catena-Poly[[trans-bis­(1,3-benzo­thia­zole-κN)manganese(II)]-di-μ-chlorido]

In the title coordination polymer, [MnCl₂(C₇H₅NS)₂]_n, the Mn^II ion is located on the inter­section of a twofold rotation axis and a mirror plane and adopts an octa­hedral coordination geometry defined by two mutually trans N atoms from benzo­thia­zole ligands which occupy the axial positions, and four Cl atoms which form the equatorial sites. The Mn^II ions are connected by two bridging Cl atoms, forming chains parallel to the c axis. The crystal packing can be descibed as alternating layers parallel to (001) featuring π–π stacking inter­actions with a centroid–centroid distance of 3.6029 (15) Å.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.042
• wR factor = 0.092
• Data-to-parameter ratio = 14.3

checkCIF/PLATON results

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Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.7 Note
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      5.981 Check

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Dimension .......          1 Info
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          1 Why ?

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

In recent years, benzothiazole and its derivatives have attracted more attention because they exhibit interesting optical and biological activities (Petkova et al., 2000; Karisson et al., 2003; Khan et al. 2011). Related structural studies are partly focused on the fact that the benzothiazole ring contains N, S and O as potential donor atoms, which exhibit good coordination capacity, and so are propitious to build novel complexes (Roh et al. 2007, Popović et al. 2003, Maniukiewicz 2004). As part of our ongoing studies of benzothiazole-based coordination networks (Bouchareb et al. 2013), we report herein the structure of a coordination polymer of manganese and a benzothiazole ligand (I). The molecular geometry and the atom-numbering scheme are shown in Fig 1.

In the title compound, the Mn^II cation is located on the intersection of a twofold rotation axis and a mirror plane. The coordination sphere is defined by two mutually trans N atoms from two neutral monodentate benzothiazole ligands occupying the axial positions, and four Cl atoms lying in the equatorial plane. All Mn–Cl bond lengths are identical [2.5232 (10)] Å by symmetry and the Mn—N bond lengths are 2.307 (4) Å. In the coordination octahedron, all N—Mn—Cl and Cl—Mn—Cl bond angles are in the range of 89.40 (7) – 90.60 (7)°. The Mn^II ions are connected by two bridging Cl atoms, resulting in a chain of octahedra parallel to the c axis (Fig. 2). The crystal packing can be descibed as alterning layers parallel to (001) (Fig. 3). The crystal structure features two π–π stacking interactions: Cg1—Cg1 = 3.6029 (15) Å and Cg1—Cg2 = 4.048 (2) Å, Where, Cg1 is the centroid of the imidazole ring (N1/C7/S1/C6/C1) and Cg2 is the centroid of the fused benzene ring (C1/C2/C3/C4/C5/C6). No hydrogen bonds are observed in the structure.

Related literature

For applications of benzothiazole and its derivatives, see: Petkova et al. (2000); Karisson et al. (2003); Khan et al. (2011). For related structures see: Bouchareb et al. (2013); Roh et al. (2007); Popović et al. (2003); Maniukiewicz (2004).

S2. Experimental

Benzothiazole (1 ml) and ethanol (1 ml) were added to a solution of MnCl₂·4H₂O (39.5 mg, 0.2 mmol) in water (10 ml). The mixture was then refluxed with stirring for 3 h and the resulting solution was left to stand at room temperature. After several days, single crystals suitable for X-ray diffraction were obtained.

S3. Refinement

All non-H atoms were refined with anisotropic displacement parameters. Approximate positions for all H atoms were first obtained from the difference electron density map. However, the H atoms were placed in idealized positions and refined in a riding-model approximation. The applied constraints were as follow: C—H = 0.93 Å and U_iso = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures

	Fig. 1. The molecular structure of, (I), with displacement ellipsoids drawn at the 50% probability level. Only the contents of the asymmetric unit are numbered. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. The coordination around the Mn^II ion in a chain of octahedra parallel to the c axis
	Fig. 3. Packing diagram of (I) viewed along the a axis showing alterning layers parallel to (001).

catena-Poly[[trans-bis(1,3-benzothiazole-κN)manganese(II)]-di-µ-chlorido]

Crystal data

[MnCl2(C7H5NS)2]	Dx = 1.685 Mg m^−3
Mr = 396.22	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/mbc	Cell parameters from 1270 reflections
Hall symbol: -P 4c 2ab	θ = 3.1–25.2°
a = 14.761 (6) Å	µ = 1.45 mm^−1
c = 7.170 (3) Å	T = 150 K
V = 1562.3 (14) Å^3	Block, colorless
Z = 4	0.19 × 0.14 × 0.12 mm
F(000) = 796

Data collection

Bruker APEXII diffractometer	918 independent reflections
Radiation source: sealed tube	685 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.117
φ and ω scans	θmax = 27.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −18→18
Tmin = 0.674, Tmax = 0.746	k = −18→18
15714 measured reflections	l = −9→9

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) = 0.092	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0376P)^2 + 1.2805P] where P = (Fo^2 + 2Fc^2)/3
918 reflections	(Δ/σ)max = 0.007
64 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.46 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	0.8908 (3)	0.2962 (3)	1	0.0160 (9)
C2	0.9693 (3)	0.2427 (3)	1	0.0242 (11)
H2	1.0264	0.2692	1	0.029*
C3	0.9597 (3)	0.1501 (3)	1	0.0337 (13)
H3	1.0112	0.1137	1	0.04*
C4	0.8742 (3)	0.1096 (3)	1	0.0423 (16)
H4	0.8697	0.0468	1	0.051*
C5	0.7963 (3)	0.1612 (3)	1	0.0398 (15)
H5	0.7395	0.134	1	0.048*
C6	0.8050 (3)	0.2547 (3)	1	0.0226 (10)
C7	0.8052 (3)	0.4183 (3)	1	0.0225 (11)
H7	0.7909	0.4796	1	0.027*
N1	0.8879 (2)	0.3912 (2)	1	0.0167 (7)
S1	0.72177 (8)	0.33651 (9)	1	0.0284 (3)
Cl1	0.91494 (5)	0.58506 (5)	0.75	0.0163 (2)
Mn1	1	0.5	1	0.0135 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.018 (2)	0.012 (2)	0.018 (2)	−0.0047 (18)	0	0
C2	0.014 (2)	0.018 (2)	0.041 (3)	−0.0029 (18)	0	0
C3	0.018 (2)	0.016 (2)	0.067 (4)	0.002 (2)	0	0
C4	0.026 (3)	0.016 (3)	0.084 (5)	−0.004 (2)	0	0
C5	0.020 (3)	0.023 (3)	0.077 (4)	−0.012 (2)	0	0
C6	0.018 (2)	0.020 (2)	0.030 (3)	−0.0039 (19)	0	0
C7	0.019 (2)	0.023 (3)	0.026 (3)	−0.004 (2)	0	0
N1	0.015 (2)	0.016 (2)	0.0192 (18)	−0.0017 (14)	0	0
S1	0.0122 (6)	0.0245 (7)	0.0484 (8)	−0.0023 (5)	0	0
Cl1	0.0161 (3)	0.0161 (3)	0.0167 (5)	0.0030 (4)	0.0004 (4)	0.0004 (4)
Mn1	0.0128 (5)	0.0128 (5)	0.0150 (4)	−0.0003 (3)	0	0

Geometric parameters (Å, º)

C1—C2	1.402 (6)	C6—S1	1.723 (5)
C1—N1	1.402 (5)	C7—N1	1.284 (6)
C1—C6	1.406 (6)	C7—S1	1.724 (5)
C2—C3	1.374 (6)	C7—H7	0.93
C2—H2	0.93	N1—Mn1	2.307 (4)
C3—C4	1.397 (7)	Cl1—Mn1^i	2.5232 (10)
C3—H3	0.93	Cl1—Mn1	2.5232 (10)
C4—C5	1.379 (7)	Mn1—N1^ii	2.307 (4)
C4—H4	0.93	Mn1—Cl1^iii	2.5232 (10)
C5—C6	1.386 (7)	Mn1—Cl1^ii	2.5232 (10)
C5—H5	0.93	Mn1—Cl1^iv	2.5232 (10)
C2—C1—N1	126.1 (4)	C7—N1—C1	109.9 (4)
C2—C1—C6	119.9 (4)	C7—N1—Mn1	117.7 (3)
N1—C1—C6	114.1 (4)	C1—N1—Mn1	132.4 (3)
C3—C2—C1	118.4 (4)	C6—S1—C7	88.9 (2)
C3—C2—H2	120.8	Mn1^i—Cl1—Mn1	90.54 (4)
C1—C2—H2	120.8	N1^ii—Mn1—N1	180
C2—C3—C4	121.2 (5)	N1^ii—Mn1—Cl1^iii	89.40 (7)
C2—C3—H3	119.4	N1—Mn1—Cl1^iii	90.60 (7)
C4—C3—H3	119.4	N1^ii—Mn1—Cl1^ii	89.40 (7)
C5—C4—C3	121.1 (5)	N1—Mn1—Cl1^ii	90.60 (7)
C5—C4—H4	119.4	Cl1^iii—Mn1—Cl1^ii	90.54 (4)
C3—C4—H4	119.4	N1^ii—Mn1—Cl1	90.60 (7)
C4—C5—C6	118.2 (5)	N1—Mn1—Cl1	89.40 (7)
C4—C5—H5	120.9	Cl1^iii—Mn1—Cl1	89.46 (4)
C6—C5—H5	120.9	Cl1^ii—Mn1—Cl1	180
C5—C6—C1	121.1 (4)	N1^ii—Mn1—Cl1^iv	90.60 (7)
C5—C6—S1	129.2 (4)	N1—Mn1—Cl1^iv	89.40 (7)
C1—C6—S1	109.7 (3)	Cl1^iii—Mn1—Cl1^iv	180
N1—C7—S1	117.4 (4)	Cl1^ii—Mn1—Cl1^iv	89.46 (4)
N1—C7—H7	121.3	Cl1—Mn1—Cl1^iv	90.54 (4)
S1—C7—H7	121.3
N1—C1—C2—C3	180	C6—C1—N1—Mn1	180
C6—C1—C2—C3	0	C5—C6—S1—C7	180
C1—C2—C3—C4	0	C1—C6—S1—C7	0
C2—C3—C4—C5	0	N1—C7—S1—C6	0
C3—C4—C5—C6	0	C7—N1—Mn1—Cl1^iii	−134.72 (2)
C4—C5—C6—C1	0	C1—N1—Mn1—Cl1^iii	45.28 (2)
C4—C5—C6—S1	180	C7—N1—Mn1—Cl1^ii	134.72 (2)
C2—C1—C6—C5	0	C1—N1—Mn1—Cl1^ii	−45.28 (2)
N1—C1—C6—C5	180	C7—N1—Mn1—Cl1	−45.28 (2)
C2—C1—C6—S1	180	C1—N1—Mn1—Cl1	134.72 (2)
N1—C1—C6—S1	0	C7—N1—Mn1—Cl1^iv	45.28 (2)
S1—C7—N1—C1	0	C1—N1—Mn1—Cl1^iv	−134.72 (2)
S1—C7—N1—Mn1	180	Mn1^i—Cl1—Mn1—N1^ii	89.39 (7)
C2—C1—N1—C7	180	Mn1^i—Cl1—Mn1—N1	−90.61 (7)
C6—C1—N1—C7	0	Mn1^i—Cl1—Mn1—Cl1^iv	180
C2—C1—N1—Mn1	0

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