Bis[2-(2-pyridylmethyl-eneamino)benzene-sulfonato-κN,N',O]manganese(II) dihydrate.

The title complex, [Mn(C(12)H(9)N(2)O(3)S)(2)]·2H(2)O, is isotypic with the previously reported Zn(II) and Cd(II) species. The complex was prepared by the reaction of the potassium salt of 2-(2-pyridylmethyl-eneamino)benzene-sulfonic acid with MnCl(2)·6H(2)O in methanol. The complex displays twofold symmetry, with the ligands coordinated in a tridentate meridional-like arrangement through pyridyl N, imine N, and sulfonate O atoms. The metal center has a strongly distorted octa-hedral coordination geometry. The uncoordin-ated water mol-ecules and the complexes participate in a hydrogen-bonding network, forming a two-dimensional structure parallel to the ab plane.

Related literature

For the synthesis of the ligand, see: Casella & Gullotti (1986 ▶). For the structures of the ZnII and CdII analogues, see: Cai et al. (2008 ▶); Ou-Yang et al. (2008 ▶). For related Schiff bases complexes, see: Correia et al. (2003 ▶); Li et al. (2007 ▶, 2008 ▶); Ou-Yang et al. (2009 ▶); Zhang et al. (2005 ▶).

Experimental

Crystal data

[Mn(C12H9N2O3S)2]·2H2O

M = 613.52

Orthorhombic,

a = 20.041 (10) Å

b = 7.918 (4) Å

c = 16.409 (8) Å

V = 2604 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.72 mm−1

T = 296 K

0.49 × 0.34 × 0.21 mm

Data collection

SMART APEX CCD diffractometer

Absorption correction: none

13313 measured reflections

2320 independent reflections

1950 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.092

S = 1.01

2320 reflections

177 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030670/bh2236sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030670/bh2236Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mn(C12H9N2O3S)2]·2H2O	F(000) = 1260
Mr = 613.52	Dx = 1.565 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4677 reflections
a = 20.041 (10) Å	θ = 2.5–28.5°
b = 7.918 (4) Å	µ = 0.72 mm−1
c = 16.409 (8) Å	T = 296 K
V = 2604 (2) Å3	Block, yellow
Z = 4	0.49 × 0.34 × 0.21 mm

SMART APEX CCD diffractometer	1950 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
graphite	θmax = 25.1°, θmin = 2.5°
φ and ω scans	h = −21→23
13313 measured reflections	k = −9→9
2320 independent reflections	l = −19→19

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) = 0.092	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0512P)2 + 1.5899P] where P = (Fo2 + 2Fc2)/3
2320 reflections	(Δ/σ)max < 0.001
177 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

	x	y	z	Uiso*/Ueq
Mn1	1.0000	0.18060 (6)	0.2500	0.02835 (15)
S1	0.87380 (3)	0.32706 (7)	0.33859 (3)	0.03333 (17)
O1	0.94725 (8)	0.3323 (2)	0.33645 (9)	0.0381 (4)
O2	0.84921 (9)	0.1575 (2)	0.32866 (10)	0.0508 (5)
O3	0.84826 (8)	0.4155 (2)	0.40879 (9)	0.0466 (4)
N1	0.99221 (9)	−0.0275 (2)	0.15711 (11)	0.0352 (4)
N2	0.90694 (8)	0.2347 (2)	0.16781 (10)	0.0303 (4)
C1	1.03597 (13)	−0.1521 (3)	0.14852 (14)	0.0444 (6)
H1	1.0708	−0.1601	0.1858	0.053*
C2	1.03222 (15)	−0.2704 (3)	0.08686 (15)	0.0495 (6)
H2	1.0641	−0.3553	0.0826	0.059*
C3	0.98074 (14)	−0.2607 (3)	0.03207 (16)	0.0503 (6)
H3	0.9767	−0.3399	−0.0095	0.060*
C4	0.93496 (13)	−0.1310 (3)	0.03971 (14)	0.0440 (6)
H4	0.8998	−0.1210	0.0031	0.053*
C5	0.94222 (11)	−0.0165 (3)	0.10256 (12)	0.0329 (5)
C6	0.89698 (11)	0.1272 (3)	0.11156 (13)	0.0360 (5)
H6	0.8610	0.1400	0.0762	0.043*
C7	0.86610 (10)	0.3806 (3)	0.17345 (12)	0.0321 (5)
C8	0.84533 (12)	0.4702 (3)	0.10524 (14)	0.0440 (6)
H8	0.8560	0.4311	0.0534	0.053*
C9	0.80902 (13)	0.6167 (4)	0.11399 (15)	0.0536 (7)
H9	0.7950	0.6754	0.0680	0.064*
C10	0.79326 (14)	0.6770 (4)	0.19056 (17)	0.0542 (7)
H10	0.7695	0.7772	0.1960	0.065*
C11	0.81279 (12)	0.5887 (3)	0.25907 (14)	0.0432 (6)
H11	0.8014	0.6283	0.3106	0.052*
C12	0.84920 (10)	0.4420 (3)	0.25118 (11)	0.0319 (5)
O4	0.79877 (12)	−0.0889 (4)	0.44087 (15)	0.1140 (12)
H1W	0.7570	−0.0869	0.4320	0.171*
H2W	0.8166	−0.0498	0.3988	0.171*

	U11	U22	U33	U12	U13	U23
Mn1	0.0279 (3)	0.0336 (3)	0.0235 (2)	0.000	−0.00482 (17)	0.000
S1	0.0326 (3)	0.0437 (3)	0.0236 (3)	0.0002 (2)	0.0001 (2)	0.0008 (2)
O1	0.0316 (8)	0.0540 (10)	0.0287 (8)	0.0050 (7)	−0.0044 (6)	−0.0070 (7)
O2	0.0606 (12)	0.0486 (11)	0.0431 (10)	−0.0120 (9)	−0.0038 (8)	0.0083 (8)
O3	0.0434 (9)	0.0699 (12)	0.0267 (8)	0.0085 (8)	0.0051 (7)	−0.0043 (8)
N1	0.0409 (10)	0.0350 (10)	0.0297 (9)	0.0024 (8)	−0.0067 (8)	−0.0015 (8)
N2	0.0280 (9)	0.0384 (10)	0.0245 (8)	0.0003 (8)	−0.0007 (7)	−0.0004 (7)
C1	0.0503 (15)	0.0428 (14)	0.0401 (13)	0.0087 (12)	−0.0108 (11)	−0.0008 (10)
C2	0.0684 (17)	0.0356 (13)	0.0445 (14)	0.0116 (12)	−0.0024 (13)	−0.0030 (11)
C3	0.0721 (18)	0.0382 (13)	0.0406 (13)	0.0020 (13)	−0.0054 (13)	−0.0095 (11)
C4	0.0510 (15)	0.0466 (14)	0.0345 (12)	−0.0044 (11)	−0.0110 (11)	−0.0076 (10)
C5	0.0350 (11)	0.0369 (12)	0.0269 (10)	−0.0033 (9)	−0.0028 (9)	−0.0003 (9)
C6	0.0318 (11)	0.0488 (13)	0.0273 (11)	−0.0008 (10)	−0.0067 (9)	−0.0017 (10)
C7	0.0243 (11)	0.0435 (13)	0.0284 (10)	0.0018 (9)	−0.0006 (8)	0.0017 (9)
C8	0.0398 (13)	0.0621 (16)	0.0302 (11)	0.0098 (12)	0.0019 (10)	0.0066 (11)
C9	0.0495 (15)	0.0690 (18)	0.0421 (14)	0.0200 (14)	0.0001 (12)	0.0159 (13)
C10	0.0497 (16)	0.0556 (17)	0.0574 (16)	0.0213 (13)	0.0015 (13)	0.0089 (13)
C11	0.0380 (13)	0.0517 (15)	0.0398 (13)	0.0107 (11)	0.0045 (10)	−0.0024 (11)
C12	0.0257 (11)	0.0415 (12)	0.0284 (11)	−0.0003 (9)	0.0002 (8)	0.0014 (9)
O4	0.0640 (15)	0.182 (3)	0.0956 (19)	−0.0353 (17)	−0.0233 (13)	0.075 (2)

Mn1—O1	2.1382 (16)	C3—C4	1.383 (4)
Mn1—O1i	2.1382 (16)	C3—H3	0.9300
Mn1—N1	2.250 (2)	C4—C5	1.381 (3)
Mn1—N1i	2.250 (2)	C4—H4	0.9300
Mn1—N2i	2.3412 (19)	C5—C6	1.463 (3)
Mn1—N2	2.3412 (19)	C6—H6	0.9300
S1—O2	1.4395 (19)	C7—C8	1.389 (3)
S1—O3	1.4420 (17)	C7—C12	1.406 (3)
S1—O1	1.4729 (18)	C8—C9	1.376 (4)
S1—C12	1.769 (2)	C8—H8	0.9300
N1—C1	1.327 (3)	C9—C10	1.381 (4)
N1—C5	1.346 (3)	C9—H9	0.9300
N2—C6	1.271 (3)	C10—C11	1.380 (3)
N2—C7	1.418 (3)	C10—H10	0.9300
C1—C2	1.381 (3)	C11—C12	1.378 (3)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.371 (4)	O4—H1W	0.8495
C2—H2	0.9300	O4—H2W	0.8364
O1—Mn1—O1i	111.67 (10)	C1—C2—H2	120.6
O1—Mn1—N1	145.73 (6)	C2—C3—C4	118.8 (2)
O1i—Mn1—N1	89.79 (7)	C2—C3—H3	120.6
O1—Mn1—N1i	89.79 (7)	C4—C3—H3	120.6
O1i—Mn1—N1i	145.73 (6)	C5—C4—C3	119.0 (2)
N1—Mn1—N1i	85.83 (10)	C5—C4—H4	120.5
O1—Mn1—N2i	84.77 (6)	C3—C4—H4	120.5
O1i—Mn1—N2i	83.42 (7)	N1—C5—C4	122.2 (2)
N1—Mn1—N2i	125.42 (7)	N1—C5—C6	116.40 (18)
N1i—Mn1—N2i	71.86 (7)	C4—C5—C6	121.4 (2)
O1—Mn1—N2	83.42 (6)	N2—C6—C5	119.80 (19)
O1i—Mn1—N2	84.77 (6)	N2—C6—H6	120.1
N1—Mn1—N2	71.86 (7)	C5—C6—H6	120.1
N1i—Mn1—N2	125.42 (7)	C8—C7—C12	118.8 (2)
N2i—Mn1—N2	158.90 (9)	C8—C7—N2	122.43 (19)
O2—S1—O3	114.95 (11)	C12—C7—N2	118.65 (18)
O2—S1—O1	111.44 (11)	C9—C8—C7	120.3 (2)
O3—S1—O1	111.11 (9)	C9—C8—H8	119.8
O2—S1—C12	107.02 (10)	C7—C8—H8	119.8
O3—S1—C12	107.40 (11)	C8—C9—C10	120.5 (2)
O1—S1—C12	104.18 (9)	C8—C9—H9	119.8
S1—O1—Mn1	119.62 (9)	C10—C9—H9	119.8
C1—N1—C5	117.98 (19)	C11—C10—C9	120.1 (2)
C1—N1—Mn1	124.77 (15)	C11—C10—H10	120.0
C5—N1—Mn1	117.04 (14)	C9—C10—H10	120.0
C6—N2—C7	120.13 (18)	C12—C11—C10	120.0 (2)
C6—N2—Mn1	114.88 (15)	C12—C11—H11	120.0
C7—N2—Mn1	124.83 (13)	C10—C11—H11	120.0
N1—C1—C2	123.1 (2)	C11—C12—C7	120.3 (2)
N1—C1—H1	118.5	C11—C12—S1	120.34 (16)
C2—C1—H1	118.5	C7—C12—S1	119.38 (17)
C3—C2—C1	118.9 (2)	H1W—O4—H2W	105.8
C3—C2—H2	120.6
O2—S1—O1—Mn1	41.05 (13)	C2—C3—C4—C5	−0.5 (4)
O3—S1—O1—Mn1	170.64 (10)	C1—N1—C5—C4	0.9 (3)
C12—S1—O1—Mn1	−74.01 (13)	Mn1—N1—C5—C4	175.90 (17)
O1i—Mn1—O1—S1	115.14 (11)	C1—N1—C5—C6	−177.0 (2)
N1—Mn1—O1—S1	−10.02 (18)	Mn1—N1—C5—C6	−2.0 (2)
N1i—Mn1—O1—S1	−92.28 (11)	C3—C4—C5—N1	−0.5 (4)
N2i—Mn1—O1—S1	−164.08 (11)	C3—C4—C5—C6	177.4 (2)
N2—Mn1—O1—S1	33.44 (10)	C7—N2—C6—C5	175.63 (19)
O1—Mn1—N1—C1	−137.89 (18)	Mn1—N2—C6—C5	0.1 (3)
O1i—Mn1—N1—C1	91.6 (2)	N1—C5—C6—N2	1.3 (3)
N1i—Mn1—N1—C1	−54.42 (17)	C4—C5—C6—N2	−176.7 (2)
N2i—Mn1—N1—C1	9.8 (2)	C6—N2—C7—C8	−40.0 (3)
N2—Mn1—N1—C1	176.1 (2)	Mn1—N2—C7—C8	135.02 (19)
O1—Mn1—N1—C5	47.5 (2)	C6—N2—C7—C12	143.7 (2)
O1i—Mn1—N1—C5	−83.05 (16)	Mn1—N2—C7—C12	−41.3 (3)
N1i—Mn1—N1—C5	130.97 (18)	C12—C7—C8—C9	0.2 (4)
N2i—Mn1—N1—C5	−164.81 (14)	N2—C7—C8—C9	−176.1 (2)
N2—Mn1—N1—C5	1.52 (15)	C7—C8—C9—C10	0.5 (4)
O1—Mn1—N2—C6	−156.78 (16)	C8—C9—C10—C11	−1.3 (4)
O1i—Mn1—N2—C6	90.65 (16)	C9—C10—C11—C12	1.3 (4)
N1—Mn1—N2—C6	−0.84 (15)	C10—C11—C12—C7	−0.6 (4)
N1i—Mn1—N2—C6	−71.75 (17)	C10—C11—C12—S1	−179.4 (2)
N2i—Mn1—N2—C6	146.83 (16)	C8—C7—C12—C11	−0.1 (3)
O1—Mn1—N2—C7	27.95 (16)	N2—C7—C12—C11	176.3 (2)
O1i—Mn1—N2—C7	−84.62 (16)	C8—C7—C12—S1	178.73 (17)
N1—Mn1—N2—C7	−176.11 (17)	N2—C7—C12—S1	−4.8 (3)
N1i—Mn1—N2—C7	112.98 (16)	O2—S1—C12—C11	124.5 (2)
N2i—Mn1—N2—C7	−28.44 (15)	O3—S1—C12—C11	0.6 (2)
C5—N1—C1—C2	−0.4 (4)	O1—S1—C12—C11	−117.32 (19)
Mn1—N1—C1—C2	−174.95 (19)	O2—S1—C12—C7	−54.3 (2)
N1—C1—C2—C3	−0.6 (4)	O3—S1—C12—C7	−178.25 (17)
C1—C2—C3—C4	1.0 (4)	O1—S1—C12—C7	63.82 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1W···O3ii	0.85	2.14	2.993 (3)	179
O4—H2W···O2	0.84	2.11	2.866 (3)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1W⋯O3i	0.85	2.14	2.993 (3)	179
O4—H2W⋯O2	0.84	2.11	2.866 (3)	151

Symmetry code: (i) .