Bis[μ(3)-N'-oxidopyridine-2-carbox-imidamidato(2-)]bis-[μ(2)-N'-oxido-pyridine-2-carboximidamidato(1-)]tetra-pyridine-tetra-nickel(II) dinitrate.

The title compound, [Ni(4)(C(6)H(5)N(3)O)(2)(C(6)H(6)N(3)O)(2)(C(5)H(5)N)(4)](NO(3))(2), is a tetra-nuclear nickel complex containing a single-decker cation, located on an inversion center. The two unique Ni(II) cations are N,N',N'',O-chelated by carbox-imid-amid-ate(2-) and carboximidamidate(1-) anions, forming a distorted four-coordinate planar structure, while the other two Ni(II) atoms are N,N',O,O'-chelated by the same bridging ligands and two pyridine mol-ecules, affording six-coordinated metals in an octa-hedral geometry. The cation is isostructural with the complex crystallized with perchlorate counter-ions in place of nitrate.

Related literature

For similar metal complexes, see: Kou et al. (2010 ▶); Papatriantafyllopoulou et al. (2008 ▶); Inglis et al. (2010 ▶); Deng & Ran (2011 ▶). For the synthesis of the ligand pyridine-2-amidoxine, see: Bernasek (1957 ▶).

Experimental

Crystal data

[Ni4(C6H5N3O)2(C6H6N3O)2(C5H5N)4](NO3)2

M = 1217.80

Triclinic,

a = 10.4356 (6) Å

b = 10.7190 (8) Å

c = 11.2908 (9) Å

α = 92.041 (6)°

β = 98.240 (5)°

γ = 100.870 (5)°

V = 1224.96 (15) Å3

Z = 1

Mo Kα radiation

μ = 1.59 mm−1

T = 293 K

0.40 × 0.38 × 0.35 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.569, T max = 0.606

9481 measured reflections

4286 independent reflections

3180 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.100

S = 1.03

4286 reflections

349 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.66 e Å−3

Δρmin = −0.52 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536811052524/bh2397sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052524/bh2397Isup2.hkl

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

[Ni4(C6H5N3O)2(C6H6N3O)2(C5H5N)4](NO3)2	Z = 1
Mr = 1217.80	F(000) = 624
Triclinic, P1	Dx = 1.651 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.4356 (6) Å	Cell parameters from 1738 reflections
b = 10.7190 (8) Å	θ = 3.1–21.8°
c = 11.2908 (9) Å	µ = 1.59 mm−1
α = 92.041 (6)°	T = 293 K
β = 98.240 (5)°	Block, brown
γ = 100.870 (5)°	0.40 × 0.38 × 0.35 mm
V = 1224.96 (15) Å3

Bruker SMART APEXII CCD area-detector diffractometer	4286 independent reflections
Radiation source: fine-focus sealed tube	3180 reflections with I > 2σ(I)
graphite	Rint = 0.039
φ and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −12→12
Tmin = 0.569, Tmax = 0.606	k = −12→11
9481 measured reflections	l = −9→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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.042P)2 + 0.4034P] where P = (Fo2 + 2Fc2)/3
4286 reflections	(Δ/σ)max = 0.001
349 parameters	Δρmax = 0.66 e Å−3
8 restraints	Δρmin = −0.52 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
Ni1	0.45373 (3)	0.49188 (3)	0.66926 (3)	0.03132 (8)
Ni2	0.37394 (3)	0.76610 (3)	0.59280 (3)	0.03324 (9)
N1	0.45234 (18)	0.33873 (19)	0.77743 (18)	0.0346 (5)
N2	0.50204 (18)	0.35800 (18)	0.55758 (17)	0.0323 (5)
N3	0.65769 (18)	0.5669 (2)	0.75316 (18)	0.0364 (6)
N4	0.24626 (18)	0.4257 (2)	0.61209 (18)	0.0371 (6)
N5	0.35016 (18)	0.70397 (19)	0.74148 (18)	0.0340 (5)
N6	0.2507 (2)	0.7224 (2)	0.9124 (2)	0.0510 (7)
H6B	0.2906 (19)	0.6662 (16)	0.941 (2)	0.061*
H6A	0.235 (2)	0.7699 (19)	0.9683 (17)	0.061*
N7	0.27188 (19)	0.88369 (19)	0.63555 (19)	0.0384 (6)
N8	0.4142 (2)	0.82419 (19)	0.44897 (19)	0.0419 (6)
H8	0.3973	0.8940	0.4213	0.050*
N9	0.2065 (2)	0.9041 (2)	0.1685 (2)	0.0626 (7)
O1	0.40271 (16)	0.60905 (16)	0.79192 (15)	0.0387 (5)
O2	0.45424 (15)	0.63556 (15)	0.55536 (14)	0.0346 (4)
O3	0.2335 (2)	0.9647 (2)	0.2650 (2)	0.0902 (8)
O4	0.1740 (3)	0.7894 (3)	0.1607 (3)	0.1234 (12)
O5	0.2296 (4)	0.9553 (3)	0.0776 (2)	0.1285 (11)
C1	0.4176 (3)	0.3303 (3)	0.8866 (2)	0.0477 (8)
H1	0.3974	0.4017	0.9234	0.057*
C2	0.4105 (3)	0.2203 (3)	0.9472 (3)	0.0562 (9)
H2	0.3853	0.2171	1.0229	0.067*
C3	0.4416 (3)	0.1151 (3)	0.8929 (3)	0.0532 (9)
H3	0.4352	0.0390	0.9307	0.064*
C4	0.4823 (2)	0.1235 (3)	0.7816 (2)	0.0410 (7)
H4	0.5067	0.0544	0.7447	0.049*
C5	0.4859 (2)	0.2373 (2)	0.7266 (2)	0.0332 (7)
C6	0.5271 (2)	0.2555 (2)	0.6071 (2)	0.0321 (6)
C7	0.7375 (2)	0.4927 (3)	0.8027 (3)	0.0480 (8)
H7	0.7126	0.4051	0.7865	0.058*
C8	0.8551 (3)	0.5403 (3)	0.8767 (3)	0.0612 (10)
H8A	0.9077	0.4856	0.9101	0.073*
C9	0.8934 (3)	0.6691 (3)	0.9002 (3)	0.0651 (11)
H9	0.9709	0.7033	0.9517	0.078*
C10	0.8154 (3)	0.7466 (3)	0.8465 (3)	0.0587 (10)
H10	0.8405	0.8347	0.8585	0.070*
C11	0.6988 (2)	0.6920 (3)	0.7743 (3)	0.0445 (8)
H11	0.6461	0.7455	0.7385	0.053*
C12	0.1604 (2)	0.4086 (3)	0.6893 (3)	0.0497 (8)
H12	0.1919	0.4291	0.7703	0.060*
C13	0.0283 (3)	0.3623 (3)	0.6558 (3)	0.0654 (10)
H13	−0.0283	0.3513	0.7128	0.079*
C14	−0.0189 (3)	0.3328 (3)	0.5370 (4)	0.0708 (11)
H14	−0.1084	0.3014	0.5114	0.085*
C15	0.0670 (3)	0.3500 (3)	0.4571 (3)	0.0664 (10)
H15	0.0371	0.3309	0.3757	0.080*
C16	0.1994 (3)	0.3960 (3)	0.4975 (3)	0.0503 (8)
H16	0.2577	0.4065	0.4419	0.060*
C17	0.2787 (2)	0.7604 (2)	0.8038 (2)	0.0374 (7)
C18	0.2286 (2)	0.8621 (2)	0.7436 (2)	0.0368 (7)
C19	0.1439 (2)	0.9336 (3)	0.7852 (3)	0.0529 (9)
H19	0.1137	0.9175	0.8577	0.063*
C20	0.1053 (3)	1.0286 (3)	0.7175 (3)	0.0617 (10)
H20	0.0498	1.0780	0.7446	0.074*
C21	0.1495 (3)	1.0495 (3)	0.6102 (3)	0.0585 (9)
H21	0.1239	1.1132	0.5639	0.070*
C22	0.2319 (3)	0.9763 (3)	0.5708 (3)	0.0488 (8)
H22	0.2608	0.9911	0.4975	0.059*

	U11	U22	U33	U12	U13	U23
Ni1	0.03287 (15)	0.03169 (17)	0.03126 (17)	0.01043 (13)	0.00592 (13)	0.00101 (13)
Ni2	0.03572 (15)	0.03221 (17)	0.03383 (17)	0.01353 (13)	0.00404 (14)	−0.00190 (14)
N1	0.0353 (10)	0.0386 (12)	0.0312 (11)	0.0102 (9)	0.0055 (9)	0.0022 (9)
N2	0.0389 (10)	0.0305 (11)	0.0292 (11)	0.0082 (9)	0.0091 (9)	0.0017 (9)
N3	0.0362 (10)	0.0368 (11)	0.0378 (12)	0.0088 (9)	0.0088 (9)	0.0010 (10)
N4	0.0353 (10)	0.0417 (12)	0.0359 (11)	0.0088 (9)	0.0094 (9)	0.0008 (10)
N5	0.0349 (10)	0.0352 (11)	0.0342 (11)	0.0131 (9)	0.0061 (9)	−0.0035 (9)
N6	0.0580 (12)	0.0633 (15)	0.0413 (13)	0.0282 (11)	0.0185 (11)	0.0009 (12)
N7	0.0382 (10)	0.0358 (11)	0.0401 (12)	0.0112 (9)	−0.0011 (10)	−0.0057 (10)
N8	0.0565 (12)	0.0310 (11)	0.0451 (13)	0.0210 (10)	0.0133 (10)	0.0057 (10)
N9	0.0837 (15)	0.0704 (16)	0.0504 (15)	0.0439 (13)	0.0246 (13)	0.0175 (13)
O1	0.0458 (9)	0.0395 (10)	0.0345 (9)	0.0176 (8)	0.0066 (8)	0.0013 (8)
O2	0.0448 (8)	0.0347 (9)	0.0299 (9)	0.0180 (7)	0.0107 (7)	0.0037 (7)
O3	0.1267 (16)	0.1144 (18)	0.0461 (13)	0.0744 (14)	0.0053 (13)	−0.0103 (13)
O4	0.151 (2)	0.079 (2)	0.138 (3)	−0.0138 (19)	0.064 (2)	0.0039 (19)
O5	0.243 (3)	0.0930 (18)	0.0743 (17)	0.0774 (19)	0.044 (2)	0.0252 (15)
C1	0.0498 (14)	0.0572 (18)	0.0381 (15)	0.0145 (13)	0.0081 (13)	0.0043 (14)
C2	0.0515 (15)	0.085 (2)	0.0355 (15)	0.0151 (16)	0.0099 (13)	0.0193 (15)
C3	0.0510 (15)	0.0552 (18)	0.0529 (17)	0.0102 (14)	0.0022 (14)	0.0224 (14)
C4	0.0394 (13)	0.0388 (15)	0.0435 (15)	0.0086 (12)	−0.0005 (12)	0.0071 (12)
C5	0.0303 (11)	0.0332 (13)	0.0347 (14)	0.0042 (10)	0.0028 (11)	0.0020 (11)
C6	0.0332 (11)	0.0274 (13)	0.0346 (13)	0.0061 (10)	0.0017 (11)	−0.0005 (11)
C7	0.0384 (13)	0.0400 (15)	0.0642 (19)	0.0097 (12)	0.0004 (14)	0.0037 (14)
C8	0.0447 (15)	0.0564 (18)	0.078 (2)	0.0122 (14)	−0.0111 (16)	0.0107 (17)
C9	0.0421 (15)	0.068 (2)	0.074 (2)	0.0004 (16)	−0.0103 (16)	−0.0087 (18)
C10	0.0466 (15)	0.0435 (17)	0.081 (2)	0.0018 (14)	0.0066 (16)	−0.0128 (16)
C11	0.0408 (13)	0.0436 (15)	0.0519 (17)	0.0136 (12)	0.0096 (13)	0.0020 (13)
C12	0.0398 (13)	0.0613 (18)	0.0474 (17)	0.0088 (13)	0.0082 (13)	−0.0031 (15)
C13	0.0443 (15)	0.060 (2)	0.096 (3)	0.0107 (14)	0.0270 (16)	−0.0007 (19)
C14	0.0370 (14)	0.0539 (19)	0.115 (3)	0.0073 (14)	−0.0030 (17)	−0.021 (2)
C15	0.0554 (17)	0.069 (2)	0.066 (2)	0.0117 (16)	−0.0144 (16)	−0.0184 (18)
C16	0.0502 (15)	0.0569 (18)	0.0431 (16)	0.0117 (14)	0.0049 (13)	−0.0024 (14)
C17	0.0351 (12)	0.0359 (14)	0.0399 (15)	0.0069 (11)	0.0032 (11)	−0.0039 (12)
C18	0.0296 (11)	0.0358 (14)	0.0429 (15)	0.0048 (11)	0.0025 (11)	−0.0080 (12)
C19	0.0429 (13)	0.0549 (17)	0.066 (2)	0.0190 (13)	0.0163 (14)	−0.0062 (15)
C20	0.0542 (15)	0.0575 (18)	0.083 (2)	0.0327 (14)	0.0162 (16)	−0.0032 (17)
C21	0.0596 (15)	0.0522 (17)	0.070 (2)	0.0339 (13)	0.0009 (16)	0.0024 (16)
C22	0.0548 (15)	0.0467 (16)	0.0481 (17)	0.0232 (13)	0.0015 (14)	0.0013 (14)

Ni1—O1	2.0295 (17)	C2—H2	0.9300
Ni1—O2	2.0410 (17)	C3—C4	1.383 (4)
Ni1—N2	2.057 (2)	C3—H3	0.9300
Ni1—N1	2.080 (2)	C4—C5	1.386 (4)
Ni1—N4	2.1435 (19)	C4—H4	0.9300
Ni1—N3	2.1900 (18)	C5—C6	1.481 (3)
Ni2—O2	1.8278 (17)	C6—N8i	1.333 (3)
Ni2—N8	1.836 (2)	C7—C8	1.381 (4)
Ni2—N5	1.860 (2)	C7—H7	0.9300
Ni2—N7	1.888 (2)	C8—C9	1.368 (4)
N1—C1	1.335 (3)	C8—H8A	0.9300
N1—C5	1.339 (3)	C9—C10	1.367 (4)
N2—C6	1.303 (3)	C9—H9	0.9300
N2—O2i	1.414 (3)	C10—C11	1.378 (4)
N3—C11	1.331 (3)	C10—H10	0.9300
N3—C7	1.336 (3)	C11—H11	0.9300
N4—C16	1.321 (3)	C12—C13	1.367 (4)
N4—C12	1.330 (3)	C12—H12	0.9300
N5—C17	1.306 (3)	C13—C14	1.366 (5)
N5—O1	1.350 (3)	C13—H13	0.9300
N6—C17	1.360 (3)	C14—C15	1.354 (5)
N6—H6B	0.843 (15)	C14—H14	0.9300
N6—H6A	0.851 (16)	C15—C16	1.380 (4)
N7—C22	1.347 (3)	C15—H15	0.9300
N7—C18	1.373 (3)	C16—H16	0.9300
N8—C6i	1.333 (3)	C17—C18	1.446 (4)
N8—H8	0.8600	C18—C19	1.391 (4)
N9—O4	1.209 (4)	C19—C20	1.381 (4)
N9—O5	1.214 (4)	C19—H19	0.9300
N9—O3	1.217 (3)	C20—C21	1.368 (5)
O2—N2i	1.414 (3)	C20—H20	0.9300
C1—C2	1.380 (4)	C21—C22	1.376 (4)
C1—H1	0.9300	C21—H21	0.9300
C2—C3	1.378 (4)	C22—H22	0.9300
O1—Ni1—O2	87.43 (7)	C2—C3—H3	120.2
O1—Ni1—N2	173.84 (8)	C4—C3—H3	120.2
O2—Ni1—N2	98.68 (7)	C3—C4—C5	118.3 (3)
O1—Ni1—N1	95.46 (8)	C3—C4—H4	120.8
O2—Ni1—N1	176.94 (7)	C5—C4—H4	120.8
N2—Ni1—N1	78.42 (8)	N1—C5—C4	122.4 (2)
O1—Ni1—N4	86.65 (7)	N1—C5—C6	115.2 (2)
O2—Ni1—N4	90.52 (7)	C4—C5—C6	122.4 (2)
N2—Ni1—N4	92.45 (8)	N2—C6—N8i	120.5 (2)
N1—Ni1—N4	88.65 (8)	N2—C6—C5	115.1 (2)
O1—Ni1—N3	85.71 (7)	N8i—C6—C5	124.5 (2)
O2—Ni1—N3	92.71 (7)	N3—C7—C8	123.0 (3)
N2—Ni1—N3	94.77 (8)	N3—C7—H7	118.5
N1—Ni1—N3	88.52 (7)	C8—C7—H7	118.5
N4—Ni1—N3	171.56 (8)	C9—C8—C7	119.1 (3)
O2—Ni2—N8	84.38 (8)	C9—C8—H8A	120.5
O2—Ni2—N5	91.50 (8)	C7—C8—H8A	120.5
N8—Ni2—N5	174.27 (9)	C10—C9—C8	118.7 (3)
O2—Ni2—N7	172.23 (8)	C10—C9—H9	120.7
N8—Ni2—N7	100.57 (9)	C8—C9—H9	120.7
N5—Ni2—N7	83.96 (9)	C9—C10—C11	118.9 (3)
C1—N1—C5	118.4 (2)	C9—C10—H10	120.6
C1—N1—Ni1	127.43 (19)	C11—C10—H10	120.6
C5—N1—Ni1	114.07 (16)	N3—C11—C10	123.4 (3)
C6—N2—O2i	109.62 (19)	N3—C11—H11	118.3
C6—N2—Ni1	115.76 (16)	C10—C11—H11	118.3
O2i—N2—Ni1	132.58 (14)	N4—C12—C13	123.4 (3)
C11—N3—C7	116.9 (2)	N4—C12—H12	118.3
C11—N3—Ni1	119.41 (17)	C13—C12—H12	118.3
C7—N3—Ni1	122.75 (16)	C14—C13—C12	118.7 (3)
C16—N4—C12	117.3 (2)	C14—C13—H13	120.7
C16—N4—Ni1	120.50 (18)	C12—C13—H13	120.7
C12—N4—Ni1	122.16 (16)	C15—C14—C13	118.7 (3)
C17—N5—O1	117.4 (2)	C15—C14—H14	120.7
C17—N5—Ni2	116.46 (18)	C13—C14—H14	120.7
O1—N5—Ni2	126.15 (15)	C14—C15—C16	119.5 (3)
C17—N6—H6B	115.2 (18)	C14—C15—H15	120.2
C17—N6—H6A	125.6 (16)	C16—C15—H15	120.2
H6B—N6—H6A	111 (2)	N4—C16—C15	122.4 (3)
C22—N7—C18	118.8 (2)	N4—C16—H16	118.8
C22—N7—Ni2	128.23 (19)	C15—C16—H16	118.8
C18—N7—Ni2	112.85 (17)	N5—C17—N6	122.5 (2)
C6i—N8—Ni2	111.45 (17)	N5—C17—C18	113.5 (2)
C6i—N8—H8	124.3	N6—C17—C18	123.9 (2)
Ni2—N8—H8	124.3	N7—C18—C19	120.8 (3)
O4—N9—O5	116.9 (3)	N7—C18—C17	113.1 (2)
O4—N9—O3	121.9 (3)	C19—C18—C17	126.1 (3)
O5—N9—O3	120.3 (3)	C20—C19—C18	119.3 (3)
N5—O1—Ni1	112.62 (13)	C20—C19—H19	120.4
N2i—O2—Ni2	114.03 (13)	C18—C19—H19	120.4
N2i—O2—Ni1	127.93 (13)	C21—C20—C19	119.4 (3)
Ni2—O2—Ni1	117.72 (8)	C21—C20—H20	120.3
N1—C1—C2	122.7 (3)	C19—C20—H20	120.3
N1—C1—H1	118.6	C20—C21—C22	120.0 (3)
C2—C1—H1	118.6	C20—C21—H21	120.0
C3—C2—C1	118.5 (3)	C22—C21—H21	120.0
C3—C2—H2	120.8	N7—C22—C21	121.8 (3)
C1—C2—H2	120.8	N7—C22—H22	119.1
C2—C3—C4	119.5 (3)	C21—C22—H22	119.1