Tetra-kis(azido-κN)(di-2-pyridyl-amine-κ(2)N(2),N(2'))platinum(IV).

In the title complex, [Pt(N(3))(4)(C(10)H(9)N(3))], the Pt(IV) ion is six-coordinated in a slightly distorted octa-hedral environment by the two pyridine N atoms of the chelating di-2-pyridyl-amine (dpa) ligand and four N atoms from four azide anions. The dpa ligand is not planar, the dihedral angle between the pyridine rings being 20.0 (3)°. The azide ligands are slightly bent [N-N-N = 173.5 (8)-175.1 (8)°]. In the crystal, the complex mol-ecules are connected by N-H⋯N hydrogen bonds, forming a chain along the b axis. An inter-molecular π-π inter-action between the chains is also present, the ring centroid-centroid distance being 3.713 (4) Å.

Related literature

For the crystal structure of the related chlorido PtIV complex [PtCl4(dpa)], see: Ha (2011 ▶).

Experimental

Crystal data

[Pt(N3)4(C10H9N3)]

M = 534.41

Monoclinic,

a = 7.0057 (4) Å

b = 14.7685 (9) Å

c = 14.9633 (9) Å

β = 98.118 (1)°

V = 1532.64 (16) Å3

Z = 4

Mo Kα radiation

μ = 9.19 mm−1

T = 200 K

0.18 × 0.07 × 0.06 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.420, T max = 0.576

9422 measured reflections

3004 independent reflections

2132 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.077

S = 0.94

3004 reflections

235 parameters

H-atom parameters constrained

Δρmax = 2.25 e Å−3

Δρmin = −0.86 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812011178/is5092sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011178/is5092Isup2.hkl

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

[Pt(N3)4(C10H9N3)]	F(000) = 1008
Mr = 534.41	Dx = 2.316 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3131 reflections
a = 7.0057 (4) Å	θ = 2.8–25.9°
b = 14.7685 (9) Å	µ = 9.19 mm−1
c = 14.9633 (9) Å	T = 200 K
β = 98.118 (1)°	Block, yellow
V = 1532.64 (16) Å3	0.18 × 0.07 × 0.06 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	3004 independent reflections
Radiation source: fine-focus sealed tube	2132 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
φ and ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
Tmin = 0.420, Tmax = 0.576	k = −18→17
9422 measured reflections	l = −18→16

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077	H-atom parameters constrained
S = 0.94	w = 1/[σ2(Fo2) + (0.0288P)2] where P = (Fo2 + 2Fc2)/3
3004 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 2.25 e Å−3
0 restraints	Δρmin = −0.86 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 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
Pt1	0.81972 (4)	0.15708 (2)	0.266198 (19)	0.02164 (11)
N1	0.8308 (9)	0.0693 (4)	0.1599 (4)	0.0190 (14)
N2	0.9443 (9)	−0.0523 (4)	0.2561 (4)	0.0229 (15)
H2N	0.9692	−0.1135	0.2562	0.034*
N3	1.0214 (9)	0.0791 (4)	0.3460 (4)	0.0200 (14)
C1	0.7670 (11)	0.0998 (5)	0.0743 (5)	0.0256 (19)
H1	0.7444	0.1627	0.0644	0.031*
C2	0.7353 (11)	0.0410 (6)	0.0027 (5)	0.0279 (19)
H2	0.6910	0.0628	−0.0563	0.033*
C3	0.7682 (12)	−0.0494 (6)	0.0174 (5)	0.032 (2)
H3	0.7438	−0.0911	−0.0313	0.038*
C4	0.8357 (12)	−0.0795 (5)	0.1014 (5)	0.0271 (19)
H4	0.8587	−0.1423	0.1115	0.033*
C5	0.8713 (11)	−0.0191 (5)	0.1725 (5)	0.0211 (17)
C6	1.0400 (11)	−0.0099 (5)	0.3320 (5)	0.0201 (17)
C7	1.1569 (11)	−0.0630 (5)	0.3944 (5)	0.0229 (18)
H7	1.1680	−0.1262	0.3847	0.028*
C8	1.2555 (11)	−0.0231 (6)	0.4697 (5)	0.0278 (19)
H8	1.3342	−0.0587	0.5132	0.033*
C9	1.2400 (11)	0.0690 (6)	0.4821 (5)	0.028 (2)
H9	1.3085	0.0978	0.5337	0.034*
C10	1.1251 (11)	0.1176 (6)	0.4191 (5)	0.0232 (18)
H10	1.1172	0.1813	0.4267	0.028*
N4	0.6200 (11)	0.2306 (5)	0.1855 (4)	0.0369 (19)
N5	0.5449 (10)	0.2945 (5)	0.2159 (4)	0.0302 (16)
N6	0.4660 (13)	0.3556 (6)	0.2374 (6)	0.063 (3)
N7	0.8045 (10)	0.2450 (5)	0.3692 (5)	0.0319 (17)
N8	0.6586 (12)	0.2401 (5)	0.4068 (4)	0.0353 (19)
N9	0.5310 (14)	0.2423 (6)	0.4464 (6)	0.059 (3)
N10	1.0370 (10)	0.2427 (4)	0.2364 (4)	0.0281 (17)
N11	1.0858 (10)	0.2358 (4)	0.1613 (5)	0.0306 (17)
N12	1.1381 (12)	0.2365 (5)	0.0918 (5)	0.041 (2)
N13	0.6117 (10)	0.0768 (4)	0.3100 (4)	0.0247 (15)
N14	0.4674 (10)	0.0646 (4)	0.2548 (4)	0.0281 (17)
N15	0.3276 (11)	0.0487 (5)	0.2071 (5)	0.043 (2)

	U11	U22	U33	U12	U13	U23
Pt1	0.02640 (18)	0.01631 (17)	0.02080 (17)	0.00107 (15)	−0.00153 (12)	−0.00106 (14)
N1	0.024 (4)	0.016 (4)	0.016 (4)	−0.002 (3)	0.001 (3)	−0.001 (3)
N2	0.035 (4)	0.013 (4)	0.019 (4)	−0.001 (3)	−0.003 (3)	0.005 (3)
N3	0.020 (4)	0.019 (4)	0.019 (4)	0.002 (3)	−0.001 (3)	0.003 (3)
C1	0.031 (5)	0.024 (5)	0.020 (5)	0.001 (4)	−0.001 (4)	0.002 (3)
C2	0.026 (5)	0.033 (5)	0.023 (5)	0.002 (4)	−0.003 (4)	0.001 (4)
C3	0.038 (5)	0.039 (6)	0.017 (4)	−0.001 (4)	−0.004 (4)	−0.007 (4)
C4	0.038 (5)	0.016 (5)	0.027 (5)	0.003 (4)	0.003 (4)	−0.006 (3)
C5	0.021 (4)	0.026 (5)	0.016 (4)	−0.004 (4)	0.004 (3)	−0.002 (3)
C6	0.018 (4)	0.020 (5)	0.024 (4)	−0.004 (3)	0.007 (3)	0.002 (3)
C7	0.018 (4)	0.021 (5)	0.030 (5)	0.003 (3)	0.003 (4)	0.005 (3)
C8	0.022 (4)	0.041 (6)	0.020 (4)	0.000 (4)	0.003 (4)	0.004 (4)
C9	0.020 (4)	0.038 (6)	0.027 (5)	0.000 (4)	0.004 (4)	−0.009 (4)
C10	0.021 (4)	0.024 (5)	0.023 (5)	0.002 (4)	−0.002 (4)	0.001 (3)
N4	0.044 (5)	0.033 (5)	0.029 (4)	0.022 (4)	−0.010 (4)	−0.002 (3)
N5	0.035 (4)	0.020 (4)	0.035 (4)	0.003 (4)	0.002 (3)	0.004 (3)
N6	0.070 (7)	0.049 (6)	0.067 (6)	0.038 (5)	0.000 (5)	−0.005 (5)
N7	0.029 (4)	0.029 (4)	0.037 (4)	0.002 (3)	0.004 (4)	−0.009 (3)
N8	0.059 (6)	0.024 (4)	0.022 (4)	−0.001 (4)	0.001 (4)	−0.013 (3)
N9	0.071 (7)	0.049 (6)	0.063 (6)	−0.022 (5)	0.038 (5)	−0.025 (4)
N10	0.039 (4)	0.018 (4)	0.027 (4)	−0.011 (3)	0.005 (3)	−0.005 (3)
N11	0.034 (4)	0.015 (4)	0.041 (5)	−0.006 (3)	−0.003 (4)	−0.002 (3)
N12	0.056 (6)	0.030 (5)	0.040 (5)	−0.007 (4)	0.014 (4)	0.001 (4)
N13	0.029 (4)	0.020 (4)	0.024 (4)	−0.002 (3)	−0.003 (3)	0.000 (3)
N14	0.031 (4)	0.028 (4)	0.027 (4)	0.003 (3)	0.011 (4)	0.003 (3)
N15	0.031 (5)	0.062 (6)	0.030 (5)	−0.005 (4)	−0.011 (4)	0.002 (4)

Pt1—N4	2.029 (7)	C4—C5	1.383 (10)
Pt1—N7	2.030 (7)	C4—H4	0.9500
Pt1—N13	2.057 (6)	C6—C7	1.393 (10)
Pt1—N1	2.061 (6)	C7—C8	1.369 (11)
Pt1—N3	2.067 (6)	C7—H7	0.9500
Pt1—N10	2.076 (6)	C8—C9	1.379 (11)
N1—C5	1.344 (9)	C8—H8	0.9500
N1—C1	1.372 (9)	C9—C10	1.356 (11)
N2—C5	1.373 (9)	C9—H9	0.9500
N2—C6	1.385 (9)	C10—H10	0.9500
N2—H2N	0.9200	N4—N5	1.200 (9)
N3—C6	1.340 (9)	N5—N6	1.129 (9)
N3—C10	1.350 (9)	N7—N8	1.236 (9)
C1—C2	1.373 (10)	N8—N9	1.141 (10)
C1—H1	0.9500	N10—N11	1.223 (9)
C2—C3	1.367 (11)	N11—N12	1.151 (9)
C2—H2	0.9500	N13—N14	1.225 (9)
C3—C4	1.353 (11)	N14—N15	1.152 (9)
C3—H3	0.9500
N4—Pt1—N7	90.2 (3)	C4—C3—H3	120.1
N4—Pt1—N13	92.2 (3)	C2—C3—H3	120.1
N7—Pt1—N13	90.6 (3)	C3—C4—C5	120.3 (8)
N4—Pt1—N1	88.6 (3)	C3—C4—H4	119.9
N7—Pt1—N1	178.8 (3)	C5—C4—H4	119.9
N13—Pt1—N1	89.4 (2)	N1—C5—N2	121.2 (6)
N4—Pt1—N3	178.4 (3)	N1—C5—C4	120.5 (7)
N7—Pt1—N3	91.3 (3)	N2—C5—C4	118.3 (7)
N13—Pt1—N3	87.3 (2)	N3—C6—N2	121.7 (7)
N1—Pt1—N3	89.9 (2)	N3—C6—C7	120.5 (7)
N4—Pt1—N10	90.6 (3)	N2—C6—C7	117.8 (7)
N7—Pt1—N10	83.8 (3)	C8—C7—C6	119.4 (8)
N13—Pt1—N10	173.8 (2)	C8—C7—H7	120.3
N1—Pt1—N10	96.2 (2)	C6—C7—H7	120.3
N3—Pt1—N10	90.1 (3)	C7—C8—C9	119.7 (8)
C5—N1—C1	119.0 (6)	C7—C8—H8	120.2
C5—N1—Pt1	122.3 (5)	C9—C8—H8	120.2
C1—N1—Pt1	118.1 (5)	C10—C9—C8	118.6 (8)
C5—N2—C6	131.3 (6)	C10—C9—H9	120.7
C5—N2—H2N	113.5	C8—C9—H9	120.7
C6—N2—H2N	111.9	N3—C10—C9	122.6 (8)
C6—N3—C10	119.1 (6)	N3—C10—H10	118.7
C6—N3—Pt1	122.0 (5)	C9—C10—H10	118.7
C10—N3—Pt1	118.6 (5)	N5—N4—Pt1	119.8 (6)
N1—C1—C2	121.0 (8)	N6—N5—N4	174.1 (9)
N1—C1—H1	119.5	N8—N7—Pt1	116.3 (5)
C2—C1—H1	119.5	N9—N8—N7	173.5 (8)
C3—C2—C1	119.2 (8)	N11—N10—Pt1	117.1 (5)
C3—C2—H2	120.4	N12—N11—N10	174.3 (8)
C1—C2—H2	120.4	N14—N13—Pt1	115.1 (5)
C4—C3—C2	119.9 (8)	N15—N14—N13	175.1 (8)
N4—Pt1—N1—C5	−149.7 (6)	C10—N3—C6—N2	−176.9 (6)
N13—Pt1—N1—C5	−57.5 (6)	Pt1—N3—C6—N2	9.2 (9)
N3—Pt1—N1—C5	29.7 (6)	C10—N3—C6—C7	3.3 (10)
N10—Pt1—N1—C5	119.8 (6)	Pt1—N3—C6—C7	−170.6 (5)
N4—Pt1—N1—C1	20.5 (6)	C5—N2—C6—N3	23.2 (12)
N13—Pt1—N1—C1	112.7 (6)	C5—N2—C6—C7	−157.0 (7)
N3—Pt1—N1—C1	−160.1 (5)	N3—C6—C7—C8	−1.0 (11)
N10—Pt1—N1—C1	−70.0 (6)	N2—C6—C7—C8	179.2 (6)
N7—Pt1—N3—C6	152.3 (6)	C6—C7—C8—C9	−0.9 (11)
N13—Pt1—N3—C6	61.7 (6)	C7—C8—C9—C10	0.6 (11)
N1—Pt1—N3—C6	−27.7 (6)	C6—N3—C10—C9	−3.7 (11)
N10—Pt1—N3—C6	−123.9 (6)	Pt1—N3—C10—C9	170.4 (6)
N7—Pt1—N3—C10	−21.7 (6)	C8—C9—C10—N3	1.8 (12)
N13—Pt1—N3—C10	−112.2 (6)	N7—Pt1—N4—N5	−4.3 (7)
N1—Pt1—N3—C10	158.4 (5)	N13—Pt1—N4—N5	86.4 (7)
N10—Pt1—N3—C10	62.1 (5)	N1—Pt1—N4—N5	175.7 (7)
C5—N1—C1—C2	3.2 (11)	N10—Pt1—N4—N5	−88.1 (7)
Pt1—N1—C1—C2	−167.4 (6)	N4—Pt1—N7—N8	74.2 (6)
N1—C1—C2—C3	0.0 (12)	N13—Pt1—N7—N8	−18.0 (6)
C1—C2—C3—C4	−1.6 (12)	N3—Pt1—N7—N8	−105.3 (6)
C2—C3—C4—C5	0.1 (12)	N10—Pt1—N7—N8	164.8 (6)
C1—N1—C5—N2	176.9 (7)	N4—Pt1—N10—N11	−73.8 (6)
Pt1—N1—C5—N2	−13.0 (9)	N7—Pt1—N10—N11	−164.0 (6)
C1—N1—C5—C4	−4.7 (10)	N1—Pt1—N10—N11	14.8 (6)
Pt1—N1—C5—C4	165.4 (6)	N3—Pt1—N10—N11	104.7 (6)
C6—N2—C5—N1	−21.0 (12)	N4—Pt1—N13—N14	31.4 (6)
C6—N2—C5—C4	160.5 (7)	N7—Pt1—N13—N14	121.6 (6)
C3—C4—C5—N1	3.2 (12)	N1—Pt1—N13—N14	−57.2 (6)
C3—C4—C5—N2	−178.4 (7)	N3—Pt1—N13—N14	−147.1 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N10i	0.92	2.13	3.031 (9)	167
N2—H2N···N11i	0.92	2.60	3.381 (9)	143

Table 1

Selected bond lengths (Å)

Pt1—N4	2.029 (7)
Pt1—N7	2.030 (7)
Pt1—N13	2.057 (6)
Pt1—N1	2.061 (6)
Pt1—N3	2.067 (6)
Pt1—N10	2.076 (6)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯N10i	0.92	2.13	3.031 (9)	167
N2—H2N⋯N11i	0.92	2.60	3.381 (9)	143

Symmetry code: (i) .