Bis(trimethyl­ammonium) deca­selenido­tetra­germanato­manganate(II)

Solvothermal reaction of Ge and Se with Mn(CH₃COO)₂·4H₂O in the presence of [(CH₃)₃NH]Cl generates the open framework quaternary selenidogerman­ate(IV) [(CH₃)₃NH]₂[MnGe₄Se₁₀], which contains corner-linked adamantanoid Ge₄Se₁₀ cages and MnSe₄ tetra­hedra. The trimethyl­ammonium counter-cations are disordered and exhibit an S₄ crystallographic site symmetry. Whereas the Ge-Se distances within the Ge₄Se₆ core lie in the range 2.357 (1)-2.370 (1) Å, a significantly shorter Ge-Se bond length of 2.284 (1) Å is observed for the bridging Se atom to the MnSe₄ units.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](e-Mn) = 0.001 Å
• H-atom completeness 91%
• Disorder in solvent or counterion
• R factor = 0.027
• wR factor = 0.066
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      60.00 Perc.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.29 Ratio
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       0.05

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C6 H20 Ge4 Mn1 N2 Se10
            Atom count from the _atom_site data:  C6 H18 Ge4 Mn1 N2 Se10
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    2
           From the CIF: _chemical_formula_sum  C6 H20 Ge4 Mn N2 Se10
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         12.00     12.00    0.00
           H         40.00     36.00    4.00
           Ge         8.00      8.00    0.00
           Mn         2.00      2.00    0.00
           N          4.00      4.00    0.00
           Se        20.00     20.00    0.00
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           24.95
           From the CIF: _reflns_number_total                859
           Count of symmetry unique reflns          617
           Completeness (_total/calc)            139.22%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       242
           Fraction of Friedel pairs measured     0.392
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: R3m/V (Siemens, 1989); cell refinement: R3m/V; data reduction: XDISK (Siemens, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1995); software used to prepare material for publication: SHELXL97.

Bis(trimethylammonium) decaselenidotetragermanatomanganate(II)

Crystal data

(C3H10N)2[MnGe4Se10]	Dx = 3.081 Mg m^−3
Mr = 1255.14	Melting point: not measured K
Tetragonal, I4	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I -4	Cell parameters from 22 reflections
a = 9.559 (2) Å	θ = 4.9–12.9°
c = 14.808 (6) Å	µ = 18.29 mm^−1
V = 1353.0 (7) Å^3	T = 293 K
Z = 2	Tetrahedron, orange
F(000) = 1126	0.16 × 0.14 × 0.12 mm

Data collection

Siemens P4 four-circle diffractometer	790 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.0°, θmin = 2.5°
ω scans	h = −1→11
Absorption correction: ψ scan (XPREP in SHELXTL-Plus; Sheldrick, 1995)	k = −1→11
Tmin = 0.069, Tmax = 0.117	l = −1→17
945 measured reflections	3 standard reflections every 97 reflections
859 independent reflections	intensity decay: 0.02%

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)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0368P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.002
859 reflections	Δρmax = 0.53 e Å^−3
59 parameters	Δρmin = −0.59 e Å^−3
0 restraints	Absolute structure: Flack (1983), 242 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	Occ. (<1)
Ge	0.17744 (8)	0.91692 (9)	0.91103 (5)	0.0248 (2)
Se1	0.0000	1.0000	0.81435 (7)	0.0338 (3)
Se2	0.09687 (9)	0.72754 (9)	1.00028 (7)	0.0342 (2)
Se3	0.34837 (10)	0.81447 (9)	0.82588 (6)	0.0375 (3)
Mn	0.5000	1.0000	0.7500	0.0252 (6)
C1	0.4546 (19)	0.6114 (17)	1.0611 (10)	0.073 (5)	0.75
H1A	0.4002	0.6786	1.0281	0.109*	0.75
H1B	0.5351	0.6566	1.0866	0.109*	0.75
H1C	0.3986	0.5721	1.1086	0.109*	0.75
N1	0.5000	0.5000	1.0000	0.159 (14)
C2	−0.112 (2)	0.565 (2)	0.801 (2)	0.122 (10)	0.75
H2A	−0.1942	0.5719	0.7643	0.183*	0.75
H2B	−0.0835	0.6571	0.8198	0.183*	0.75
H2C	−0.1322	0.5096	0.8537	0.183*	0.75
N2	0.0000	0.5000	0.7500	0.28 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge	0.0265 (4)	0.0242 (4)	0.0238 (4)	0.0012 (4)	0.0063 (4)	−0.0014 (4)
Se1	0.0406 (7)	0.0406 (7)	0.0204 (6)	0.0046 (7)	0.000	0.000
Se2	0.0375 (5)	0.0259 (4)	0.0391 (5)	0.0051 (4)	0.0116 (5)	0.0051 (4)
Se3	0.0435 (5)	0.0254 (5)	0.0437 (5)	0.0060 (4)	0.0232 (5)	0.0030 (4)
Mn	0.0266 (8)	0.0266 (8)	0.0226 (14)	0.000	0.000	0.000
C1	0.079 (11)	0.059 (9)	0.081 (12)	−0.002 (9)	0.001 (10)	−0.019 (10)
N1	0.122 (16)	0.122 (16)	0.23 (4)	0.000	0.000	0.000
C2	0.070 (12)	0.100 (18)	0.20 (3)	0.028 (14)	−0.039 (17)	0.025 (19)
N2	0.31 (6)	0.31 (6)	0.23 (7)	0.000	0.000	0.000

Geometric parameters (Å, º)

Ge—Se3	2.2843 (12)	C1—H1B	0.9600
Ge—Se2^i	2.3471 (13)	C1—H1C	0.9600
Ge—Se1	2.3574 (11)	N1—C1^vii	1.463 (14)
Ge—Se2	2.3699 (13)	N1—C1^viii	1.463 (13)
Se1—Ge^ii	2.3574 (11)	N1—C1^ix	1.463 (14)
Se2—Ge^iii	2.3471 (13)	C2—N2	1.45 (2)
Se3—Mn	2.5512 (10)	C2—H2A	0.9600
Mn—Se3^iv	2.5512 (10)	C2—H2B	0.9600
Mn—Se3^v	2.5512 (10)	C2—H2C	0.9600
Mn—Se3^vi	2.5512 (10)	N2—C2^x	1.45 (2)
C1—N1	1.463 (13)	N2—C2^xi	1.45 (2)
C1—H1A	0.9600	N2—C2^xii	1.45 (2)
Se3—Ge—Se2^i	110.26 (5)	H1B—C1—H1C	109.5
Se3—Ge—Se1	108.89 (5)	C1^vii—N1—C1	112.5 (7)
Se2^i—Ge—Se1	111.80 (4)	C1^vii—N1—C1^viii	112.5 (7)
Se3—Ge—Se2	102.29 (5)	C1—N1—C1^viii	103.6 (14)
Se2^i—Ge—Se2	111.93 (4)	C1^vii—N1—C1^ix	103.6 (14)
Se1—Ge—Se2	111.23 (4)	C1—N1—C1^ix	112.5 (7)
Ge—Se1—Ge^ii	105.21 (6)	C1^viii—N1—C1^ix	112.5 (7)
Ge^iii—Se2—Ge	104.76 (5)	N2—C2—H2A	109.5
Ge—Se3—Mn	110.58 (4)	N2—C2—H2B	109.5
Se3^iv—Mn—Se3^v	101.19 (2)	H2A—C2—H2B	109.5
Se3^iv—Mn—Se3	127.73 (5)	N2—C2—H2C	109.5
Se3^v—Mn—Se3	101.19 (2)	H2A—C2—H2C	109.5
Se3^iv—Mn—Se3^vi	101.19 (2)	H2B—C2—H2C	109.5
Se3^v—Mn—Se3^vi	127.73 (5)	C2^x—N2—C2^xi	117 (2)
Se3—Mn—Se3^vi	101.19 (2)	C2^x—N2—C2^xii	105.9 (9)
N1—C1—H1A	109.5	C2^xi—N2—C2^xii	105.9 (9)
N1—C1—H1B	109.5	C2^x—N2—C2	105.9 (9)
H1A—C1—H1B	109.5	C2^xi—N2—C2	105.9 (9)
N1—C1—H1C	109.5	C2^xii—N2—C2	117 (2)
H1A—C1—H1C	109.5
Se3—Ge—Se1—Ge^ii	174.85 (5)	Se2^i—Ge—Se3—Mn	−46.50 (6)
Se2^i—Ge—Se1—Ge^ii	−63.07 (4)	Se1—Ge—Se3—Mn	76.50 (5)
Se2—Ge—Se1—Ge^ii	62.87 (3)	Se2—Ge—Se3—Mn	−165.70 (4)
Se3—Ge—Se2—Ge^iii	−179.05 (5)	Ge—Se3—Mn—Se3^iv	61.80 (4)
Se2^i—Ge—Se2—Ge^iii	62.93 (4)	Ge—Se3—Mn—Se3^v	175.57 (5)
Se1—Ge—Se2—Ge^iii	−62.94 (6)	Ge—Se3—Mn—Se3^vi	−51.97 (3)

Symmetry codes: (i) −y+1, x+1, −z+2; (ii) −x, −y+2, z; (iii) y−1, −x+1, −z+2; (iv) −x+1, −y+2, z; (v) −y+3/2, x+1/2, −z+3/2; (vi) y−1/2, −x+3/2, −z+3/2; (vii) −y+1, x, −z+2; (viii) −x+1, −y+1, z; (ix) y, −x+1, −z+2; (x) −y+1/2, x+1/2, −z+3/2; (xi) y−1/2, −x+1/2, −z+3/2; (xii) −x, −y+1, z.