Diazido-bis-[4,4,5,5-tetra-methyl-2-(1,3-thia-zol-2-yl)-2-imidazoline-1-oxyl 3-oxide-κN,O]nickel(II).

In the title compound, [Ni(N(3))(2)(C(10)H(14)N(3)O(2)S)(2)], the Ni(II) atom lies on an inversion center and adopts a distorted trans-NiO(2)N(4) octa-hedral geometry, coordinated by two N,O-bidentate 4,4,5,5-tetra-methyl-2-(5-methyl-imidazol-4-yl)-2-imidazoline-1-oxyl 3-oxide nitronyl nitroxide radical ligands and two monodentate azide anions.

Related literature

For general background to mol­ecular magnetic materials and metal-radical magnetic materials, see: Vostrikova et al. (2000 ▶); Fegy et al. (1998 ▶); Kahn et al. (2000 ▶); Omata et al. (2001 ▶); Yamamoto et al. (2001 ▶); Fursova et al. (2003 ▶); Sroh et al. (2003 ▶); Chang et al. (2009 ▶); Schatzschneider et al. (2001 ▶). For the synthesis of nitronyl nitroxide radical ligands and the title compound, see: Ullman et al. (1970 ▶, 1972 ▶).

Experimental

Crystal data

[Ni(N3)2(C10H14N3O2S)2]

M = 623.37

Monoclinic,

a = 9.9212 (7) Å

b = 12.1732 (8) Å

c = 11.1795 (8) Å

β = 102.695 (1)°

V = 1317.17 (16) Å3

Z = 2

Mo Kα radiation

μ = 0.95 mm−1

T = 291 K

0.40 × 0.22 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.703, T max = 0.874

7812 measured reflections

3005 independent reflections

2834 reflections with I > 2σ(I)

R int = 0.010

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.065

S = 1.06

3005 reflections

182 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.27 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, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810042455/sj5040sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042455/sj5040Isup2.hkl

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

[Ni(N3)2(C10H14N3O2S)2]	F(000) = 648
Mr = 623.37	Dx = 1.572 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5712 reflections
a = 9.9212 (7) Å	θ = 2.7–29.3°
b = 12.1732 (8) Å	µ = 0.95 mm−1
c = 11.1795 (8) Å	T = 291 K
β = 102.695 (1)°	Block, dark purple
V = 1317.17 (16) Å3	0.40 × 0.22 × 0.15 mm
Z = 2

Bruker SMART APEX CCD diffractometer	3005 independent reflections
Radiation source: fine-focus sealed tube	2834 reflections with I > 2σ(I)
graphite	Rint = 0.010
φ and ω scans	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick , 1996)	h = −12→9
Tmin = 0.703, Tmax = 0.874	k = −14→15
7812 measured reflections	l = −14→13

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.065	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.031P)2 + 0.5195P] where P = (Fo2 + 2Fc2)/3
3005 reflections	(Δ/σ)max = 0.001
182 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.27 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 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 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
Ni1	0.5000	1.0000	0.5000	0.02603 (8)
S1	0.75033 (4)	1.27825 (3)	0.38125 (4)	0.04133 (11)
O1	0.64775 (12)	0.90740 (9)	0.43831 (12)	0.0486 (3)
O2	0.89398 (15)	1.14747 (11)	0.24875 (14)	0.0611 (4)
N1	0.60808 (11)	1.13921 (9)	0.47330 (10)	0.0272 (2)
N2	0.72751 (11)	0.94577 (9)	0.37164 (10)	0.0285 (2)
N3	0.84655 (12)	1.05745 (10)	0.28101 (11)	0.0360 (3)
N4	0.61887 (17)	0.99070 (14)	0.67735 (14)	0.0568 (4)
N5	0.58855 (14)	0.95757 (10)	0.76655 (12)	0.0380 (3)
N6	0.5618 (2)	0.92594 (14)	0.85593 (15)	0.0652 (5)
C1	0.64979 (16)	1.32436 (12)	0.47626 (15)	0.0391 (3)
H1	0.6423	1.3976	0.4976	0.047*
C2	0.58239 (15)	1.24038 (11)	0.51644 (13)	0.0329 (3)
H2A	0.5231	1.2506	0.5694	0.039*
C3	0.69761 (13)	1.14629 (10)	0.40176 (12)	0.0269 (2)
C4	0.75220 (13)	1.05162 (11)	0.35158 (12)	0.0273 (3)
C5	0.79699 (14)	0.86855 (11)	0.29890 (12)	0.0312 (3)
C6	0.90436 (14)	0.94677 (12)	0.25934 (13)	0.0337 (3)
C7	0.8572 (2)	0.77211 (15)	0.37997 (18)	0.0535 (5)
H7A	0.9144	0.7992	0.4548	0.080*
H7B	0.9117	0.7275	0.3378	0.080*
H7C	0.7834	0.7288	0.3984	0.080*
C8	0.68251 (19)	0.82790 (16)	0.19319 (16)	0.0524 (4)
H8A	0.6110	0.7937	0.2256	0.079*
H8B	0.7201	0.7755	0.1452	0.079*
H8C	0.6447	0.8890	0.1424	0.079*
C9	1.04886 (16)	0.94066 (17)	0.34192 (17)	0.0527 (4)
H9A	1.1050	0.9986	0.3207	0.079*
H9B	1.0898	0.8709	0.3310	0.079*
H9C	1.0427	0.9486	0.4260	0.079*
C10	0.9140 (2)	0.93844 (17)	0.12542 (15)	0.0534 (4)
H10A	0.8244	0.9506	0.0736	0.080*
H10B	0.9463	0.8666	0.1099	0.080*
H10C	0.9772	0.9929	0.1084	0.080*

	U11	U22	U33	U12	U13	U23
Ni1	0.02752 (13)	0.02314 (12)	0.03225 (13)	−0.00064 (8)	0.01700 (9)	0.00075 (8)
S1	0.0393 (2)	0.02794 (18)	0.0629 (2)	−0.00619 (14)	0.02443 (18)	0.00477 (16)
O1	0.0554 (7)	0.0281 (5)	0.0793 (8)	0.0016 (5)	0.0519 (6)	0.0040 (5)
O2	0.0673 (8)	0.0448 (7)	0.0892 (10)	−0.0049 (6)	0.0564 (8)	0.0112 (6)
N1	0.0276 (5)	0.0250 (5)	0.0319 (5)	0.0002 (4)	0.0125 (4)	0.0003 (4)
N2	0.0263 (5)	0.0278 (5)	0.0360 (6)	0.0008 (4)	0.0166 (4)	−0.0009 (4)
N3	0.0350 (6)	0.0362 (6)	0.0439 (6)	−0.0003 (5)	0.0238 (5)	0.0031 (5)
N4	0.0533 (9)	0.0743 (11)	0.0408 (8)	−0.0261 (8)	0.0058 (7)	0.0125 (7)
N5	0.0436 (7)	0.0299 (6)	0.0405 (7)	−0.0034 (5)	0.0091 (5)	0.0021 (5)
N6	0.1006 (14)	0.0528 (9)	0.0498 (9)	−0.0085 (9)	0.0332 (9)	0.0077 (7)
C1	0.0374 (7)	0.0253 (6)	0.0563 (9)	−0.0016 (5)	0.0136 (7)	−0.0045 (6)
C2	0.0341 (7)	0.0276 (6)	0.0392 (7)	0.0018 (5)	0.0128 (6)	−0.0042 (5)
C3	0.0244 (6)	0.0252 (6)	0.0326 (6)	−0.0015 (5)	0.0098 (5)	0.0023 (5)
C4	0.0242 (6)	0.0302 (6)	0.0300 (6)	−0.0003 (5)	0.0114 (5)	0.0021 (5)
C5	0.0307 (6)	0.0327 (7)	0.0337 (6)	0.0056 (5)	0.0145 (5)	−0.0028 (5)
C6	0.0293 (7)	0.0421 (8)	0.0339 (7)	0.0037 (6)	0.0159 (5)	−0.0027 (6)
C7	0.0550 (10)	0.0485 (10)	0.0647 (11)	0.0239 (8)	0.0300 (9)	0.0160 (8)
C8	0.0515 (10)	0.0551 (10)	0.0507 (9)	−0.0137 (8)	0.0115 (8)	−0.0167 (8)
C9	0.0299 (8)	0.0678 (12)	0.0603 (10)	0.0029 (7)	0.0095 (7)	−0.0120 (9)
C10	0.0586 (11)	0.0703 (12)	0.0397 (8)	0.0009 (9)	0.0288 (8)	−0.0049 (8)

Ni1—N1	2.0619 (11)	C2—H2A	0.9300
Ni1—N1i	2.0619 (11)	C3—C4	1.4387 (18)
Ni1—N4i	2.0753 (15)	C5—C7	1.523 (2)
Ni1—N4	2.0753 (15)	C5—C8	1.530 (2)
Ni1—O1	2.0831 (10)	C5—C6	1.563 (2)
Ni1—O1i	2.0832 (10)	C6—C10	1.5243 (19)
S1—C1	1.7040 (16)	C6—C9	1.527 (2)
S1—C3	1.7204 (13)	C7—H7A	0.9600
O1—N2	1.2880 (14)	C7—H7B	0.9600
O2—N3	1.2756 (17)	C7—H7C	0.9600
N1—C3	1.3222 (16)	C8—H8A	0.9600
N1—C2	1.3669 (17)	C8—H8B	0.9600
N2—C4	1.3398 (18)	C8—H8C	0.9600
N2—C5	1.5055 (16)	C9—H9A	0.9600
N3—C4	1.3520 (16)	C9—H9B	0.9600
N3—C6	1.5047 (19)	C9—H9C	0.9600
N4—N5	1.1745 (19)	C10—H10A	0.9600
N5—N6	1.1547 (19)	C10—H10B	0.9600
C1—C2	1.351 (2)	C10—H10C	0.9600
C1—H1	0.9300
N1—Ni1—N1i	180.00 (5)	N2—C4—C3	127.35 (11)
N1—Ni1—N4i	91.22 (5)	N3—C4—C3	123.63 (12)
N1i—Ni1—N4i	88.78 (5)	N2—C5—C7	109.04 (11)
N1—Ni1—N4	88.78 (5)	N2—C5—C8	105.60 (12)
N1i—Ni1—N4	91.22 (5)	C7—C5—C8	109.74 (15)
N4i—Ni1—N4	180.0	N2—C5—C6	101.18 (10)
N1—Ni1—O1	88.32 (4)	C7—C5—C6	115.82 (12)
N1i—Ni1—O1	91.68 (4)	C8—C5—C6	114.50 (12)
N4i—Ni1—O1	90.39 (7)	N3—C6—C10	109.03 (13)
N4—Ni1—O1	89.61 (7)	N3—C6—C9	106.66 (13)
N1—Ni1—O1i	91.68 (4)	C10—C6—C9	109.73 (13)
N1i—Ni1—O1i	88.32 (4)	N3—C6—C5	101.08 (10)
N4i—Ni1—O1i	89.61 (7)	C10—C6—C5	115.53 (13)
N4—Ni1—O1i	90.38 (7)	C9—C6—C5	114.01 (13)
O1—Ni1—O1i	180.0	C5—C7—H7A	109.5
C1—S1—C3	89.29 (7)	C5—C7—H7B	109.5
N2—O1—Ni1	124.18 (8)	H7A—C7—H7B	109.5
C3—N1—C2	110.91 (11)	C5—C7—H7C	109.5
C3—N1—Ni1	125.52 (9)	H7A—C7—H7C	109.5
C2—N1—Ni1	123.11 (9)	H7B—C7—H7C	109.5
O1—N2—C4	127.15 (11)	C5—C8—H8A	109.5
O1—N2—C5	119.91 (11)	C5—C8—H8B	109.5
C4—N2—C5	112.82 (10)	H8A—C8—H8B	109.5
O2—N3—C4	123.76 (12)	C5—C8—H8C	109.5
O2—N3—C6	123.12 (11)	H8A—C8—H8C	109.5
C4—N3—C6	112.60 (11)	H8B—C8—H8C	109.5
N5—N4—Ni1	129.20 (13)	C6—C9—H9A	109.5
N6—N5—N4	178.30 (19)	C6—C9—H9B	109.5
C2—C1—S1	110.99 (11)	H9A—C9—H9B	109.5
C2—C1—H1	124.5	C6—C9—H9C	109.5
S1—C1—H1	124.5	H9A—C9—H9C	109.5
C1—C2—N1	114.84 (12)	H9B—C9—H9C	109.5
C1—C2—H2A	122.6	C6—C10—H10A	109.5
N1—C2—H2A	122.6	C6—C10—H10B	109.5
N1—C3—C4	122.97 (11)	H10A—C10—H10B	109.5
N1—C3—S1	113.94 (10)	C6—C10—H10C	109.5
C4—C3—S1	122.99 (9)	H10A—C10—H10C	109.5
N2—C4—N3	108.88 (11)	H10B—C10—H10C	109.5
N1—Ni1—O1—N2	−21.29 (12)	O1—N2—C4—N3	177.25 (14)
N1i—Ni1—O1—N2	158.71 (12)	C5—N2—C4—N3	−6.89 (15)
N4i—Ni1—O1—N2	69.92 (13)	O1—N2—C4—C3	1.4 (2)
N4—Ni1—O1—N2	−110.08 (13)	C5—N2—C4—C3	177.22 (13)
O1i—Ni1—O1—N2	−114 (16)	O2—N3—C4—N2	−178.14 (14)
N1i—Ni1—N1—C3	177 (16)	C6—N3—C4—N2	−6.19 (16)
N4i—Ni1—N1—C3	−70.05 (12)	O2—N3—C4—C3	−2.1 (2)
N4—Ni1—N1—C3	109.95 (12)	C6—N3—C4—C3	169.88 (12)
O1—Ni1—N1—C3	20.30 (11)	N1—C3—C4—N2	−2.8 (2)
O1i—Ni1—N1—C3	−159.70 (11)	S1—C3—C4—N2	173.34 (11)
N1i—Ni1—N1—C2	−11 (16)	N1—C3—C4—N3	−178.16 (13)
N4i—Ni1—N1—C2	101.39 (12)	S1—C3—C4—N3	−1.98 (19)
N4—Ni1—N1—C2	−78.61 (12)	O1—N2—C5—C7	−45.32 (18)
O1—Ni1—N1—C2	−168.26 (11)	C4—N2—C5—C7	138.49 (14)
O1i—Ni1—N1—C2	11.74 (11)	O1—N2—C5—C8	72.54 (16)
Ni1—O1—N2—C4	15.2 (2)	C4—N2—C5—C8	−103.65 (14)
Ni1—O1—N2—C5	−160.42 (9)	O1—N2—C5—C6	−167.85 (12)
N1—Ni1—N4—N5	148.00 (19)	C4—N2—C5—C6	15.96 (14)
N1i—Ni1—N4—N5	−32.00 (19)	O2—N3—C6—C10	−50.34 (19)
N4i—Ni1—N4—N5	21 (16)	C4—N3—C6—C10	137.65 (14)
O1—Ni1—N4—N5	−123.68 (18)	O2—N3—C6—C9	68.08 (18)
O1i—Ni1—N4—N5	56.32 (18)	C4—N3—C6—C9	−103.93 (14)
Ni1—N4—N5—N6	−172 (100)	O2—N3—C6—C5	−172.49 (14)
C3—S1—C1—C2	−0.63 (12)	C4—N3—C6—C5	15.50 (15)
S1—C1—C2—N1	−0.18 (17)	N2—C5—C6—N3	−17.26 (12)
C3—N1—C2—C1	1.19 (18)	C7—C5—C6—N3	−134.97 (13)
Ni1—N1—C2—C1	−171.36 (10)	C8—C5—C6—N3	95.77 (14)
C2—N1—C3—C4	174.82 (12)	N2—C5—C6—C10	−134.76 (13)
Ni1—N1—C3—C4	−12.85 (18)	C7—C5—C6—C10	107.53 (16)
C2—N1—C3—S1	−1.67 (15)	C8—C5—C6—C10	−21.73 (19)
Ni1—N1—C3—S1	170.66 (6)	N2—C5—C6—C9	96.76 (13)
C1—S1—C3—N1	1.34 (11)	C7—C5—C6—C9	−20.95 (18)
C1—S1—C3—C4	−175.14 (12)	C8—C5—C6—C9	−150.21 (14)