Bis[2-meth-oxy-6-(phenyl-iminiomethyl)phenolate-κO,O']bis-(thio-cyanato-κN)manganese(II).

The Mn(II) atom in the title complex, [Mn(NCS)(2)(C(14)H(13)NO(2))(2)], lies on a center of inversion in a MnO(4)N(2) octa-hedral geometry. The Schiff base is present in its zwitterionic form and is O,O'-chelated to the metal atom. The imino N atom is protonated and is involved in an intra-molecular hydrogen bond with the phenolate O atom.

Related literature

For Schiff base ligands derived from o-vanillin and aniline and their rare earth complexes, see: Li et al. (2008 ▶); Liu et al. (2009 ▶); Xian et al. (2008 ▶); Zhao et al. (2005 ▶, 2007 ▶).

Experimental

Crystal data

[Mn(NCS)2(C14H13NO2)2]

M = 625.61

Triclinic,

a = 9.0204 (2) Å

b = 9.3070 (2) Å

c = 9.4087 (2) Å

α = 87.417 (1)°

β = 82.010 (1)°

γ = 65.693 (1)°

V = 712.81 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.65 mm−1

T = 296 K

0.29 × 0.17 × 0.05 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.877, T max = 0.970

9483 measured reflections

2509 independent reflections

2233 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.077

S = 1.06

2509 reflections

188 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.24 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009330/ng5130sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009330/ng5130Isup2.hkl

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

[Mn(NCS)2(C14H13NO2)2]	Z = 1
Mr = 625.61	F(000) = 323
Triclinic, P1	Dx = 1.457 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0204 (2) Å	Cell parameters from 4271 reflections
b = 9.3070 (2) Å	θ = 2.2–25.0°
c = 9.4087 (2) Å	µ = 0.65 mm−1
α = 87.417 (1)°	T = 296 K
β = 82.010 (1)°	Block, red
γ = 65.693 (1)°	0.29 × 0.17 × 0.05 mm
V = 712.81 (3) Å3

Bruker APEXII area-detector diffractometer	2509 independent reflections
Radiation source: fine-focus sealed tube	2233 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.877, Tmax = 0.970	k = −11→11
9483 measured reflections	l = −11→11

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0423P)2 + 0.1242P] where P = (Fo2 + 2Fc2)/3
2509 reflections	(Δ/σ)max = 0.001
188 parameters	Δρmax = 0.17 e Å−3
2 restraints	Δρmin = −0.24 e Å−3

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.

	x	y	z	Uiso*/Ueq
Mn1	0.0000	0.5000	0.5000	0.03697 (13)
S1	0.00911 (6)	0.11697 (6)	0.14672 (6)	0.05653 (16)
O1	0.24701 (13)	0.46530 (13)	0.41948 (12)	0.0385 (3)
N1	0.48105 (16)	0.51194 (15)	0.24678 (14)	0.0354 (3)
H1A	0.3779	0.5397	0.2737	0.043*
O2	0.16157 (14)	0.30666 (15)	0.63303 (13)	0.0465 (3)
C7	0.36297 (19)	0.35112 (18)	0.47429 (16)	0.0320 (3)
C13	0.32723 (19)	0.25949 (19)	0.58901 (17)	0.0361 (4)
C9	0.53201 (19)	0.31088 (19)	0.42564 (17)	0.0354 (4)
C15	0.01407 (19)	0.2348 (2)	0.26679 (19)	0.0401 (4)
C8	0.58045 (19)	0.3952 (2)	0.31424 (18)	0.0389 (4)
H8A	0.6924	0.3648	0.2870	0.047*
C4	0.5244 (2)	0.59880 (19)	0.13313 (17)	0.0358 (4)
C3	0.6852 (2)	0.5520 (2)	0.06908 (19)	0.0451 (4)
H3A	0.7678	0.4615	0.0990	0.054*
C12	0.4481 (2)	0.1394 (2)	0.64754 (19)	0.0452 (4)
H12A	0.4207	0.0812	0.7213	0.054*
C5	0.4016 (2)	0.7315 (2)	0.08693 (19)	0.0441 (4)
H5A	0.2935	0.7612	0.1290	0.053*
C2	0.7210 (2)	0.6418 (2)	−0.0399 (2)	0.0537 (5)
H2A	0.8288	0.6114	−0.0832	0.064*
N2	0.01391 (19)	0.3211 (2)	0.35072 (18)	0.0554 (4)
C10	0.6546 (2)	0.1866 (2)	0.4902 (2)	0.0475 (4)
H10A	0.7647	0.1625	0.4585	0.057*
C1	0.5992 (3)	0.7757 (2)	−0.0853 (2)	0.0551 (5)
H1B	0.6248	0.8357	−0.1583	0.066*
C11	0.6141 (2)	0.1025 (2)	0.5974 (2)	0.0514 (5)
H11A	0.6960	0.0202	0.6380	0.062*
C6	0.4396 (2)	0.8202 (2)	−0.0220 (2)	0.0529 (5)
H6A	0.3570	0.9103	−0.0526	0.063*
C14	0.1088 (3)	0.2163 (3)	0.7377 (3)	0.0723 (7)
H14A	0.1511	0.2175	0.8256	0.108*
H14B	0.1487	0.1096	0.7035	0.108*
H14C	−0.0089	0.2609	0.7546	0.108*

	U11	U22	U33	U12	U13	U23
Mn1	0.02590 (19)	0.0477 (2)	0.0377 (2)	−0.01664 (16)	−0.00189 (14)	0.00535 (15)
S1	0.0503 (3)	0.0525 (3)	0.0652 (3)	−0.0210 (2)	0.0012 (2)	−0.0120 (2)
O1	0.0265 (6)	0.0450 (7)	0.0419 (6)	−0.0142 (5)	−0.0032 (5)	0.0135 (5)
N1	0.0272 (7)	0.0401 (8)	0.0386 (7)	−0.0153 (6)	0.0018 (6)	0.0017 (6)
O2	0.0352 (6)	0.0583 (8)	0.0466 (7)	−0.0229 (6)	−0.0025 (5)	0.0208 (6)
C7	0.0309 (8)	0.0344 (8)	0.0321 (8)	−0.0152 (7)	−0.0033 (6)	0.0011 (6)
C13	0.0345 (9)	0.0419 (9)	0.0347 (8)	−0.0188 (7)	−0.0038 (7)	0.0027 (7)
C9	0.0306 (8)	0.0381 (9)	0.0355 (8)	−0.0132 (7)	−0.0018 (6)	0.0021 (7)
C15	0.0272 (8)	0.0426 (10)	0.0477 (10)	−0.0136 (7)	0.0009 (7)	0.0048 (7)
C8	0.0263 (8)	0.0460 (10)	0.0418 (9)	−0.0139 (7)	0.0010 (7)	0.0012 (7)
C4	0.0367 (9)	0.0379 (9)	0.0359 (8)	−0.0199 (7)	0.0000 (7)	−0.0004 (7)
C3	0.0359 (9)	0.0495 (11)	0.0469 (10)	−0.0175 (8)	0.0016 (8)	0.0083 (8)
C12	0.0488 (11)	0.0445 (10)	0.0409 (9)	−0.0184 (8)	−0.0078 (8)	0.0120 (8)
C5	0.0382 (10)	0.0441 (10)	0.0468 (10)	−0.0154 (8)	−0.0008 (8)	0.0022 (8)
C2	0.0426 (10)	0.0636 (12)	0.0546 (11)	−0.0263 (10)	0.0068 (9)	0.0085 (9)
N2	0.0465 (9)	0.0663 (11)	0.0562 (10)	−0.0280 (8)	0.0035 (8)	−0.0098 (8)
C10	0.0306 (9)	0.0516 (11)	0.0512 (11)	−0.0089 (8)	−0.0038 (8)	0.0063 (8)
C1	0.0620 (13)	0.0575 (12)	0.0500 (11)	−0.0318 (11)	−0.0014 (9)	0.0142 (9)
C11	0.0422 (10)	0.0481 (11)	0.0531 (11)	−0.0073 (8)	−0.0115 (8)	0.0139 (9)
C6	0.0541 (12)	0.0450 (11)	0.0542 (11)	−0.0160 (9)	−0.0076 (9)	0.0124 (9)
C14	0.0556 (13)	0.0807 (16)	0.0782 (15)	−0.0333 (12)	0.0049 (11)	0.0363 (12)

Mn1—O1	2.1455 (10)	C4—C5	1.379 (2)
Mn1—O1i	2.1455 (10)	C4—C3	1.384 (2)
Mn1—N2	2.1794 (16)	C3—C2	1.381 (2)
Mn1—N2i	2.1794 (16)	C3—H3A	0.9300
Mn1—O2	2.2525 (12)	C12—C11	1.406 (3)
Mn1—O2i	2.2525 (12)	C12—H12A	0.9300
S1—C15	1.6270 (19)	C5—C6	1.381 (3)
O1—C7	1.2942 (19)	C5—H5A	0.9300
N1—C8	1.297 (2)	C2—C1	1.378 (3)
N1—C4	1.420 (2)	C2—H2A	0.9300
N1—H1A	0.8600	C10—C11	1.351 (3)
O2—C13	1.3790 (19)	C10—H10A	0.9300
O2—C14	1.424 (2)	C1—C6	1.376 (3)
C7—C9	1.423 (2)	C1—H1B	0.9300
C7—C13	1.429 (2)	C11—H11A	0.9300
C13—C12	1.360 (2)	C6—H6A	0.9300
C9—C8	1.409 (2)	C14—H14A	0.9600
C9—C10	1.414 (2)	C14—H14B	0.9600
C15—N2	1.151 (2)	C14—H14C	0.9600
C8—H8A	0.9300
O1—Mn1—O1i	180.0	C5—C4—C3	120.42 (16)
O1—Mn1—N2	90.41 (5)	C5—C4—N1	118.22 (14)
O1i—Mn1—N2	89.59 (5)	C3—C4—N1	121.36 (15)
O1—Mn1—N2i	89.59 (5)	C2—C3—C4	119.02 (17)
O1i—Mn1—N2i	90.41 (5)	C2—C3—H3A	120.5
N2—Mn1—N2i	180.00 (7)	C4—C3—H3A	120.5
O1—Mn1—O2	74.23 (4)	C13—C12—C11	120.51 (16)
O1i—Mn1—O2	105.77 (4)	C13—C12—H12A	119.7
N2—Mn1—O2	88.99 (6)	C11—C12—H12A	119.7
N2i—Mn1—O2	91.01 (6)	C4—C5—C6	119.83 (16)
O1—Mn1—O2i	105.77 (4)	C4—C5—H5A	120.1
O1i—Mn1—O2i	74.23 (4)	C6—C5—H5A	120.1
N2—Mn1—O2i	91.01 (6)	C1—C2—C3	120.86 (17)
N2i—Mn1—O2i	88.99 (6)	C1—C2—H2A	119.6
O2—Mn1—O2i	180.00 (5)	C3—C2—H2A	119.6
C7—O1—Mn1	116.71 (9)	C15—N2—Mn1	175.35 (17)
C8—N1—C4	126.92 (14)	C11—C10—C9	120.88 (16)
C8—N1—H1A	116.5	C11—C10—H10A	119.6
C4—N1—H1A	116.5	C9—C10—H10A	119.6
C13—O2—C14	119.03 (14)	C6—C1—C2	119.66 (18)
C13—O2—Mn1	114.02 (9)	C6—C1—H1B	120.2
C14—O2—Mn1	126.09 (12)	C2—C1—H1B	120.2
O1—C7—C9	122.31 (14)	C10—C11—C12	120.05 (17)
O1—C7—C13	121.33 (14)	C10—C11—H11A	120.0
C9—C7—C13	116.36 (14)	C12—C11—H11A	120.0
C12—C13—O2	124.73 (15)	C1—C6—C5	120.20 (18)
C12—C13—C7	121.84 (15)	C1—C6—H6A	119.9
O2—C13—C7	113.42 (14)	C5—C6—H6A	119.9
C8—C9—C10	118.78 (15)	O2—C14—H14A	109.5
C8—C9—C7	120.86 (15)	O2—C14—H14B	109.5
C10—C9—C7	120.35 (15)	H14A—C14—H14B	109.5
N2—C15—S1	178.24 (18)	O2—C14—H14C	109.5
N1—C8—C9	125.08 (14)	H14A—C14—H14C	109.5
N1—C8—H8A	117.5	H14B—C14—H14C	109.5
C9—C8—H8A	117.5
N2—Mn1—O1—C7	−84.38 (11)	C13—C7—C9—C8	−179.21 (15)
N2i—Mn1—O1—C7	95.62 (11)	O1—C7—C9—C10	179.05 (15)
O2—Mn1—O1—C7	4.46 (10)	C13—C7—C9—C10	−0.2 (2)
O2i—Mn1—O1—C7	−175.54 (10)	C4—N1—C8—C9	−179.22 (15)
O1—Mn1—O2—C13	−4.72 (10)	C10—C9—C8—N1	−179.53 (16)
O1i—Mn1—O2—C13	175.28 (10)	C7—C9—C8—N1	−0.5 (3)
N2—Mn1—O2—C13	85.99 (11)	C8—N1—C4—C5	−172.09 (16)
N2i—Mn1—O2—C13	−94.01 (11)	C8—N1—C4—C3	8.3 (3)
O1—Mn1—O2—C14	−173.90 (17)	C5—C4—C3—C2	1.1 (3)
O1i—Mn1—O2—C14	6.10 (17)	N1—C4—C3—C2	−179.25 (16)
N2—Mn1—O2—C14	−83.19 (17)	O2—C13—C12—C11	−178.46 (16)
N2i—Mn1—O2—C14	96.81 (17)	C7—C13—C12—C11	0.8 (3)
Mn1—O1—C7—C9	176.96 (11)	C3—C4—C5—C6	−1.3 (3)
Mn1—O1—C7—C13	−3.79 (19)	N1—C4—C5—C6	179.06 (16)
C14—O2—C13—C12	−6.3 (3)	C4—C3—C2—C1	−0.3 (3)
Mn1—O2—C13—C12	−176.32 (13)	C8—C9—C10—C11	179.98 (17)
C14—O2—C13—C7	174.40 (17)	C7—C9—C10—C11	1.0 (3)
Mn1—O2—C13—C7	4.39 (17)	C3—C2—C1—C6	−0.5 (3)
O1—C7—C13—C12	−179.92 (15)	C9—C10—C11—C12	−0.9 (3)
C9—C7—C13—C12	−0.6 (2)	C13—C12—C11—C10	0.0 (3)
O1—C7—C13—O2	−0.6 (2)	C2—C1—C6—C5	0.3 (3)
C9—C7—C13—O2	178.68 (13)	C4—C5—C6—C1	0.6 (3)
O1—C7—C9—C8	0.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	1.97	2.6501 (16)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.86	1.97	2.6501 (16)	135