Synthesis, crystal structure and phase transitions of novel hybrid perovskite: bis­(1,2-di­amino­propane) di-μ-chloro-bis­[di­aqua­dichloro­manganate(II)] dichloride

Single crystals of bis­(1,2-di­amine­propane) di-μ-chloro-bis­[di­aqua­dichloro­manganate(II)] dichloride have been prepared by evaporation from ethanoic solution. The triclinic X-ray crystal structure is built as layers of centrosymmetric dimers of [Mn(Cl)₄(H₂O)₂]²⁻ octahedra and 1,2-diaminopropane. The inorganic part consists of Mn octahedra sharing one edge and distributed in the basal ac plane along the a direction. These doubly negative charged layers are separated along the b axis by a positively charged diamine propane layer. One Cl⁻ anion contributes to the electroneutrality of the crystal interacting with both inorganic – through a hydrogen bond network to the two water molecules coordinated to Mn – and organic layers via the NH₃⁺ ammonium group. Differential scanning calorimetry shows two endothermic main peaks at T = 366 K and T = 375 K related to the release of the water molecules. The resulting dehydrated material is C-centered monoclinic as shown by powder X-ray diffraction.

Computing details

Program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: olex2.refine (Bourhis et al., 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(I)

Crystal data

Cl3H4MnO2·C3H12N2·Cl	V = 589.58 (4) Å^3
Mr = 308.92	Z = 2
Triclinic, P1	F(000) = 315.9491
a = 5.9138 (2) Å	Dx = 1.740 Mg m^−3
b = 9.8318 (4) Å	Mo Kα radiation, λ = 0.71073 Å
c = 10.8908 (4) Å	µ = 2.00 mm^−1
α = 73.154 (4)°	T = 100 K
β = 76.691 (3)°	90 × 80 × 50 mm
γ = 87.551 (3)°

Data collection

Rigaku Oxford Diffraction SuperNova dual Mo/Cu Atlas diffractometer	Rint = 0.060
Absorption correction: analytical and empirical (using intensity measurements)	θmax = 37.7°, θmin = 2.0°
	h = −10→9
29228 measured reflections	k = −16→16
6040 independent reflections	l = −18→18
4678 reflections with I ≥ 2u(I)

Refinement

Refinement on F^2	17 constraints
Least-squares matrix: full	Primary atom site location: heavy-atom method
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0258P)^2 + 0.0524P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.015
6040 reflections	Δρmax = 0.90 e Å^−3
128 parameters	Δρmin = −0.88 e Å^−3
0 restraints

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

	x	y	z	Uiso*/Ueq
Mn1	0.47245 (3)	0.96232 (2)	0.181975 (19)	0.00828 (5)
Cl2	0.70019 (5)	0.86690 (3)	−0.00200 (3)	0.00990 (6)
Cl3	0.66450 (5)	0.78506 (4)	0.34910 (3)	0.01115 (6)
Cl1	0.25141 (5)	1.07432 (4)	0.34761 (3)	0.01048 (6)
N2	0.7309 (2)	1.18161 (12)	0.39608 (11)	0.0107 (2)
H2a	0.6651 (17)	1.1425 (4)	0.3461 (4)	0.0128 (2)*
H2b	0.8572 (4)	1.1312 (3)	0.4154 (9)	0.0128 (2)*
H2c	0.6256 (14)	1.17954 (15)	0.4722 (5)	0.0128 (2)*
N1	0.6603 (2)	1.55174 (12)	0.18403 (11)	0.0109 (2)
H1a	0.6638 (19)	1.6136 (3)	0.23161 (12)	0.0163 (3)*
H1b	0.8032 (9)	1.5500 (3)	0.1310 (7)	0.0163 (3)*
H1c	0.5540 (11)	1.5801 (5)	0.1337 (8)	0.0163 (3)*
C2	0.8045 (2)	1.33230 (14)	0.32150 (13)	0.0093 (2)
H2	0.9310 (2)	1.33297 (14)	0.24255 (13)	0.0112 (3)*
C1	0.5943 (2)	1.40664 (15)	0.27542 (13)	0.0109 (2)
H1d	0.4733 (2)	1.41388 (15)	0.35278 (13)	0.0131 (3)*
H1e	0.5285 (2)	1.34953 (15)	0.22998 (13)	0.0131 (3)*
C3	0.8989 (3)	1.39886 (16)	0.41028 (14)	0.0141 (3)
H3a	0.7752 (6)	1.4001 (11)	0.4873 (6)	0.0211 (4)*
H3b	1.0280 (13)	1.3429 (7)	0.4394 (9)	0.0211 (4)*
H3c	0.9541 (19)	1.4964 (4)	0.3613 (4)	0.0211 (4)*
Cl4	0.21278 (5)	0.58776 (4)	0.06365 (3)	0.01125 (6)
O1	0.20070 (19)	0.80415 (12)	0.22497 (11)	0.0147 (2)
O2	0.75961 (18)	1.11725 (12)	0.14286 (10)	0.01130 (18)
Hw2a	0.745 (4)	1.193 (3)	0.088 (2)	0.030 (6)*
Hw2b	0.886 (4)	1.094 (3)	0.123 (2)	0.033 (6)*
Hw1a	0.203 (4)	0.762 (3)	0.176 (2)	0.042 (7)*
Hw1b	0.065 (4)	0.811 (2)	0.265 (2)	0.030 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.00810 (9)	0.00842 (9)	0.00808 (9)	−0.00005 (6)	−0.00124 (7)	−0.00245 (7)
Cl2	0.00987 (13)	0.01029 (14)	0.00877 (13)	0.00221 (10)	−0.00138 (10)	−0.00240 (10)
Cl3	0.01033 (13)	0.01310 (15)	0.00946 (13)	0.00249 (10)	−0.00206 (10)	−0.00284 (11)
Cl1	0.01003 (13)	0.01094 (14)	0.00974 (13)	0.00181 (10)	−0.00025 (10)	−0.00365 (10)
N2	0.0124 (5)	0.0092 (5)	0.0099 (5)	0.0005 (4)	−0.0034 (4)	−0.0014 (4)
N1	0.0116 (5)	0.0091 (5)	0.0115 (5)	0.0006 (4)	−0.0032 (4)	−0.0019 (4)
C2	0.0096 (5)	0.0081 (5)	0.0088 (5)	0.0000 (4)	−0.0014 (4)	−0.0008 (4)
C1	0.0102 (5)	0.0084 (6)	0.0126 (6)	−0.0009 (4)	−0.0030 (4)	−0.0002 (4)
C3	0.0159 (6)	0.0136 (7)	0.0142 (6)	−0.0014 (5)	−0.0066 (5)	−0.0036 (5)
Cl4	0.00986 (13)	0.01085 (14)	0.01324 (14)	−0.00024 (10)	−0.00241 (10)	−0.00387 (11)
O1	0.0109 (4)	0.0167 (5)	0.0174 (5)	−0.0035 (4)	0.0011 (4)	−0.0088 (4)
O2	0.0089 (4)	0.0118 (5)	0.0119 (4)	−0.0008 (3)	−0.0008 (3)	−0.0025 (4)

Geometric parameters (Å, º)

Mn1—Cl2^i	2.5634 (4)	Mn1—O2	2.2131 (11)
Mn1—Cl2	2.5393 (4)	N2—C2	1.4963 (18)
Mn1—Cl3	2.5660 (4)	N1—C1	1.4912 (18)
Mn1—Cl1	2.4734 (4)	C2—C1	1.5254 (19)
Mn1—O1	2.1599 (11)	C2—C3	1.5236 (19)
Cl3—Mn1—Cl2	90.619 (12)	O2—Mn1—Cl2	89.52 (3)
Cl3—Mn1—Cl2^i	175.883 (12)	O2—Mn1—Cl2^i	90.25 (3)
Cl1—Mn1—Cl2	175.328 (14)	O2—Mn1—Cl3	89.34 (3)
Cl1—Mn1—Cl2^i	90.686 (12)	O2—Mn1—Cl1	88.14 (3)
Cl1—Mn1—Cl3	93.395 (12)	O2—Mn1—O1	177.51 (5)
O1—Mn1—Cl2	90.07 (3)	C1—C2—N2	107.32 (11)
O1—Mn1—Cl2^i	92.17 (3)	C3—C2—N2	108.63 (11)
O1—Mn1—Cl3	88.20 (3)	C3—C2—C1	114.11 (11)
O1—Mn1—Cl1	92.44 (3)	C2—C1—N1	111.01 (11)

Symmetry code: (i) −x+1, −y+2, −z.