Synthesis, structure and red-light emission of a manganese halide directed by a methyl­diphenyl­phosphine oxide com­plex

Controlling the optical activity of halide perovskite materials through modulation of the coordination configurations of the metal ions is important. Herein, a novel manganese-based halide, specifically di­aqua­tetra­kis­(methyl­diphenyl­phosphine oxide)manganese(II) tetra­chlorido­manganate(II), [Mn(C₁₃H₁₃OP)₄(H₂O)₂][MnCl₄] or [Mn(MDPPO)₄(H₂O)₂][MnCl₄] (MDPPO is methyl­di­phenyl­phosphine oxide), was synthesized through the solvothermal reaction of MnCl₂ with the neutral mol­ecule MDPPO. In this com­pound, [Mn(MDPPO)₄(H₂O)₂]²⁺ acts as the cation, while [MnCl₄]²⁻ serves as the anion, enabling the co-existence of tetra­hedral and octa­hedral structures within the same system. Remarkably, the com­pound exhibits efficient red-light emission at 662 nm, distinct from the green-light emission typically observed in MnX₄-based halides. Theoretical calculations show that the red emission comes from the charge transfer from the MDPPO to the Mn²⁺ of [MnCl₄]²⁻. This work provides a new perspective for the design and synthesis of red-light-emitting manganese-based halides with unique structures.

Computing details

Diaquatetrakis(methyldiphenylphosphine oxide)manganese(II) tetrachloridomanganate(II)

Crystal data

[Mn(C13H13OP)4(H2O)2][MnCl4]	Dx = 1.424 Mg m^−3
Mr = 1152.52	Ga Kα radiation, λ = 1.34135 Å
Tetragonal, I41/a	Cell parameters from 5007 reflections
a = 21.0944 (3) Å	θ = 3.7–55.9°
c = 12.0785 (2) Å	µ = 4.84 mm^−1
V = 5374.62 (18) Å^3	T = 100 K
Z = 4	Block, colourless
F(000) = 2376	0.15 × 0.12 × 0.08 mm

Data collection

Rigaku XtaLAB Synergy Custom system with a HyPix detector diffractometer	2619 independent reflections
Radiation source: micro-focus metaljet	2311 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.032
Detector resolution: 10.0000 pixels mm^-1	θmax = 56.0°, θmin = 3.7°
ω scans	h = −15→24
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2023)	k = −26→25
Tmin = 0.673, Tmax = 1.000	l = −7→14
7472 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0433P)^2 + 4.6502P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2619 reflections	Δρmax = 0.39 e Å^−3
158 parameters	Δρmin = −0.41 e Å^−3
1 restraint

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. The single-crystal data for the compound were obtained using a Synergy Custom ROD system with a HyPix diffractometer and Ga Kα radiation (λ = 1.34050 Å) at 100 K. The structures were solved and refined using full matrixcs methods against F² with the SHELXL2014 software package and OLEX2 (Dolomanov et al., 2003). Anisotropic thermal parameters refined all non-hydrogen atoms.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	1.0000	0.7500	−0.1250	0.01375 (15)
Cl1	0.97709 (2)	0.66074 (2)	−0.01258 (4)	0.02123 (14)
Mn2	1.0000	0.7500	0.3750	0.01049 (14)
P1	0.87598 (2)	0.64948 (2)	0.32708 (4)	0.01330 (13)
O1	0.94307 (6)	0.66565 (6)	0.35768 (10)	0.0152 (3)
O2	1.0000	0.7500	0.19301 (15)	0.0214 (4)
H2A	1.0137	0.7807	0.1513	0.032*	0.5
H2B	1.0048	0.7161	0.1528	0.032*	0.5
C1	0.82315 (9)	0.65755 (8)	0.44271 (15)	0.0149 (4)
C2	0.75770 (10)	0.66511 (9)	0.43074 (17)	0.0204 (4)
H2	0.7395	0.6669	0.3589	0.025*
C3	0.71928 (10)	0.67008 (10)	0.52348 (17)	0.0223 (4)
H3	0.6748	0.6750	0.5152	0.027*
C4	0.74589 (10)	0.66784 (10)	0.62839 (16)	0.0221 (5)
H4	0.7196	0.6719	0.6918	0.027*
C5	0.81060 (10)	0.65974 (10)	0.64114 (16)	0.0214 (4)
H5	0.8285	0.6576	0.7132	0.026*
C6	0.84932 (9)	0.65476 (9)	0.54862 (16)	0.0186 (4)
H6	0.8937	0.6494	0.5575	0.022*
C7	0.87123 (9)	0.56818 (9)	0.28307 (14)	0.0144 (4)
C8	0.92077 (9)	0.54419 (9)	0.21885 (15)	0.0176 (4)
H8	0.9557	0.5705	0.2002	0.021*
C9	0.91883 (9)	0.48181 (9)	0.18227 (16)	0.0192 (4)
H9	0.9526	0.4655	0.1386	0.023*
C10	0.86775 (10)	0.44320 (9)	0.20923 (16)	0.0202 (4)
H10	0.8666	0.4005	0.1842	0.024*
C11	0.81839 (10)	0.46693 (10)	0.27270 (16)	0.0210 (4)
H11	0.7834	0.4405	0.2909	0.025*
C12	0.82000 (10)	0.52918 (9)	0.30968 (15)	0.0186 (4)
H12	0.7861	0.5453	0.3532	0.022*
C13	0.84538 (10)	0.69750 (9)	0.21683 (15)	0.0190 (4)
H13A	0.8442	0.7419	0.2404	0.028*
H13B	0.8024	0.6835	0.1981	0.028*
H13C	0.8728	0.6933	0.1517	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0161 (2)	0.0161 (2)	0.0091 (3)	0.000	0.000	0.000
Cl1	0.0304 (3)	0.0183 (2)	0.0150 (2)	−0.00579 (19)	−0.00100 (19)	0.00150 (17)
Mn2	0.01206 (19)	0.01206 (19)	0.0073 (3)	0.000	0.000	0.000
P1	0.0147 (2)	0.0139 (2)	0.0112 (2)	−0.00171 (17)	0.00010 (17)	−0.00011 (17)
O1	0.0145 (7)	0.0163 (7)	0.0148 (6)	−0.0026 (5)	−0.0004 (5)	−0.0003 (5)
O2	0.0363 (12)	0.0187 (10)	0.0093 (9)	−0.0092 (9)	0.000	0.000
C1	0.0162 (9)	0.0121 (9)	0.0165 (9)	−0.0031 (7)	0.0018 (7)	−0.0002 (7)
C2	0.0207 (10)	0.0212 (10)	0.0194 (10)	−0.0019 (8)	−0.0016 (8)	−0.0012 (8)
C3	0.0168 (10)	0.0218 (10)	0.0282 (11)	−0.0030 (8)	0.0039 (8)	−0.0021 (8)
C4	0.0247 (11)	0.0199 (10)	0.0217 (11)	−0.0026 (9)	0.0104 (8)	−0.0001 (8)
C5	0.0273 (11)	0.0221 (11)	0.0147 (10)	−0.0017 (9)	0.0019 (8)	0.0018 (8)
C6	0.0184 (10)	0.0196 (10)	0.0177 (10)	0.0006 (8)	0.0014 (8)	0.0005 (8)
C7	0.0164 (9)	0.0165 (9)	0.0103 (8)	−0.0007 (7)	−0.0031 (7)	0.0003 (7)
C8	0.0171 (10)	0.0203 (10)	0.0154 (9)	−0.0034 (8)	−0.0021 (7)	−0.0008 (7)
C9	0.0190 (10)	0.0223 (10)	0.0164 (9)	0.0037 (8)	−0.0041 (8)	−0.0040 (8)
C10	0.0284 (11)	0.0162 (10)	0.0161 (10)	0.0007 (8)	−0.0062 (8)	−0.0008 (8)
C11	0.0263 (11)	0.0196 (10)	0.0171 (10)	−0.0076 (8)	−0.0004 (8)	0.0015 (8)
C12	0.0223 (10)	0.0198 (10)	0.0139 (9)	−0.0014 (8)	0.0028 (8)	−0.0006 (8)
C13	0.0231 (10)	0.0179 (10)	0.0159 (9)	−0.0014 (8)	−0.0024 (8)	0.0019 (8)

Geometric parameters (Å, º)

Mn1—Cl1	2.3712 (4)	C3—C4	1.387 (3)
Mn1—Cl1^i	2.3712 (4)	C4—H4	0.9500
Mn1—Cl1^ii	2.3712 (4)	C4—C5	1.384 (3)
Mn1—Cl1^iii	2.3712 (4)	C5—H5	0.9500
Mn2—O1^i	2.1568 (13)	C5—C6	1.388 (3)
Mn2—O1^iv	2.1568 (13)	C6—H6	0.9500
Mn2—O1^v	2.1568 (13)	C7—C8	1.396 (3)
Mn2—O1	2.1568 (13)	C7—C12	1.396 (3)
Mn2—O2	2.1982 (18)	C8—H8	0.9500
Mn2—O2^iv	2.1982 (18)	C8—C9	1.389 (3)
P1—O1	1.5019 (14)	C9—H9	0.9500
P1—C1	1.7950 (19)	C9—C10	1.390 (3)
P1—C7	1.7981 (19)	C10—H10	0.9500
P1—C13	1.7934 (19)	C10—C11	1.387 (3)
O2—H2A	0.8702	C11—H11	0.9500
O2—H2B	0.8698	C11—C12	1.387 (3)
C1—C2	1.397 (3)	C12—H12	0.9500
C1—C6	1.394 (3)	C13—H13A	0.9800
C2—H2	0.9500	C13—H13B	0.9800
C2—C3	1.387 (3)	C13—H13C	0.9800
C3—H3	0.9500
Cl1—Mn1—Cl1^i	110.13 (2)	C2—C3—H3	120.0
Cl1—Mn1—Cl1^ii	109.144 (11)	C2—C3—C4	119.94 (19)
Cl1^i—Mn1—Cl1^ii	109.143 (11)	C4—C3—H3	120.0
Cl1—Mn1—Cl1^iii	109.144 (11)	C3—C4—H4	119.8
Cl1^i—Mn1—Cl1^iii	109.143 (11)	C5—C4—C3	120.33 (18)
Cl1^ii—Mn1—Cl1^iii	110.13 (2)	C5—C4—H4	119.8
O1—Mn2—O1^i	168.87 (7)	C4—C5—H5	120.0
O1^v—Mn2—O1^iv	168.87 (7)	C4—C5—C6	120.00 (19)
O1^i—Mn2—O1^v	90.539 (7)	C6—C5—H5	120.0
O1—Mn2—O1^v	90.539 (6)	C1—C6—H6	119.9
O1^i—Mn2—O1^iv	90.539 (7)	C5—C6—C1	120.16 (19)
O1—Mn2—O1^iv	90.539 (7)	C5—C6—H6	119.9
O1—Mn2—O2	84.43 (3)	C8—C7—P1	117.92 (14)
O1^i—Mn2—O2	84.43 (3)	C12—C7—P1	122.50 (15)
O1^iv—Mn2—O2^iv	84.43 (3)	C12—C7—C8	119.58 (17)
O1^iv—Mn2—O2	95.57 (3)	C7—C8—H8	120.1
O1^i—Mn2—O2^iv	95.57 (3)	C9—C8—C7	119.88 (18)
O1^v—Mn2—O2	95.57 (3)	C9—C8—H8	120.1
O1^v—Mn2—O2^iv	84.43 (3)	C8—C9—H9	119.9
O1—Mn2—O2^iv	95.57 (3)	C8—C9—C10	120.25 (18)
O2—Mn2—O2^iv	180.0	C10—C9—H9	119.9
O1—P1—C1	111.84 (8)	C9—C10—H10	120.0
O1—P1—C7	109.99 (8)	C11—C10—C9	120.02 (18)
O1—P1—C13	113.18 (9)	C11—C10—H10	120.0
C1—P1—C7	106.61 (8)	C10—C11—H11	120.0
C13—P1—C1	107.50 (9)	C10—C11—C12	120.09 (19)
C13—P1—C7	107.40 (9)	C12—C11—H11	120.0
P1—O1—Mn2	137.38 (8)	C7—C12—H12	119.9
Mn2—O2—H2A	125.4	C11—C12—C7	120.19 (18)
Mn2—O2—H2B	123.9	C11—C12—H12	119.9
H2A—O2—H2B	104.5	P1—C13—H13A	109.5
C2—C1—P1	122.94 (15)	P1—C13—H13B	109.5
C6—C1—P1	117.64 (15)	P1—C13—H13C	109.5
C6—C1—C2	119.40 (18)	H13A—C13—H13B	109.5
C1—C2—H2	119.9	H13A—C13—H13C	109.5
C3—C2—C1	120.16 (19)	H13B—C13—H13C	109.5
C3—C2—H2	119.9
P1—C1—C2—C3	178.97 (15)	C6—C1—C2—C3	0.3 (3)
P1—C1—C6—C5	−179.01 (15)	C7—P1—O1—Mn2	159.22 (10)
P1—C7—C8—C9	−179.48 (14)	C7—P1—C1—C2	−80.54 (17)
P1—C7—C12—C11	179.37 (15)	C7—P1—C1—C6	98.16 (16)
O1—P1—C1—C2	159.20 (15)	C7—C8—C9—C10	0.1 (3)
O1—P1—C1—C6	−22.10 (17)	C8—C7—C12—C11	0.1 (3)
O1—P1—C7—C8	−38.91 (16)	C8—C9—C10—C11	0.1 (3)
O1—P1—C7—C12	141.83 (15)	C9—C10—C11—C12	−0.2 (3)
C1—P1—O1—Mn2	−82.52 (13)	C10—C11—C12—C7	0.1 (3)
C1—P1—C7—C8	−160.35 (14)	C12—C7—C8—C9	−0.2 (3)
C1—P1—C7—C12	20.38 (18)	C13—P1—O1—Mn2	39.08 (14)
C1—C2—C3—C4	0.3 (3)	C13—P1—C1—C2	34.38 (18)
C2—C1—C6—C5	−0.3 (3)	C13—P1—C1—C6	−146.92 (15)
C2—C3—C4—C5	−0.9 (3)	C13—P1—C7—C8	84.67 (16)
C3—C4—C5—C6	0.9 (3)	C13—P1—C7—C12	−94.60 (17)
C4—C5—C6—C1	−0.4 (3)

Symmetry codes: (i) −x+2, −y+3/2, z; (ii) y+1/4, −x+7/4, −z−1/4; (iii) −y+7/4, x−1/4, −z−1/4; (iv) y+1/4, −x+7/4, −z+3/4; (v) −y+7/4, x−1/4, −z+3/4.