Tetra-kis[3-(2-pyridylamino)pyridine-κN]nickel(II) diperchlorate ethanol disolvate.

In the title compound, [Ni(C(10)H(9)N(3))(4)](ClO(4))(2)·2C(2)H(5)OH, the metal centre exhibits a four-coordinated environment with four pyridine N atoms of the four different dipyridylamine ligands. A twofold rotation axis passes through the Ni atom. N-H⋯O and N-H⋯N hydrogen bonds are present in the crystal structure.

Related literature

For related literature, see: Moulton & Zaworotko (2001 ▶); Su et al. (2003 ▶); Zhou et al. (2006 ▶); Biradha et al. (1999 ▶); Gudbjartson et al. (1999 ▶).

Experimental

Crystal data

[Ni(C10H9N3)4](ClO4)2·2C2H6O

M = 1034.55

Monoclinic,

a = 27.767 (4) Å

b = 10.7067 (14) Å

c = 18.144 (2) Å

β = 115.891 (9)°

V = 4852.6 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.58 mm−1

T = 298 (2) K

0.32 × 0.22 × 0.17 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.836, T max = 0.908

11042 measured reflections

4315 independent reflections

2875 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.134

S = 1.08

4315 reflections

314 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536808006569/at2548sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006569/at2548Isup2.hkl

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

[Ni(C10H9N3)4](ClO4)2·2C2H6O	F000 = 2152
Mr = 1034.55	Dx = 1.416 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4315 reflections
a = 27.767 (4) Å	θ = 1.6–25.1º
b = 10.7067 (14) Å	µ = 0.58 mm−1
c = 18.144 (2) Å	T = 298 (2) K
β = 115.891 (9)º	Block, green
V = 4852.6 (11) Å3	0.32 × 0.22 × 0.17 mm
Z = 4

Bruker APEXII area-detector diffractometer	4315 independent reflections
Radiation source: fine-focus sealed tube	2875 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.044
T = 298(2) K	θmax = 25.1º
φ and ω scans	θmin = 1.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)	h = −33→33
Tmin = 0.836, Tmax = 0.908	k = −12→12
11042 measured reflections	l = −21→21

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H-atom parameters constrained
wR(F2) = 0.134	w = 1/[σ2(Fo2) + (0.0501P)2 + 1.1196P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.084
4315 reflections	Δρmax = 0.35 e Å−3
314 parameters	Δρmin = −0.36 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
Ni1	0.5000	0.23720 (5)	0.7500	0.0397 (2)
N1	0.54118 (10)	0.1032 (2)	0.72421 (16)	0.0455 (6)
N2	0.60983 (11)	−0.1938 (3)	0.80972 (17)	0.0586 (8)
H2	0.6337	−0.2349	0.8016	0.070*
N3	0.56191 (11)	−0.1786 (3)	0.88745 (18)	0.0577 (7)
N4	0.54239 (10)	0.3700 (2)	0.72509 (16)	0.0438 (6)
N5	0.68140 (10)	0.4606 (3)	0.79766 (17)	0.0550 (7)
H5B	0.6945	0.3923	0.8237	0.066*
N6	0.69860 (11)	0.6684 (3)	0.77848 (18)	0.0574 (7)
C1	0.56303 (12)	0.0085 (3)	0.77601 (19)	0.0456 (8)
H1	0.5621	0.0104	0.8267	0.055*
C2	0.58706 (13)	−0.0930 (3)	0.7574 (2)	0.0474 (8)
C3	0.58891 (14)	−0.0912 (3)	0.6822 (2)	0.0547 (9)
H3	0.6051	−0.1566	0.6677	0.066*
C4	0.56711 (14)	0.0061 (3)	0.6297 (2)	0.0565 (9)
H4	0.5684	0.0073	0.5794	0.068*
C5	0.54302 (13)	0.1029 (3)	0.6514 (2)	0.0515 (8)
H5	0.5279	0.1687	0.6152	0.062*
C6	0.59913 (15)	−0.2364 (3)	0.8729 (2)	0.0544 (9)
C7	0.62701 (16)	−0.3403 (4)	0.9173 (2)	0.0682 (11)
H7	0.6529	−0.3791	0.9058	0.082*
C8	0.61504 (17)	−0.3838 (4)	0.9787 (2)	0.0757 (11)
H8	0.6324	−0.4540	1.0089	0.091*
C9	0.57742 (17)	−0.3231 (4)	0.9951 (2)	0.0720 (11)
H9	0.5692	−0.3502	1.0369	0.086*
C10	0.55247 (15)	−0.2224 (4)	0.9489 (2)	0.0643 (10)
H10	0.5272	−0.1812	0.9606	0.077*
C11	0.59564 (12)	0.3773 (3)	0.76688 (19)	0.0437 (7)
H11	0.6127	0.3229	0.8106	0.052*
C12	0.62665 (12)	0.4614 (3)	0.74861 (19)	0.0426 (7)
C13	0.60115 (12)	0.5367 (3)	0.6812 (2)	0.0477 (8)
H13	0.6208	0.5904	0.6645	0.057*
C14	0.54629 (13)	0.5316 (3)	0.6387 (2)	0.0525 (8)
H14	0.5285	0.5841	0.5942	0.063*
C15	0.51777 (13)	0.4489 (3)	0.6622 (2)	0.0515 (8)
H15	0.4806	0.4475	0.6339	0.062*
C16	0.71742 (12)	0.5563 (3)	0.8097 (2)	0.0480 (8)
C17	0.77153 (13)	0.5330 (4)	0.8563 (2)	0.0653 (10)
H17	0.7835	0.4542	0.8784	0.078*
C18	0.80698 (16)	0.6289 (5)	0.8690 (3)	0.0827 (13)
H18	0.8434	0.6163	0.9007	0.099*
C19	0.78839 (18)	0.7437 (4)	0.8349 (3)	0.0815 (13)
H19	0.8118	0.8094	0.8415	0.098*
C20	0.73503 (16)	0.7584 (4)	0.7913 (3)	0.0701 (11)
H20	0.7226	0.8366	0.7686	0.084*
Cl1	0.39899 (4)	0.22782 (8)	0.51603 (5)	0.0580 (3)
O1	0.42456 (13)	0.2385 (3)	0.60132 (16)	0.0903 (10)
O2	0.43498 (15)	0.2706 (3)	0.4854 (2)	0.1180 (13)
O3	0.38628 (16)	0.1017 (3)	0.4956 (2)	0.1268 (14)
O4	0.35263 (17)	0.2973 (5)	0.4863 (4)	0.196 (2)
O5	0.7269 (3)	0.2376 (3)	0.8974 (3)	0.166 (2)
H5A	0.7075	0.2571	0.9190	0.249*
C21	0.7270 (3)	0.0252 (6)	0.9344 (4)	0.143 (2)
H21A	0.7532	0.0553	0.9863	0.215*
H21B	0.7396	−0.0506	0.9206	0.215*
H21C	0.6940	0.0094	0.9378	0.215*
C22	0.7186 (3)	0.1150 (6)	0.8741 (4)	0.151 (3)
H22A	0.7416	0.0948	0.8482	0.181*
H22B	0.6819	0.1068	0.8327	0.181*

	U11	U22	U33	U12	U13	U23
Ni1	0.0470 (3)	0.0271 (3)	0.0562 (4)	0.000	0.0329 (3)	0.000
N1	0.0539 (16)	0.0367 (15)	0.0564 (16)	0.0018 (12)	0.0340 (14)	0.0022 (13)
N2	0.070 (2)	0.0493 (17)	0.0644 (19)	0.0226 (15)	0.0365 (17)	0.0081 (15)
N3	0.0660 (19)	0.0489 (18)	0.0645 (19)	0.0046 (14)	0.0344 (17)	0.0068 (15)
N4	0.0470 (16)	0.0328 (14)	0.0556 (16)	0.0043 (12)	0.0261 (14)	0.0038 (13)
N5	0.0428 (16)	0.0420 (16)	0.071 (2)	0.0045 (12)	0.0166 (15)	0.0154 (14)
N6	0.0506 (17)	0.0438 (18)	0.073 (2)	−0.0016 (14)	0.0221 (16)	0.0044 (15)
C1	0.057 (2)	0.0342 (17)	0.0531 (19)	0.0017 (15)	0.0311 (17)	0.0019 (16)
C2	0.0508 (19)	0.0390 (18)	0.058 (2)	0.0035 (15)	0.0285 (17)	−0.0007 (16)
C3	0.065 (2)	0.046 (2)	0.064 (2)	0.0063 (17)	0.0384 (19)	−0.0056 (18)
C4	0.072 (2)	0.052 (2)	0.059 (2)	0.0061 (18)	0.041 (2)	0.0009 (18)
C5	0.063 (2)	0.046 (2)	0.058 (2)	0.0033 (16)	0.0376 (18)	0.0063 (17)
C6	0.061 (2)	0.044 (2)	0.054 (2)	0.0017 (17)	0.0212 (18)	−0.0013 (17)
C7	0.079 (3)	0.054 (2)	0.068 (3)	0.017 (2)	0.029 (2)	0.011 (2)
C8	0.086 (3)	0.056 (3)	0.065 (3)	0.003 (2)	0.014 (2)	0.012 (2)
C9	0.075 (3)	0.075 (3)	0.059 (2)	−0.012 (2)	0.023 (2)	0.014 (2)
C10	0.061 (2)	0.069 (3)	0.065 (2)	−0.0037 (19)	0.029 (2)	0.006 (2)
C11	0.045 (2)	0.0372 (18)	0.0494 (19)	0.0069 (14)	0.0213 (16)	0.0081 (15)
C12	0.0455 (18)	0.0325 (16)	0.0498 (18)	0.0019 (13)	0.0208 (16)	0.0001 (14)
C13	0.051 (2)	0.0383 (18)	0.054 (2)	−0.0073 (15)	0.0230 (17)	0.0052 (16)
C14	0.048 (2)	0.0414 (19)	0.057 (2)	−0.0002 (15)	0.0123 (17)	0.0124 (16)
C15	0.0446 (19)	0.0412 (19)	0.063 (2)	−0.0004 (15)	0.0184 (17)	0.0032 (17)
C16	0.0405 (18)	0.047 (2)	0.056 (2)	−0.0021 (15)	0.0204 (16)	−0.0038 (16)
C17	0.043 (2)	0.061 (2)	0.079 (3)	0.0068 (17)	0.0141 (19)	0.003 (2)
C18	0.043 (2)	0.095 (4)	0.101 (3)	−0.008 (2)	0.024 (2)	−0.006 (3)
C19	0.064 (3)	0.077 (3)	0.096 (3)	−0.026 (2)	0.029 (3)	−0.005 (3)
C20	0.067 (3)	0.054 (2)	0.078 (3)	−0.0135 (19)	0.022 (2)	0.006 (2)
Cl1	0.0655 (6)	0.0541 (6)	0.0529 (5)	−0.0062 (4)	0.0243 (5)	−0.0040 (4)
O1	0.104 (2)	0.120 (3)	0.0521 (16)	−0.0282 (18)	0.0392 (17)	−0.0173 (15)
O2	0.150 (3)	0.146 (3)	0.084 (2)	−0.053 (2)	0.076 (2)	0.000 (2)
O3	0.183 (4)	0.082 (2)	0.152 (3)	−0.060 (2)	0.106 (3)	−0.062 (2)
O4	0.095 (3)	0.162 (4)	0.274 (6)	0.057 (3)	0.026 (4)	0.053 (4)
O5	0.221 (6)	0.067 (2)	0.128 (4)	0.010 (3)	0.001 (3)	0.019 (2)
C21	0.189 (7)	0.092 (4)	0.147 (6)	−0.001 (4)	0.072 (5)	0.004 (4)
C22	0.187 (7)	0.080 (4)	0.129 (5)	−0.028 (4)	0.017 (5)	0.013 (4)

Ni1—N1i	2.013 (2)	C9—C10	1.356 (5)
Ni1—N1	2.013 (2)	C9—H9	0.9300
Ni1—N4	2.019 (2)	C10—H10	0.9300
Ni1—N4i	2.019 (2)	C11—C12	1.382 (4)
N1—C1	1.335 (4)	C11—H11	0.9300
N1—C5	1.344 (4)	C12—C13	1.375 (4)
N2—C6	1.382 (4)	C13—C14	1.375 (4)
N2—C2	1.393 (4)	C13—H13	0.9300
N2—H2	0.8600	C14—C15	1.373 (4)
N3—C6	1.326 (4)	C14—H14	0.9300
N3—C10	1.336 (4)	C15—H15	0.9300
N4—C11	1.337 (4)	C16—C17	1.388 (5)
N4—C15	1.342 (4)	C17—C18	1.371 (5)
N5—C16	1.381 (4)	C17—H17	0.9300
N5—C12	1.386 (4)	C18—C19	1.371 (6)
N5—H5B	0.8600	C18—H18	0.9300
N6—C16	1.332 (4)	C19—C20	1.350 (6)
N6—C20	1.342 (4)	C19—H19	0.9300
C1—C2	1.392 (4)	C20—H20	0.9300
C1—H1	0.9300	Cl1—O4	1.377 (4)
C2—C3	1.388 (4)	Cl1—O1	1.397 (3)
C3—C4	1.362 (5)	Cl1—O3	1.404 (3)
C3—H3	0.9300	Cl1—O2	1.415 (3)
C4—C5	1.381 (4)	O5—C22	1.368 (6)
C4—H4	0.9300	O5—H5A	0.8200
C5—H5	0.9300	C21—C22	1.397 (7)
C6—C7	1.394 (5)	C21—H21A	0.9600
C7—C8	1.376 (5)	C21—H21B	0.9600
C7—H7	0.9300	C21—H21C	0.9600
C8—C9	1.369 (5)	C22—H22A	0.9700
C8—H8	0.9300	C22—H22B	0.9700
N1i—Ni1—N1	89.08 (14)	N4—C11—C12	123.5 (3)
N1i—Ni1—N4	179.09 (11)	N4—C11—H11	118.2
N1—Ni1—N4	90.24 (10)	C12—C11—H11	118.2
N1i—Ni1—N4i	90.24 (10)	C13—C12—C11	117.5 (3)
N1—Ni1—N4i	179.09 (11)	C13—C12—N5	124.7 (3)
N4—Ni1—N4i	90.44 (13)	C11—C12—N5	117.7 (3)
C1—N1—C5	119.3 (3)	C12—C13—C14	119.3 (3)
C1—N1—Ni1	120.49 (19)	C12—C13—H13	120.4
C5—N1—Ni1	120.0 (2)	C14—C13—H13	120.4
C6—N2—C2	128.5 (3)	C15—C14—C13	120.0 (3)
C6—N2—H2	115.7	C15—C14—H14	120.0
C2—N2—H2	115.7	C13—C14—H14	120.0
C6—N3—C10	117.1 (3)	N4—C15—C14	121.4 (3)
C11—N4—C15	118.2 (3)	N4—C15—H15	119.3
C11—N4—Ni1	121.5 (2)	C14—C15—H15	119.3
C15—N4—Ni1	120.2 (2)	N6—C16—N5	118.6 (3)
C16—N5—C12	127.8 (3)	N6—C16—C17	122.7 (3)
C16—N5—H5B	116.1	N5—C16—C17	118.7 (3)
C12—N5—H5B	116.1	C18—C17—C16	118.4 (4)
C16—N6—C20	116.6 (3)	C18—C17—H17	120.8
N1—C1—C2	122.8 (3)	C16—C17—H17	120.8
N1—C1—H1	118.6	C17—C18—C19	119.6 (4)
C2—C1—H1	118.6	C17—C18—H18	120.2
C3—C2—C1	117.0 (3)	C19—C18—H18	120.2
C3—C2—N2	118.7 (3)	C20—C19—C18	118.0 (4)
C1—C2—N2	124.3 (3)	C20—C19—H19	121.0
C4—C3—C2	120.2 (3)	C18—C19—H19	121.0
C4—C3—H3	119.9	N6—C20—C19	124.7 (4)
C2—C3—H3	119.9	N6—C20—H20	117.7
C3—C4—C5	119.8 (3)	C19—C20—H20	117.7
C3—C4—H4	120.1	O4—Cl1—O1	109.0 (3)
C5—C4—H4	120.1	O4—Cl1—O3	109.4 (3)
N1—C5—C4	120.9 (3)	O1—Cl1—O3	108.6 (2)
N1—C5—H5	119.6	O4—Cl1—O2	111.8 (3)
C4—C5—H5	119.6	O1—Cl1—O2	107.7 (2)
N3—C6—N2	118.7 (3)	O3—Cl1—O2	110.3 (2)
N3—C6—C7	122.8 (3)	C22—O5—H5A	109.5
N2—C6—C7	118.5 (3)	C22—C21—H21A	109.5
C8—C7—C6	118.0 (4)	C22—C21—H21B	109.5
C8—C7—H7	121.0	H21A—C21—H21B	109.5
C6—C7—H7	121.0	C22—C21—H21C	109.5
C9—C8—C7	119.5 (4)	H21A—C21—H21C	109.5
C9—C8—H8	120.3	H21B—C21—H21C	109.5
C7—C8—H8	120.3	O5—C22—C21	118.1 (6)
C10—C9—C8	118.4 (4)	O5—C22—H22A	107.8
C10—C9—H9	120.8	C21—C22—H22A	107.8
C8—C9—H9	120.8	O5—C22—H22B	107.8
N3—C10—C9	124.2 (4)	C21—C22—H22B	107.8
N3—C10—H10	117.9	H22A—C22—H22B	107.1
C9—C10—H10	117.9
N1i—Ni1—N1—C1	−48.8 (2)	C6—C7—C8—C9	−1.2 (6)
N4—Ni1—N1—C1	130.6 (2)	C7—C8—C9—C10	1.0 (6)
N1i—Ni1—N1—C5	125.6 (3)	C6—N3—C10—C9	−1.8 (6)
N4—Ni1—N1—C5	−55.0 (3)	C8—C9—C10—N3	0.5 (6)
N1—Ni1—N4—C11	−59.8 (2)	C15—N4—C11—C12	−0.2 (4)
N4i—Ni1—N4—C11	120.8 (3)	Ni1—N4—C11—C12	175.7 (2)
N1—Ni1—N4—C15	116.0 (2)	N4—C11—C12—C13	−3.4 (4)
N4i—Ni1—N4—C15	−63.4 (2)	N4—C11—C12—N5	179.0 (3)
C5—N1—C1—C2	−1.2 (5)	C16—N5—C12—C13	25.5 (5)
Ni1—N1—C1—C2	173.2 (2)	C16—N5—C12—C11	−157.0 (3)
N1—C1—C2—C3	1.7 (5)	C11—C12—C13—C14	4.5 (4)
N1—C1—C2—N2	−179.5 (3)	N5—C12—C13—C14	−178.0 (3)
C6—N2—C2—C3	−157.8 (3)	C12—C13—C14—C15	−2.2 (5)
C6—N2—C2—C1	23.3 (6)	C11—N4—C15—C14	2.7 (4)
C1—C2—C3—C4	−0.9 (5)	Ni1—N4—C15—C14	−173.3 (2)
N2—C2—C3—C4	−179.9 (3)	C13—C14—C15—N4	−1.5 (5)
C2—C3—C4—C5	−0.2 (5)	C20—N6—C16—N5	−179.7 (3)
C1—N1—C5—C4	0.0 (5)	C20—N6—C16—C17	2.8 (5)
Ni1—N1—C5—C4	−174.4 (2)	C12—N5—C16—N6	7.6 (5)
C3—C4—C5—N1	0.6 (5)	C12—N5—C16—C17	−174.8 (3)
C10—N3—C6—N2	179.8 (3)	N6—C16—C17—C18	−1.5 (5)
C10—N3—C6—C7	1.5 (5)	N5—C16—C17—C18	−179.0 (3)
C2—N2—C6—N3	1.4 (6)	C16—C17—C18—C19	−0.9 (6)
C2—N2—C6—C7	179.8 (3)	C17—C18—C19—C20	1.8 (7)
N3—C6—C7—C8	−0.1 (6)	C16—N6—C20—C19	−1.9 (6)
N2—C6—C7—C8	−178.4 (3)	C18—C19—C20—N6	−0.4 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5B···O5	0.86	2.07	2.928 (5)	174
N2—H2···N6ii	0.86	2.27	3.129 (4)	176

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5B⋯O5	0.86	2.07	2.928 (5)	174
N2—H2⋯N6i	0.86	2.27	3.129 (4)	176

Symmetry code: (i) .