Bis(nitrato-κO)bis­[4,4,5,5-tetra­methyl-2-(5-methyl-1H-imidazol-4-yl-κN3)-2-imidazoline-1-oxyl 3-oxide-κO]nickel(II)

Chang, J.L.; Gao, Z.Y.

doi:10.1107/S1600536811040402

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1506

doi:10.1107/S1600536811040402

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Bis(nitrato-κO)bis[4,4,5,5-tetramethyl-2-(5-methyl-1H-imidazol-4-yl-κN³)-2-imidazoline-1-oxyl 3-oxide-κO]nickel(II)

Jiu Li Chang ^a and Zhi Yong Gao ^a ^*

^aCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453002, People's Republic of China
^*Correspondence e-mail: gaozhy201@sohu.com

(Received 4 September 2011; accepted 30 September 2011; online 8 October 2011)

In the centrosymmetric mononuclear title complex, [Ni(NO₃)₂(C₁₁H₁₇N₄O₂)₂], the Ni^II atom displays a distorted octahedral coordination geometry and is six-coordinated by two N,O-bidentate nitronyl nitroxide radical ligands and two monodentate nitrate anions.

Related literature

For general background to molecular magnetic materials, see: Li et al. (2004 ); Wang et al. (2008 ); Yamamoto et al. (2001 ). For the synthesis, see: Ullman et al. (1970 , 1972 ). For the related isomorphous Co complex, see: Gao et al. (2010 ).

Experimental

Crystal data

[Ni(NO₃)₂(C₁₁H₁₇N₄O₂)₂]
M_r = 657.30
Monoclinic, P 2₁ /n
a = 7.8313 (5) Å
b = 10.7772 (8) Å
c = 17.3009 (12) Å
β = 101.464 (1)°
V = 1431.07 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 295 K
0.43 × 0.17 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.741, T_max = 0.939
12170 measured reflections
3280 independent reflections
2891 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.084
S = 1.03
3280 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.29 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811040402/bg2419sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040402/bg2419Isup2.hkl

checkCIF report

Comment top

The design and synthesis of molecular-based magnetic materials with ferromagnetic ordering is one of the focus in molecular materials research (Yamamoto et al., 2001). In the preparation of molecular magnetic materials,transition metal complexes with organic radical ligands have found widespread interest in recent years (Li et al., 2004; Gao et al., 2010; Wang et al., 2008). A wide variety of transition metal complexes have been prepared with nitronyl nitroxide radical ligands. In this contribution, we report the synthesis and crystal structure of the title Ni^II complex Ni(NO₃)₂(C₁₁H₁₇N₄O₂)₂ (I).

An ellipsoid plot of I is shown in Fig.1. The nickel(II) ion presents a distorted octahedral coordination environment, and it is coordinated by two monodentate nitrate anions and two chelating nitronyl nitroxide radicals which lead two six-membered rings.

The complex is very similar to a recently published one (Gao et al., 2010) where the nitrate anions in (I) are replaced by methanol molecules, and charge balance is achieved via two non bonded perchlorate counteranions.

Related literature top

For general background to molecular magnetic materials, see: Li et al. (2004); Wang et al. (2008); Yamamoto et al. (2001). For the synthesis, see: Ullman et al. (1970, 1972). For a related structure, see: Gao et al. (2010).

Experimental top

The nitronyl nitroxide radical, 4,4,5,5-tetramethyl-2-(5-methylimidazol-4-yl)-2-imidazoline-1-oxyl-3-oxide, was prepared according to the literature method (Ullman et al. 1970; Ullman et al. 1972). The title complex [Ni(NO₃)₂(C₁₁H₁₇N₄O₂)₂] was synthesized by adding Ni(NO₃)₂.6H₂O (0.25 mmol) to 25 ml of an ethanol solution containing the nitroxide radical ligands(0.50 mmol). The mixture was stirred for 3 h at room temperature and then filtered off. The blue filtrate was allowed to stand at room temperature and dark blue crystals suitable for X-ray analysis were obtained after two weeks.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker , 2002); data reduction: SAINT (Bruker , 2002); 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).

Figures top

Fig. 1. Ellipsoid plot of the title complex with atom labelling. Displacement ellipsoids are drawn at 50% probability level [symmetry code A:-x,-y + 2,-z].

Bis(nitrato-κO)bis[4,4,5,5-tetramethyl-2-(5-methyl-1H-imidazol- 4-yl-κN³)-2-imidazoline-1-oxyl 3-oxide-κO]nickel(II) top

Crystal data top

[Ni(NO₃)₂(C₁₁H₁₇N₄O₂)₂]	F(000) = 688
M_r = 657.30	D_x = 1.525 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4292 reflections
a = 7.8313 (5) Å	θ = 2.7–28.3°
b = 10.7772 (8) Å	µ = 0.75 mm⁻¹
c = 17.3009 (12) Å	T = 295 K
β = 101.464 (1)°	Block, dark blue
V = 1431.07 (17) Å³	0.43 × 0.17 × 0.09 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	3280 independent reflections
Radiation source: fine-focus sealed tube	2891 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→10
T_min = 0.741, T_max = 0.939	k = −13→14
12170 measured reflections	l = −22→22

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.047P)² + 0.4906P] where P = (F_o² + 2F_c²)/3
3280 reflections	(Δ/σ)_max < 0.001
201 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Ni(NO₃)₂(C₁₁H₁₇N₄O₂)₂]	V = 1431.07 (17) Å³
M_r = 657.30	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.8313 (5) Å	µ = 0.75 mm⁻¹
b = 10.7772 (8) Å	T = 295 K
c = 17.3009 (12) Å	0.43 × 0.17 × 0.09 mm
β = 101.464 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3280 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2891 reflections with I > 2σ(I)
T_min = 0.741, T_max = 0.939	R_int = 0.016
12170 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.03	Δρ_max = 0.54 e Å⁻³
3280 reflections	Δρ_min = −0.29 e Å⁻³
201 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Ni1	0.0000	1.0000	0.0000	0.02551 (9)
O1	0.00030 (13)	0.87872 (10)	0.09062 (7)	0.0356 (3)
O2	0.56556 (16)	0.72951 (13)	0.14208 (11)	0.0628 (4)
O3	−0.11891 (17)	1.14165 (13)	0.06167 (9)	0.0535 (4)
O4	0.0728 (2)	1.27774 (17)	0.11237 (13)	0.0793 (5)
O5	−0.1945 (2)	1.29491 (15)	0.12542 (11)	0.0695 (5)
N1	0.13496 (15)	0.80628 (12)	0.11228 (7)	0.0293 (3)
N2	0.40216 (17)	0.73607 (13)	0.13945 (9)	0.0389 (3)
N3	0.25299 (15)	1.03606 (12)	0.04597 (7)	0.0288 (3)
N4	0.50665 (16)	1.12494 (12)	0.08397 (8)	0.0341 (3)
H4D	0.5873	1.1801	0.0877	0.041*
N5	−0.07686 (18)	1.23919 (14)	0.10055 (9)	0.0409 (3)
C1	0.30161 (18)	0.83775 (14)	0.11699 (9)	0.0293 (3)
C2	0.1134 (2)	0.68040 (14)	0.14566 (10)	0.0335 (3)
C3	0.2948 (2)	0.62185 (15)	0.14399 (10)	0.0378 (4)
C4	0.0799 (3)	0.70293 (19)	0.22840 (12)	0.0527 (5)
H4A	−0.0233	0.7523	0.2252	0.079*
H4B	0.1775	0.7459	0.2593	0.079*
H4C	0.0644	0.6248	0.2528	0.079*
C5	−0.0410 (2)	0.61400 (18)	0.09556 (13)	0.0506 (5)
H5A	−0.1470	0.6545	0.1013	0.076*
H5B	−0.0432	0.5293	0.1125	0.076*
H5C	−0.0305	0.6162	0.0412	0.076*
C6	0.3723 (3)	0.5458 (2)	0.21666 (14)	0.0598 (6)
H6A	0.4829	0.5128	0.2109	0.090*
H6B	0.2949	0.4789	0.2224	0.090*
H6C	0.3880	0.5979	0.2626	0.090*
C7	0.3019 (3)	0.5479 (2)	0.06956 (14)	0.0571 (5)
H7A	0.4210	0.5298	0.0677	0.086*
H7B	0.2505	0.5957	0.0240	0.086*
H7C	0.2386	0.4717	0.0701	0.086*
C8	0.36190 (18)	0.95783 (14)	0.09802 (9)	0.0276 (3)
C9	0.52150 (19)	1.01413 (14)	0.12285 (9)	0.0299 (3)
C10	0.34633 (19)	1.13445 (15)	0.03893 (10)	0.0337 (3)
H10A	0.3070	1.2021	0.0070	0.040*
C11	0.6814 (2)	0.98292 (17)	0.18240 (11)	0.0404 (4)
H11C	0.7305	1.0575	0.2080	0.061*
H11D	0.7650	0.9439	0.1566	0.061*
H11A	0.6515	0.9273	0.2210	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01760 (14)	0.02601 (15)	0.03174 (15)	−0.00258 (9)	0.00206 (10)	0.00404 (10)
O1	0.0231 (5)	0.0370 (6)	0.0476 (6)	0.0047 (4)	0.0095 (5)	0.0158 (5)
O2	0.0250 (6)	0.0460 (8)	0.1147 (13)	0.0068 (5)	0.0077 (7)	0.0061 (8)
O3	0.0379 (7)	0.0565 (8)	0.0675 (9)	−0.0097 (6)	0.0138 (6)	−0.0187 (7)
O4	0.0414 (8)	0.0697 (11)	0.1226 (15)	−0.0215 (8)	0.0061 (9)	−0.0141 (10)
O5	0.0641 (10)	0.0521 (9)	0.0981 (13)	−0.0120 (7)	0.0301 (9)	−0.0232 (8)
N1	0.0246 (6)	0.0287 (6)	0.0341 (6)	0.0005 (5)	0.0043 (5)	0.0069 (5)
N2	0.0255 (6)	0.0314 (7)	0.0570 (9)	0.0015 (5)	0.0010 (6)	0.0022 (6)
N3	0.0213 (6)	0.0293 (6)	0.0349 (7)	−0.0026 (5)	0.0038 (5)	0.0022 (5)
N4	0.0240 (6)	0.0355 (7)	0.0426 (7)	−0.0093 (5)	0.0065 (5)	0.0005 (6)
N5	0.0339 (7)	0.0410 (8)	0.0465 (8)	−0.0070 (6)	0.0048 (6)	0.0088 (6)
C1	0.0228 (7)	0.0301 (7)	0.0335 (7)	−0.0003 (5)	0.0022 (5)	0.0008 (6)
C2	0.0318 (8)	0.0281 (7)	0.0389 (8)	−0.0039 (6)	0.0026 (6)	0.0081 (6)
C3	0.0334 (8)	0.0277 (7)	0.0481 (9)	0.0001 (6)	−0.0021 (7)	0.0029 (7)
C4	0.0653 (13)	0.0497 (11)	0.0470 (10)	0.0018 (9)	0.0204 (9)	0.0140 (8)
C5	0.0362 (9)	0.0387 (9)	0.0703 (13)	−0.0094 (7)	−0.0052 (8)	0.0032 (9)
C6	0.0520 (12)	0.0473 (11)	0.0704 (14)	0.0064 (9)	−0.0113 (10)	0.0195 (10)
C7	0.0538 (12)	0.0469 (11)	0.0690 (14)	0.0022 (9)	0.0082 (10)	−0.0133 (10)
C8	0.0219 (7)	0.0289 (7)	0.0319 (7)	0.0002 (5)	0.0048 (5)	−0.0008 (6)
C9	0.0226 (7)	0.0356 (8)	0.0320 (7)	−0.0013 (6)	0.0064 (6)	−0.0031 (6)
C10	0.0265 (7)	0.0334 (8)	0.0408 (8)	−0.0039 (6)	0.0060 (6)	0.0049 (6)
C11	0.0240 (8)	0.0500 (10)	0.0443 (9)	−0.0005 (7)	−0.0004 (7)	−0.0003 (7)

Geometric parameters (Å, º) top

Ni1—N3ⁱ	2.0206 (12)	C2—C4	1.525 (3)
Ni1—N3	2.0206 (12)	C2—C3	1.560 (2)
Ni1—O1ⁱ	2.0408 (10)	C3—C7	1.525 (3)
Ni1—O1	2.0408 (10)	C3—C6	1.522 (3)
Ni1—O3	2.1751 (13)	C4—H4A	0.9600
Ni1—O3ⁱ	2.1751 (13)	C4—H4B	0.9600
O1—N1	1.3057 (16)	C4—H4C	0.9600
O2—N2	1.2733 (18)	C5—H5A	0.9600
O3—N5	1.256 (2)	C5—H5B	0.9600
O4—N5	1.221 (2)	C5—H5C	0.9600
O5—N5	1.246 (2)	C6—H6A	0.9600
N1—C1	1.3351 (18)	C6—H6B	0.9600
N1—C2	1.4971 (19)	C6—H6C	0.9600
N2—C1	1.3603 (19)	C7—H7A	0.9600
N2—C3	1.501 (2)	C7—H7B	0.9600
N3—C10	1.3073 (19)	C7—H7C	0.9600
N3—C8	1.3942 (19)	C8—C9	1.379 (2)
N4—C10	1.344 (2)	C9—C11	1.493 (2)
N4—C9	1.364 (2)	C10—H10A	0.9300
N4—H4D	0.8600	C11—H11C	0.9600
C1—C8	1.438 (2)	C11—H11D	0.9600
C2—C5	1.520 (2)	C11—H11A	0.9600

N3ⁱ—Ni1—N3	180.0	C7—C3—C6	109.94 (17)
N3ⁱ—Ni1—O1ⁱ	88.25 (5)	N2—C3—C2	101.00 (12)
N3—Ni1—O1ⁱ	91.75 (5)	C7—C3—C2	114.39 (14)
N3ⁱ—Ni1—O1	91.75 (5)	C6—C3—C2	114.66 (16)
N3—Ni1—O1	88.25 (5)	C2—C4—H4A	109.5
O1ⁱ—Ni1—O1	180.00 (4)	C2—C4—H4B	109.5
N3ⁱ—Ni1—O3	81.15 (5)	H4A—C4—H4B	109.5
N3—Ni1—O3	98.85 (5)	C2—C4—H4C	109.5
O1ⁱ—Ni1—O3	89.55 (5)	H4A—C4—H4C	109.5
O1—Ni1—O3	90.45 (5)	H4B—C4—H4C	109.5
N3ⁱ—Ni1—O3ⁱ	98.85 (5)	C2—C5—H5A	109.5
N3—Ni1—O3ⁱ	81.15 (5)	C2—C5—H5B	109.5
O1ⁱ—Ni1—O3ⁱ	90.45 (5)	H5A—C5—H5B	109.5
O1—Ni1—O3ⁱ	89.55 (5)	C2—C5—H5C	109.5
O3—Ni1—O3ⁱ	180.00 (6)	H5A—C5—H5C	109.5
N1—O1—Ni1	118.74 (8)	H5B—C5—H5C	109.5
N5—O3—Ni1	139.27 (11)	C3—C6—H6A	109.5
O1—N1—C1	126.13 (13)	C3—C6—H6B	109.5
O1—N1—C2	120.40 (11)	H6A—C6—H6B	109.5
C1—N1—C2	112.98 (12)	C3—C6—H6C	109.5
O2—N2—C1	125.14 (14)	H6A—C6—H6C	109.5
O2—N2—C3	121.44 (13)	H6B—C6—H6C	109.5
C1—N2—C3	112.16 (12)	C3—C7—H7A	109.5
C10—N3—C8	105.61 (12)	C3—C7—H7B	109.5
C10—N3—Ni1	129.94 (11)	H7A—C7—H7B	109.5
C8—N3—Ni1	124.33 (10)	C3—C7—H7C	109.5
C10—N4—C9	109.33 (13)	H7A—C7—H7C	109.5
C10—N4—H4D	125.3	H7B—C7—H7C	109.5
C9—N4—H4D	125.3	C9—C8—N3	109.59 (13)
O4—N5—O5	121.93 (17)	C9—C8—C1	130.05 (14)
O4—N5—O3	120.99 (17)	N3—C8—C1	120.35 (13)
O5—N5—O3	117.07 (15)	N4—C9—C8	104.39 (13)
N1—C1—N2	108.43 (13)	N4—C9—C11	121.00 (14)
N1—C1—C8	125.18 (13)	C8—C9—C11	134.40 (15)
N2—C1—C8	126.34 (13)	N3—C10—N4	111.07 (14)
N1—C2—C5	110.16 (13)	N3—C10—H10A	124.5
N1—C2—C4	105.75 (14)	N4—C10—H10A	124.5
C5—C2—C4	110.14 (16)	C9—C11—H11C	109.5
N1—C2—C3	100.75 (12)	C9—C11—H11D	109.5
C5—C2—C3	115.06 (15)	H11C—C11—H11D	109.5
C4—C2—C3	114.15 (14)	C9—C11—H11A	109.5
N2—C3—C7	105.64 (15)	H11C—C11—H11A	109.5
N2—C3—C6	110.44 (15)	H11D—C11—H11A	109.5

Symmetry code: (i) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Ni(NO₃)₂(C₁₁H₁₇N₄O₂)₂]
M_r	657.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.8313 (5), 10.7772 (8), 17.3009 (12)
β (°)	101.464 (1)
V (Å³)	1431.07 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.43 × 0.17 × 0.09

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.741, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	12170, 3280, 2891
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.084, 1.03
No. of reflections	3280
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.29

Computer programs: SMART (Bruker, 2002), SAINT (Bruker , 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Acknowledgements

This work was supported by the Natural Science Foundation and Basic Research Program of Henan Province (No. 092300410195 and No. 092300410240).

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