Molecular building blocks for solid-state chalcogenides: solvothermal synthesis of [Mn(en)₃]Te₄ and [Fe(en)₃]₂(Sb₂Se₅)

Two new molecular metal chalcogenides, tris­(ethyl­enedi­amine-N,N′)­manganese(II) tetratelluride, [Mn(C₂H₈N₂)₃]Te₄, (I), and bis­[tris­(ethyl­enedi­amine-N,N′)­iron(II)] penta­seleno­diantimonate(III), [Fe(C₂H₈N₂)₃]₂(Sb₂Se₅), (II), containing the isolated molecular building blocks Te₄²⁻ and Sb₂Se₅⁴⁻, have been synthesized by solvothermal reactions in an ethyl­enedi­amine solution at 433 K. The anion Te₄²⁻ in (I) is a zigzag oligometric chain with Te—Te bond lengths in the range 2.709–2.751 Å. There is a very short contact [3.329 (1) Å] between a pair of neighboring Te₄²⁻ anions. In (II), each Sb atom is surrounded by three Se atoms to give a tripodal coordination. One of the three independent Se atoms is a μ₂-bridging ligand between two Sb atoms; the other two are terminal.

Computing details

For both compounds, data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: CAD-4-PC Software; data reduction: XCAD4/PC (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SCHAKAL92 (Keller, 1992) and ORTEX (McArdle, 1993); software used to prepare material for publication: SHELXL97.

(I) tri(ethylenediamino)manganous telluride

Crystal data

[Mn(C2H8N2)3]Te4	F(000) = 1340
Mr = 745.65	Dx = 2.622 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.461 (2) Å	Cell parameters from 25 reflections
b = 15.653 (3) Å	θ = 8.0–13.8°
c = 14.269 (3) Å	µ = 6.75 mm^−1
β = 91.37 (3)°	T = 293 K
V = 1889.2 (7) Å^3	Block, black
Z = 4	0.33 × 0.3 × 0.3 mm

Data collection

Enraf-Nonius CAD4 diffractometer	2382 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
ω–scans	h = −10→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→18
Tmin = 0.120, Tmax = 0.132	l = 0→16
3444 measured reflections	3 standard reflections every 120 min
3306 independent reflections	intensity decay: 5.2%

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)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.072	Calculated w = 1/[σ^2(Fo^2) + (0.001P)^2 + 5.0P] where P = (Fo^2 + 2Fc^2)/3
S = 1.34	(Δ/σ)max = 0.001
3306 reflections	Δρmax = 1.37 e Å^−3
155 parameters	Δρmin = −0.77 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00129 (4)

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.

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

	x	y	z	Uiso*/Ueq
Te1	0.35396 (8)	1.16959 (5)	0.37880 (5)	0.0639 (2)
Te2	0.37486 (9)	0.99798 (5)	0.40030 (5)	0.0708 (2)
Te3	0.26166 (7)	0.91945 (4)	0.23989 (5)	0.0549 (2)
Te4	0.47529 (7)	0.94980 (4)	0.10143 (5)	0.0544 (2)
Mn1	0.36862 (15)	0.32343 (8)	0.68448 (10)	0.0451 (3)
N1	0.3190 (9)	0.1835 (4)	0.6486 (5)	0.057 (2)
H1A	0.3746	0.1488	0.6874	0.100*
H1B	0.3463	0.1722	0.5893	0.100*
N2	0.1023 (8)	0.3228 (4)	0.6625 (5)	0.054 (2)
H2A	0.0721	0.3675	0.6268	0.100*
H2B	0.0547	0.3269	0.7181	0.100*
N3	0.3973 (11)	0.2888 (5)	0.8385 (6)	0.079 (3)
H3A	0.4984	0.2740	0.8511	0.100*
H3B	0.3356	0.2437	0.8511	0.100*
N4	0.3508 (10)	0.4521 (5)	0.7598 (6)	0.066 (2)
H4A	0.2562	0.4762	0.7468	0.100*
H4B	0.4266	0.4876	0.7398	0.100*
N5	0.3894 (8)	0.3698 (5)	0.5331 (5)	0.059 (2)
H5A	0.3301	0.4170	0.5244	0.100*
H5B	0.3529	0.3292	0.4935	0.100*
N6	0.6308 (8)	0.3190 (6)	0.6567 (5)	0.066 (2)
H6A	0.6719	0.2702	0.6801	0.100*
H6B	0.6793	0.3631	0.6859	0.100*
C1	0.1487 (12)	0.1702 (6)	0.6595 (8)	0.072 (3)
H1C	0.1272	0.1679	0.7252	0.100*
H1D	0.1160	0.1170	0.6317	0.100*
C2	0.0569 (11)	0.2428 (6)	0.6161 (7)	0.060 (3)
H2C	0.0816	0.2465	0.5509	0.100*
H2D	−0.0546	0.2330	0.6208	0.100*
C3	0.3539 (14)	0.3555 (7)	0.8968 (7)	0.084 (4)
H3C	0.4149	0.3520	0.9542	0.100*
H3D	0.2450	0.3476	0.9122	0.100*
C4	0.3693 (19)	0.4414 (7)	0.8583 (8)	0.112 (5)
H4C	0.2940	0.4772	0.8887	0.100*
H4D	0.4725	0.4616	0.8769	0.100*
C5	0.5541 (10)	0.3891 (7)	0.5128 (8)	0.069 (3)
H5C	0.5811	0.4440	0.5385	0.100*
H5D	0.5687	0.3911	0.4463	0.100*
C6	0.6591 (10)	0.3234 (7)	0.5567 (7)	0.063 (3)
H6C	0.6351	0.2689	0.5291	0.100*
H6D	0.7679	0.3364	0.5454	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Te1	0.0514 (4)	0.0720 (5)	0.0678 (5)	−0.0014 (4)	−0.0050 (3)	−0.0119 (4)
Te2	0.0811 (5)	0.0779 (5)	0.0528 (4)	0.0252 (4)	−0.0100 (4)	0.0035 (4)
Te3	0.0449 (3)	0.0515 (4)	0.0685 (5)	−0.0040 (3)	0.0019 (3)	0.0035 (3)
Te4	0.0471 (4)	0.0478 (4)	0.0683 (4)	−0.0068 (3)	0.0023 (3)	−0.0129 (3)
Mn1	0.0388 (7)	0.0389 (8)	0.0574 (9)	0.0036 (6)	−0.0021 (6)	0.0017 (7)
N1	0.058 (5)	0.041 (5)	0.073 (6)	0.012 (4)	0.003 (4)	−0.005 (4)
N2	0.038 (4)	0.045 (5)	0.079 (6)	0.005 (4)	−0.002 (4)	0.003 (4)
N3	0.119 (8)	0.056 (6)	0.062 (6)	0.017 (6)	0.008 (5)	0.006 (5)
N4	0.075 (6)	0.042 (5)	0.082 (6)	−0.001 (4)	−0.013 (5)	−0.009 (5)
N5	0.045 (5)	0.064 (5)	0.067 (5)	0.002 (4)	−0.007 (4)	0.019 (4)
N6	0.044 (5)	0.095 (7)	0.060 (6)	0.014 (5)	−0.004 (4)	0.010 (5)
C1	0.070 (7)	0.032 (5)	0.113 (9)	−0.001 (5)	0.006 (6)	0.007 (6)
C2	0.044 (6)	0.048 (6)	0.087 (8)	−0.006 (5)	−0.006 (5)	−0.008 (5)
C3	0.084 (8)	0.100 (10)	0.067 (8)	0.030 (8)	−0.008 (6)	0.001 (7)
C4	0.196 (16)	0.065 (9)	0.076 (9)	−0.021 (9)	0.048 (10)	−0.012 (7)
C5	0.046 (6)	0.071 (7)	0.089 (8)	0.006 (5)	0.007 (6)	0.026 (6)
C6	0.038 (5)	0.076 (7)	0.076 (8)	−0.005 (5)	−0.001 (5)	0.002 (6)

Geometric parameters (Å, º)

Te1—Te2	2.7091 (12)	N1—C1	1.468 (11)
Te2—Te3	2.7500 (12)	N2—C2	1.464 (11)
Te3—Te4	2.7509 (12)	N3—C3	1.389 (12)
Mn1—N6	2.264 (7)	N4—C4	1.420 (13)
Mn1—N2	2.267 (7)	N5—C5	1.462 (11)
Mn1—N3	2.271 (8)	N6—C6	1.454 (11)
Mn1—N1	2.287 (7)	C1—C2	1.502 (12)
Mn1—N5	2.289 (7)	C3—C4	1.460 (8)
Mn1—N4	2.290 (7)	C5—C6	1.488 (12)
Te1—Te2—Te3	109.17 (3)	N1—Mn1—N4	159.1 (3)
Te2—Te3—Te4	107.39 (3)	N5—Mn1—N4	99.9 (3)
N6—Mn1—N2	161.9 (3)	C1—N1—Mn1	106.7 (5)
N6—Mn1—N3	94.6 (3)	C2—N2—Mn1	108.4 (5)
N2—Mn1—N3	102.4 (3)	C3—N3—Mn1	112.1 (6)
N6—Mn1—N1	96.1 (3)	C4—N4—Mn1	110.7 (6)
N2—Mn1—N1	77.8 (3)	C5—N5—Mn1	110.4 (6)
N3—Mn1—N1	90.2 (3)	C6—N6—Mn1	110.9 (5)
N6—Mn1—N5	75.3 (3)	N1—C1—C2	110.4 (8)
N2—Mn1—N5	88.3 (3)	N2—C2—C1	109.4 (8)
N3—Mn1—N5	168.5 (3)	C4—C3—N3	116.1 (10)
N1—Mn1—N5	96.3 (3)	C3—C4—N4	118.1 (10)
N6—Mn1—N4	100.7 (3)	N5—C5—C6	109.6 (8)
N2—Mn1—N4	89.6 (3)	N6—C6—C5	109.6 (8)
N3—Mn1—N4	76.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	H···A	D—H···A
N1—H1B···Te1^i	3.01 (1)	163 (1)
N2—H2A···Te4^ii	2.99	152
N2—H2B···Te1^ii	2.89	170
N5—H5B···Te1^i	2.99	158

Symmetry codes: (i) x, y−1, z; (ii) x−1/2, −y+3/2, z+1/2.

(II) di[tri(ethylenediamino)ferro] antimony selenide

Crystal data

[Fe(C2H8N2)3]2·Sb2Se5	F(000) = 2112
Mr = 1110.62	Dx = 2.184 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 15.774 (3) Å	θ = 7.5–12.0°
b = 11.739 (2) Å	µ = 7.84 mm^−1
c = 18.239 (4) Å	T = 293 K
V = 3377.3 (11) Å^3	Block, brown
Z = 4	0.5 × 0.3 × 0.2 mm

Data collection

Enraf-Nonius CAD4 diffractometer	1719 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.115
Graphite monochromator	θmax = 26.0°, θmin = 2.4°
ω–scans	h = −18→19
Absorption correction: ψ scan (North et al,, 1968)	k = −13→14
Tmin = 0.018, Tmax = 0.211	l = −22→21
6283 measured reflections	3 standard reflections every 120 min
3321 independent reflections	intensity decay: 5.0%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.082	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H-atom parameters constrained
S = 1.07	Calculated w = 1/[σ^2(Fo^2) + (0.0556P)^2 + 2.0077P] where P = (Fo^2 + 2Fc^2)/3
3321 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.79 e Å^−3
0 restraints	Δρmin = −0.95 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sb1A	−0.01282 (11)	0.58523 (14)	0.59096 (10)	0.0327 (4)	0.50
Sb1B	−0.07394 (11)	0.60183 (14)	0.55827 (10)	0.0336 (4)	0.50
Se1	0.06665 (17)	0.4912 (2)	0.53384 (15)	0.0377 (6)	0.50
Se2	−0.12032 (9)	0.50891 (11)	0.67726 (8)	0.0453 (4)
Se3	−0.03644 (17)	0.79041 (11)	0.59416 (11)	0.0824 (8)
Fe1	0.09569 (12)	0.86241 (14)	0.35846 (11)	0.0388 (5)
N1	−0.0019 (8)	0.7559 (9)	0.3055 (7)	0.051 (3)
H1A	0.0155	0.6829	0.3038	0.080*
H1B	−0.0097	0.7802	0.2592	0.080*
N2	−0.0177 (8)	0.9189 (9)	0.4169 (7)	0.050 (3)
H2A	−0.0173	0.9951	0.4220	0.080*
H2B	−0.0189	0.8873	0.4619	0.080*
N3	0.1825 (8)	0.9632 (9)	0.4281 (7)	0.050 (3)
H3A	0.1594	1.0318	0.4373	0.080*
H3B	0.2325	0.9742	0.4055	0.080*
N4	0.1281 (10)	0.7378 (10)	0.4411 (7)	0.066 (4)
H4A	0.1391	0.6700	0.4201	0.080*
H4B	0.0844	0.7290	0.4722	0.080*
N5	0.1962 (8)	0.8039 (9)	0.2840 (7)	0.053 (3)
H5A	0.1940	0.7277	0.2789	0.080*
H5B	0.2475	0.8227	0.3018	0.080*
N6	0.0891 (8)	0.9956 (9)	0.2745 (7)	0.054 (3)
H6A	0.0891	1.0649	0.2956	0.080*
H6B	0.0412	0.9881	0.2481	0.080*
C1	−0.0808 (11)	0.7632 (12)	0.3474 (9)	0.064 (5)
H1C	−0.0804	0.7093	0.3869	0.080*
H1D	−0.1270	0.7444	0.3154	0.080*
C2	−0.0936 (9)	0.8836 (12)	0.3748 (10)	0.060 (4)
H2C	−0.1030	0.9360	0.3352	0.080*
H2D	−0.1427	0.8848	0.4059	0.080*
C3	0.1950 (10)	0.9043 (13)	0.4984 (10)	0.067 (5)
H3C	0.1474	0.9163	0.5303	0.080*
H3D	0.2447	0.9336	0.5223	0.080*
C4	0.2045 (11)	0.7757 (14)	0.4836 (11)	0.075 (5)
H4C	0.2547	0.7623	0.4553	0.080*
H4D	0.2097	0.7357	0.5293	0.080*
C5	0.1822 (9)	0.8603 (13)	0.2127 (8)	0.055 (4)
H5C	0.1361	0.8245	0.1873	0.080*
H5D	0.2323	0.8536	0.1831	0.080*
C6	0.1621 (10)	0.9834 (12)	0.2262 (9)	0.059 (4)
H6C	0.2101	1.0194	0.2488	0.080*
H6D	0.1515	1.0209	0.1803	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sb1A	0.0325 (9)	0.0304 (8)	0.0351 (10)	0.0035 (7)	0.0008 (9)	−0.0040 (8)
Sb1B	0.0350 (10)	0.0282 (8)	0.0377 (11)	0.0050 (7)	−0.0017 (9)	−0.0013 (7)
Se1	0.0430 (15)	0.0347 (12)	0.0353 (16)	0.0069 (12)	0.0015 (13)	−0.0043 (12)
Se2	0.0513 (8)	0.0394 (7)	0.0452 (9)	0.0012 (6)	0.0129 (7)	0.0017 (7)
Se3	0.158 (2)	0.0226 (6)	0.0661 (13)	0.0006 (9)	0.0425 (13)	−0.0042 (7)
Fe1	0.0455 (11)	0.0252 (8)	0.0458 (13)	0.0004 (8)	0.0038 (10)	0.0003 (8)
N1	0.057 (8)	0.032 (6)	0.065 (9)	−0.006 (5)	−0.005 (7)	−0.010 (5)
N2	0.070 (8)	0.027 (5)	0.055 (8)	−0.003 (6)	−0.008 (7)	−0.007 (5)
N3	0.046 (7)	0.051 (7)	0.053 (9)	−0.008 (6)	0.000 (6)	−0.017 (6)
N4	0.098 (11)	0.043 (7)	0.058 (10)	0.002 (7)	0.003 (9)	0.015 (6)
N5	0.063 (8)	0.044 (6)	0.053 (9)	0.010 (6)	0.004 (7)	−0.009 (6)
N6	0.070 (8)	0.039 (6)	0.054 (8)	0.009 (7)	0.005 (7)	0.010 (6)
C1	0.082 (12)	0.052 (8)	0.058 (12)	−0.031 (9)	0.011 (10)	−0.021 (8)
C2	0.048 (9)	0.055 (9)	0.077 (12)	−0.012 (7)	0.010 (9)	−0.012 (8)
C3	0.053 (10)	0.073 (10)	0.077 (13)	−0.011 (9)	−0.006 (9)	−0.018 (10)
C4	0.065 (11)	0.084 (12)	0.076 (14)	0.017 (10)	−0.004 (10)	0.026 (10)
C5	0.039 (8)	0.089 (11)	0.037 (9)	−0.008 (8)	0.006 (7)	−0.003 (8)
C6	0.062 (10)	0.047 (8)	0.068 (12)	−0.012 (8)	−0.004 (9)	0.017 (8)

Geometric parameters (Å, º)

Sb1A—Se3	2.438 (2)	Fe1—N1	2.206 (11)
Sb1A—Se2	2.481 (2)	Fe1—N3	2.211 (11)
Sb1A—Se1^i	2.590 (3)	N1—C1	1.463 (19)
Sb1B—Se3	2.383 (2)	N2—C2	1.481 (18)
Sb1B—Se2	2.537 (2)	N3—C3	1.47 (2)
Sb1B—Se1	2.609 (3)	N4—C4	1.50 (2)
Se1—Sb1A^i	2.590 (3)	N5—C5	1.475 (18)
Fe1—N4	2.161 (12)	N6—C6	1.456 (18)
Fe1—N2	2.185 (13)	C1—C2	1.513 (19)
Fe1—N6	2.192 (11)	C3—C4	1.54 (2)
Fe1—N5	2.198 (11)	C5—C6	1.50 (2)
Se3—Sb1A—Se2	103.72 (8)	N4—Fe1—N3	79.4 (5)
Se3—Sb1A—Se1^i	108.24 (10)	N2—Fe1—N3	93.7 (4)
Se2—Sb1A—Se1^i	102.03 (9)	N6—Fe1—N3	92.8 (5)
Se3—Sb1B—Se2	103.66 (9)	N5—Fe1—N3	94.3 (5)
Se3—Sb1B—Se1	107.37 (11)	N1—Fe1—N3	170.8 (5)
Se2—Sb1B—Se1	100.20 (9)	C1—N1—Fe1	109.3 (9)
Sb1A^i—Se1—Sb1B	92.51 (10)	C2—N2—Fe1	108.9 (9)
N4—Fe1—N2	93.4 (5)	C3—N3—Fe1	109.4 (9)
N4—Fe1—N6	168.9 (5)	C4—N4—Fe1	110.5 (10)
N2—Fe1—N6	94.9 (4)	C5—N5—Fe1	107.3 (9)
N4—Fe1—N5	92.8 (5)	C6—N6—Fe1	108.4 (9)
N2—Fe1—N5	170.7 (5)	N1—C1—C2	110.0 (12)
N6—Fe1—N5	79.9 (4)	N2—C2—C1	108.9 (13)
N4—Fe1—N1	95.0 (5)	N3—C3—C4	108.7 (13)
N2—Fe1—N1	79.3 (4)	N4—C4—C3	107.7 (13)
N6—Fe1—N1	93.7 (5)	N5—C5—C6	108.6 (12)
N5—Fe1—N1	93.2 (5)	N6—C6—C5	111.2 (12)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	H···A	D—H···A
N1—H1A···Se2^i	2.81	159
N2—H2A···Se3^ii	2.67	158
N2—H2B···Se3	2.68	175
N3—H3A···Se3^ii	2.91	151
N3—H3B···Se2^iii	2.78	173
N4—H4A···Se2^i	2.77	158
N5—H5B···Se2^iii	2.90	150
N6—H6A···Se3^ii	2.76	150
N6—H6B···Se2^iv	2.86	172

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