Bis­[tris(1,3-di­amino­propane)­manganese(II)] octasulfidotetraantimonate(III) dihydrate

Yellow crystals of [Mn(pn)₃]₂[Sb₄S₈]·2H₂O (pn = 1,2-di­amino­propane) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in an aqueous solution of 1,2-di­amino­propane. The structure is composed of cyclic [Sb₄S₈]^4- anions and octahedral [Mn(pn)₃]²⁺ cations, both stacked in a rod-like manner along the a axis. The anion sits on a centre of symmetry. Between the anions and the cations there is an extended hydrogen-bonding network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.032
• wR factor = 0.092
• Data-to-parameter ratio = 30.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_735  Alert B D-H     Calc     0.85(5), Rep   0.848(10) ....       5.00 su-Ratio
                     O1   -H1O     1.555   1.555

PLAT_735  Alert B D-H     Calc     0.84(7), Rep   0.849(10) ....       7.00 su-Ratio
                     O1   -H2O     1.555   1.555


 Alert Level C:



WEIGH_01  Alert C Extra text has been found in the
          _refine_ls_weighting_scheme field. This should be in the
          _refine_ls_weighting_details field.
          Weighting scheme given as calc w = 1/[\s^2^(Fo^2^)+(0.0455P)^2^+2.987
          Weighting scheme identified as calc

PLAT_420  Alert C D-H Without Acceptor       N(1)   -   H(1A)             ?

PLAT_420  Alert C D-H Without Acceptor       N(1)   -   H(1B)             ?

PLAT_420  Alert C D-H Without Acceptor       N(2)   -   H(2A)             ?

PLAT_420  Alert C D-H Without Acceptor       N(3)   -   H(3B)             ?

PLAT_420  Alert C D-H Without Acceptor       N(4)   -   H(4A)             ?

PLAT_420  Alert C D-H Without Acceptor       N(6)   -   H(6B)             ?


 0 Alert Level A = Potentially serious problem

 2 Alert Level B = Potential problem

 7 Alert Level C = Please check

---

S1. Comment

During the last few years, a large number of thioantimonates(III) were reported demonstrating the rich structural diversity of this class of compounds. In the structures, the primary SbS₃ trigonal pyramid is often interconnected forming so-called secondary building units (SBU) like Sb₂S₂, Sb₃S₃, Sb₄S₄ hetero-rings or the Sb₃S₄ semicube. Until now only a few thioantimonates(III) have been reported containing isolated SbS anions. The isolated [SbS₃]³⁻ anion is found in M₃SbS₃ (M = Ag, Cu, Tl; Wattenberg & Hellner, 1966; Pfitzner, 1994; Rey et al., 1984). Using a cut-off for the Sb—S distance of 3 Å isolated SbS₃ and Sb₂S₄ units co-exist in Ca₂Sb₂S₅ (Cordier & Schäfer, 1981). In Ba₈Sb₆S₁₇ and in BaSb₂S₄, chain-like Sb₃S₈ anions and isolated SbS₃ pyramids were observed (Dörrscheidt & Schäfer, 1986; Cordier et al., 1984). The isolated Sb₂S₅⁴⁻ anion is found in Sr₂Sb₂S₅.15H₂O (Cordier et al., 1985). It should be noted that besides these isolated anions only one compound with an isolated ring anion was reported so far (Bensch et al., 2001). In the anion of the title compound, (I), four pyramidal SbS₃ units sharing common corners form a Sb₄S₄ hetero-ring that adopts a chair conformation. Each Sb atom has a terminal S atom to form the [Sb₄S₈]⁴⁻ ring anion (Fig. 1). The bridging Sb—S distances are between 2.4598 (10) and 2.4919 (10) Å (Table 1). As expected, the terminal Sb—S bonds (Sb1—S2 and Sb2—S4) are significantly shorter with values of 2.3322 (11) and 2.3442 (10) Å. The S—Sb—S angles vary between 92.33 (4) and 104.37 (3)°. The terminal Sb—S distances in the recently reported compound [Ni[C₄H₁₃N₃)₂]₂Sb₄S₈ are between 2.315 (3) and 2.337 (2) Å, and the bond lengths within the Sb₄S₄ ring range from 2.426 (2) to 2.497 (2) Å. The S—Sb—S angles scatter over a larger range than in the title compound [87.92 (7)–107.53 (8)°; Bensch et al., 2001]. The differences of the geometrical parameters in the two compounds demonstrate the high flexibility of the Sb—S bonds and S—Sb—S angles to accomodate an optimal arrangement of cations and anions in the structure. The Mn²⁺ cation is in an octahedral environment of six N atoms of three bidentate amine molecules (Fig. 1). The Mn—N distances are between 2.258 (3) and 2.322 (3) Å (Table 1) and are in accordance with literature data (Laskowski & Hendrickson, 1978; Wendland et al., 2000). The N—Mn—N angles vary from 76.37 (11) to 171.97 (12)°, indicative of a relatively strong distorted octahedral environment. The three-dimensional interconnection of anions and cations is achieved by ten N—H···S interactions. Only three of the four unique S atoms are involved and the N—H···S distances range between 2.62 and 3.03 Å, with corresponding angles ranging from 136.0 to 172.0° (Table 2). We note that in [Ni[C₄H₁₃N₃)₂]₂Sb₄S₈ the H···S contacts are signficantly shorter (2.513–2.837 Å), which may have an influence on the geometrical parameters of the anions, as mentioned above. The water molecule acts as a hydrogen-bond donor and acceptor. Two short contacts are observed to S2 and S4 and on to N5 (Table 2). Cations and anions form separate stacks parallel to the a and c axes. A view of the arrangement of the cations and anions with view along [100] is displayed in Fig. 2. The disordered water molecule is situated between the cations.

S2. Experimental

The title compound was prepared by solvothermal synthesis of elemental Mn (54.94 mg, 1 mmol), Sb (121.75 mg, 1 mmol) and S (80.15 mg, 2.5 mmol) in a 70% aqueous solution of 1,2-diaminopropane (5 ml). The mixture was heated for 7 d in a Teflon-lined steel autoclave at 383 K. The yield was about 60% based on Mn after washing with water and acetone.

S3. Refinement

The positions of the H atoms were located from difference maps. H atoms bound to C atoms were positioned with idealized geometry and refined with fixed isotropic displacement parameters [U_iso(H) = 1.2U_eqC] using a riding model with the parameters C—H(tertiary) = 0.98 Å, C—H(secondary) = 0.97 Å and C—H(primary) = 0.96 Å. The positions of the H atoms of the NH₂ groups were idealized, with N—H distances of 0.90 Å, then refined as rigid groups allowed to rotate but not tip. These H atoms were refined using fixed isotropic displacement parameters [U_iso(H) = 1.5U_eqN]. The H atoms of H₂O were refined with restraints setting the distances for O—H to 0.84 (1) Å and for H···H to 1.40 (1) Å. The isotropic displacement parameters were fixed [U_iso(H) = 1.5U_eqO].

Computing details

Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL.

Figures

	Fig. 1. The cation (top) and the anion (bottom) in the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (') 1 − x, −y, 1 − z.]
	Fig. 2. The crystal structure of the title compound, viewed in the direction of the crystallographic a axis. O atoms have been omitted and hydrogen bonding is shown as dashed lines.

(I)

Crystal data

[Mn(C3H10N2)3]2[Sb4S8]·2H2O	F(000) = 1308
Mr = 1334.17	Dx = 1.897 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4773 (19) Å	Cell parameters from 126 reflections
b = 19.579 (4) Å	θ = 12–19°
c = 12.592 (3) Å	µ = 3.20 mm^−1
β = 91.56 (3)°	T = 293 K
V = 2335.6 (8) Å^3	Polyhedra, yellow
Z = 2	0.22 × 0.19 × 0.16 mm

Data collection

Philips PW1100 diffractometer	5895 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Graphite monochromator	θmax = 30.0°, θmin = 2.6°
ω scans	h = 0→12
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)	k = −27→1
Tmin = 0.495, Tmax = 0.641	l = −17→17
7248 measured reflections	3 standard reflections every 120 min
6515 independent reflections	intensity decay: none

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	Calculated w = 1/[σ^2(Fo^2) + (0.0455P)^2 + 2.9874P] where P = (Fo^2 + 2Fc^2)/3
6518 reflections	(Δ/σ)max = 0.002
214 parameters	Δρmax = 1.69 e Å^−3
3 restraints	Δρmin = −1.06 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.

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
Mn1	0.89270 (6)	0.21041 (3)	0.46332 (4)	0.03759 (12)
N1	1.0165 (3)	0.18843 (18)	0.3102 (3)	0.0444 (7)
H1A	1.0093	0.2243	0.2656	0.053*
H1B	1.1085	0.1818	0.3268	0.053*
N2	0.7544 (4)	0.1342 (2)	0.3751 (3)	0.0487 (8)
H2A	0.7619	0.0929	0.4063	0.058*
H2B	0.6636	0.1475	0.3765	0.058*
N3	0.7623 (3)	0.21612 (15)	0.6156 (2)	0.0389 (6)
H3A	0.7786	0.2561	0.6489	0.047*
H3B	0.6696	0.2136	0.5985	0.047*
N4	0.9987 (4)	0.13341 (18)	0.5731 (3)	0.0450 (7)
H4A	0.9720	0.0910	0.5540	0.054*
H4B	1.0930	0.1364	0.5676	0.054*
N5	0.7914 (4)	0.30858 (18)	0.4008 (2)	0.0452 (7)
H5A	0.7948	0.3096	0.3295	0.054*
H5B	0.7002	0.3101	0.4189	0.054*
N6	1.0509 (4)	0.29247 (17)	0.5146 (3)	0.0464 (7)
H6A	1.0411	0.3025	0.5837	0.056*
H6B	1.1395	0.2774	0.5055	0.056*
C1	0.9571 (5)	0.1274 (2)	0.2588 (3)	0.0513 (9)
H1	0.9889	0.0880	0.3012	0.062*
C2	0.8006 (5)	0.1298 (3)	0.2637 (4)	0.0572 (11)
H2C	0.7655	0.1692	0.2244	0.069*
H2D	0.7608	0.0891	0.2306	0.069*
C3	1.0051 (5)	0.1158 (3)	0.1466 (3)	0.0546 (10)
H3C	1.1063	0.1145	0.1463	0.066*
H3D	0.9714	0.1523	0.1018	0.066*
H3E	0.9680	0.0731	0.1205	0.066*
C4	0.9598 (4)	0.14625 (19)	0.6841 (3)	0.0390 (7)
H4	1.0082	0.1880	0.7082	0.047*
C5	0.8031 (4)	0.1590 (2)	0.6867 (3)	0.0458 (8)
H5C	0.7527	0.1181	0.6646	0.055*
H5D	0.7768	0.1697	0.7588	0.055*
C6	1.0044 (5)	0.0882 (2)	0.7588 (4)	0.0568 (11)
H6C	1.1044	0.0811	0.7551	0.068*
H6D	0.9558	0.0471	0.7381	0.068*
H6E	0.9811	0.0999	0.8302	0.068*
C7	1.0243 (5)	0.3541 (2)	0.4487 (3)	0.0481 (9)
H7	1.0521	0.3439	0.3761	0.058*
C8	0.8678 (5)	0.3682 (2)	0.4465 (3)	0.0480 (9)
H8A	0.8366	0.3768	0.5180	0.058*
H8B	0.8477	0.4084	0.4038	0.058*
C9	1.1098 (7)	0.4156 (3)	0.4877 (4)	0.0699 (14)
H9A	1.2085	0.4046	0.4878	0.084*
H9B	1.0830	0.4272	0.5584	0.084*
H9C	1.0918	0.4537	0.4413	0.084*
Sb1	0.44836 (2)	0.092969 (10)	0.550951 (16)	0.03000 (6)
Sb2	0.33911 (2)	0.042109 (12)	0.274505 (16)	0.03448 (7)
S1	0.25047 (9)	0.03300 (5)	0.45579 (7)	0.03606 (17)
S2	0.34266 (11)	0.18915 (4)	0.62605 (7)	0.04116 (19)
S3	0.43326 (10)	0.01756 (5)	0.70648 (7)	0.04195 (19)
S4	0.41252 (12)	0.15576 (5)	0.27104 (8)	0.0478 (2)
O1	0.4653 (9)	0.2783 (3)	0.4355 (4)	0.119 (2)
H1O	0.438 (10)	0.267 (5)	0.497 (3)	0.179*
H2O	0.417 (9)	0.258 (5)	0.388 (5)	0.179*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0369 (3)	0.0400 (3)	0.0359 (2)	0.0023 (2)	−0.0006 (2)	−0.0025 (2)
N1	0.0346 (15)	0.0499 (17)	0.0489 (17)	−0.0041 (13)	0.0064 (13)	−0.0067 (14)
N2	0.0394 (17)	0.065 (2)	0.0423 (16)	−0.0146 (15)	0.0067 (13)	−0.0068 (15)
N3	0.0331 (14)	0.0375 (14)	0.0460 (16)	0.0028 (11)	−0.0003 (12)	−0.0064 (12)
N4	0.0418 (17)	0.0499 (18)	0.0432 (16)	0.0131 (14)	0.0022 (13)	−0.0042 (13)
N5	0.0468 (18)	0.0534 (18)	0.0350 (14)	0.0090 (14)	−0.0029 (12)	0.0035 (13)
N6	0.0417 (17)	0.0470 (17)	0.0503 (18)	0.0018 (13)	−0.0049 (14)	0.0022 (14)
C1	0.052 (2)	0.057 (2)	0.045 (2)	−0.0043 (19)	0.0074 (17)	−0.0075 (17)
C2	0.053 (2)	0.071 (3)	0.047 (2)	−0.011 (2)	0.0023 (18)	−0.004 (2)
C3	0.055 (2)	0.064 (3)	0.045 (2)	0.008 (2)	0.0094 (18)	−0.0034 (19)
C4	0.0376 (18)	0.0408 (17)	0.0384 (16)	−0.0020 (13)	−0.0020 (13)	−0.0015 (13)
C5	0.0365 (18)	0.050 (2)	0.051 (2)	−0.0035 (15)	0.0068 (15)	0.0040 (16)
C6	0.055 (3)	0.056 (2)	0.058 (2)	−0.0012 (19)	−0.011 (2)	0.0125 (19)
C7	0.058 (2)	0.050 (2)	0.0356 (17)	−0.0070 (18)	0.0048 (16)	0.0040 (15)
C8	0.064 (3)	0.0398 (18)	0.0401 (18)	0.0077 (17)	0.0041 (17)	0.0063 (14)
C9	0.086 (4)	0.061 (3)	0.062 (3)	−0.027 (3)	−0.008 (3)	0.012 (2)
Sb1	0.02437 (11)	0.03266 (11)	0.03318 (11)	−0.00047 (7)	0.00439 (7)	−0.00220 (7)
Sb2	0.03559 (12)	0.03858 (12)	0.02891 (10)	0.00252 (8)	−0.00602 (8)	−0.00381 (8)
S1	0.0287 (4)	0.0413 (4)	0.0384 (4)	−0.0011 (3)	0.0037 (3)	−0.0065 (3)
S2	0.0496 (5)	0.0324 (4)	0.0416 (4)	0.0029 (3)	0.0052 (4)	−0.0073 (3)
S3	0.0410 (5)	0.0471 (5)	0.0383 (4)	0.0105 (4)	0.0108 (3)	0.0079 (3)
S4	0.0558 (6)	0.0371 (4)	0.0503 (5)	0.0015 (4)	−0.0027 (4)	0.0083 (4)
O1	0.209 (7)	0.081 (3)	0.069 (3)	−0.054 (4)	0.030 (4)	−0.010 (2)

Geometric parameters (Å, º)

Sb1—S2	2.3442 (10)	N1—C1	1.463 (5)
Sb1—S3	2.4598 (10)	N2—C2	1.483 (5)
Sb1—S1	2.4919 (10)	N3—C5	1.477 (5)
Sb2—S4	2.3322 (11)	N4—C4	1.477 (5)
Sb2—S3^i	2.4593 (10)	N5—C8	1.482 (6)
Sb2—S1	2.4602 (11)	N6—C7	1.481 (5)
S3—Sb2^i	2.4593 (10)	C1—C2	1.487 (6)
Mn1—N2	2.258 (3)	C1—C3	1.513 (6)
Mn1—N4	2.262 (3)	C4—C5	1.507 (5)
Mn1—N6	2.279 (3)	C4—C6	1.528 (6)
Mn1—N5	2.279 (3)	C7—C8	1.508 (6)
Mn1—N3	2.312 (3)	C7—C9	1.526 (6)
Mn1—N1	2.322 (3)
N2—Mn1—N4	95.87 (14)	N1—C1—C2	109.2 (4)
N2—Mn1—N6	166.85 (13)	N1—C1—C3	114.4 (4)
N4—Mn1—N6	91.09 (13)	C2—C1—C3	111.6 (4)
N2—Mn1—N5	98.86 (14)	N2—C2—C1	111.2 (4)
N4—Mn1—N5	161.64 (12)	N4—C4—C5	108.7 (3)
N6—Mn1—N5	76.76 (12)	N4—C4—C6	112.6 (3)
N2—Mn1—N3	97.10 (11)	C5—C4—C6	111.5 (3)
N4—Mn1—N3	76.37 (11)	N3—C5—C4	110.7 (3)
N6—Mn1—N3	95.37 (12)	N6—C7—C8	108.2 (3)
N5—Mn1—N3	90.92 (12)	N6—C7—C9	112.5 (4)
N2—Mn1—N1	76.64 (12)	C8—C7—C9	112.0 (4)
N4—Mn1—N1	99.05 (12)	N5—C8—C7	109.4 (3)
N6—Mn1—N1	91.28 (13)	S2—Sb1—S3	97.25 (4)
N5—Mn1—N1	94.99 (13)	S2—Sb1—S1	104.37 (3)
N3—Mn1—N1	171.97 (12)	S3—Sb1—S1	92.33 (4)
C1—N1—Mn1	108.7 (2)	S4—Sb2—S3^i	101.17 (4)
C2—N2—Mn1	108.7 (3)	S4—Sb2—S1	101.31 (4)
C5—N3—Mn1	109.2 (2)	S3^i—Sb2—S1	101.30 (4)
C4—N4—Mn1	110.3 (2)	Sb2—S1—Sb1	98.07 (4)
C8—N5—Mn1	109.4 (2)	Sb2^i—S3—Sb1	107.02 (4)
C7—N6—Mn1	108.4 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···S4	0.90	2.70	3.487 (4)	147
N1—H1A···S2^ii	0.90	2.88	3.692 (4)	150
N1—H1B···S4^iii	0.90	3.03	3.853 (4)	153
N2—H2A···S1^i	0.90	3.02	3.906 (4)	168
N3—H3A···S4^iv	0.90	2.62	3.464 (3)	157
N4—H4B···S2^iii	0.90	2.67	3.484 (4)	152
N4—H4B···S1^iii	0.90	2.90	3.454 (3)	121
N5—H5A···S2^ii	0.90	2.61	3.506 (3)	172
N5—H5B···O1	0.90	2.33	3.188 (8)	160
N6—H6A···S4^iv	0.90	2.81	3.662 (4)	159
N6—H6B···S2^iii	0.90	2.97	3.674 (4)	136
O1—H1O···S2	0.85 (1)	2.43 (5)	3.211 (5)	154 (9)
O1—H2O···S4	0.85 (1)	2.48 (7)	3.199 (5)	143 (10)

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