2)
C12	0.4881 (9)	1.0436 (10)	0.3386 (5)	0.086 (4)
C11	0.6281 (10)	1.0700 (12)	0.3987 (6)	0.099 (4)
H11A	0.688814	1.099493	0.413900	0.118*
C10	0.5857 (10)	0.9854 (12)	0.4223 (7)	0.105 (4)
H10A	0.611980	0.944362	0.457336	0.126*
C9	0.5742 (11)	0.4656 (12)	0.1534 (7)	0.130 (5)
H9A	0.551142	0.414223	0.121661	0.195*
H9B	0.574182	0.530020	0.130383	0.195*
H9C	0.642150	0.449876	0.169143	0.195*
C8	0.4219 (10)	0.4131 (11)	0.2213 (8)	0.111 (5)
H8A	0.396999	0.364339	0.190708	0.133*
C7	0.3819 (10)	0.4391 (11)	0.2805 (8)	0.107 (4)
H7A	0.324045	0.411231	0.300358	0.129*
C2	0.4018 (11)	1.0475 (13)	0.2912 (7)	0.156 (8)
H2A	0.359003	0.989496	0.298382	0.234*
H2B	0.363311	1.108099	0.299305	0.234*
H2C	0.425751	1.047370	0.244420	0.234*
C5	0.5980 (9)	0.6058 (10)	0.2732 (10)	0.150 (7)
H5A	0.588790	0.642006	0.315758	0.225*
H5B	0.662822	0.571935	0.274295	0.225*
H5C	0.595991	0.652585	0.235123	0.225*
C3	0.5820 (16)	1.1908 (12)	0.3052 (7)	0.174 (9)
H3A	0.642556	1.225653	0.320492	0.262*
H3B	0.590074	1.169283	0.258130	0.262*
H3C	0.524488	1.235558	0.308133	0.262*
C1	0.4316 (13)	0.8807 (14)	0.3963 (8)	0.155 (6)
H1A	0.374031	0.886254	0.365292	0.232*
H1B	0.468688	0.819892	0.386244	0.232*
H1C	0.408190	0.878472	0.443182	0.232*
C4	0.4228 (15)	0.5683 (16)	0.3687 (9)	0.188 (9)
H4A	0.363160	0.541887	0.390689	0.282*
H4B	0.480671	0.561332	0.399337	0.282*
H4C	0.412528	0.638572	0.358008	0.282*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.03390 (12)	0.03697 (14)	0.04742 (14)	0.00356 (10)	−0.00225 (10)	0.00017 (10)
Bi2	0.03586 (12)	0.03523 (13)	0.04307 (14)	0.00142 (10)	−0.00168 (10)	0.00005 (10)
I3	0.0406 (2)	0.0411 (2)	0.0436 (2)	0.00345 (18)	0.00047 (18)	−0.00244 (18)
I4	0.0803 (3)	0.0409 (3)	0.0439 (2)	0.0019 (2)	−0.0012 (2)	−0.00337 (19)
I5	0.0755 (4)	0.0645 (3)	0.0470 (3)	−0.0003 (3)	−0.0021 (2)	0.0024 (2)
I6	0.0459 (3)	0.0356 (2)	0.0870 (4)	0.00324 (19)	−0.0012 (2)	−0.0082 (2)
I7	0.0703 (3)	0.0394 (3)	0.0866 (4)	0.0022 (2)	−0.0120 (3)	−0.0089 (3)
I8	0.0365 (2)	0.0739 (4)	0.0688 (3)	0.0060 (2)	0.0005 (2)	−0.0024 (3)
I9	0.0730 (4)	0.0706 (4)	0.0484 (3)	0.0022 (3)	−0.0096 (2)	0.0087 (2)
I10	0.0354 (2)	0.0841 (4)	0.0927 (4)	0.0096 (3)	0.0016 (3)	0.0000 (3)
N4	0.095 (7)	0.077 (6)	0.094 (7)	0.019 (5)	−0.009 (5)	0.026 (5)
N2	0.088 (6)	0.120 (8)	0.073 (5)	0.025 (6)	−0.014 (5)	−0.036 (6)
N3	0.106 (8)	0.109 (8)	0.081 (6)	0.030 (7)	−0.014 (6)	0.019 (6)
N1	0.133 (9)	0.103 (8)	0.060 (5)	0.026 (7)	0.018 (6)	−0.022 (5)
C13	0.063 (5)	0.060 (5)	0.089 (7)	0.018 (4)	−0.011 (5)	0.023 (5)
C12	0.088 (7)	0.114 (9)	0.055 (5)	0.053 (7)	−0.019 (5)	−0.036 (6)
C11	0.092 (8)	0.134 (12)	0.070 (7)	0.023 (8)	−0.009 (6)	−0.022 (7)
C10	0.105 (9)	0.121 (11)	0.087 (8)	0.024 (8)	−0.032 (7)	−0.008 (8)
C9	0.134 (12)	0.142 (13)	0.114 (11)	0.060 (10)	0.010 (9)	0.024 (9)
C8	0.100 (9)	0.104 (10)	0.127 (11)	−0.022 (8)	−0.019 (8)	0.059 (9)
C7	0.096 (9)	0.110 (10)	0.116 (10)	−0.033 (8)	−0.019 (8)	0.050 (9)
C2	0.146 (13)	0.216 (18)	0.105 (10)	0.108 (13)	−0.061 (9)	−0.069 (11)
C5	0.089 (9)	0.081 (9)	0.28 (2)	−0.015 (7)	−0.075 (11)	0.045 (11)
C3	0.33 (3)	0.098 (11)	0.100 (10)	0.062 (14)	0.084 (14)	0.006 (8)
C1	0.157 (14)	0.163 (15)	0.144 (13)	−0.002 (11)	−0.024 (11)	−0.056 (12)
C4	0.20 (2)	0.23 (2)	0.131 (14)	0.102 (18)	0.010 (14)	0.022 (15)

Geometric parameters (Å, º)

Bi1—I10	2.8836 (6)	N4—C9	1.477 (15)
Bi1—I5	2.9339 (6)	N2—C10	1.324 (14)
Bi1—I6	3.0217 (6)	N2—C12	1.361 (15)
Bi1—I4	3.1656 (6)	N2—C1	1.488 (19)
Bi1—I3^i	3.2779 (5)	N3—C13	1.337 (14)
Bi1—I3	3.3843 (5)	N3—C7	1.358 (16)
Bi2—I7	2.9034 (6)	N3—C4	1.402 (19)
Bi2—I8	2.9050 (6)	N1—C12	1.303 (15)
Bi2—I9	2.9458 (6)	N1—C11	1.340 (15)
Bi2—I4^i	3.2471 (6)	N1—C3	1.436 (17)
Bi2—I3	3.3092 (5)	C13—C5	1.433 (15)
Bi2—I6	3.3517 (6)	C12—C2	1.447 (14)
N4—C13	1.308 (13)	C11—C10	1.331 (18)
N4—C8	1.332 (14)	C8—C7	1.310 (19)
I10—Bi1—I5	93.183 (19)	I3—Bi2—I6	83.856 (12)
I10—Bi1—I6	90.833 (18)	Bi1^i—I3—Bi2	92.347 (12)
I5—Bi1—I6	92.685 (18)	Bi1^i—I3—Bi1	95.886 (12)
I10—Bi1—I4	95.520 (19)	Bi2—I3—Bi1	91.057 (12)
I5—Bi1—I4	92.494 (16)	Bi1—I4—Bi2^i	95.638 (14)
I6—Bi1—I4	171.567 (16)	Bi1—I6—Bi2	96.954 (14)
I10—Bi1—I3^i	88.418 (17)	C13—N4—C8	111.5 (12)
I5—Bi1—I3^i	178.241 (17)	C13—N4—C9	123.0 (12)
I6—Bi1—I3^i	88.017 (15)	C8—N4—C9	125.6 (14)
I4—Bi1—I3^i	86.623 (13)	C10—N2—C12	109.2 (12)
I10—Bi1—I3	172.454 (18)	C10—N2—C1	124.8 (13)
I5—Bi1—I3	94.298 (16)	C12—N2—C1	125.9 (11)
I6—Bi1—I3	87.833 (13)	C13—N3—C7	109.0 (11)
I4—Bi1—I3	85.146 (14)	C13—N3—C4	124.4 (15)
I3^i—Bi1—I3	84.114 (12)	C7—N3—C4	126.6 (16)
I7—Bi2—I8	94.337 (18)	C12—N1—C11	111.6 (12)
I7—Bi2—I9	93.808 (19)	C12—N1—C3	121.8 (14)
I8—Bi2—I9	93.960 (18)	C11—N1—C3	126.4 (15)
I7—Bi2—I4^i	96.049 (17)	N4—C13—N3	105.3 (10)
I8—Bi2—I4^i	86.844 (17)	N4—C13—C5	127.1 (13)
I9—Bi2—I4^i	170.022 (17)	N3—C13—C5	127.6 (13)
I7—Bi2—I3	168.816 (16)	N1—C12—N2	105.0 (9)
I8—Bi2—I3	96.845 (15)	N1—C12—C2	132.2 (15)
I9—Bi2—I3	85.239 (15)	N2—C12—C2	122.8 (15)
I4^i—Bi2—I3	84.790 (13)	C10—C11—N1	106.0 (13)
I7—Bi2—I6	85.081 (16)	N2—C10—C11	108.1 (12)
I8—Bi2—I6	172.577 (18)	C7—C8—N4	107.0 (14)
I9—Bi2—I6	93.462 (17)	C8—C7—N3	107.3 (13)
I4^i—Bi2—I6	85.860 (16)

Symmetry code: (i) −x+1, −y+2, −z.