Poly[[(penta­ethyl­enehexa­mine)­man­ganese(II)] [hepta-[mu]-selenido-tri­tin(IV)]]: a tin-selenium net with remarkable flexibility

The title compound, {[Mn(C₁₀H₂₈N₆)][Sn₃Se₇]}_n, consists of anionic _[infinity]{[Sn₃Se₇]^2-} layers interspersed by [Mn(peha)]²⁺ complex cations (peha is penta­ethyl­ene­hexa­mine). Pseudo­cubic (Sn₃Se₄) cluster units within each layer are held together to form a 6³ net with a hole size of 8.74 × 13.87 Å. Weak N-H...Se inter­actions between the host inorganic frameworks and metal complexes extend the components into a three-dimensional network. The incorporation of metal complexes into the flexible anion layer dictates the distortion of the holes.

S1. Comment

Since the extension of established synthetic methodologies for zeolites to metal sulfides (Bedard et al., 1989), chalcogenidometalates have been of considerable interest because of the combination of the microporous features of zeolites and their intrinsic semiconducting behaviour. Organic amines play an important role in the formation of these materials by acting as templates and charge-balancing counter-ions. Synthesis of organic–inorganic hybrid tin chalcogenides is generally performed in the presence of nonchelating organic amines, and a series of dimeric anions with general formula [Sn₂Q₆]^4- (Q = S, Se and Te; Li et al., 1999) have been prepared with in-situ-generated metal–amine complexes. However, little (Li et al., 2000) is known about the incorporation of metal complexes into two-dimensional or three-dimensional networks of tin chalcogenides. It is known that the tendancy of Sn^IV to extend its coordination number from 4 to 5 or 6 allows the formation of a variety of two- and three-dimensional anionic structures. The most important feature of metal complexes is the integration of their electronic, optical and magnetic properties with the host inorganic frameworks, which helps to provide complementary properties and synergistic effects. We report here the crystal structure of such a compound, {[Mn(peha)][Sn₃Se₇]}_n {peha is pentaethylenehexamine; [-CH₂(NHCH₂CH₂)₂NH₂]₂}.

As shown in Figs. 1 and 2, compound (I) consists of anionic _∞[Sn₃Se₇]^2- layers with metal complexes [Mn(peha)]²⁺ accommodated between adjacent layers. Within the _∞[Sn₃Se₇]^2- layer, semicubic cluster units (Sn₃Se₄) are connected by edge sharing of five-coordinated tin polyhedra to form a 6³ net with cavities surrounded by 12 Sn–Se polyhedra (Fig. 3). While all Sn atoms are coordinated in a trigonal-bipyramidal fashion, the Se atom located intermediately between three Sn atoms (Sn1, Sn2 and Sn3) is trigonally coordinated, and the remaining Se atoms are bicoordinated. In the metal complex [Mn(peha)]²⁺, the Mn centre is six-coordinated by N atoms from the peha molecule, displaying a distorted octahedral configuration. Atoms N1, N2 and N3 are meridional, as are the other three N atoms (N4, N5 and N6). The peha molecules are generated from the decomposition and rearrangement of triethylenetetramine {teta; [–CH₂NH(CH₂)₂NH₂]₂}.

Each Sn atom of (I) adopts a coordination environment with the µ₃-Se atoms in axial (ax) positions [the opposite axial atoms are Se1 for Sn1, Se7ⁱⁱ for Sn2 and Se2ⁱⁱⁱ for Sn3; symmetry codes: (ii) -x + 1, -y + 1, -z; (iii) -x + 1/2, y + 1/2, -z + 1/2]. The axial Se—Sn bond lengths are significantly longer than those for equatorial sites, which are similar to the distances found in the literature (Parise et al., 1994). The Se_ax—Sn—Se_ax angles are 170.79 (3) (Se4—Sn1—Se1), 178.20 (3) (Se4—Sn2—Se7ⁱⁱ) and 176.02 (4)° (Se4—Sn3—Se2ⁱⁱⁱ), so the structures can be described as slightly distorted trigonal bipyramids.

In [Mn(peha)]²⁺, the Mn—N distances range from 2.254 (9) to 2.340 (9) Å and are in the normal range (Wendland et al., 1998). The heavy distortion of the octahedral environment in the metal centre is manifested by the trans angles, which range from 128.9 (3) to 151.0 (3)°, and the cis angles, which lie in the range 73.2 (3)–129.1 (3)°.

As shown in Fig. 2 and Table 2, the title compound forms a three-dimensional network via weak N—H···Se interactions between N atoms of peha molecules and µ₂-Se atoms from two adjacent polyanion layers. The layers are oriented normal to the b axis and along the ac direction. All Sn atoms within each layer are nearly coplanar (the mean deviation from the plane is 0.0597 Å). The average interlayer separation as measured between the tin planes is 9.23 Å. Both (I) and the previously reported compound TMA–SnSe (TMA is trimethyl amine; Ahari, Ozin et al., 1995; Ahari, Bowes et al., 1995) contain anionic _∞[Sn₃Se₇]^2- layers, but the steric requirements of charge-balancing cations in the two structures are different. The flexibility of the Sn₃Se₇ framework has been verified by varying the organic template or including molecular guests in the two structures. It is obvious that the distortion of the cavities in the title compound is a result of the bulk of the Mn complexes. On the basis of the Se···Se distances (Fig. 3), the holes have the approximate dimensions of 8.74 × 13.87 Å and are significantly distorted from a regular hexagonal shape. Therefore, the incorporation of metal complexes into such structures not only explores its flexibility [please clarify what this means] but may be able to introduce new properties into semiconductors.

Related literature

For related literature, see: Ahari et al. (1995a); Bedard et al. (1989); Li et al. (1999, 2000); Parise et al. (1994); Wendland et al. (1998).

S2. Experimental

A mixture of Sn power (0.0594 g, 0.5 mmol) and Se (0.0789 g, 1.0 mmol) with MnCl₂.4H₂O (0.1980 g, 1.0 mmol) in 3.0 ml of teta/glycol (v/v 1:2) was stirred for 30 min in a 17.0 ml Teflon-lined stainless steel vessel. The vessel was sealed and heated at 463 K for one week. Orange block crystals were isolated by washing with ethanol and water.

S3. Refinement

All H atoms bound to C atoms were refined using a riding model with C—H distances of 0.97 Å and U_iso(H) values of 1.2U_eq(C). The imine H atoms were refined using a riding model with N—H distances of 0.91 Å and U_iso(H) set at 1.2U_eq(N). The amine H atoms were located in a difference Fourier map and refined isotropically with U_iso(H) set at 1.5U_eq(N).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I). Displacement ellipsoids are drawn at the 30% probability level and all H atoms have been omitted for clarity. Atoms labelled with the suffixes A and B are at the symmetry positions (-x + 1, -y + 1, -z) and (-x + 1/2, y + 1/2, -z + 1/2), respectively.
	Fig. 2. A packing diagram for (I), showing a three-dimensional network formed via weak N—H···Se interactions (dashed lines). Atoms labelled with the suffixes A and B are at the symmetry positions (-x + 1, -y, -z) and (-x + 1, y, z), respectively.
	Fig. 3. The Sn3Se7 framework of the crystal structure of (I). Atoms labelled with the suffixes A, B, C and D are at the symmetry positions (-x + 1/2, y - 3/2, -z + 1/2), (x - 1/2, -y + 1/2, z + 1/2), (-x + 1/2, y + 1/2, -z + 1/2) and (x - 1/2, -y - 1/2, z + 1/2), respectively.

poly[[(pentaethylenehexamine)manganese(II)] [hepta-µ-selenido-tritin(IV)]]

Crystal data

[Mn(C10H28N6)][Sn3Se7]	F(000) = 2172
Mr = 1196.11	Dx = 2.953 Mg m^−3
Monoclinic, P21/n	Melting point: not measured K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71069 Å
a = 11.893 (5) Å	θ = 1.9–26.1°
b = 13.322 (5) Å	µ = 12.69 mm^−1
c = 17.097 (5) Å	T = 207 K
β = 96.659 (5)°	Block, orange
V = 2690.5 (17) Å^3	0.12 × 0.12 × 0.08 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	5291 independent reflections
Radiation source: fine-focus sealed tube	3945 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scan	θmax = 26.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→14
Tmin = 0.230, Tmax = 0.308	k = −16→16
14868 measured reflections	l = −15→21

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0273P)^2] where P = (Fo^2 + 2Fc^2)/3
5291 reflections	(Δ/σ)max = 0.001
256 parameters	Δρmax = 1.20 e Å^−3
6 restraints	Δρmin = −0.88 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
C1	1.0151 (8)	0.2378 (7)	−0.0479 (6)	0.041 (3)
H1A	1.0381	0.2501	−0.0996	0.049*
H1B	1.0701	0.1929	−0.0199	0.049*
C2	1.0141 (8)	0.3334 (7)	−0.0047 (6)	0.041 (3)
H2A	1.0910	0.3581	0.0071	0.049*
H2B	0.9711	0.3829	−0.0373	0.049*
C3	0.9266 (10)	0.4091 (8)	0.0970 (6)	0.058 (3)
H3A	0.8718	0.4397	0.0577	0.070*
H3B	0.9899	0.4550	0.1074	0.070*
C4	0.8715 (9)	0.3929 (9)	0.1737 (7)	0.058 (3)
H4A	0.8388	0.4552	0.1897	0.069*
H4B	0.9283	0.3712	0.2157	0.069*
C5	0.7640 (9)	0.2531 (7)	0.2305 (6)	0.046 (3)
H5A	0.7641	0.2990	0.2746	0.055*
H5B	0.6926	0.2171	0.2248	0.055*
C6	0.8566 (8)	0.1832 (7)	0.2453 (5)	0.038 (2)
H6A	0.8450	0.1423	0.2906	0.046*
H6B	0.9264	0.2204	0.2579	0.046*
C7	0.7910 (9)	0.0288 (7)	0.1775 (6)	0.046 (3)
H7A	0.8147	−0.0144	0.2221	0.056*
H7B	0.7143	0.0513	0.1816	0.056*
C8	0.7955 (10)	−0.0257 (7)	0.1040 (6)	0.052 (3)
H8A	0.7460	−0.0837	0.1025	0.062*
H8B	0.8720	−0.0492	0.1009	0.062*
C9	0.6359 (9)	0.0475 (7)	0.0148 (5)	0.045 (3)
H9A	0.5993	0.0600	0.0617	0.054*
H9B	0.6076	−0.0157	−0.0079	0.054*
C10	0.6074 (8)	0.1318 (7)	−0.0442 (6)	0.041 (3)
H10A	0.6415	0.1186	−0.0921	0.050*
H10B	0.5261	0.1365	−0.0576	0.050*
N1	0.9061 (8)	0.1906 (7)	−0.0563 (5)	0.046 (2)
H11	0.910 (8)	0.1237 (17)	−0.058 (5)	0.069*
H12	0.869 (8)	0.232 (5)	−0.092 (4)	0.069*
N2	0.9642 (8)	0.3202 (6)	0.0677 (5)	0.046 (2)
H2	1.0205	0.2975	0.1040	0.055*
N3	0.7761 (8)	0.3099 (7)	0.1578 (5)	0.062 (3)
H3	0.7091	0.3403	0.1409	0.074*
N4	0.8683 (6)	0.1165 (5)	0.1773 (5)	0.037 (2)
H4	0.9410	0.0943	0.1801	0.045*
N5	0.7596 (7)	0.0408 (5)	0.0362 (5)	0.040 (2)
H5	0.7909	0.0173	−0.0063	0.048*
N6	0.6527 (7)	0.2277 (6)	−0.0075 (5)	0.041 (2)
H13	0.607 (7)	0.237 (6)	0.031 (4)	0.062*
H14	0.656 (8)	0.273 (5)	−0.047 (4)	0.062*
Mn1	0.82375 (12)	0.20223 (10)	0.06120 (8)	0.0321 (4)
Se1	0.15410 (7)	0.07534 (6)	0.13339 (5)	0.0223 (2)
Se2	0.44058 (7)	0.07885 (6)	0.24427 (6)	0.0274 (2)
Se3	0.34580 (8)	0.26259 (6)	0.03677 (5)	0.0239 (2)
Se4	0.45946 (7)	0.37623 (6)	0.22809 (5)	0.0202 (2)
Se5	0.16816 (7)	0.30535 (6)	0.24788 (5)	0.0242 (2)
Se6	0.26315 (8)	0.55473 (6)	0.11141 (5)	0.0253 (2)
Se7	0.61897 (8)	0.50332 (7)	0.07738 (5)	0.0266 (2)
Sn1	0.32590 (5)	0.22048 (4)	0.18025 (3)	0.01988 (15)
Sn2	0.41900 (5)	0.44057 (4)	0.07331 (3)	0.01951 (15)
Sn3	0.25791 (5)	0.47987 (4)	0.24775 (3)	0.02007 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.036 (6)	0.050 (7)	0.035 (7)	−0.004 (5)	−0.002 (5)	−0.001 (5)
C2	0.035 (6)	0.043 (7)	0.045 (7)	0.001 (5)	0.007 (5)	0.014 (5)
C3	0.066 (9)	0.057 (8)	0.053 (8)	0.004 (6)	0.012 (7)	0.005 (6)
C4	0.053 (8)	0.060 (8)	0.058 (8)	0.010 (6)	−0.002 (6)	−0.017 (6)
C5	0.066 (8)	0.036 (6)	0.038 (7)	0.006 (5)	0.019 (6)	−0.001 (5)
C6	0.043 (6)	0.045 (6)	0.024 (6)	−0.005 (5)	−0.004 (5)	0.007 (5)
C7	0.063 (8)	0.033 (6)	0.043 (7)	−0.001 (5)	0.004 (6)	0.013 (5)
C8	0.095 (10)	0.016 (5)	0.046 (7)	0.005 (5)	0.019 (7)	0.010 (5)
C9	0.074 (8)	0.038 (6)	0.027 (6)	−0.014 (6)	0.025 (6)	−0.004 (5)
C10	0.040 (6)	0.050 (7)	0.036 (7)	−0.003 (5)	0.011 (5)	−0.008 (5)
N1	0.047 (6)	0.050 (6)	0.044 (6)	−0.016 (5)	0.016 (5)	−0.004 (5)
N2	0.074 (7)	0.029 (5)	0.031 (5)	−0.009 (5)	−0.007 (5)	−0.003 (4)
N3	0.085 (8)	0.045 (6)	0.055 (7)	0.028 (6)	0.002 (6)	−0.008 (5)
N4	0.033 (5)	0.028 (4)	0.051 (6)	0.009 (4)	0.004 (4)	0.008 (4)
N5	0.058 (6)	0.028 (5)	0.037 (5)	−0.002 (4)	0.023 (4)	−0.007 (4)
N6	0.047 (6)	0.032 (5)	0.048 (6)	−0.004 (4)	0.019 (4)	0.005 (4)
Mn1	0.0464 (9)	0.0240 (8)	0.0273 (9)	−0.0057 (7)	0.0100 (7)	−0.0008 (6)
Se1	0.0312 (5)	0.0165 (4)	0.0198 (5)	−0.0024 (4)	0.0046 (4)	0.0000 (4)
Se2	0.0234 (5)	0.0192 (5)	0.0405 (6)	0.0015 (4)	0.0068 (4)	0.0103 (4)
Se3	0.0363 (5)	0.0168 (4)	0.0198 (5)	−0.0045 (4)	0.0085 (4)	−0.0017 (4)
Se4	0.0254 (5)	0.0168 (4)	0.0187 (5)	0.0011 (4)	0.0045 (4)	0.0025 (4)
Se5	0.0266 (5)	0.0163 (4)	0.0320 (6)	−0.0012 (4)	0.0131 (4)	−0.0021 (4)
Se6	0.0341 (5)	0.0208 (5)	0.0219 (5)	0.0102 (4)	0.0071 (4)	0.0047 (4)
Se7	0.0298 (5)	0.0309 (5)	0.0193 (5)	−0.0080 (4)	0.0031 (4)	0.0053 (4)
Sn1	0.0274 (3)	0.0127 (3)	0.0212 (3)	0.0026 (2)	0.0096 (3)	0.0027 (2)
Sn2	0.0268 (3)	0.0144 (3)	0.0189 (3)	−0.0004 (2)	0.0092 (3)	0.0016 (2)
Sn3	0.0293 (3)	0.0140 (3)	0.0183 (3)	0.0006 (2)	0.0085 (3)	−0.0010 (2)

Geometric parameters (Å, º)

C1—N1	1.433 (12)	C10—H10B	0.9700
C1—C2	1.474 (12)	N1—Mn1	2.340 (9)
C1—H1A	0.9700	N1—H11	0.89 (2)
C1—H1B	0.9700	N1—H12	0.90 (2)
C2—N2	1.444 (11)	N2—Mn1	2.287 (8)
C2—H2A	0.9700	N2—H2	0.9100
C2—H2B	0.9700	N3—Mn1	2.308 (8)
C3—N2	1.381 (12)	N3—H3	0.9100
C3—C4	1.547 (14)	N4—Mn1	2.299 (8)
C3—H3A	0.9700	N4—H4	0.9100
C3—H3B	0.9700	N5—Mn1	2.306 (7)
C4—N3	1.585 (13)	N5—H5	0.9100
C4—H4A	0.9700	N6—Mn1	2.254 (9)
C4—H4B	0.9700	N6—H13	0.91 (2)
C5—C6	1.442 (12)	N6—H14	0.91 (2)
C5—N3	1.476 (12)	Se1—Sn3^i	2.5197 (12)
C5—H5A	0.9700	Se1—Sn1	2.8592 (13)
C5—H5B	0.9700	Se2—Sn1	2.5044 (12)
C6—N4	1.481 (11)	Se2—Sn3^i	2.7211 (14)
C6—H6A	0.9700	Se3—Sn1	2.5540 (12)
C6—H6B	0.9700	Se3—Sn2	2.5776 (13)
C7—C8	1.458 (13)	Se4—Sn1	2.6826 (12)
C7—N4	1.487 (11)	Se4—Sn2	2.7701 (12)
C7—H7A	0.9700	Se4—Sn3	2.8200 (13)
C7—H7B	0.9700	Se5—Sn3	2.5584 (13)
C8—N5	1.482 (11)	Se5—Sn1	2.5764 (12)
C8—H8A	0.9700	Se6—Sn2	2.5402 (12)
C8—H8B	0.9700	Se6—Sn3	2.5429 (12)
C9—N5	1.477 (12)	Se7—Sn2	2.5142 (14)
C9—C10	1.521 (13)	Se7—Sn2^ii	2.6703 (13)
C9—H9A	0.9700	Sn2—Se7^ii	2.6703 (13)
C9—H9B	0.9700	Sn3—Se1^iii	2.5197 (12)
C10—N6	1.496 (12)	Sn3—Se2^iii	2.7211 (14)
C10—H10A	0.9700
N1—C1—C2	111.7 (8)	C5—N3—H3	109.1
N1—C1—H1A	109.3	C4—N3—H3	109.1
C2—C1—H1A	109.3	Mn1—N3—H3	109.1
N1—C1—H1B	109.3	C6—N4—C7	110.8 (7)
C2—C1—H1B	109.3	C6—N4—Mn1	110.2 (5)
H1A—C1—H1B	107.9	C7—N4—Mn1	108.2 (6)
N2—C2—C1	110.6 (8)	C6—N4—H4	109.2
N2—C2—H2A	109.5	C7—N4—H4	109.2
C1—C2—H2A	109.5	Mn1—N4—H4	109.2
N2—C2—H2B	109.5	C9—N5—C8	114.7 (8)
C1—C2—H2B	109.5	C9—N5—Mn1	106.8 (6)
H2A—C2—H2B	108.1	C8—N5—Mn1	110.7 (6)
N2—C3—C4	112.0 (9)	C9—N5—H5	108.2
N2—C3—H3A	109.2	C8—N5—H5	108.2
C4—C3—H3A	109.2	Mn1—N5—H5	108.2
N2—C3—H3B	109.2	C10—N6—Mn1	110.4 (6)
C4—C3—H3B	109.2	C10—N6—H13	101 (6)
H3A—C3—H3B	107.9	Mn1—N6—H13	103 (6)
C3—C4—N3	108.5 (9)	C10—N6—H14	108 (6)
C3—C4—H4A	110.0	Mn1—N6—H14	112 (6)
N3—C4—H4A	110.0	H13—N6—H14	122 (4)
C3—C4—H4B	110.0	N6—Mn1—N2	122.1 (3)
N3—C4—H4B	110.0	N6—Mn1—N4	128.9 (3)
H4A—C4—H4B	108.4	N2—Mn1—N4	101.9 (3)
C6—C5—N3	109.3 (8)	N6—Mn1—N5	77.5 (3)
C6—C5—H5A	109.8	N2—Mn1—N5	151.0 (3)
N3—C5—H5A	109.8	N4—Mn1—N5	74.6 (3)
C6—C5—H5B	109.8	N6—Mn1—N3	89.9 (3)
N3—C5—H5B	109.8	N2—Mn1—N3	77.1 (3)
H5A—C5—H5B	108.3	N4—Mn1—N3	75.0 (3)
C5—C6—N4	113.0 (8)	N5—Mn1—N3	127.5 (3)
C5—C6—H6A	109.0	N6—Mn1—N1	90.3 (3)
N4—C6—H6A	109.0	N2—Mn1—N1	73.2 (3)
C5—C6—H6B	109.0	N4—Mn1—N1	129.1 (3)
N4—C6—H6B	109.0	N5—Mn1—N1	86.6 (3)
H6A—C6—H6B	107.8	N3—Mn1—N1	144.9 (3)
C8—C7—N4	107.7 (8)	Sn3^i—Se1—Sn1	84.20 (4)
C8—C7—H7A	110.2	Sn1—Se2—Sn3^i	87.44 (4)
N4—C7—H7A	110.2	Sn1—Se3—Sn2	92.04 (3)
C8—C7—H7B	110.2	Sn1—Se4—Sn2	85.24 (3)
N4—C7—H7B	110.2	Sn1—Se4—Sn3	86.19 (4)
H7A—C7—H7B	108.5	Sn2—Se4—Sn3	84.64 (3)
C7—C8—N5	109.9 (8)	Sn3—Se5—Sn1	94.18 (4)
C7—C8—H8A	109.7	Sn2—Se6—Sn3	95.54 (4)
N5—C8—H8A	109.7	Sn2—Se7—Sn2^ii	90.73 (3)
C7—C8—H8B	109.7	Se2—Sn1—Se3	118.61 (4)
N5—C8—H8B	109.7	Se2—Sn1—Se5	121.50 (4)
H8A—C8—H8B	108.2	Se3—Sn1—Se5	119.21 (4)
N5—C9—C10	110.3 (8)	Se2—Sn1—Se4	100.15 (4)
N5—C9—H9A	109.6	Se3—Sn1—Se4	90.31 (3)
C10—C9—H9A	109.6	Se5—Sn1—Se4	87.71 (4)
N5—C9—H9B	109.6	Se2—Sn1—Se1	87.04 (4)
C10—C9—H9B	109.6	Se3—Sn1—Se1	91.27 (3)
H9A—C9—H9B	108.1	Se5—Sn1—Se1	83.61 (4)
N6—C10—C9	108.1 (8)	Se4—Sn1—Se1	170.79 (3)
N6—C10—H10A	110.1	Se7—Sn2—Se6	120.65 (4)
C9—C10—H10A	110.1	Se7—Sn2—Se3	127.18 (4)
N6—C10—H10B	110.1	Se6—Sn2—Se3	112.14 (4)
C9—C10—H10B	110.1	Se7—Sn2—Se7^ii	89.27 (3)
H10A—C10—H10B	108.4	Se6—Sn2—Se7^ii	91.89 (4)
C1—N1—Mn1	110.4 (6)	Se3—Sn2—Se7^ii	90.52 (4)
C1—N1—H11	113 (7)	Se7—Sn2—Se4	91.00 (3)
Mn1—N1—H11	97 (7)	Se6—Sn2—Se4	89.51 (3)
C1—N1—H12	100 (7)	Se3—Sn2—Se4	87.90 (3)
Mn1—N1—H12	108 (7)	Se7^ii—Sn2—Se4	178.20 (3)
H11—N1—H12	128 (4)	Se1^iii—Sn3—Se6	119.30 (4)
C3—N2—C2	112.9 (8)	Se1^iii—Sn3—Se5	126.32 (4)
C3—N2—Mn1	110.0 (7)	Se6—Sn3—Se5	114.31 (4)
C2—N2—Mn1	114.4 (6)	Se1^iii—Sn3—Se2^iii	89.81 (4)
C3—N2—H2	106.3	Se6—Sn3—Se2^iii	88.25 (3)
C2—N2—H2	106.3	Se5—Sn3—Se2^iii	94.35 (4)
Mn1—N2—H2	106.3	Se1^iii—Sn3—Se4	93.67 (4)
C5—N3—C4	110.5 (9)	Se6—Sn3—Se4	88.35 (3)
C5—N3—Mn1	109.9 (6)	Se5—Sn3—Se4	85.16 (4)
C4—N3—Mn1	109.0 (6)	Se2^iii—Sn3—Se4	176.02 (4)
N1—C1—C2—N2	50.4 (11)	C4—N3—Mn1—N1	−36.8 (10)
N2—C3—C4—N3	−53.5 (12)	C1—N1—Mn1—N6	141.8 (7)
N3—C5—C6—N4	−54.2 (11)	C1—N1—Mn1—N2	18.1 (7)
N4—C7—C8—N5	−59.6 (11)	C1—N1—Mn1—N4	−73.7 (8)
N5—C9—C10—N6	−59.0 (10)	C1—N1—Mn1—N5	−140.7 (7)
C2—C1—N1—Mn1	−42.2 (10)	C1—N1—Mn1—N3	51.6 (10)
C4—C3—N2—C2	179.0 (9)	Sn3^i—Se2—Sn1—Se3	−113.77 (4)
C4—C3—N2—Mn1	49.9 (11)	Sn3^i—Se2—Sn1—Se5	56.71 (5)
C1—C2—N2—C3	−159.7 (9)	Sn3^i—Se2—Sn1—Se4	150.27 (3)
C1—C2—N2—Mn1	−32.9 (10)	Sn3^i—Se2—Sn1—Se1	−23.94 (3)
C6—C5—N3—C4	−76.0 (10)	Sn2—Se3—Sn1—Se2	−118.49 (5)
C6—C5—N3—Mn1	44.3 (10)	Sn2—Se3—Sn1—Se5	70.80 (5)
C3—C4—N3—C5	149.6 (8)	Sn2—Se3—Sn1—Se4	−16.74 (3)
C3—C4—N3—Mn1	28.7 (10)	Sn2—Se3—Sn1—Se1	154.19 (3)
C5—C6—N4—C7	−84.0 (10)	Sn3—Se5—Sn1—Se2	121.22 (4)
C5—C6—N4—Mn1	35.7 (9)	Sn3—Se5—Sn1—Se3	−68.35 (5)
C8—C7—N4—C6	172.3 (8)	Sn3—Se5—Sn1—Se4	20.72 (3)
C8—C7—N4—Mn1	51.4 (9)	Sn3—Se5—Sn1—Se1	−156.23 (4)
C10—C9—N5—C8	169.1 (8)	Sn2—Se4—Sn1—Se2	134.76 (3)
C10—C9—N5—Mn1	46.1 (8)	Sn3—Se4—Sn1—Se2	−140.31 (3)
C7—C8—N5—C9	−83.6 (10)	Sn2—Se4—Sn1—Se3	15.59 (3)
C7—C8—N5—Mn1	37.2 (10)	Sn3—Se4—Sn1—Se3	100.52 (3)
C9—C10—N6—Mn1	39.9 (9)	Sn2—Se4—Sn1—Se5	−103.63 (3)
C10—N6—Mn1—N2	144.6 (6)	Sn3—Se4—Sn1—Se5	−18.71 (3)
C10—N6—Mn1—N4	−70.3 (7)	Sn2—Se4—Sn1—Se1	−84.3 (2)
C10—N6—Mn1—N5	−12.1 (6)	Sn3—Se4—Sn1—Se1	0.6 (2)
C10—N6—Mn1—N3	−140.8 (6)	Sn3^i—Se1—Sn1—Se2	26.10 (3)
C10—N6—Mn1—N1	74.4 (6)	Sn3^i—Se1—Sn1—Se3	144.69 (3)
C3—N2—Mn1—N6	57.1 (8)	Sn3^i—Se1—Sn1—Se5	−96.05 (4)
C2—N2—Mn1—N6	−71.2 (7)	Sn3^i—Se1—Sn1—Se4	−115.5 (2)
C3—N2—Mn1—N4	−95.9 (7)	Sn2^ii—Se7—Sn2—Se6	−91.77 (4)
C2—N2—Mn1—N4	135.9 (6)	Sn2^ii—Se7—Sn2—Se3	90.10 (5)
C3—N2—Mn1—N5	−175.5 (7)	Sn2^ii—Se7—Sn2—Se7^ii	0.0
C2—N2—Mn1—N5	56.2 (10)	Sn2^ii—Se7—Sn2—Se4	178.22 (3)
C3—N2—Mn1—N3	−24.5 (7)	Sn3—Se6—Sn2—Se7	−102.10 (4)
C2—N2—Mn1—N3	−152.7 (7)	Sn3—Se6—Sn2—Se3	76.29 (4)
C3—N2—Mn1—N1	136.5 (7)	Sn3—Se6—Sn2—Se7^ii	167.63 (3)
C2—N2—Mn1—N1	8.3 (6)	Sn3—Se6—Sn2—Se4	−11.23 (3)
C6—N4—Mn1—N6	−85.2 (7)	Sn1—Se3—Sn2—Se7	105.86 (4)
C7—N4—Mn1—N6	36.0 (7)	Sn1—Se3—Sn2—Se6	−72.40 (4)
C6—N4—Mn1—N2	65.1 (6)	Sn1—Se3—Sn2—Se7^ii	−164.66 (3)
C7—N4—Mn1—N2	−173.6 (6)	Sn1—Se3—Sn2—Se4	16.21 (3)
C6—N4—Mn1—N5	−144.6 (6)	Sn1—Se4—Sn2—Se7	−142.63 (3)
C7—N4—Mn1—N5	−23.3 (6)	Sn3—Se4—Sn2—Se7	130.76 (4)
C6—N4—Mn1—N3	−7.9 (6)	Sn1—Se4—Sn2—Se6	96.73 (4)
C7—N4—Mn1—N3	113.4 (6)	Sn3—Se4—Sn2—Se6	10.11 (3)
C6—N4—Mn1—N1	143.0 (6)	Sn1—Se4—Sn2—Se3	−15.46 (3)
C7—N4—Mn1—N1	−95.7 (6)	Sn3—Se4—Sn2—Se3	−102.07 (4)
C9—N5—Mn1—N6	−18.0 (5)	Sn1—Se4—Sn2—Se7^ii	−44.2 (11)
C8—N5—Mn1—N6	−143.5 (7)	Sn3—Se4—Sn2—Se7^ii	−130.8 (11)
C9—N5—Mn1—N2	−154.5 (6)	Sn2—Se6—Sn3—Se1^iii	104.32 (5)
C8—N5—Mn1—N2	80.0 (8)	Sn2—Se6—Sn3—Se5	−72.90 (5)
C9—N5—Mn1—N4	118.7 (6)	Sn2—Se6—Sn3—Se2^iii	−166.88 (3)
C8—N5—Mn1—N4	−6.8 (6)	Sn2—Se6—Sn3—Se4	11.04 (3)
C9—N5—Mn1—N3	62.0 (7)	Sn1—Se5—Sn3—Se1^iii	−110.73 (5)
C8—N5—Mn1—N3	−63.5 (8)	Sn1—Se5—Sn3—Se6	66.27 (4)
C9—N5—Mn1—N1	−109.1 (6)	Sn1—Se5—Sn3—Se2^iii	156.31 (3)
C8—N5—Mn1—N1	125.4 (7)	Sn1—Se5—Sn3—Se4	−19.72 (3)
C5—N3—Mn1—N6	111.6 (7)	Sn1—Se4—Sn3—Se1^iii	145.08 (3)
C4—N3—Mn1—N6	−127.1 (7)	Sn2—Se4—Sn3—Se1^iii	−129.36 (3)
C5—N3—Mn1—N2	−125.3 (8)	Sn1—Se4—Sn3—Se6	−95.67 (4)
C4—N3—Mn1—N2	−4.0 (6)	Sn2—Se4—Sn3—Se6	−10.11 (3)
C5—N3—Mn1—N4	−19.0 (7)	Sn1—Se4—Sn3—Se5	18.90 (3)
C4—N3—Mn1—N4	102.2 (7)	Sn2—Se4—Sn3—Se5	104.46 (3)
C5—N3—Mn1—N5	37.5 (9)	Sn1—Se4—Sn3—Se2^iii	−64.2 (5)
C4—N3—Mn1—N5	158.8 (6)	Sn2—Se4—Sn3—Se2^iii	21.4 (5)
C5—N3—Mn1—N1	−158.1 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···Se1^iv	0.89 (2)	3.01 (5)	3.818 (9)	152 (7)
N5—H5···Se1^iv	0.91	2.65	3.542 (7)	168
N4—H4···Se1^v	0.91	2.76	3.607 (8)	156
N3—H3···Se7	0.91	2.60	3.380 (9)	144
N2—H2···Se5^v	0.91	2.85	3.699 (8)	155

Symmetry codes: (iv) −x+1, −y, −z; (v) x+1, y, z.