Diazido­bis[4,4,5,5-tetra­methyl-2-(1,3-thia­zol-2-yl)-2-imidazoline-1-oxyl-3-oxide-κ² O,N]manganese(II)

Abstract

In the crystal structure of the title compound, [Mn(N₃)₂(C₁₀H₁₄N₃O₂S)₂], the Mn(II) atom exhibits a roughly octa­hedral coordination geometry. The Mn(II) atom lies on an inversion centre, thus the asymmetric unit comprises one half-mol­ecule. The metal center is six-coordinated by two azide anions and by two chelating 4,4,5,5-tetra­methyl-2-(1,3-thia­zol-2-yl)-2-imidazoline-1-oxyl-3-oxide nitronyl nitroxide radical ligands, leading to two six-membered chelate rings.

Related literature

For the design and synthesis of mol­ecule-based magnetic materials, see: Aoki et al. (2003 ▶). For nitronyl nitroxide radicals, see: Minguet et al. (2000 ▶); Catala et al. (2005 ▶). For transition metal–radical complexes, see: Wang et al. (2005 ▶). For paramagnetic metal complexes of nitronyl nitroxide radicals, see: Li et al. (2002 ▶); Liu et al. (2001 ▶). For the synthesis, see: Ullman et al. (1970 ▶, 1972 ▶)

Experimental

Crystal data

• [Mn(N₃)₂(C₁₀H₁₄N₃O₂S)₂]

• M _r = 619.60

• Monoclinic,

• a = 9.9600 (18) Å

• b = 12.272 (2) Å

• c = 11.353 (2) Å

• β = 103.714 (3)°

• V = 1348.1 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 0.70 mm⁻¹

• T = 291 (2) K

• 0.45 × 0.30 × 0.25 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.745, T _max = 0.846

• 7966 measured reflections

• 3061 independent reflections

• 2628 reflections with I > 2σ(I)

• R _int = 0.036

Refinement

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.110

• S = 1.06

• 3061 reflections

• 182 parameters

• H-atom parameters constrained

• Δρ_max = 0.37 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); 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: publCIF (Westrip, 2009 ▶).

Supplementary Material

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

supplementary crystallographic information

Comment

The design and synthesis of molecule-based magnetic materials is one of the major subjects of materials science(Aoki et al. 2003). In many different types of organic radicals, research has focused on the nitronyl nitroxide radicals (NITR) family because of their flexibility and functionality (Minguet et al. 2000; Catala et al. 2005). The nitroxide derivatives can be bound to the metal center through the oxygen atoms of O–N groups, affording a good variety of transition metal–radical complexes (Wang et al. 2005;). There have been many magnetic studies on transition metal complexes with nitronyl nitroxide and imino nitroxide radicals and paramagnetic metal complexes of nitronyl nitroxide radicals have been extensively studied (Li et al. 2002; Liu et al. 2001). In the present paper, we report the synthesis and crystal structure of the title compound Mn(N₃)₂(NIT2-thz)₂.

Experimental

NIT2-thz [NIT2-thz = 4,4,5,5-tetramethyl-2-(1,3-thiazol-2-yl)-2-imidazoline-1-oxyl-3-oxide] was synthesized using a method in the literatrue (Ullman et al. 1970; Ullman et al. 1972). Mn (Ac)₂. 4H₂O(1 mmol) and NIT2-thz (2 mmol) were mixed in 30 ml of methanol. An aqueous solution (10 ml) of NaN₃ (2 mmol) was added to this solution. The mixture was stirred for an 1 h and filtered off. The filtrate was kept at room temperatrue for 1 meek, and well formed dark brown crstals of Mn(N₃)₂(NIT2-thz)₂ were obtained.

Refinement

The H atoms were positioned geometrically and refined using the riding-model approximation, with C—H = 0.93 or 0.96Å and U_iso(H) = 1.2Ueq(carrier) or U_iso(H) = 1.5Ueq(methyl carrier).

Figures

Fig. 1.

ORTEP drawing of the title compound with atom labeling. The thermal ellipsoids are drawn at 30% probability level.[symmetry codes: x,-y,-z + 1].

Crystal data

[Mn(N3)2(C10H14N3O2S)2]	F(000) = 642
Mr = 619.60	Dx = 1.526 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4318 reflections
a = 9.9600 (18) Å	θ = 2.5–28.2°
b = 12.272 (2) Å	µ = 0.70 mm−1
c = 11.353 (2) Å	T = 291 K
β = 103.714 (3)°	Block, dark brown
V = 1348.1 (4) Å3	0.45 × 0.30 × 0.25 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	3061 independent reflections
Radiation source: fine-focus sealed tube	2628 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.745, Tmax = 0.846	k = −15→15
7966 measured reflections	l = −12→14

Refinement

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0605P)2 + 0.2559P] where P = (Fo2 + 2Fc2)/3
3061 reflections	(Δ/σ)max < 0.001
182 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.25 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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon 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
Mn1	0.0000	0.0000	0.5000	0.03345 (14)
S1	0.25159 (5)	0.27889 (4)	0.36683 (5)	0.05049 (17)
O1	0.17034 (15)	−0.08711 (11)	0.44955 (14)	0.0504 (4)
O2	0.38630 (18)	0.14599 (13)	0.23568 (17)	0.0660 (5)
N1	0.12384 (15)	0.14413 (11)	0.47278 (13)	0.0337 (3)
N2	0.23912 (14)	−0.05108 (11)	0.37542 (13)	0.0336 (3)
N3	0.34509 (15)	0.05765 (13)	0.27421 (14)	0.0407 (4)
N4	−0.1080 (2)	0.00819 (18)	0.31193 (18)	0.0641 (6)
N5	−0.08511 (17)	0.04681 (12)	0.22465 (15)	0.0433 (4)
N6	−0.0640 (3)	0.08223 (18)	0.13715 (19)	0.0761 (7)
C1	0.1569 (2)	0.32772 (15)	0.4616 (2)	0.0495 (5)
H1	0.1479	0.4012	0.4782	0.059*
C2	0.0969 (2)	0.24624 (14)	0.50955 (17)	0.0412 (4)
H2	0.0413	0.2584	0.5635	0.049*
C3	0.20718 (16)	0.14870 (12)	0.39806 (15)	0.0318 (3)
C4	0.25886 (16)	0.05337 (13)	0.34979 (15)	0.0317 (3)
C5	0.40415 (19)	−0.05207 (16)	0.25646 (16)	0.0406 (4)
C6	0.30045 (18)	−0.12873 (14)	0.29998 (16)	0.0382 (4)
C7	0.4089 (3)	−0.0651 (2)	0.12397 (19)	0.0628 (6)
H7A	0.3179	−0.0551	0.0732	0.094*
H7B	0.4417	−0.1367	0.1114	0.094*
H7C	0.4702	−0.0116	0.1039	0.094*
C8	0.5497 (2)	−0.0545 (2)	0.3366 (2)	0.0601 (6)
H8A	0.6029	0.0037	0.3137	0.090*
H8B	0.5923	−0.1230	0.3269	0.090*
H8C	0.5461	−0.0455	0.4197	0.090*
C9	0.1798 (2)	−0.1673 (2)	0.1994 (2)	0.0595 (6)
H9A	0.1102	−0.1990	0.2346	0.089*
H9B	0.2118	−0.2208	0.1507	0.089*
H9C	0.1413	−0.1064	0.1496	0.089*
C10	0.3643 (3)	−0.22455 (19)	0.3780 (2)	0.0620 (6)
H10A	0.4243	−0.1981	0.4515	0.093*
H10B	0.4167	−0.2680	0.3345	0.093*
H10C	0.2925	−0.2682	0.3974	0.093*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Mn1	0.0362 (2)	0.0333 (2)	0.0373 (2)	−0.00148 (13)	0.02166 (16)	0.00206 (13)
S1	0.0483 (3)	0.0342 (2)	0.0743 (4)	−0.00716 (19)	0.0251 (3)	0.0074 (2)
O1	0.0597 (9)	0.0351 (6)	0.0717 (10)	0.0065 (6)	0.0459 (8)	0.0095 (6)
O2	0.0697 (10)	0.0592 (9)	0.0861 (12)	−0.0037 (8)	0.0525 (10)	0.0169 (8)
N1	0.0365 (7)	0.0299 (7)	0.0381 (7)	0.0019 (5)	0.0156 (6)	−0.0003 (5)
N2	0.0325 (7)	0.0336 (7)	0.0395 (8)	0.0037 (5)	0.0182 (6)	0.0003 (6)
N3	0.0371 (8)	0.0466 (8)	0.0452 (8)	0.0000 (6)	0.0230 (7)	0.0038 (7)
N4	0.0681 (13)	0.0827 (14)	0.0416 (10)	−0.0251 (10)	0.0134 (9)	0.0060 (9)
N5	0.0497 (9)	0.0360 (8)	0.0453 (9)	−0.0042 (6)	0.0138 (7)	0.0000 (7)
N6	0.121 (2)	0.0587 (12)	0.0582 (12)	−0.0128 (12)	0.0400 (13)	0.0104 (10)
C1	0.0490 (11)	0.0305 (8)	0.0668 (13)	0.0003 (8)	0.0093 (10)	−0.0061 (8)
C2	0.0449 (10)	0.0352 (8)	0.0444 (10)	0.0065 (7)	0.0122 (8)	−0.0065 (7)
C3	0.0297 (8)	0.0302 (7)	0.0372 (8)	−0.0012 (6)	0.0113 (6)	0.0028 (6)
C4	0.0277 (8)	0.0361 (8)	0.0335 (8)	0.0006 (6)	0.0118 (6)	0.0029 (6)
C5	0.0346 (9)	0.0556 (11)	0.0361 (9)	0.0076 (7)	0.0170 (7)	−0.0030 (8)
C6	0.0369 (9)	0.0404 (9)	0.0402 (9)	0.0095 (7)	0.0151 (7)	−0.0048 (7)
C7	0.0640 (14)	0.0898 (17)	0.0422 (11)	0.0087 (12)	0.0277 (10)	−0.0064 (11)
C8	0.0358 (10)	0.0856 (16)	0.0599 (13)	0.0054 (10)	0.0133 (10)	−0.0127 (12)
C9	0.0569 (13)	0.0618 (13)	0.0587 (13)	−0.0084 (10)	0.0117 (11)	−0.0173 (10)
C10	0.0695 (15)	0.0542 (12)	0.0703 (15)	0.0292 (11)	0.0324 (13)	0.0111 (11)

Geometric parameters (Å, °)

Mn1—N4i	2.153 (2)	C2—H2	0.9300
Mn1—N4	2.153 (2)	C3—C4	1.438 (2)
Mn1—O1i	2.1931 (12)	C5—C8	1.518 (3)
Mn1—O1	2.1931 (12)	C5—C7	1.525 (3)
Mn1—N1	2.2194 (14)	C5—C6	1.561 (3)
Mn1—N1i	2.2194 (14)	C6—C10	1.518 (3)
S1—C1	1.699 (2)	C6—C9	1.524 (3)
S1—C3	1.7170 (16)	C7—H7A	0.9600
O1—N2	1.2832 (17)	C7—H7B	0.9600
O2—N3	1.273 (2)	C7—H7C	0.9600
N1—C3	1.321 (2)	C8—H8A	0.9600
N1—C2	1.367 (2)	C8—H8B	0.9600
N2—C4	1.339 (2)	C8—H8C	0.9600
N2—C6	1.504 (2)	C9—H9A	0.9600
N3—C4	1.3513 (19)	C9—H9B	0.9600
N3—C5	1.502 (2)	C9—H9C	0.9600
N4—N5	1.168 (2)	C10—H10A	0.9600
N5—N6	1.148 (2)	C10—H10B	0.9600
C1—C2	1.345 (3)	C10—H10C	0.9600
C1—H1	0.9300
N4i—Mn1—N4	180.0	N2—C4—C3	127.70 (14)
N4i—Mn1—O1i	89.95 (8)	N3—C4—C3	123.31 (15)
N4—Mn1—O1i	90.05 (8)	N3—C5—C8	106.60 (17)
N4i—Mn1—O1	90.05 (8)	N3—C5—C7	109.34 (17)
N4—Mn1—O1	89.95 (8)	C8—C5—C7	109.88 (17)
O1i—Mn1—O1	180.0	N3—C5—C6	100.84 (13)
N4i—Mn1—N1	90.68 (6)	C8—C5—C6	114.10 (17)
N4—Mn1—N1	89.32 (6)	C7—C5—C6	115.27 (18)
O1i—Mn1—N1	97.92 (5)	N2—C6—C10	109.20 (15)
O1—Mn1—N1	82.08 (5)	N2—C6—C9	105.59 (15)
N4i—Mn1—N1i	89.32 (6)	C10—C6—C9	110.10 (19)
N4—Mn1—N1i	90.68 (6)	N2—C6—C5	100.77 (13)
O1i—Mn1—N1i	82.08 (5)	C10—C6—C5	115.73 (16)
O1—Mn1—N1i	97.92 (5)	C9—C6—C5	114.43 (16)
N1—Mn1—N1i	180.0	C5—C7—H7A	109.5
C1—S1—C3	89.35 (9)	C5—C7—H7B	109.5
N2—O1—Mn1	124.73 (10)	H7A—C7—H7B	109.5
C3—N1—C2	110.83 (14)	C5—C7—H7C	109.5
C3—N1—Mn1	125.29 (11)	H7A—C7—H7C	109.5
C2—N1—Mn1	122.15 (11)	H7B—C7—H7C	109.5
O1—N2—C4	126.95 (13)	C5—C8—H8A	109.5
O1—N2—C6	120.47 (13)	C5—C8—H8B	109.5
C4—N2—C6	112.47 (13)	H8A—C8—H8B	109.5
O2—N3—C4	123.82 (15)	C5—C8—H8C	109.5
O2—N3—C5	123.29 (14)	H8A—C8—H8C	109.5
C4—N3—C5	112.24 (14)	H8B—C8—H8C	109.5
N5—N4—Mn1	135.07 (17)	C6—C9—H9A	109.5
N6—N5—N4	178.1 (2)	C6—C9—H9B	109.5
C2—C1—S1	111.16 (14)	H9A—C9—H9B	109.5
C2—C1—H1	124.4	C6—C9—H9C	109.5
S1—C1—H1	124.4	H9A—C9—H9C	109.5
C1—C2—N1	114.81 (16)	H9B—C9—H9C	109.5
C1—C2—H2	122.6	C6—C10—H10A	109.5
N1—C2—H2	122.6	C6—C10—H10B	109.5
N1—C3—C4	123.11 (14)	H10A—C10—H10B	109.5
N1—C3—S1	113.83 (12)	C6—C10—H10C	109.5
C4—C3—S1	123.04 (12)	H10A—C10—H10C	109.5
N2—C4—N3	108.87 (14)	H10B—C10—H10C	109.5
N4i—Mn1—O1—N2	−122.97 (15)	O1—N2—C4—N3	175.59 (17)
N4—Mn1—O1—N2	57.03 (15)	C6—N2—C4—N3	−8.19 (19)
O1i—Mn1—O1—N2	105 (8)	O1—N2—C4—C3	−0.6 (3)
N1—Mn1—O1—N2	−32.28 (14)	C6—N2—C4—C3	175.65 (17)
N1i—Mn1—O1—N2	147.72 (14)	O2—N3—C4—N2	−178.27 (17)
N4i—Mn1—N1—C3	118.52 (15)	C5—N3—C4—N2	−7.24 (19)
N4—Mn1—N1—C3	−61.48 (15)	O2—N3—C4—C3	−1.9 (3)
O1i—Mn1—N1—C3	−151.43 (14)	C5—N3—C4—C3	169.12 (16)
O1—Mn1—N1—C3	28.57 (14)	N1—C3—C4—N2	−3.7 (3)
N1i—Mn1—N1—C3	24.5 (17)	S1—C3—C4—N2	174.59 (14)
N4i—Mn1—N1—C2	−77.84 (15)	N1—C3—C4—N3	−179.39 (16)
N4—Mn1—N1—C2	102.16 (15)	S1—C3—C4—N3	−1.1 (2)
O1i—Mn1—N1—C2	12.20 (15)	O2—N3—C5—C8	70.0 (2)
O1—Mn1—N1—C2	−167.80 (15)	C4—N3—C5—C8	−101.13 (18)
N1i—Mn1—N1—C2	−171.9 (18)	O2—N3—C5—C7	−48.8 (2)
Mn1—O1—N2—C4	26.1 (2)	C4—N3—C5—C7	140.13 (18)
Mn1—O1—N2—C6	−149.81 (13)	O2—N3—C5—C6	−170.64 (18)
N4i—Mn1—N4—N5	−71 (2)	C4—N3—C5—C6	18.27 (18)
O1i—Mn1—N4—N5	118.9 (3)	O1—N2—C6—C10	−42.4 (2)
O1—Mn1—N4—N5	−61.1 (3)	C4—N2—C6—C10	141.14 (17)
N1—Mn1—N4—N5	21.0 (3)	O1—N2—C6—C9	76.0 (2)
N1i—Mn1—N4—N5	−159.0 (3)	C4—N2—C6—C9	−100.50 (18)
Mn1—N4—N5—N6	137 (8)	O1—N2—C6—C5	−164.65 (15)
C3—S1—C1—C2	−0.76 (16)	C4—N2—C6—C5	18.85 (18)
S1—C1—C2—N1	−0.1 (2)	N3—C5—C6—N2	−20.40 (16)
C3—N1—C2—C1	1.2 (2)	C8—C5—C6—N2	93.45 (18)
Mn1—N1—C2—C1	−164.58 (14)	C7—C5—C6—N2	−138.01 (17)
C2—N1—C3—C4	176.71 (16)	N3—C5—C6—C10	−138.01 (17)
Mn1—N1—C3—C4	−18.1 (2)	C8—C5—C6—C10	−24.2 (2)
C2—N1—C3—S1	−1.76 (19)	C7—C5—C6—C10	104.4 (2)
Mn1—N1—C3—S1	163.46 (8)	N3—C5—C6—C9	92.35 (18)
C1—S1—C3—N1	1.47 (15)	C8—C5—C6—C9	−153.79 (17)
C1—S1—C3—C4	−177.00 (16)	C7—C5—C6—C9	−25.3 (2)

Symmetry codes: (i) −x, −y, −z+1.