Bis(tri-2-pyridyl-amine)-nickel(II) bis-(perchlorate).

In the title compound, [Ni(C(15)H(12)N(4))(2)](ClO(4))(2), the Ni(II) atom lies on an inversion center and is octa-hedrally coordinated by the N atoms of two tridentate tri-2-pyridyl-amine ligands. The two perchlorate anions are disordered over two sites with a refined occupancy ratio of 0.528 (19):0.472 (19).

Related literature

For background to luminescent coordination compounds, see: Liu et al. (1997 ▶). For related complexes, including the synthesis of 2,2′,2′′-tpa (tpa is tri-2-pyridylamine), see: Yang et al. (1999 ▶). For information on the use of 2,2′,2′′-tpa as a bidentate ligand, see: Wang et al. (2009 ▶).

Experimental

Crystal data

[Ni(C15H12N4)2](ClO4)2

M = 754.18

Monoclinic,

a = 8.360 (4) Å

b = 17.570 (8) Å

c = 11.165 (5) Å

β = 99.542 (5)°

V = 1617.3 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.83 mm−1

T = 296 K

0.22 × 0.15 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.861, T max = 0.920

14055 measured reflections

3895 independent reflections

2611 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.096

S = 1.03

3895 reflections

269 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810051627/nk2079sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051627/nk2079Isup2.hkl

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

[Ni(C15H12N4)2](ClO4)2	F(000) = 772
Mr = 754.18	Dx = 1.549 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7662 reflections
a = 8.360 (4) Å	θ = 2.2–27.9°
b = 17.570 (8) Å	µ = 0.83 mm−1
c = 11.165 (5) Å	T = 296 K
β = 99.542 (5)°	Block, purple
V = 1617.3 (13) Å3	0.22 × 0.15 × 0.10 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	3895 independent reflections
Radiation source: fine-focus sealed tube	2611 reflections with I > 2σ(I)
graphite	Rint = 0.040
Detector resolution: 8.366 pixels mm-1	θmax = 28.4°, θmin = 2.3°
phi and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −23→23
Tmin = 0.861, Tmax = 0.920	l = −14→14
14055 measured reflections

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) = 0.096	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0415P)2 + 0.1545P] where P = (Fo2 + 2Fc2)/3
3895 reflections	(Δ/σ)max = 0.001
269 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

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 > 2sigma(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	Occ. (<1)
Ni1	0.0000	0.0000	0.0000	0.03843 (14)
N1	0.1260 (2)	−0.05805 (10)	−0.21770 (15)	0.0415 (4)
N2	0.1529 (2)	−0.09211 (10)	−0.00942 (15)	0.0425 (4)
N3	−0.1341 (2)	−0.04164 (10)	−0.16286 (16)	0.0425 (5)
N4	0.1399 (2)	0.05822 (10)	−0.10841 (16)	0.0428 (4)
C1	0.1923 (3)	−0.10685 (12)	−0.11845 (19)	0.0398 (5)
C2	0.2910 (3)	−0.16666 (13)	−0.1379 (2)	0.0491 (6)
H2	0.3180	−0.1751	−0.2143	0.059*
C3	0.3487 (3)	−0.21360 (14)	−0.0420 (2)	0.0588 (7)
H3	0.4148	−0.2548	−0.0528	0.071*
C4	0.3080 (3)	−0.19915 (13)	0.0696 (2)	0.0546 (6)
H4	0.3456	−0.2305	0.1354	0.066*
C5	0.2114 (3)	−0.13810 (13)	0.0829 (2)	0.0496 (6)
H5	0.1852	−0.1281	0.1591	0.060*
C6	−0.0476 (3)	−0.06409 (12)	−0.24704 (19)	0.0414 (5)
C7	−0.1176 (3)	−0.09311 (14)	−0.3578 (2)	0.0547 (6)
H7	−0.0542	−0.1076	−0.4150	0.066*
C8	−0.2834 (4)	−0.10013 (15)	−0.3818 (2)	0.0647 (7)
H8	−0.3339	−0.1197	−0.4559	0.078*
C9	−0.3738 (3)	−0.07818 (14)	−0.2965 (2)	0.0577 (7)
H9	−0.4861	−0.0832	−0.3110	0.069*
C10	−0.2954 (3)	−0.04864 (14)	−0.1890 (2)	0.0533 (6)
H10	−0.3572	−0.0327	−0.1317	0.064*
C11	0.1900 (3)	0.13045 (13)	−0.0929 (2)	0.0492 (6)
H11	0.1612	0.1583	−0.0290	0.059*
C12	0.2822 (3)	0.16462 (14)	−0.1682 (2)	0.0575 (7)
H12	0.3156	0.2149	−0.1552	0.069*
C13	0.3246 (3)	0.12403 (16)	−0.2624 (2)	0.0627 (7)
H13	0.3886	0.1461	−0.3136	0.075*
C14	0.2716 (3)	0.05020 (14)	−0.2809 (2)	0.0527 (6)
H14	0.2970	0.0219	−0.3456	0.063*
C15	0.1808 (3)	0.01931 (12)	−0.20188 (19)	0.0402 (5)
Cl1	0.2377 (6)	0.3455 (4)	0.0694 (3)	0.0463 (11)	0.472 (19)
O1	0.1538 (19)	0.3916 (9)	0.1111 (12)	0.128 (5)	0.472 (19)
O2	0.224 (3)	0.2727 (6)	0.1240 (8)	0.153 (7)	0.472 (19)
O3	0.3932 (15)	0.3751 (8)	0.1296 (13)	0.129 (4)	0.472 (19)
O4	0.214 (2)	0.3370 (9)	−0.0534 (9)	0.140 (6)	0.472 (19)
Cl1'	0.2323 (10)	0.3362 (6)	0.0668 (6)	0.095 (2)	0.528 (19)
O1'	0.1418 (16)	0.4114 (7)	0.0767 (15)	0.133 (5)	0.528 (19)
O2'	0.1138 (18)	0.2869 (8)	0.0907 (17)	0.169 (5)	0.528 (19)
O3'	0.3760 (15)	0.3273 (15)	0.1348 (13)	0.205 (9)	0.528 (19)
O4'	0.2693 (18)	0.3279 (7)	−0.0504 (11)	0.109 (4)	0.528 (19)

	U11	U22	U33	U12	U13	U23
Ni1	0.0488 (3)	0.0391 (2)	0.0291 (2)	0.00336 (19)	0.01177 (17)	−0.00443 (17)
N1	0.0529 (12)	0.0401 (10)	0.0331 (10)	0.0029 (9)	0.0114 (9)	−0.0027 (8)
N2	0.0543 (12)	0.0416 (10)	0.0319 (10)	0.0059 (9)	0.0082 (8)	−0.0038 (8)
N3	0.0476 (12)	0.0456 (11)	0.0343 (10)	0.0033 (9)	0.0069 (9)	−0.0043 (8)
N4	0.0525 (12)	0.0421 (10)	0.0355 (10)	−0.0008 (9)	0.0125 (9)	−0.0026 (8)
C1	0.0457 (13)	0.0387 (12)	0.0355 (11)	0.0002 (10)	0.0079 (10)	−0.0066 (9)
C2	0.0524 (15)	0.0475 (13)	0.0496 (14)	0.0036 (11)	0.0149 (12)	−0.0110 (11)
C3	0.0608 (17)	0.0466 (14)	0.0683 (17)	0.0154 (12)	0.0091 (14)	−0.0037 (13)
C4	0.0587 (16)	0.0474 (14)	0.0553 (15)	0.0077 (12)	0.0022 (13)	0.0065 (12)
C5	0.0603 (16)	0.0517 (14)	0.0369 (13)	0.0048 (12)	0.0080 (11)	0.0005 (11)
C6	0.0542 (15)	0.0386 (12)	0.0321 (11)	0.0019 (10)	0.0092 (10)	−0.0034 (9)
C7	0.0695 (18)	0.0591 (15)	0.0352 (13)	0.0035 (13)	0.0073 (12)	−0.0110 (11)
C8	0.075 (2)	0.0696 (18)	0.0440 (15)	−0.0041 (15)	−0.0063 (14)	−0.0125 (13)
C9	0.0534 (16)	0.0610 (16)	0.0549 (16)	−0.0016 (13)	−0.0021 (13)	−0.0030 (13)
C10	0.0530 (16)	0.0580 (15)	0.0489 (14)	0.0027 (12)	0.0082 (12)	−0.0058 (12)
C11	0.0578 (16)	0.0439 (13)	0.0462 (14)	−0.0016 (11)	0.0095 (12)	−0.0046 (11)
C12	0.0610 (17)	0.0502 (14)	0.0608 (17)	−0.0084 (13)	0.0091 (13)	0.0075 (13)
C13	0.0621 (17)	0.0682 (18)	0.0627 (17)	−0.0046 (14)	0.0242 (14)	0.0156 (14)
C14	0.0595 (16)	0.0600 (16)	0.0426 (14)	0.0065 (13)	0.0199 (12)	0.0062 (11)
C15	0.0434 (13)	0.0465 (13)	0.0317 (11)	0.0049 (10)	0.0095 (10)	0.0010 (9)
Cl1	0.046 (2)	0.072 (2)	0.0231 (16)	0.0105 (14)	0.0106 (12)	−0.0077 (12)
O1	0.158 (8)	0.140 (10)	0.099 (5)	0.080 (7)	0.058 (6)	0.001 (6)
O2	0.31 (2)	0.084 (6)	0.070 (5)	−0.006 (9)	0.037 (8)	0.018 (4)
O3	0.095 (6)	0.186 (10)	0.100 (6)	−0.052 (7)	0.000 (4)	−0.031 (6)
O4	0.195 (12)	0.199 (9)	0.023 (4)	0.091 (8)	0.013 (5)	−0.005 (4)
Cl1'	0.109 (4)	0.101 (3)	0.075 (3)	0.037 (3)	0.014 (3)	−0.020 (2)
O1'	0.107 (5)	0.070 (5)	0.211 (13)	0.027 (4)	−0.004 (6)	−0.036 (6)
O2'	0.169 (9)	0.122 (7)	0.251 (13)	0.007 (7)	0.139 (9)	0.013 (7)
O3'	0.086 (8)	0.36 (3)	0.148 (8)	0.120 (11)	−0.033 (7)	−0.089 (13)
O4'	0.144 (8)	0.120 (6)	0.080 (6)	−0.018 (6)	0.068 (6)	−0.032 (4)

Ni1—N2	2.0755 (19)	C7—C8	1.373 (4)
Ni1—N2i	2.0755 (19)	C7—H7	0.9300
Ni1—N4	2.0851 (18)	C8—C9	1.367 (4)
Ni1—N4i	2.0851 (18)	C8—H8	0.9300
Ni1—N3i	2.1029 (19)	C9—C10	1.370 (3)
Ni1—N3	2.1029 (19)	C9—H9	0.9300
N1—C15	1.436 (3)	C10—H10	0.9300
N1—C1	1.437 (3)	C11—C12	1.370 (3)
N1—C6	1.438 (3)	C11—H11	0.9300
N2—C5	1.337 (3)	C12—C13	1.366 (4)
N2—C1	1.338 (3)	C12—H12	0.9300
N3—C6	1.337 (3)	C13—C14	1.375 (3)
N3—C10	1.337 (3)	C13—H13	0.9300
N4—C15	1.339 (3)	C14—C15	1.368 (3)
N4—C11	1.339 (3)	C14—H14	0.9300
C1—C2	1.375 (3)	Cl1—O1	1.212 (13)
C2—C3	1.374 (3)	Cl1—O4	1.361 (11)
C2—H2	0.9300	Cl1—O2	1.430 (13)
C3—C4	1.369 (3)	Cl1—O3	1.457 (12)
C3—H3	0.9300	Cl1'—O3'	1.320 (11)
C4—C5	1.366 (3)	Cl1'—O2'	1.375 (14)
C4—H4	0.9300	Cl1'—O4'	1.401 (11)
C5—H5	0.9300	Cl1'—O1'	1.537 (15)
C6—C7	1.375 (3)
N2—Ni1—N2i	180.0	N3—C6—C7	122.9 (2)
N2—Ni1—N4	86.78 (7)	N3—C6—N1	117.46 (18)
N2i—Ni1—N4	93.22 (7)	C7—C6—N1	119.7 (2)
N2—Ni1—N4i	93.22 (7)	C8—C7—C6	118.3 (2)
N2i—Ni1—N4i	86.78 (7)	C8—C7—H7	120.9
N4—Ni1—N4i	180.0	C6—C7—H7	120.9
N2—Ni1—N3i	94.05 (7)	C9—C8—C7	119.7 (2)
N2i—Ni1—N3i	85.95 (7)	C9—C8—H8	120.1
N4—Ni1—N3i	93.52 (8)	C7—C8—H8	120.1
N4i—Ni1—N3i	86.48 (8)	C8—C9—C10	118.5 (3)
N2—Ni1—N3	85.95 (7)	C8—C9—H9	120.7
N2i—Ni1—N3	94.05 (7)	C10—C9—H9	120.7
N4—Ni1—N3	86.48 (8)	N3—C10—C9	123.0 (2)
N4i—Ni1—N3	93.52 (8)	N3—C10—H10	118.5
N3i—Ni1—N3	180.0	C9—C10—H10	118.5
C15—N1—C1	113.30 (17)	N4—C11—C12	122.2 (2)
C15—N1—C6	112.77 (17)	N4—C11—H11	118.9
C1—N1—C6	112.15 (17)	C12—C11—H11	118.9
C5—N2—C1	118.06 (19)	C13—C12—C11	119.2 (2)
C5—N2—Ni1	125.59 (15)	C13—C12—H12	120.4
C1—N2—Ni1	116.34 (14)	C11—C12—H12	120.4
C6—N3—C10	117.54 (19)	C12—C13—C14	119.3 (2)
C6—N3—Ni1	115.96 (15)	C12—C13—H13	120.3
C10—N3—Ni1	126.49 (15)	C14—C13—H13	120.3
C15—N4—C11	118.01 (19)	C15—C14—C13	118.5 (2)
C15—N4—Ni1	116.26 (15)	C15—C14—H14	120.8
C11—N4—Ni1	125.72 (15)	C13—C14—H14	120.8
N2—C1—C2	122.4 (2)	N4—C15—C14	122.8 (2)
N2—C1—N1	117.66 (18)	N4—C15—N1	117.50 (18)
C2—C1—N1	119.90 (19)	C14—C15—N1	119.74 (19)
C3—C2—C1	118.5 (2)	O1—Cl1—O4	117.6 (10)
C3—C2—H2	120.7	O1—Cl1—O2	109.8 (9)
C1—C2—H2	120.7	O4—Cl1—O2	108.8 (9)
C4—C3—C2	119.3 (2)	O1—Cl1—O3	96.5 (10)
C4—C3—H3	120.3	O4—Cl1—O3	118.3 (10)
C2—C3—H3	120.3	O2—Cl1—O3	104.7 (9)
C5—C4—C3	119.0 (2)	O3'—Cl1'—O2'	115.5 (11)
C5—C4—H4	120.5	O3'—Cl1'—O4'	101.8 (10)
C3—C4—H4	120.5	O2'—Cl1'—O4'	113.2 (9)
N2—C5—C4	122.6 (2)	O3'—Cl1'—O1'	118.1 (12)
N2—C5—H5	118.7	O2'—Cl1'—O1'	98.6 (8)
C4—C5—H5	118.7	O4'—Cl1'—O1'	110.1 (9)
N4—Ni1—N2—C5	138.49 (19)	C2—C3—C4—C5	−0.3 (4)
N4i—Ni1—N2—C5	−41.51 (19)	C1—N2—C5—C4	−0.4 (3)
N3i—Ni1—N2—C5	45.18 (19)	Ni1—N2—C5—C4	178.09 (17)
N3—Ni1—N2—C5	−134.82 (19)	C3—C4—C5—N2	0.9 (4)
N4—Ni1—N2—C1	−42.98 (16)	C10—N3—C6—C7	0.4 (3)
N4i—Ni1—N2—C1	137.02 (16)	Ni1—N3—C6—C7	179.54 (18)
N3i—Ni1—N2—C1	−136.29 (16)	C10—N3—C6—N1	−178.68 (19)
N3—Ni1—N2—C1	43.71 (16)	Ni1—N3—C6—N1	0.4 (2)
N2—Ni1—N3—C6	−44.10 (16)	C15—N1—C6—N3	−65.0 (2)
N2i—Ni1—N3—C6	135.90 (16)	C1—N1—C6—N3	64.4 (2)
N4—Ni1—N3—C6	42.92 (16)	C15—N1—C6—C7	115.9 (2)
N4i—Ni1—N3—C6	−137.08 (16)	C1—N1—C6—C7	−114.8 (2)
N2—Ni1—N3—C10	134.9 (2)	N3—C6—C7—C8	−0.9 (4)
N2i—Ni1—N3—C10	−45.1 (2)	N1—C6—C7—C8	178.2 (2)
N4—Ni1—N3—C10	−138.1 (2)	C6—C7—C8—C9	0.2 (4)
N4i—Ni1—N3—C10	41.9 (2)	C7—C8—C9—C10	0.8 (4)
N2—Ni1—N4—C15	43.27 (16)	C6—N3—C10—C9	0.7 (3)
N2i—Ni1—N4—C15	−136.73 (16)	Ni1—N3—C10—C9	−178.30 (18)
N3i—Ni1—N4—C15	137.13 (16)	C8—C9—C10—N3	−1.3 (4)
N3—Ni1—N4—C15	−42.87 (16)	C15—N4—C11—C12	−0.8 (3)
N2—Ni1—N4—C11	−137.4 (2)	Ni1—N4—C11—C12	179.82 (18)
N2i—Ni1—N4—C11	42.6 (2)	N4—C11—C12—C13	0.1 (4)
N3i—Ni1—N4—C11	−43.5 (2)	C11—C12—C13—C14	1.0 (4)
N3—Ni1—N4—C11	136.5 (2)	C12—C13—C14—C15	−1.5 (4)
C5—N2—C1—C2	−0.6 (3)	C11—N4—C15—C14	0.3 (3)
Ni1—N2—C1—C2	−179.22 (17)	Ni1—N4—C15—C14	179.77 (18)
C5—N2—C1—N1	178.7 (2)	C11—N4—C15—N1	−179.87 (19)
Ni1—N2—C1—N1	0.1 (3)	Ni1—N4—C15—N1	−0.4 (3)
C15—N1—C1—N2	64.0 (3)	C13—C14—C15—N4	0.8 (4)
C6—N1—C1—N2	−65.1 (2)	C13—C14—C15—N1	−179.0 (2)
C15—N1—C1—C2	−116.7 (2)	C1—N1—C15—N4	−63.5 (3)
C6—N1—C1—C2	114.2 (2)	C6—N1—C15—N4	65.3 (2)
N2—C1—C2—C3	1.1 (3)	C1—N1—C15—C14	116.3 (2)
N1—C1—C2—C3	−178.2 (2)	C6—N1—C15—C14	−115.0 (2)
C1—C2—C3—C4	−0.6 (4)