Bis(2-amino-3H-benzothia­zolium) bis­(7-oxabicyclo­[2.2.1]heptane-2,3-di­carbox­yl­ato)manganate(II) hexa­hydrate

Wang, N.; Wen, Y.-H.; Lin, Q.-Y.; Feng, J.

doi:10.1107/S160053681002091X

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page m762

doi:10.1107/S160053681002091X

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Bis(2-amino-3H-benzothiazolium) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato)manganate(II) hexahydrate

Na Wang,^a,^b Yi-Hang Wen,^a,^b Qiu-Yue Lin ^a,^b ^* and Jie Feng ^b

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China, and ^bCollege of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004, Zhejiang, People's Republic of China
^*Correspondence e-mail: sky51@zjnu.cn

(Received 13 May 2010; accepted 1 June 2010; online 9 June 2010)

In the crystal structure of the title salt, (C₇H₇N₂S)₂[Mn(C₈H₈O₅)₂]·6H₂O, the heterocyclic N atom of the 2-aminobenzothiazole molecule is protonated. The Mn^II atom (site symmetry $[\overline{1}]$ ) has a slightly distorted octahedral MnO₆ coordination defined by the bridging O atoms of the bicycloheptane unit and four carboxylate O atoms of two symmetry-related and fully deprotonated ligands. The crystal packing is stabilized by N—H⋯O hydrogen bonds between the cations and anions and by O—H⋯O hydrogen bonds including the crystal water molecules.

Related literature

7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (norcantharidin) is a lower toxicity anticancer drug, see: Shimi et al. (1982 ). Manganese is a cofactor or required metal ion for many enzymes, see: Dukhande et al. (2006 ). For the isotypic structure of the Co analogue, see: Wang et al. (2010 ).

Experimental

Crystal data

(C₇H₇N₂S)₂[Mn(C₈H₈O₅)₂]·6H₂O
M_r = 833.76
Triclinic, $[P \overline 1]$
a = 6.6937 (1) Å
b = 10.2209 (1) Å
c = 13.1163 (2) Å
α = 89.527 (1)°
β = 88.831 (1)°
γ = 81.514 (1)°
V = 887.34 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 296 K
0.15 × 0.13 × 0.10 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.916, T_max = 0.944
14148 measured reflections
4089 independent reflections
3426 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.093
S = 0.97
4089 reflections
262 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O4	2.1083 (11)
Mn1—O2	2.1883 (11)
Mn1—O5	2.2598 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.84 (2)	1.84 (2)	2.6822 (18)	178 (2)
N2—H2B⋯O2ⁱ	0.86	2.00	2.8490 (19)	170
N2—H2C⋯O2Wⁱⁱ	0.86	2.00	2.824 (2)	160
O1W—H1WA⋯O1	0.81 (2)	2.03 (2)	2.8250 (19)	166 (3)
O1W—H1WB⋯O2W	0.85 (2)	1.95 (2)	2.792 (2)	170 (3)
O2W—H2WA⋯O3	0.83 (2)	1.87 (2)	2.6806 (19)	169 (3)
O2W—H2WB⋯O3Wⁱⁱⁱ	0.84 (2)	1.93 (2)	2.768 (2)	178 (3)
O3W—H3WA⋯O1Wⁱⁱ	0.80 (2)	2.21 (2)	3.004 (2)	169 (3)
O3W—H3WB⋯O1W	0.82 (2)	1.97 (2)	2.784 (2)	173 (3)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+1; (iii) x+1, y, z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681002091X/wm2350sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681002091X/wm2350Isup2.hkl

checkCIF report

Comment top

7-Oxabicyclo[2,2,1] heptane-2,3-dicarboxylic anhydride (norcantharidin) derived from cantharidin is a lower toxicity anticancer drug (Shimi et al., 1982). Manganese is an important trace element needed for normal physiological functions and development. It is also a cofactor or required metal ion for many enzymes, such as superoxide dismutase, glutamine synthetase and arginase (Dukhande et al., 2006).

In the title complex, (C₇H₇N₂S)⁺₂[Mn(C₈H₈O₅)₂]^2-(H₂O)₆, the Mn^II ion is located on a crystallographic centre of inversion. Two bridging oxygen atoms of the bicycloheptane units and four carboxylate oxygen atoms give rise to a slightly distorted octahedral coordination environment around the Mn^II atom. The bond angles O2—Mn1—O2ⁱ, O4—Mn1—O4ⁱ and O5—Mn1—O5ⁱ (i: -x+2, -y, -z) are 180°, while the bond angles O4—Mn1—O2 and O2—Mn1—O4ⁱ open up slightly from 86.35 (5)° to 93.65 (5)°, resulting in a slight distortion from the ideal octahedral geometry. The crystal packing is stabilized by N—H···O hydrogen bonds between the cations and anions and by O—H···O hydrogen bonds including the crystal water molecules.

The crystal structure of (C₇H₇N₂S)⁺₂[Mn(C₈H₈O₅)₂]^2-(H₂O)₆ is isotypic with that of the Co analogue (Wang et al., 2010) where slightly shorter metal—oxygen bonds are observed.

Related literature top

7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (norcantharidin) is a lower toxicity anticancer drug, see: Shimi et al. (1982). Manganese is a cofactor or required metal ion for many enzymes, see: Dukhande et al. (2006). For the isotypic structure of the Co analogue, see: Wang et al. (2010).

Experimental top

Norcantharidin, manganese acetate and 2-aminobenzothiazole were dissolved in 15 mL distilled water. The mixture was sealed in a 25 mL Teflon-lined stainless vessel and heated at 443 K for 3 d, then cooled slowly to room temperature. Colourless crystals suitable for X-ray diffraction were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecular units of the title salt showing the atom-labelling scheme with displacement ellipsoids drawn at the 30% probability. Symmetry code: A (-x+2, -y, -z).

Bis(2-amino-3H-benzothiazolium) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato)manganate(II) hexahydrate top

Crystal data top

(C₇H₇N₂S)₂[Mn(C₈H₈O₅)₂]·6H₂O	Z = 1
M_r = 833.76	F(000) = 435
Triclinic, P1	D_x = 1.560 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6937 (1) Å	Cell parameters from 5204 reflections
b = 10.2209 (1) Å	θ = 1.6–27.6°
c = 13.1163 (2) Å	µ = 0.57 mm⁻¹
α = 89.527 (1)°	T = 296 K
β = 88.831 (1)°	Block, colourless
γ = 81.514 (1)°	0.15 × 0.13 × 0.10 mm
V = 887.34 (2) Å³

Data collection top

Bruker APEXII area-detector diffractometer	4089 independent reflections
Radiation source: fine-focus sealed tube	3426 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.6°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.916, T_max = 0.944	k = −12→13
14148 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0536P)² + 0.2749P] where P = (F_o² + 2F_c²)/3
4089 reflections	(Δ/σ)_max = 0.001
262 parameters	Δρ_max = 0.31 e Å⁻³
10 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

(C₇H₇N₂S)₂[Mn(C₈H₈O₅)₂]·6H₂O	γ = 81.514 (1)°
M_r = 833.76	V = 887.34 (2) Å³
Triclinic, P1	Z = 1
a = 6.6937 (1) Å	Mo Kα radiation
b = 10.2209 (1) Å	µ = 0.57 mm⁻¹
c = 13.1163 (2) Å	T = 296 K
α = 89.527 (1)°	0.15 × 0.13 × 0.10 mm
β = 88.831 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	4089 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3426 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.944	R_int = 0.026
14148 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	10 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.31 e Å⁻³
4089 reflections	Δρ_min = −0.35 e Å⁻³
262 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	1.0000	0.0000	0.0000	0.02770 (11)
S1	0.17382 (7)	0.26390 (4)	0.52462 (3)	0.03610 (12)
N1	0.2239 (2)	0.03022 (14)	0.60022 (10)	0.0278 (3)
H1N	0.236 (3)	−0.0300 (18)	0.6447 (14)	0.042*
N2	0.1568 (2)	0.19534 (15)	0.72262 (11)	0.0369 (3)
H2B	0.1649	0.1382	0.7714	0.044*
H2C	0.1309	0.2784	0.7360	0.044*
O1	0.7284 (2)	0.16252 (12)	0.25851 (8)	0.0361 (3)
O1W	0.6844 (3)	0.39782 (16)	0.37356 (12)	0.0552 (4)
H1WA	0.679 (4)	0.335 (2)	0.336 (2)	0.083*
H1WB	0.777 (4)	0.440 (2)	0.352 (2)	0.083*
O2	0.7957 (2)	0.01642 (11)	0.13318 (9)	0.0357 (3)
O2W	0.9775 (2)	0.52942 (14)	0.28069 (12)	0.0493 (4)
H2WA	1.013 (4)	0.480 (2)	0.2319 (15)	0.074*
H2WB	1.076 (3)	0.534 (3)	0.3180 (17)	0.074*
O3	1.12534 (19)	0.34977 (13)	0.14033 (10)	0.0392 (3)
O3W	0.3055 (3)	0.5480 (2)	0.40200 (13)	0.0654 (5)
H3WA	0.292 (5)	0.564 (3)	0.4616 (14)	0.098*
H3WB	0.416 (3)	0.505 (3)	0.389 (2)	0.098*
O4	1.12511 (18)	0.15814 (12)	0.06293 (10)	0.0356 (3)
O5	0.77654 (18)	0.16207 (11)	−0.06930 (8)	0.0303 (3)
C1	0.7329 (2)	0.13207 (16)	0.16658 (12)	0.0271 (3)
C2	0.6576 (2)	0.24024 (15)	0.09025 (11)	0.0260 (3)
H2A	0.5468	0.3013	0.1213	0.031*
C3	0.5877 (2)	0.18764 (16)	−0.00995 (12)	0.0298 (3)
H3A	0.5198	0.1095	−0.0011	0.036*
C4	0.4672 (3)	0.29791 (17)	−0.07160 (14)	0.0356 (4)
H4A	0.3680	0.3523	−0.0291	0.043*
H4B	0.3994	0.2628	−0.1277	0.043*
C5	0.6338 (3)	0.37615 (17)	−0.11049 (13)	0.0345 (4)
H5A	0.6423	0.3773	−0.1844	0.041*
H5B	0.6116	0.4663	−0.0856	0.041*
C6	0.8217 (3)	0.29710 (15)	−0.06493 (11)	0.0284 (3)
H6A	0.9469	0.3094	−0.1014	0.034*
C7	0.8286 (2)	0.32037 (15)	0.05059 (11)	0.0254 (3)
H7A	0.7900	0.4146	0.0654	0.030*
C8	1.0415 (2)	0.27264 (16)	0.08941 (12)	0.0279 (3)
C9	0.2250 (3)	0.12947 (18)	0.44134 (12)	0.0318 (4)
C10	0.2425 (3)	0.1306 (2)	0.33572 (13)	0.0420 (4)
H10A	0.2271	0.2098	0.2993	0.050*
C11	0.2835 (3)	0.0109 (2)	0.28654 (14)	0.0460 (5)
H11A	0.2955	0.0092	0.2158	0.055*
C12	0.3070 (3)	−0.1066 (2)	0.34058 (14)	0.0438 (5)
H12A	0.3348	−0.1860	0.3053	0.053*
C13	0.2903 (3)	−0.10923 (18)	0.44609 (13)	0.0346 (4)
H13A	0.3066	−0.1887	0.4822	0.042*
C14	0.2484 (2)	0.01083 (17)	0.49553 (12)	0.0281 (3)
C15	0.1837 (2)	0.15576 (16)	0.62770 (12)	0.0286 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0344 (2)	0.01988 (18)	0.02706 (18)	0.00148 (14)	0.00271 (14)	−0.00338 (13)
S1	0.0469 (3)	0.0276 (2)	0.0324 (2)	−0.00140 (19)	−0.00021 (18)	0.00664 (17)
N1	0.0333 (7)	0.0255 (7)	0.0245 (6)	−0.0037 (6)	−0.0022 (5)	0.0037 (5)
N2	0.0529 (9)	0.0294 (8)	0.0276 (7)	−0.0034 (7)	0.0011 (6)	−0.0010 (6)
O1	0.0524 (8)	0.0284 (6)	0.0259 (6)	−0.0013 (5)	0.0028 (5)	0.0018 (5)
O1W	0.0639 (10)	0.0472 (9)	0.0544 (9)	−0.0090 (8)	0.0123 (7)	−0.0130 (7)
O2	0.0485 (7)	0.0245 (6)	0.0308 (6)	0.0045 (5)	0.0086 (5)	0.0026 (5)
O2W	0.0571 (9)	0.0365 (8)	0.0530 (9)	−0.0023 (7)	0.0064 (7)	−0.0124 (6)
O3	0.0376 (7)	0.0359 (7)	0.0449 (7)	−0.0064 (5)	−0.0048 (5)	−0.0132 (6)
O3W	0.0619 (11)	0.0738 (12)	0.0557 (10)	0.0070 (9)	−0.0036 (8)	−0.0071 (9)
O4	0.0322 (6)	0.0270 (6)	0.0461 (7)	0.0012 (5)	−0.0041 (5)	−0.0074 (5)
O5	0.0380 (6)	0.0235 (6)	0.0276 (5)	0.0021 (5)	−0.0013 (5)	−0.0050 (4)
C1	0.0276 (8)	0.0256 (8)	0.0274 (7)	−0.0030 (6)	0.0052 (6)	0.0024 (6)
C2	0.0273 (8)	0.0218 (7)	0.0272 (7)	0.0012 (6)	0.0043 (6)	0.0002 (6)
C3	0.0314 (8)	0.0238 (8)	0.0344 (8)	−0.0045 (6)	−0.0023 (6)	0.0000 (6)
C4	0.0362 (9)	0.0313 (9)	0.0381 (9)	−0.0001 (7)	−0.0094 (7)	0.0004 (7)
C5	0.0460 (10)	0.0268 (8)	0.0297 (8)	−0.0014 (7)	−0.0050 (7)	0.0046 (6)
C6	0.0339 (8)	0.0249 (8)	0.0255 (7)	−0.0025 (6)	0.0029 (6)	0.0015 (6)
C7	0.0307 (8)	0.0178 (7)	0.0272 (7)	−0.0023 (6)	0.0006 (6)	−0.0010 (6)
C8	0.0324 (8)	0.0261 (8)	0.0256 (7)	−0.0060 (7)	0.0017 (6)	−0.0017 (6)
C9	0.0303 (8)	0.0358 (9)	0.0289 (8)	−0.0038 (7)	−0.0031 (6)	0.0027 (7)
C10	0.0423 (10)	0.0552 (12)	0.0284 (8)	−0.0067 (9)	−0.0033 (7)	0.0094 (8)
C11	0.0425 (11)	0.0701 (14)	0.0257 (8)	−0.0088 (10)	−0.0021 (7)	−0.0047 (9)
C12	0.0360 (10)	0.0560 (12)	0.0399 (10)	−0.0073 (9)	0.0010 (8)	−0.0181 (9)
C13	0.0310 (9)	0.0358 (9)	0.0373 (9)	−0.0051 (7)	−0.0026 (7)	−0.0057 (7)
C14	0.0247 (8)	0.0334 (9)	0.0263 (7)	−0.0045 (6)	−0.0021 (6)	0.0002 (6)
C15	0.0293 (8)	0.0273 (8)	0.0292 (8)	−0.0037 (6)	−0.0024 (6)	0.0027 (6)

Geometric parameters (Å, º) top

Mn1—O4	2.1083 (11)	C1—C2	1.522 (2)
Mn1—O4ⁱ	2.1083 (11)	C2—C3	1.532 (2)
Mn1—O2	2.1883 (11)	C2—C7	1.581 (2)
Mn1—O2ⁱ	2.1883 (11)	C2—H2A	0.9800
Mn1—O5ⁱ	2.2598 (11)	C3—C4	1.523 (2)
Mn1—O5	2.2598 (11)	C3—H3A	0.9800
S1—C15	1.7354 (16)	C4—C5	1.542 (3)
S1—C9	1.7519 (18)	C4—H4A	0.9700
N1—C15	1.323 (2)	C4—H4B	0.9700
N1—C14	1.392 (2)	C5—C6	1.521 (2)
N1—H1N	0.841 (15)	C5—H5A	0.9700
N2—C15	1.313 (2)	C5—H5B	0.9700
N2—H2B	0.8600	C6—C7	1.538 (2)
N2—H2C	0.8600	C6—H6A	0.9800
O1—C1	1.2465 (19)	C7—C8	1.532 (2)
O1W—H1WA	0.812 (16)	C7—H7A	0.9800
O1W—H1WB	0.847 (16)	C9—C10	1.388 (2)
O2—C1	1.2729 (19)	C9—C14	1.391 (2)
O2W—H2WA	0.826 (16)	C10—C11	1.377 (3)
O2W—H2WB	0.835 (16)	C10—H10A	0.9300
O3—C8	1.2397 (19)	C11—C12	1.381 (3)
O3W—H3WA	0.802 (17)	C11—H11A	0.9300
O3W—H3WB	0.823 (17)	C12—C13	1.387 (3)
O4—C8	1.268 (2)	C12—H12A	0.9300
O5—C6	1.4577 (19)	C13—C14	1.382 (2)
O5—C3	1.462 (2)	C13—H13A	0.9300

O4—Mn1—O4ⁱ	180.00 (7)	C5—C4—H4A	111.4
O4—Mn1—O2	86.35 (5)	C3—C4—H4B	111.4
O4ⁱ—Mn1—O2	93.65 (5)	C5—C4—H4B	111.4
O4—Mn1—O2ⁱ	93.65 (5)	H4A—C4—H4B	109.3
O4ⁱ—Mn1—O2ⁱ	86.35 (5)	C6—C5—C4	101.69 (13)
O2—Mn1—O2ⁱ	180.00 (8)	C6—C5—H5A	111.4
O4—Mn1—O5ⁱ	95.79 (4)	C4—C5—H5A	111.4
O4ⁱ—Mn1—O5ⁱ	84.21 (4)	C6—C5—H5B	111.4
O2—Mn1—O5ⁱ	94.16 (4)	C4—C5—H5B	111.4
O2ⁱ—Mn1—O5ⁱ	85.84 (4)	H5A—C5—H5B	109.3
O4—Mn1—O5	84.21 (4)	O5—C6—C5	102.21 (13)
O4ⁱ—Mn1—O5	95.79 (4)	O5—C6—C7	102.25 (11)
O2—Mn1—O5	85.84 (4)	C5—C6—C7	111.05 (13)
O2ⁱ—Mn1—O5	94.16 (4)	O5—C6—H6A	113.4
O5ⁱ—Mn1—O5	180.00 (9)	C5—C6—H6A	113.4
C15—S1—C9	90.04 (8)	C7—C6—H6A	113.4
C15—N1—C14	114.40 (13)	C8—C7—C6	110.03 (13)
C15—N1—H1N	120.2 (15)	C8—C7—C2	115.94 (12)
C14—N1—H1N	125.4 (15)	C6—C7—C2	100.67 (12)
C15—N2—H2B	120.0	C8—C7—H7A	109.9
C15—N2—H2C	120.0	C6—C7—H7A	109.9
H2B—N2—H2C	120.0	C2—C7—H7A	109.9
H1WA—O1W—H1WB	109 (2)	O3—C8—O4	123.92 (16)
C1—O2—Mn1	117.36 (10)	O3—C8—C7	118.49 (14)
H2WA—O2W—H2WB	110 (2)	O4—C8—C7	117.49 (13)
H3WA—O3W—H3WB	112 (2)	C10—C9—C14	120.86 (17)
C8—O4—Mn1	130.31 (11)	C10—C9—S1	128.60 (15)
C6—O5—C3	95.66 (11)	C14—C9—S1	110.53 (12)
C6—O5—Mn1	117.76 (9)	C11—C10—C9	117.93 (18)
C3—O5—Mn1	112.38 (9)	C11—C10—H10A	121.0
O1—C1—O2	123.97 (15)	C9—C10—H10A	121.0
O1—C1—C2	117.61 (14)	C10—C11—C12	121.05 (17)
O2—C1—C2	118.42 (13)	C10—C11—H11A	119.5
C1—C2—C3	113.69 (13)	C12—C11—H11A	119.5
C1—C2—C7	113.13 (13)	C11—C12—C13	121.61 (18)
C3—C2—C7	101.24 (12)	C11—C12—H12A	119.2
C1—C2—H2A	109.5	C13—C12—H12A	119.2
C3—C2—H2A	109.5	C14—C13—C12	117.40 (17)
C7—C2—H2A	109.5	C14—C13—H13A	121.3
O5—C3—C4	101.85 (13)	C12—C13—H13A	121.3
O5—C3—C2	102.11 (12)	C13—C14—C9	121.14 (15)
C4—C3—C2	111.14 (13)	C13—C14—N1	126.60 (15)
O5—C3—H3A	113.5	C9—C14—N1	112.26 (14)
C4—C3—H3A	113.5	N2—C15—N1	124.04 (15)
C2—C3—H3A	113.5	N2—C15—S1	123.19 (13)
C3—C4—C5	101.90 (14)	N1—C15—S1	112.76 (12)
C3—C4—H4A	111.4

O4—Mn1—O2—C1	36.93 (12)	Mn1—O5—C6—C7	−60.82 (13)
O4ⁱ—Mn1—O2—C1	−143.07 (12)	C4—C5—C6—O5	34.93 (15)
O5ⁱ—Mn1—O2—C1	132.48 (12)	C4—C5—C6—C7	−73.49 (16)
O5—Mn1—O2—C1	−47.52 (12)	O5—C6—C7—C8	87.29 (14)
O2—Mn1—O4—C8	−55.66 (14)	C5—C6—C7—C8	−164.32 (13)
O2ⁱ—Mn1—O4—C8	124.34 (14)	O5—C6—C7—C2	−35.56 (14)
O5ⁱ—Mn1—O4—C8	−149.48 (14)	C5—C6—C7—C2	72.82 (15)
O5—Mn1—O4—C8	30.52 (14)	C1—C2—C7—C8	3.37 (18)
O4—Mn1—O5—C6	12.07 (10)	C3—C2—C7—C8	−118.65 (14)
O4ⁱ—Mn1—O5—C6	−167.93 (10)	C1—C2—C7—C6	122.02 (14)
O2—Mn1—O5—C6	98.81 (10)	C3—C2—C7—C6	−0.01 (14)
O2ⁱ—Mn1—O5—C6	−81.19 (10)	Mn1—O4—C8—O3	168.08 (12)
O4—Mn1—O5—C3	−97.64 (10)	Mn1—O4—C8—C7	−15.5 (2)
O4ⁱ—Mn1—O5—C3	82.36 (10)	C6—C7—C8—O3	127.93 (15)
O2—Mn1—O5—C3	−10.90 (9)	C2—C7—C8—O3	−118.70 (16)
O2ⁱ—Mn1—O5—C3	169.10 (9)	C6—C7—C8—O4	−48.67 (18)
Mn1—O2—C1—O1	−134.48 (14)	C2—C7—C8—O4	64.70 (18)
Mn1—O2—C1—C2	45.82 (17)	C15—S1—C9—C10	179.41 (17)
O1—C1—C2—C3	−156.51 (14)	C15—S1—C9—C14	−0.48 (13)
O2—C1—C2—C3	23.2 (2)	C14—C9—C10—C11	0.0 (3)
O1—C1—C2—C7	88.73 (17)	S1—C9—C10—C11	−179.86 (14)
O2—C1—C2—C7	−91.56 (17)	C9—C10—C11—C12	−0.2 (3)
C6—O5—C3—C4	56.86 (13)	C10—C11—C12—C13	0.1 (3)
Mn1—O5—C3—C4	−179.98 (9)	C11—C12—C13—C14	0.2 (3)
C6—O5—C3—C2	−58.10 (13)	C12—C13—C14—C9	−0.3 (2)
Mn1—O5—C3—C2	65.06 (12)	C12—C13—C14—N1	179.42 (16)
C1—C2—C3—O5	−86.20 (14)	C10—C9—C14—C13	0.2 (3)
C7—C2—C3—O5	35.44 (14)	S1—C9—C14—C13	−179.86 (13)
C1—C2—C3—C4	165.85 (13)	C10—C9—C14—N1	−179.55 (16)
C7—C2—C3—C4	−72.52 (16)	S1—C9—C14—N1	0.36 (17)
O5—C3—C4—C5	−35.17 (15)	C15—N1—C14—C13	−179.74 (16)
C2—C3—C4—C5	72.95 (17)	C15—N1—C14—C9	0.0 (2)
C3—C4—C5—C6	0.24 (16)	C14—N1—C15—N2	−179.49 (15)
C3—O5—C6—C5	−56.87 (13)	C14—N1—C15—S1	−0.41 (18)
Mn1—O5—C6—C5	−175.85 (9)	C9—S1—C15—N2	179.61 (15)
C3—O5—C6—C7	58.16 (13)	C9—S1—C15—N1	0.51 (13)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱⁱ	0.84 (2)	1.84 (2)	2.6822 (18)	178 (2)
N2—H2B···O2ⁱⁱ	0.86	2.00	2.8490 (19)	170
N2—H2C···O2Wⁱⁱⁱ	0.86	2.00	2.824 (2)	160
O1W—H1WA···O1	0.81 (2)	2.03 (2)	2.8250 (19)	166 (3)
O1W—H1WB···O2W	0.85 (2)	1.95 (2)	2.792 (2)	170 (3)
O2W—H2WA···O3	0.83 (2)	1.87 (2)	2.6806 (19)	169 (3)
O2W—H2WB···O3W^iv	0.84 (2)	1.93 (2)	2.768 (2)	178 (3)
O3W—H3WA···O1Wⁱⁱⁱ	0.80 (2)	2.21 (2)	3.004 (2)	169 (3)
O3W—H3WB···O1W	0.82 (2)	1.97 (2)	2.784 (2)	173 (3)

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

Experimental details

Crystal data
Chemical formula	(C₇H₇N₂S)₂[Mn(C₈H₈O₅)₂]·6H₂O
M_r	833.76
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.6937 (1), 10.2209 (1), 13.1163 (2)
α, β, γ (°)	89.527 (1), 88.831 (1), 81.514 (1)
V (Å³)	887.34 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.15 × 0.13 × 0.10

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.916, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	14148, 4089, 3426
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.093, 0.97
No. of reflections	4089
No. of parameters	262
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.35

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mn1—O4	2.1083 (11)	Mn1—O5	2.2598 (11)
Mn1—O2	2.1883 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.841 (15)	1.842 (16)	2.6822 (18)	178 (2)
N2—H2B···O2ⁱ	0.86	2.00	2.8490 (19)	170.3
N2—H2C···O2Wⁱⁱ	0.86	2.00	2.824 (2)	159.5
O1W—H1WA···O1	0.812 (16)	2.030 (18)	2.8250 (19)	166 (3)
O1W—H1WB···O2W	0.847 (16)	1.953 (18)	2.792 (2)	170 (3)
O2W—H2WA···O3	0.826 (16)	1.866 (18)	2.6806 (19)	169 (3)
O2W—H2WB···O3Wⁱⁱⁱ	0.835 (16)	1.933 (16)	2.768 (2)	178 (3)
O3W—H3WA···O1Wⁱⁱ	0.802 (17)	2.212 (18)	3.004 (2)	169 (3)
O3W—H3WB···O1W	0.823 (17)	1.965 (18)	2.784 (2)	173 (3)

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

Acknowledgements

The authors thank the Natural Science Foundation of Zhejiang Province, China (grant No. Y407301) for financial support.

References

Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dukhande, V. V., Malthankar-Phatak, G. H., Hugus, J. J., Daniels, C. K. & Lai, J. C. K. (2006). Neurochem. Res. 31, 1349–1357. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shimi, I. R., Zaki, Z., Shoukry, S. & Medhat, A. M. (1982). Eur. J. Cancer Clin. Oncol. 18, 785–789. CrossRef CAS PubMed Web of Science Google Scholar
Wang, N., Lin, Q.-Y., Feng, J., Li, S.-K. & Zhao, J.-J. (2010). Acta Cryst. E66, m763–m764. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 66| Part 7| July 2010| Page m762

doi:10.1107/S160053681002091X

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(2-amino-3H-benzo­thia­zolium) bis­­(7-oxabi­cyclo­[2.2.1]heptane-2,3-di­carbox­yl­ato)manganate(II) hexa­hydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis(2-amino-3H-benzothiazolium) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato)manganate(II) hexahydrate