Two complexes of Pt^IV and Au^III with 2,2′-dipyridylamine and 2,2′-di­pyridyl­aminide ligands

Two noble metal complexes involving ancillary chloride ligands and chelating 2,2′-bipyridylamine (Hdpa) or its de­protonated derivative (dpa), namely [bis(pyridin-2-yl-κN)amine]tetrachloridoplatinum(IV), [PtCl₄(C₁₀H₉N₃)], and [bis(pyridin-2-yl-κN)aminido]dichloridogold(III), [AuCl₂(C₁₀H₈N₃)], are presented and structurally characterized. The metal atom in the former has a slightly distorted octahedral coordination environment, formed by four chloride ligands and two pyridyl N atoms of Hdpa, while the metal atom in the latter has a slightly distorted square-planar coordination environment, formed by two chloride ligands and two pyridyl N atoms of dpa. The difference in conjugation between the pyridine rings in normal and deprotonated 2,2′-dipyridylamine is discussed on the basis of the structural features of these complexes. The influence of weak interactions on the supramolecular structures of the complexes, providing one-dimensional chains of [PtCl₄(C₁₀H₉N₃)] and dimers of [AuCl₂(C₁₀H₈N₃)], are discussed.

S1. Experimental

S1.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

S2. Results and discussion

S3. Refinement

H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.95 Å, N—H = 0.88 Å, and U_iso(H) = 1.2U_eq(parent atom). The highest peak is located 0.65 Å from atom H2N and the deepest hole is located 0.84 Å from atom Pt1.

Computing details

Data collection: APEX2 (Bruker AXS, 2010) for (I); APEX2 (Bruker, 2010) for (II). Cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997) for (I); SAINT (Bruker, 2009) for (II). Data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997) for (I); SAINT (Bruker, 2009) for (II). For both compounds, program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2008).

Figures

	Fig. 1.
	Fig. 2.
	Fig. 3.
	Fig. 4.

(I) [bis(pyridin-2-yl-κN)amine]tetrachloridoplatinum(IV)

Crystal data

[PtCl4(C10H9N3)]	Dx = 2.627 Mg m^−3
Mr = 508.09	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 3819 reflections
a = 7.5599 (4) Å	θ = 1.0–30.0°
b = 13.9247 (7) Å	µ = 11.74 mm^−1
c = 12.2049 (5) Å	T = 120 K
V = 1284.80 (11) Å^3	Block, yellow
Z = 4	0.08 × 0.07 × 0.05 mm
F(000) = 944

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer	1527 independent reflections
Radiation source: fine-focus sealed tube	1370 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.039
Detector resolution: 16 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ scans, and ω scans with κ offset	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	k = −18→18
Tmin = 0.327, Tmax = 0.433	l = −15→15
10671 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.056	w = 1/[σ^2(Fo^2) + (0.0166P)^2 + 7.8844P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
1527 reflections	Δρmax = 2.43 e Å^−3
88 parameters	Δρmin = −1.42 e Å^−3

Special details

Experimental. Absorption correction: SADABS-2008/1 (Sheldrick, 2008) Additional spherical absorption correction applied with mu*r = 0.6000 Lambda/2 correction factor = 0.0015

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pt1	0.19563 (3)	0.2500	0.50415 (2)	0.01079 (9)
Cl1	0.3660 (2)	0.2500	0.34678 (12)	0.0170 (3)
Cl3	0.0218 (2)	0.2500	0.66257 (12)	0.0146 (3)
Cl2	0.01586 (15)	0.36515 (9)	0.42526 (9)	0.0189 (2)
C3	0.5708 (6)	0.5000 (3)	0.6458 (4)	0.0155 (9)
H3	0.6453	0.5514	0.6679	0.019*
C2	0.3876 (6)	0.5119 (3)	0.6435 (4)	0.0162 (9)
H2	0.3353	0.5706	0.6665	0.019*
C1	0.2846 (6)	0.4374 (3)	0.6075 (4)	0.0159 (9)
H1	0.1599	0.4453	0.6056	0.019*
N1	0.3555 (5)	0.3522 (3)	0.5744 (3)	0.0113 (7)
N2	0.6043 (7)	0.2500	0.5590 (4)	0.0144 (11)
H1N	0.7072	0.2500	0.5254	0.017*
C5	0.5310 (6)	0.3386 (3)	0.5829 (3)	0.0133 (9)
C4	0.6429 (6)	0.4133 (3)	0.6159 (4)	0.0162 (9)
H4	0.7674	0.4042	0.6176	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.00951 (13)	0.01141 (12)	0.01143 (13)	0.000	−0.00096 (9)	0.000
Cl1	0.0212 (8)	0.0151 (7)	0.0149 (7)	0.000	0.0037 (6)	0.000
Cl3	0.0125 (7)	0.0164 (7)	0.0149 (7)	0.000	0.0012 (6)	0.000
Cl2	0.0174 (5)	0.0187 (5)	0.0206 (5)	0.0044 (4)	−0.0039 (5)	0.0021 (4)
C3	0.020 (2)	0.013 (2)	0.013 (2)	−0.0022 (18)	−0.0024 (19)	0.0015 (16)
C2	0.021 (2)	0.014 (2)	0.014 (2)	0.0020 (19)	0.0021 (18)	0.0001 (16)
C1	0.017 (2)	0.016 (2)	0.015 (2)	0.0010 (18)	0.0005 (19)	0.0028 (17)
N1	0.0123 (17)	0.0102 (18)	0.0114 (16)	−0.0014 (14)	−0.0013 (14)	0.0009 (13)
N2	0.012 (3)	0.014 (3)	0.016 (3)	0.000	0.002 (2)	0.000
C5	0.017 (2)	0.015 (2)	0.0077 (18)	0.0000 (17)	0.0002 (17)	0.0011 (16)
C4	0.013 (2)	0.018 (2)	0.017 (2)	−0.0019 (18)	−0.0021 (18)	0.0010 (17)

Geometric parameters (Å, º)

Pt1—N1	2.054 (4)	C2—H2	0.9500
Pt1—N1^i	2.054 (4)	C1—N1	1.363 (6)
Pt1—Cl2^i	2.3119 (11)	C1—H1	0.9500
Pt1—Cl2	2.3119 (11)	N1—C5	1.344 (6)
Pt1—Cl1	2.3125 (15)	N2—C5	1.384 (5)
Pt1—Cl3	2.3380 (15)	N2—C5^i	1.384 (5)
C3—C4	1.373 (7)	N2—H1N	0.8800
C3—C2	1.396 (7)	C5—C4	1.400 (6)
C3—H3	0.9500	C4—H4	0.9500
C2—C1	1.370 (7)
N1—Pt1—N1^i	87.7 (2)	C1—C2—C3	118.6 (4)
N1—Pt1—Cl2^i	179.91 (11)	C1—C2—H2	120.7
N1^i—Pt1—Cl2^i	92.26 (11)	C3—C2—H2	120.7
N1—Pt1—Cl2	92.26 (11)	N1—C1—C2	122.1 (4)
N1^i—Pt1—Cl2	179.92 (11)	N1—C1—H1	118.9
Cl2^i—Pt1—Cl2	87.82 (6)	C2—C1—H1	118.9
N1—Pt1—Cl1	91.10 (10)	C5—N1—C1	119.2 (4)
N1^i—Pt1—Cl1	91.10 (10)	C5—N1—Pt1	121.0 (3)
Cl2^i—Pt1—Cl1	88.94 (4)	C1—N1—Pt1	119.7 (3)
Cl2—Pt1—Cl1	88.94 (4)	C5—N2—C5^i	126.2 (5)
N1—Pt1—Cl3	89.17 (10)	C5—N2—H1N	116.9
N1^i—Pt1—Cl3	89.17 (10)	C5^i—N2—H1N	116.9
Cl2^i—Pt1—Cl3	90.80 (4)	N1—C5—N2	120.3 (4)
Cl2—Pt1—Cl3	90.80 (4)	N1—C5—C4	121.0 (4)
Cl1—Pt1—Cl3	179.63 (6)	N2—C5—C4	118.8 (4)
C4—C3—C2	119.6 (4)	C3—C4—C5	119.3 (4)
C4—C3—H3	120.2	C3—C4—H4	120.4
C2—C3—H3	120.2	C5—C4—H4	120.4
C4—C3—C2—C1	−2.3 (6)	Pt1—N1—C5—C4	170.6 (3)
C3—C2—C1—N1	0.2 (7)	C5^i—N2—C5—N1	−37.7 (8)
C2—C1—N1—C5	3.8 (6)	C5^i—N2—C5—C4	142.3 (5)
C2—C1—N1—Pt1	−172.6 (3)	C2—C3—C4—C5	0.4 (7)
C1—N1—C5—N2	174.3 (4)	N1—C5—C4—C3	3.7 (7)
Pt1—N1—C5—N2	−9.4 (6)	N2—C5—C4—C3	−176.4 (4)
C1—N1—C5—C4	−5.7 (6)

Symmetry code: (i) x, −y+1/2, z.

(II) [bis(pyridin-2-yl-κN)aminido]dichloridogold(III)

Crystal data

[AuCl2(C10H8N3)]	Z = 2
Mr = 438.06	F(000) = 404
Triclinic, P1	Dx = 2.682 Mg m^−3
a = 7.6126 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8933 (7) Å	Cell parameters from 9134 reflections
c = 9.5996 (8) Å	θ = 3.2–36.1°
α = 115.042 (4)°	µ = 14.02 mm^−1
β = 98.263 (5)°	T = 100 K
γ = 105.452 (6)°	Block, violet
V = 542.49 (11) Å^3	0.23 × 0.12 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	2678 independent reflections
Flat graphite crystal monochromator	2525 reflections with I > 2σ(I)
Detector resolution: 16 pixels mm^-1	Rint = 0.038
ϕ and ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: numerical (SADABS; Sheldrick, 2008)	h = −10→10
Tmin = 0.171, Tmax = 0.477	k = −11→11
9771 measured reflections	l = −12→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.0396P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2678 reflections	Δρmax = 1.95 e Å^−3
145 parameters	Δρmin = −2.72 e Å^−3

Special details

Experimental. Absorption correction: SADABS-2008/1 (Sheldrick, 2008) Additional spherical absorption correction applied with mu*r = 0.0000 Lambda/2 correction factor = 0.0015

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Au1	−0.02407 (2)	0.51542 (2)	0.29235 (2)	0.01206 (7)
Cl1	−0.32067 (14)	0.43165 (13)	0.32316 (13)	0.0174 (2)
Cl2	0.03352 (14)	0.78881 (13)	0.50429 (13)	0.0178 (2)
N1	0.2383 (5)	0.5960 (4)	0.2664 (4)	0.0133 (7)
N2	0.1315 (5)	0.3975 (4)	−0.0204 (4)	0.0146 (7)
N3	−0.0789 (5)	0.2751 (4)	0.1009 (4)	0.0125 (6)
C1	0.3868 (6)	0.7263 (5)	0.3972 (5)	0.0168 (8)
H1	0.3744	0.7544	0.5015	0.020*
C2	0.5517 (6)	0.8174 (5)	0.3838 (5)	0.0162 (8)
H2	0.6550	0.9043	0.4767	0.019*
C3	0.5656 (5)	0.7802 (5)	0.2300 (5)	0.0167 (8)
H3	0.6761	0.8475	0.2175	0.020*
C4	0.4201 (6)	0.6467 (5)	0.0976 (5)	0.0158 (8)
H4	0.4293	0.6234	−0.0067	0.019*
C5	0.2548 (5)	0.5419 (5)	0.1139 (5)	0.0140 (8)
C6	−0.0078 (5)	0.2663 (5)	−0.0238 (5)	0.0134 (7)
C7	−0.0855 (5)	0.1016 (5)	−0.1711 (5)	0.0158 (8)
H7	−0.0463	0.0947	−0.2625	0.019*
C8	−0.2155 (6)	−0.0463 (5)	−0.1827 (5)	0.0178 (8)
H8	−0.2648	−0.1555	−0.2810	0.021*
C9	−0.2752 (6)	−0.0354 (5)	−0.0487 (5)	0.0174 (8)
H9	−0.3618	−0.1377	−0.0533	0.021*
C10	−0.2067 (5)	0.1251 (5)	0.0888 (5)	0.0160 (8)
H10	−0.2489	0.1332	0.1793	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.00992 (9)	0.00941 (9)	0.01223 (9)	−0.00101 (6)	0.00210 (6)	0.00430 (6)
Cl1	0.0127 (4)	0.0158 (4)	0.0205 (5)	0.0006 (3)	0.0060 (4)	0.0084 (4)
Cl2	0.0154 (4)	0.0134 (4)	0.0160 (5)	0.0007 (4)	0.0034 (3)	0.0029 (4)
N1	0.0082 (14)	0.0122 (15)	0.0175 (17)	0.0009 (12)	0.0020 (12)	0.0077 (13)
N2	0.0125 (15)	0.0142 (15)	0.0142 (17)	0.0033 (12)	0.0005 (12)	0.0062 (13)
N3	0.0114 (14)	0.0116 (15)	0.0120 (16)	0.0006 (12)	0.0008 (12)	0.0064 (13)
C1	0.0149 (18)	0.0119 (17)	0.016 (2)	−0.0010 (14)	0.0023 (15)	0.0045 (15)
C2	0.0133 (17)	0.0138 (17)	0.0147 (19)	0.0003 (14)	−0.0001 (14)	0.0052 (15)
C3	0.0101 (17)	0.0160 (18)	0.022 (2)	0.0015 (14)	0.0042 (15)	0.0097 (16)
C4	0.0136 (17)	0.0139 (17)	0.019 (2)	0.0028 (14)	0.0067 (15)	0.0072 (15)
C5	0.0121 (17)	0.0109 (16)	0.017 (2)	0.0019 (14)	0.0035 (14)	0.0063 (15)
C6	0.0096 (16)	0.0128 (17)	0.0138 (19)	0.0033 (14)	0.0005 (13)	0.0044 (15)
C7	0.0128 (17)	0.0144 (18)	0.015 (2)	0.0016 (14)	0.0025 (14)	0.0046 (15)
C8	0.0141 (18)	0.0116 (17)	0.017 (2)	−0.0011 (14)	−0.0007 (14)	0.0029 (15)
C9	0.0151 (18)	0.0092 (17)	0.021 (2)	−0.0020 (14)	0.0008 (15)	0.0065 (15)
C10	0.0141 (17)	0.0109 (17)	0.018 (2)	−0.0011 (14)	0.0024 (14)	0.0070 (15)

Geometric parameters (Å, º)

Au1—N1	2.024 (3)	C2—H2	0.9500
Au1—N3	2.024 (3)	C3—C4	1.367 (5)
Au1—Cl1	2.2853 (10)	C3—H3	0.9500
Au1—Cl2	2.2872 (10)	C4—C5	1.425 (5)
N1—C1	1.364 (5)	C4—H4	0.9500
N1—C5	1.371 (5)	C6—C7	1.428 (5)
N2—C6	1.337 (5)	C7—C8	1.369 (5)
N2—C5	1.342 (5)	C7—H7	0.9500
N3—C6	1.364 (5)	C8—C9	1.398 (6)
N3—C10	1.373 (5)	C8—H8	0.9500
C1—C2	1.357 (5)	C9—C10	1.364 (5)
C1—H1	0.9500	C9—H9	0.9500
C2—C3	1.396 (6)	C10—H10	0.9500
N1—Au1—N3	87.86 (14)	C3—C4—C5	120.9 (4)
N1—Au1—Cl1	178.48 (9)	C3—C4—H4	119.6
N3—Au1—Cl1	93.32 (10)	C5—C4—H4	119.6
N1—Au1—Cl2	92.41 (10)	N2—C5—N1	125.9 (4)
N3—Au1—Cl2	178.50 (10)	N2—C5—C4	117.3 (4)
Cl1—Au1—Cl2	86.39 (4)	N1—C5—C4	116.9 (4)
C1—N1—C5	120.8 (3)	N2—C6—N3	125.9 (4)
C1—N1—Au1	119.7 (3)	N2—C6—C7	116.3 (4)
C5—N1—Au1	118.4 (3)	N3—C6—C7	117.7 (3)
C6—N2—C5	124.9 (4)	C8—C7—C6	121.1 (4)
C6—N3—C10	120.4 (3)	C8—C7—H7	119.5
C6—N3—Au1	119.7 (3)	C6—C7—H7	119.5
C10—N3—Au1	119.4 (3)	C7—C8—C9	119.5 (4)
C2—C1—N1	122.4 (4)	C7—C8—H8	120.3
C2—C1—H1	118.8	C9—C8—H8	120.3
N1—C1—H1	118.8	C10—C9—C8	118.7 (4)
C1—C2—C3	118.3 (4)	C10—C9—H9	120.6
C1—C2—H2	120.8	C8—C9—H9	120.6
C3—C2—H2	120.8	C9—C10—N3	122.3 (4)
C4—C3—C2	119.9 (4)	C9—C10—H10	118.8
C4—C3—H3	120.0	N3—C10—H10	118.8
C2—C3—H3	120.0
C5—N1—C1—C2	4.8 (7)	C5—N2—C6—N3	17.3 (7)
Au1—N1—C1—C2	−163.0 (3)	C5—N2—C6—C7	−161.5 (4)
N1—C1—C2—C3	2.5 (7)	C10—N3—C6—N2	−172.4 (4)
C1—C2—C3—C4	−4.2 (6)	Au1—N3—C6—N2	15.9 (6)
C2—C3—C4—C5	−1.2 (6)	C10—N3—C6—C7	6.4 (6)
C6—N2—C5—N1	−12.9 (7)	Au1—N3—C6—C7	−165.3 (3)
C6—N2—C5—C4	165.6 (4)	N2—C6—C7—C8	173.7 (4)
C1—N1—C5—N2	168.6 (4)	N3—C6—C7—C8	−5.2 (6)
Au1—N1—C5—N2	−23.4 (6)	C6—C7—C8—C9	0.9 (6)
C1—N1—C5—C4	−9.9 (6)	C7—C8—C9—C10	2.3 (7)
Au1—N1—C5—C4	158.1 (3)	C8—C9—C10—N3	−1.2 (7)
C3—C4—C5—N2	−170.5 (4)	C6—N3—C10—C9	−3.4 (6)
C3—C4—C5—N1	8.2 (6)	Au1—N3—C10—C9	168.3 (3)