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The crystal structure of the pristine (I) and aged (II) crystals of CH3NH3PbI3 (hereafter MAPbI3) hybrid organic–inorganic lead iodide has been studied at 293 K with high-precision single-crystal X-ray diffraction using a synchrotron light source. We show that (I) and (II) are characterized by an identical tetragonal unit cell but different space groups: I422 for (I) and P42212 for (II). Both space groups are subgroups of I4/mcm, which is widely used for MAPbI3. The main difference between (I) and (II) comes from the difference in hydrogen bonds between the MA+ cation and the PbI3 framework which is the direct consequence of H2O insertion in the aged crystal (II).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520616010428/dk5045sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010428/dk5045Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520616010428/dk5045IIsup3.hkl
Contains datablock II

CCDC references: 1487955; 1487956

Computing details top

For both compounds, data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01); cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01); program(s) used to solve structure: Palatinus L. & Chapuis G. (2007). J. Appl. Cryst. 40, 786-790; program(s) used to refine structure: Petricek, V., Dusek, M. & Palatinus L. (2014). Z. Kristallogr. 229 (5), 345-352.

(I) top
Crystal data top
I3Pb·CH6NDx = 4.108 Mg m3
Mr = 619.97Synchrotron radiation, λ = 0.68362 Å
Tetragonal, I422Cell parameters from 4261 reflections
Hall symbol: I 4 2θ = 2.7–31.3°
a = 8.88375 (18) ŵ = 23.28 mm1
c = 12.7010 (3) ÅT = 293 K
V = 1002.38 (5) Å3Irregular, dark grey
Z = 40.0025 × 0.0020 × 0.0015 mm
F(000) = 1040
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
721 reflections with I > 3σ(I)
Radiation source: synchrotronRint = 0.029
Synchrotron monochromatorθmax = 31.3°, θmin = 2.7°
Absorption correction: empirical (using intensity measurements)
CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
h = 1313
Tmin = 0.582, Tmax = 1.000k = 1313
4261 measured reflectionsl = 1313
773 independent reflections
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
R[F2 > 2σ(F2)] = 0.012(Δ/σ)max = 0.045
wR(F2) = 0.015Δρmax = 0.40 e Å3
S = 1.19Δρmin = 0.36 e Å3
773 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
67 parametersExtinction coefficient: 394E1 (9)
1 restraintAbsolute structure: 305 of Friedel pairs used in the refinement
31 constraintsAbsolute structure parameter: 0.25 (13)
H-atom parameters constrained
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pb1110.74980 (5)0.0374 (3)
I1_1110.50.0764 (7)
I1_21110.1027 (12)
I20.28604 (17)0.78604 (17)0.750.0873 (4)
C1.0436 (15)0.4947 (16)0.5240 (14)0.066 (6)*0.25
N0.934 (3)0.574 (3)0.4677 (11)0.086 (3)*0.25
H1n0.8503810.6031860.5160580.1031*0.25
H2n0.8941250.5093880.40980.1031*0.25
H3n0.9803790.6670290.436880.1031*0.25
H1c1.0307730.3843590.5112180.0791*0.25
H2c1.0320760.516040.6009240.0791*0.25
H3c1.145990.5267340.5002920.0791*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb10.0369 (3)0.0369 (3)0.0385 (6)000
I1_10.0951 (12)0.0951 (12)0.0389 (15)000
I1_20.142 (2)0.142 (2)0.0233 (13)000
I20.0711 (5)0.0711 (5)0.1198 (10)0.0413 (4)0.0037 (5)0.0037 (5)
Geometric parameters (Å, º) top
Pb1—I1_13.1727 (7)Pb1—I2iii3.1733 (15)
Pb1—I1_23.1777 (7)Pb1—I2iv3.1733 (15)
Pb1—I2i3.1733 (15)C—N1.40 (3)
Pb1—I2ii3.1733 (15)
I1_1—Pb1—I1_2180.0 (5)I2i—Pb1—I2ii179.91 (2)
I1_1—Pb1—I2i90.045 (12)I2i—Pb1—I2iii90.00 (4)
I1_1—Pb1—I2ii90.045 (12)I2i—Pb1—I2iv90.00 (4)
I1_1—Pb1—I2iii90.045 (12)I2ii—Pb1—I2iii90.00 (4)
I1_1—Pb1—I2iv90.045 (12)I2ii—Pb1—I2iv90.00 (4)
I1_2—Pb1—I2i89.955 (12)I2iii—Pb1—I2iv179.91 (2)
I1_2—Pb1—I2ii89.955 (12)Pb1—I1_1—Pb1v180.0 (5)
I1_2—Pb1—I2iii89.955 (12)Pb1—I1_2—Pb1vi180.0 (5)
I1_2—Pb1—I2iv89.955 (12)Pb1vii—I2—Pb1viii163.59 (5)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+2, z; (iii) y+2, x+1, z; (iv) y, x+1, z; (v) x+2, y, z+1; (vi) x+2, y, z+2; (vii) x1, y, z; (viii) x+3/2, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H1n···I2iv1.003.184.017 (17)141.93
N—H2n···I2ix1.003.003.99 (2)173.69
N—H3n···I1_11.003.073.85 (3)135.68
N—H3n···I2x1.003.183.92 (2)131.83
Symmetry codes: (iv) y, x+1, z; (ix) x+1/2, y1/2, z1/2; (x) x+3/2, y+3/2, z1/2.
(II) top
Crystal data top
I2.982Pb·0.925(CH6N)·0.088(O)Dx = 4.085 Mg m3
Mr = 616.41Synchrotron radiation, λ = 0.68362 Å
Tetragonal, P42212Cell parameters from 17735 reflections
Hall symbol: P 4n 2nθ = 2.7–31.6°
a = 8.8829 (3) ŵ = 23.23 mm1
c = 12.7008 (4) ÅT = 293 K
V = 1002.17 (7) Å3Irregular, black
Z = 40.0025 × 0.0020 × 0.0015 mm
F(000) = 1032.8
Data collection top
Dectris-CrysAlisPro-abstract goniometer imported dectris images
diffractometer
4191 independent reflections
Radiation source: synchrotron1704 reflections with I > 3σ(I)
Synchrotron monochromatorRint = 0.071
ω scansθmax = 31.6°, θmin = 2.7°
Absorption correction: empirical (using intensity measurements)
CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
h = 1212
Tmin = 0.399, Tmax = 1.000k = 1313
17735 measured reflectionsl = 1818
Refinement top
Refinement on FWeighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2)
R[F2 > 2σ(F2)] = 0.041(Δ/σ)max = 0.049
wR(F2) = 0.068Δρmax = 0.66 e Å3
S = 1.52Δρmin = 0.88 e Å3
4191 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
195 parametersExtinction coefficient: 19E1 (5)
2 restraintsAbsolute structure: 1031 of Friedel pairs used in the refinement
14 constraintsAbsolute structure parameter: 0.09 (5)
H-atom parameters constrained
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pb1000.7490 (6)0.050 (2)
I1_1000.50.111 (5)0.96 (2)
I1_20000.092 (4)
I20.2838 (4)0.7681 (4)0.7494 (3)0.122 (2)
C10.033 (5)0.497 (6)0.559 (3)0.053 (10)*0.167 (12)
C20.032 (5)0.504 (6)0.472 (3)0.045 (9)*0.295 (12)
N10.085 (5)0.568 (5)0.467 (3)0.041 (9)*0.167 (12)
N20.080 (4)0.442 (5)0.536 (3)0.081 (12)*0.295 (12)
H1n10.1927010.5986380.4770150.0497*0.167 (12)
H1n20.181010.4797060.5132530.0965*0.295 (12)
H2n10.0226090.6592760.4529150.0497*0.167 (12)
H2n20.0777220.3295940.5302910.0965*0.295 (12)
H3n10.0776350.4970490.4062590.0497*0.167 (12)
H3n20.0622610.4715820.6112390.0965*0.295 (12)
O10.510.811 (5)0.010 (5)*0.088 (18)
H1c10.0790870.4927890.5574280.0633*0.167 (12)
H2c10.0745370.3919960.561620.0633*0.167 (12)
H3c10.0677210.5543660.6217240.0633*0.167 (12)
H1c20.1205230.4348090.4701330.0545*0.295 (12)
H2c20.0636080.6036470.5017990.0545*0.295 (12)
H3c20.0083070.5185310.3995360.0545*0.295 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb10.070 (4)0.053 (3)0.026 (4)0.0009 (4)00
I1_10.164 (11)0.164 (11)0.004 (2)0.028 (4)00
I1_20.137 (9)0.137 (9)0.003 (2)0.000 (3)00
I20.066 (3)0.150 (4)0.149 (5)0.043 (3)0.022 (3)0.033 (3)
Geometric parameters (Å, º) top
Pb1—I1_13.162 (7)C1—N11.40 (6)
Pb1—I1_2i3.188 (7)C1—O1vii1.68 (8)
Pb1—I2ii3.255 (3)C2—N21.40 (6)
Pb1—I2iii3.255 (3)C2—O1vii2.76 (8)
Pb1—I2iv3.060 (3)N1—O1vii2.97 (8)
Pb1—I2v3.060 (3)N2—O1vii2.12 (7)
I2—O1vi2.924 (19)
I1_1—Pb1—I1_2i180.0 (5)I2ii—Pb1—I2iv90.37 (9)
I1_1—Pb1—I2ii90.10 (14)I2ii—Pb1—I2v89.63 (9)
I1_1—Pb1—I2iii90.10 (14)I2iii—Pb1—I2iv89.63 (9)
I1_1—Pb1—I2iv90.37 (15)I2iii—Pb1—I2v90.37 (9)
I1_1—Pb1—I2v90.37 (15)I2iv—Pb1—I2v179.3 (3)
I1_2i—Pb1—I2ii89.90 (14)Pb1—I1_1—Pb1viii180.0 (5)
I1_2i—Pb1—I2iii89.90 (14)Pb1ix—I1_2—Pb1viii180.0 (5)
I1_2i—Pb1—I2iv89.63 (15)Pb1x—I2—Pb1xi168.13 (12)
I1_2i—Pb1—I2v89.63 (15)Pb1x—I2—O1vi93.64 (9)
I2ii—Pb1—I2iii179.8 (3)Pb1xi—I2—O1vi97.71 (13)
Symmetry codes: (i) x, y, z+1; (ii) x, y1, z; (iii) x, y+1, z; (iv) x+1/2, y1/2, z+3/2; (v) x1/2, y+1/2, z+3/2; (vi) x+1, y, z; (vii) x1/2, y1/2, z+3/2; (viii) y, x, z+1; (ix) x, y, z1; (x) x, y+1, z; (xi) x+1/2, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n1···I1_2xii1.002.883.76 (5)146.48
N2—H1n2···I1_2xii1.002.843.79 (4)158.44
N1—H2n1···I1_1x1.003.093.93 (5)142.64
N2—H2n2···I1_11.003.034.02 (4)167.76
N1—H3n1···I2xiii1.003.063.95 (4)149.20
N1—H3n1···O1xiv1.002.853.67 (8)139.55
N2—H3n2···O1vii1.001.162.12 (7)160.58
C1—H3c1···I2xv1.002.633.60 (5)163.83
C2—H3c2···O1xiv1.002.693.62 (8)154.90
Symmetry codes: (vii) x1/2, y1/2, z+3/2; (x) x, y+1, z; (xii) y1/2, x+1/2, z+1/2; (xiii) y1, x, z+1; (xiv) y1, x+1, z+1; (xv) x1/2, y+3/2, z+3/2.
 

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