Download citation
Download citation
link to html
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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614021548/dt3029sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614021548/dt30291sup2.hkl
Contains datablock 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614021548/dt30292sup3.hkl
Contains datablock 2

CCDC references: 1026709; 1026710

Experimental top

Refinement top

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

Results and discussion top

Refinement top

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 Uiso(H) = 1.2Ueq(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 top

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 top
[Figure 1] Fig. 1.
[Figure 2] Fig. 2.
[Figure 3] Fig. 3.
[Figure 4] Fig. 4.
(I) [bis(pyridin-2-yl-κN)amine]tetrachloridoplatinum(IV) top
Crystal data top
[PtCl4(C10H9N3)]Dx = 2.627 Mg m3
Mr = 508.09Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 3819 reflections
a = 7.5599 (4) Åθ = 1.0–30.0°
b = 13.9247 (7) ŵ = 11.74 mm1
c = 12.2049 (5) ÅT = 120 K
V = 1284.80 (11) Å3Block, yellow
Z = 40.08 × 0.07 × 0.05 mm
F(000) = 944
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
1527 independent reflections
Radiation source: fine-focus sealed tube1370 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromatorRint = 0.039
Detector resolution: 16 pixels mm-1θmax = 27.5°, θmin = 3.2°
ϕ scans, and ω scans with κ offseth = 99
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
k = 1818
Tmin = 0.327, Tmax = 0.433l = 1515
10671 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.056 w = 1/[σ2(Fo2) + (0.0166P)2 + 7.8844P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
1527 reflectionsΔρmax = 2.43 e Å3
88 parametersΔρmin = 1.42 e Å3
Crystal data top
[PtCl4(C10H9N3)]V = 1284.80 (11) Å3
Mr = 508.09Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 7.5599 (4) ŵ = 11.74 mm1
b = 13.9247 (7) ÅT = 120 K
c = 12.2049 (5) Å0.08 × 0.07 × 0.05 mm
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
1527 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
1370 reflections with I > 2σ(I)
Tmin = 0.327, Tmax = 0.433Rint = 0.039
10671 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.056H-atom parameters constrained
S = 1.12Δρmax = 2.43 e Å3
1527 reflectionsΔρmin = 1.42 e Å3
88 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Pt10.19563 (3)0.25000.50415 (2)0.01079 (9)
Cl10.3660 (2)0.25000.34678 (12)0.0170 (3)
Cl30.0218 (2)0.25000.66257 (12)0.0146 (3)
Cl20.01586 (15)0.36515 (9)0.42526 (9)0.0189 (2)
C30.5708 (6)0.5000 (3)0.6458 (4)0.0155 (9)
H30.64530.55140.66790.019*
C20.3876 (6)0.5119 (3)0.6435 (4)0.0162 (9)
H20.33530.57060.66650.019*
C10.2846 (6)0.4374 (3)0.6075 (4)0.0159 (9)
H10.15990.44530.60560.019*
N10.3555 (5)0.3522 (3)0.5744 (3)0.0113 (7)
N20.6043 (7)0.25000.5590 (4)0.0144 (11)
H1N0.70720.25000.52540.017*
C50.5310 (6)0.3386 (3)0.5829 (3)0.0133 (9)
C40.6429 (6)0.4133 (3)0.6159 (4)0.0162 (9)
H40.76740.40420.61760.019*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.00951 (13)0.01141 (12)0.01143 (13)0.0000.00096 (9)0.000
Cl10.0212 (8)0.0151 (7)0.0149 (7)0.0000.0037 (6)0.000
Cl30.0125 (7)0.0164 (7)0.0149 (7)0.0000.0012 (6)0.000
Cl20.0174 (5)0.0187 (5)0.0206 (5)0.0044 (4)0.0039 (5)0.0021 (4)
C30.020 (2)0.013 (2)0.013 (2)0.0022 (18)0.0024 (19)0.0015 (16)
C20.021 (2)0.014 (2)0.014 (2)0.0020 (19)0.0021 (18)0.0001 (16)
C10.017 (2)0.016 (2)0.015 (2)0.0010 (18)0.0005 (19)0.0028 (17)
N10.0123 (17)0.0102 (18)0.0114 (16)0.0014 (14)0.0013 (14)0.0009 (13)
N20.012 (3)0.014 (3)0.016 (3)0.0000.002 (2)0.000
C50.017 (2)0.015 (2)0.0077 (18)0.0000 (17)0.0002 (17)0.0011 (16)
C40.013 (2)0.018 (2)0.017 (2)0.0019 (18)0.0021 (18)0.0010 (17)
Geometric parameters (Å, º) top
Pt1—N12.054 (4)C2—H20.9500
Pt1—N1i2.054 (4)C1—N11.363 (6)
Pt1—Cl2i2.3119 (11)C1—H10.9500
Pt1—Cl22.3119 (11)N1—C51.344 (6)
Pt1—Cl12.3125 (15)N2—C51.384 (5)
Pt1—Cl32.3380 (15)N2—C5i1.384 (5)
C3—C41.373 (7)N2—H1N0.8800
C3—C21.396 (7)C5—C41.400 (6)
C3—H30.9500C4—H40.9500
C2—C11.370 (7)
N1—Pt1—N1i87.7 (2)C1—C2—C3118.6 (4)
N1—Pt1—Cl2i179.91 (11)C1—C2—H2120.7
N1i—Pt1—Cl2i92.26 (11)C3—C2—H2120.7
N1—Pt1—Cl292.26 (11)N1—C1—C2122.1 (4)
N1i—Pt1—Cl2179.92 (11)N1—C1—H1118.9
Cl2i—Pt1—Cl287.82 (6)C2—C1—H1118.9
N1—Pt1—Cl191.10 (10)C5—N1—C1119.2 (4)
N1i—Pt1—Cl191.10 (10)C5—N1—Pt1121.0 (3)
Cl2i—Pt1—Cl188.94 (4)C1—N1—Pt1119.7 (3)
Cl2—Pt1—Cl188.94 (4)C5—N2—C5i126.2 (5)
N1—Pt1—Cl389.17 (10)C5—N2—H1N116.9
N1i—Pt1—Cl389.17 (10)C5i—N2—H1N116.9
Cl2i—Pt1—Cl390.80 (4)N1—C5—N2120.3 (4)
Cl2—Pt1—Cl390.80 (4)N1—C5—C4121.0 (4)
Cl1—Pt1—Cl3179.63 (6)N2—C5—C4118.8 (4)
C4—C3—C2119.6 (4)C3—C4—C5119.3 (4)
C4—C3—H3120.2C3—C4—H4120.4
C2—C3—H3120.2C5—C4—H4120.4
C4—C3—C2—C12.3 (6)Pt1—N1—C5—C4170.6 (3)
C3—C2—C1—N10.2 (7)C5i—N2—C5—N137.7 (8)
C2—C1—N1—C53.8 (6)C5i—N2—C5—C4142.3 (5)
C2—C1—N1—Pt1172.6 (3)C2—C3—C4—C50.4 (7)
C1—N1—C5—N2174.3 (4)N1—C5—C4—C33.7 (7)
Pt1—N1—C5—N29.4 (6)N2—C5—C4—C3176.4 (4)
C1—N1—C5—C45.7 (6)
Symmetry code: (i) x, y+1/2, z.
(II) [bis(pyridin-2-yl-κN)aminido]dichloridogold(III) top
Crystal data top
[AuCl2(C10H8N3)]Z = 2
Mr = 438.06F(000) = 404
Triclinic, P1Dx = 2.682 Mg m3
a = 7.6126 (13) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.8933 (7) ÅCell parameters from 9134 reflections
c = 9.5996 (8) Åθ = 3.2–36.1°
α = 115.042 (4)°µ = 14.02 mm1
β = 98.263 (5)°T = 100 K
γ = 105.452 (6)°Block, violet
V = 542.49 (11) Å30.23 × 0.12 × 0.12 mm
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
2678 independent reflections
Flat graphite crystal monochromator2525 reflections with I > 2σ(I)
Detector resolution: 16 pixels mm-1Rint = 0.038
ϕ and ω scansθmax = 28.3°, θmin = 2.5°
Absorption correction: numerical
(SADABS; Sheldrick, 2008)
h = 1010
Tmin = 0.171, Tmax = 0.477k = 1111
9771 measured reflectionsl = 1212
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.060 w = 1/[σ2(Fo2) + (0.0396P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2678 reflectionsΔρmax = 1.95 e Å3
145 parametersΔρmin = 2.72 e Å3
Crystal data top
[AuCl2(C10H8N3)]γ = 105.452 (6)°
Mr = 438.06V = 542.49 (11) Å3
Triclinic, P1Z = 2
a = 7.6126 (13) ÅMo Kα radiation
b = 8.8933 (7) ŵ = 14.02 mm1
c = 9.5996 (8) ÅT = 100 K
α = 115.042 (4)°0.23 × 0.12 × 0.12 mm
β = 98.263 (5)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
2678 independent reflections
Absorption correction: numerical
(SADABS; Sheldrick, 2008)
2525 reflections with I > 2σ(I)
Tmin = 0.171, Tmax = 0.477Rint = 0.038
9771 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.060H-atom parameters constrained
S = 1.04Δρmax = 1.95 e Å3
2678 reflectionsΔρmin = 2.72 e Å3
145 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Au10.02407 (2)0.51542 (2)0.29235 (2)0.01206 (7)
Cl10.32067 (14)0.43165 (13)0.32316 (13)0.0174 (2)
Cl20.03352 (14)0.78881 (13)0.50429 (13)0.0178 (2)
N10.2383 (5)0.5960 (4)0.2664 (4)0.0133 (7)
N20.1315 (5)0.3975 (4)0.0204 (4)0.0146 (7)
N30.0789 (5)0.2751 (4)0.1009 (4)0.0125 (6)
C10.3868 (6)0.7263 (5)0.3972 (5)0.0168 (8)
H10.37440.75440.50150.020*
C20.5517 (6)0.8174 (5)0.3838 (5)0.0162 (8)
H20.65500.90430.47670.019*
C30.5656 (5)0.7802 (5)0.2300 (5)0.0167 (8)
H30.67610.84750.21750.020*
C40.4201 (6)0.6467 (5)0.0976 (5)0.0158 (8)
H40.42930.62340.00670.019*
C50.2548 (5)0.5419 (5)0.1139 (5)0.0140 (8)
C60.0078 (5)0.2663 (5)0.0238 (5)0.0134 (7)
C70.0855 (5)0.1016 (5)0.1711 (5)0.0158 (8)
H70.04630.09470.26250.019*
C80.2155 (6)0.0463 (5)0.1827 (5)0.0178 (8)
H80.26480.15550.28100.021*
C90.2752 (6)0.0354 (5)0.0487 (5)0.0174 (8)
H90.36180.13770.05330.021*
C100.2067 (5)0.1251 (5)0.0888 (5)0.0160 (8)
H100.24890.13320.17930.019*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au10.00992 (9)0.00941 (9)0.01223 (9)0.00101 (6)0.00210 (6)0.00430 (6)
Cl10.0127 (4)0.0158 (4)0.0205 (5)0.0006 (3)0.0060 (4)0.0084 (4)
Cl20.0154 (4)0.0134 (4)0.0160 (5)0.0007 (4)0.0034 (3)0.0029 (4)
N10.0082 (14)0.0122 (15)0.0175 (17)0.0009 (12)0.0020 (12)0.0077 (13)
N20.0125 (15)0.0142 (15)0.0142 (17)0.0033 (12)0.0005 (12)0.0062 (13)
N30.0114 (14)0.0116 (15)0.0120 (16)0.0006 (12)0.0008 (12)0.0064 (13)
C10.0149 (18)0.0119 (17)0.016 (2)0.0010 (14)0.0023 (15)0.0045 (15)
C20.0133 (17)0.0138 (17)0.0147 (19)0.0003 (14)0.0001 (14)0.0052 (15)
C30.0101 (17)0.0160 (18)0.022 (2)0.0015 (14)0.0042 (15)0.0097 (16)
C40.0136 (17)0.0139 (17)0.019 (2)0.0028 (14)0.0067 (15)0.0072 (15)
C50.0121 (17)0.0109 (16)0.017 (2)0.0019 (14)0.0035 (14)0.0063 (15)
C60.0096 (16)0.0128 (17)0.0138 (19)0.0033 (14)0.0005 (13)0.0044 (15)
C70.0128 (17)0.0144 (18)0.015 (2)0.0016 (14)0.0025 (14)0.0046 (15)
C80.0141 (18)0.0116 (17)0.017 (2)0.0011 (14)0.0007 (14)0.0029 (15)
C90.0151 (18)0.0092 (17)0.021 (2)0.0020 (14)0.0008 (15)0.0065 (15)
C100.0141 (17)0.0109 (17)0.018 (2)0.0011 (14)0.0024 (14)0.0070 (15)
Geometric parameters (Å, º) top
Au1—N12.024 (3)C2—H20.9500
Au1—N32.024 (3)C3—C41.367 (5)
Au1—Cl12.2853 (10)C3—H30.9500
Au1—Cl22.2872 (10)C4—C51.425 (5)
N1—C11.364 (5)C4—H40.9500
N1—C51.371 (5)C6—C71.428 (5)
N2—C61.337 (5)C7—C81.369 (5)
N2—C51.342 (5)C7—H70.9500
N3—C61.364 (5)C8—C91.398 (6)
N3—C101.373 (5)C8—H80.9500
C1—C21.357 (5)C9—C101.364 (5)
C1—H10.9500C9—H90.9500
C2—C31.396 (6)C10—H100.9500
N1—Au1—N387.86 (14)C3—C4—C5120.9 (4)
N1—Au1—Cl1178.48 (9)C3—C4—H4119.6
N3—Au1—Cl193.32 (10)C5—C4—H4119.6
N1—Au1—Cl292.41 (10)N2—C5—N1125.9 (4)
N3—Au1—Cl2178.50 (10)N2—C5—C4117.3 (4)
Cl1—Au1—Cl286.39 (4)N1—C5—C4116.9 (4)
C1—N1—C5120.8 (3)N2—C6—N3125.9 (4)
C1—N1—Au1119.7 (3)N2—C6—C7116.3 (4)
C5—N1—Au1118.4 (3)N3—C6—C7117.7 (3)
C6—N2—C5124.9 (4)C8—C7—C6121.1 (4)
C6—N3—C10120.4 (3)C8—C7—H7119.5
C6—N3—Au1119.7 (3)C6—C7—H7119.5
C10—N3—Au1119.4 (3)C7—C8—C9119.5 (4)
C2—C1—N1122.4 (4)C7—C8—H8120.3
C2—C1—H1118.8C9—C8—H8120.3
N1—C1—H1118.8C10—C9—C8118.7 (4)
C1—C2—C3118.3 (4)C10—C9—H9120.6
C1—C2—H2120.8C8—C9—H9120.6
C3—C2—H2120.8C9—C10—N3122.3 (4)
C4—C3—C2119.9 (4)C9—C10—H10118.8
C4—C3—H3120.0N3—C10—H10118.8
C2—C3—H3120.0
C5—N1—C1—C24.8 (7)C5—N2—C6—N317.3 (7)
Au1—N1—C1—C2163.0 (3)C5—N2—C6—C7161.5 (4)
N1—C1—C2—C32.5 (7)C10—N3—C6—N2172.4 (4)
C1—C2—C3—C44.2 (6)Au1—N3—C6—N215.9 (6)
C2—C3—C4—C51.2 (6)C10—N3—C6—C76.4 (6)
C6—N2—C5—N112.9 (7)Au1—N3—C6—C7165.3 (3)
C6—N2—C5—C4165.6 (4)N2—C6—C7—C8173.7 (4)
C1—N1—C5—N2168.6 (4)N3—C6—C7—C85.2 (6)
Au1—N1—C5—N223.4 (6)C6—C7—C8—C90.9 (6)
C1—N1—C5—C49.9 (6)C7—C8—C9—C102.3 (7)
Au1—N1—C5—C4158.1 (3)C8—C9—C10—N31.2 (7)
C3—C4—C5—N2170.5 (4)C6—N3—C10—C93.4 (6)
C3—C4—C5—N18.2 (6)Au1—N3—C10—C9168.3 (3)

Experimental details

(I)
Crystal data
Chemical formula[PtCl4(C10H9N3)]
Mr508.09
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)120
a, b, c (Å)7.5599 (4), 13.9247 (7), 12.2049 (5)
V3)1284.80 (11)
Z4
Radiation typeMo Kα
µ (mm1)11.74
Crystal size (mm)0.08 × 0.07 × 0.05
Data collection
DiffractometerBruker Kappa APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008)
Tmin, Tmax0.327, 0.433
No. of measured, independent and
observed [I > 2σ(I)] reflections
10671, 1527, 1370
Rint0.039
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.056, 1.12
No. of reflections1527
No. of parameters88
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)2.43, 1.42

Computer programs: APEX2 (Bruker AXS, 2010), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL2014 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Selected geometric parameters (Å, º) for (I) top
Pt1—N12.054 (4)Pt1—Cl32.3380 (15)
Pt1—Cl22.3119 (11)N2—C51.384 (5)
Pt1—Cl12.3125 (15)
N1—Pt1—Cl292.26 (11)Cl1—Pt1—Cl3179.63 (6)
N1—Pt1—Cl191.10 (10)C5—N2—C5i126.2 (5)
Cl2—Pt1—Cl390.80 (4)
Symmetry code: (i) x, y+1/2, z.
Selected geometric parameters (Å, º) for (II) top
Au1—N12.024 (3)Au1—Cl22.2872 (10)
Au1—N32.024 (3)N2—C61.337 (5)
Au1—Cl12.2853 (10)N2—C51.342 (5)
N1—Au1—N387.86 (14)C6—N2—C5124.9 (4)
Cl1—Au1—Cl286.39 (4)
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds