A two-dimensional organic–inorganic lead iodide perovskite: poly[bis­(3-fluoro­cyclo­butyl­ammonium) [di-μ-iodido-di­iodido­plumbate(VI)]]

In recent years, great technological advances have been achieved in the growth of hybrid organic–inorganic perovskites (HOIPs) and these have attracted extensive attention due to their optoelectronic properties, structural tunability and stability. We present here a new two-dimensional hybrid organic–inorganic perovskite, namely, poly[bis­(3-fluoro­cyclo­butyl­ammonium) [di-μ-iodido-di­iodido­plumbate(VI)]], {(C₄H₉FN)₂[PbI₄]}_n, showing a two-dimensional reticular layer with the organic cations in the middle of the meshes. The calculated experimental band gap is 2.44 eV and the band gap is calculated as 2.20 eV theoretically, which further suggests the potential of this com­pound as a semiconductor.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Poly[bis(3-fluorocyclobutylammonium) [di-µ-iodido-diiodidoplumbate(VI)]]

Crystal data

(C4H9FN)2[PbI4]	F(000) = 784
Mr = 895.03	Dx = 2.991 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.6842 (5) Å	Cell parameters from 6193 reflections
b = 8.5302 (3) Å	θ = 2.5–30.5°
c = 8.9518 (3) Å	µ = 14.70 mm^−1
β = 107.996 (4)°	T = 293 K
V = 993.81 (6) Å^3	Block, yellow
Z = 2	0.16 × 0.16 × 0.15 mm

Data collection

XtaLAB Synergy R, DW system, HyPix diffractometer	Rint = 0.036
ω scans	θmax = 30.8°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −18→17
Tmin = 0.110, Tmax = 0.119	k = −11→12
8813 measured reflections	l = −11→10
2537 independent reflections	6193 standard reflections every 0 reflections
2191 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	24 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0435P)^2 + 2.3818P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
2537 reflections	Δρmax = 1.41 e Å^−3
79 parameters	Δρmin = −1.63 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
Pb1	0.0000	0.5000	0.0000	0.03910 (10)
I1	0.04490 (4)	0.30746 (5)	0.32397 (4)	0.05175 (13)
I3	0.23936 (4)	0.57359 (6)	0.08670 (5)	0.06083 (15)
N1	0.2047 (5)	0.5207 (8)	0.6732 (8)	0.0659 (17)
H1A	0.1482	0.4862	0.6013	0.099*
H1B	0.1956	0.5189	0.7673	0.099*
H1C	0.2177	0.6184	0.6501	0.099*
F1	0.4838 (6)	0.3014 (11)	0.6462 (13)	0.165 (4)
C1	0.2927 (7)	0.4184 (11)	0.6745 (11)	0.078 (2)
H1D	0.2767	0.3069	0.6791	0.117*
C2	0.3934 (9)	0.4616 (16)	0.7896 (12)	0.101 (3)
H2A	0.4172	0.3880	0.8758	0.151*
H2B	0.3959	0.5683	0.8282	0.151*
C3	0.4441 (10)	0.4411 (17)	0.6632 (15)	0.107 (3)
H3A	0.4891	0.5288	0.6579	0.129*
C4	0.3406 (9)	0.4540 (17)	0.5475 (13)	0.107 (3)
H4A	0.3267	0.3752	0.4655	0.128*
H4B	0.3248	0.5581	0.5029	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.0509 (2)	0.03570 (16)	0.03248 (15)	−0.00137 (11)	0.01549 (12)	0.00018 (10)
I1	0.0702 (3)	0.0445 (2)	0.0418 (2)	0.00003 (18)	0.01929 (18)	0.01497 (15)
I3	0.0558 (3)	0.0680 (3)	0.0569 (3)	−0.0057 (2)	0.0148 (2)	−0.0059 (2)
N1	0.058 (4)	0.074 (4)	0.067 (4)	0.005 (3)	0.022 (3)	−0.010 (3)
F1	0.096 (5)	0.137 (6)	0.248 (9)	0.047 (5)	0.035 (5)	−0.035 (6)
C1	0.073 (5)	0.078 (5)	0.081 (5)	−0.001 (4)	0.020 (4)	−0.005 (4)
C2	0.078 (7)	0.154 (10)	0.073 (6)	−0.021 (7)	0.026 (5)	−0.006 (6)
C3	0.104 (7)	0.110 (7)	0.114 (7)	−0.005 (6)	0.043 (6)	−0.017 (6)
C4	0.102 (7)	0.147 (7)	0.081 (5)	0.029 (6)	0.042 (5)	0.004 (5)

Geometric parameters (Å, º)

Pb1—I3^i	3.1865 (5)	F1—C3	1.338 (14)
Pb1—I3	3.1865 (5)	C1—C2	1.489 (14)
Pb1—I1^ii	3.2151 (4)	C1—C4	1.509 (13)
Pb1—I1^iii	3.2151 (4)	C1—H1D	0.9800
Pb1—I1	3.2225 (3)	C2—C3	1.509 (16)
Pb1—I1^i	3.2225 (3)	C2—H2A	0.9700
I1—Pb1^iv	3.2152 (4)	C2—H2B	0.9700
N1—C1	1.483 (11)	C3—C4	1.477 (16)
N1—H1A	0.8900	C3—H3A	0.9800
N1—H1B	0.8900	C4—H4A	0.9700
N1—H1C	0.8900	C4—H4B	0.9700
I3^i—Pb1—I3	180.0	N1—C1—C4	114.6 (9)
I3^i—Pb1—I1^ii	93.302 (12)	C2—C1—C4	86.9 (8)
I3—Pb1—I1^ii	86.698 (12)	N1—C1—H1D	112.4
I3^i—Pb1—I1^iii	86.698 (12)	C2—C1—H1D	112.4
I3—Pb1—I1^iii	93.302 (12)	C4—C1—H1D	112.4
I1^ii—Pb1—I1^iii	180.000 (16)	C1—C2—C3	89.7 (8)
I3^i—Pb1—I1	90.838 (12)	C1—C2—H2A	113.7
I3—Pb1—I1	89.162 (13)	C3—C2—H2A	113.7
I1^ii—Pb1—I1	90.753 (5)	C1—C2—H2B	113.7
I1^iii—Pb1—I1	89.247 (5)	C3—C2—H2B	113.7
I3^i—Pb1—I1^i	89.163 (13)	H2A—C2—H2B	110.9
I3—Pb1—I1^i	90.837 (12)	F1—C3—C4	108.8 (11)
I1^ii—Pb1—I1^i	89.246 (5)	F1—C3—C2	119.1 (13)
I1^iii—Pb1—I1^i	90.754 (5)	C4—C3—C2	87.3 (9)
I1—Pb1—I1^i	180.0	F1—C3—H3A	113.0
Pb1^iv—I1—Pb1	147.634 (15)	C4—C3—H3A	113.0
C1—N1—H1A	109.5	C2—C3—H3A	113.0
C1—N1—H1B	109.5	C3—C4—C1	90.2 (9)
H1A—N1—H1B	109.5	C3—C4—H4A	113.6
C1—N1—H1C	109.5	C1—C4—H4A	113.6
H1A—N1—H1C	109.5	C3—C4—H4B	113.6
H1B—N1—H1C	109.5	C1—C4—H4B	113.6
N1—C1—C2	115.8 (9)	H4A—C4—H4B	110.9
N1—C1—C2—C3	−133.9 (10)	F1—C3—C4—C1	101.7 (11)
C4—C1—C2—C3	−18.0 (10)	C2—C3—C4—C1	−18.1 (10)
C1—C2—C3—F1	−91.7 (13)	N1—C1—C4—C3	135.4 (9)
C1—C2—C3—C4	18.4 (10)	C2—C1—C4—C3	18.4 (10)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···F1^v	0.97	2.55	3.308 (13)	135
N1—H1A···I1	0.89	2.88	3.693 (7)	152
N1—H1B···I3^vi	0.89	2.77	3.612 (7)	158
N1—H1C···I3^vii	0.89	2.72	3.609 (7)	174

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