A new gold(III) complex of di-2-pyridylamine (DPA), [AuCl
2(C
19H
9N
3)]Cl, has been synthesized and characterized by ESI–MS,
1H NMR spectroscopy, elemental analysis and X-ray structural analysis. The compound possesses crystallographically imposed mirror symmetry. The DPA ligand coordinates to the gold(III) centre in a bidentate mode. The distance between the metal centre and the Cl
− anion is 3.037 (2) Å. The cations are linked into layers parallel to the
bc plane through N—H
Cl and C—H
Cl hydrogen-bond interactions. The title complex is more cytotoxic than cisplatin against A-549 and HCT-116 tumour cell lines.
Supporting information
CCDC reference: 611219
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.009 Å
- R factor = 0.031
- wR factor = 0.082
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Dichloro(di-2-pyridylamine)gold(III) chloride
top
Crystal data top
[AuCl2(C10H9N3)]Cl | F(000) = 880 |
Mr = 474.52 | Dx = 2.488 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 3897 reflections |
a = 12.549 (4) Å | θ = 2.3–28.0° |
b = 12.313 (4) Å | µ = 12.22 mm−1 |
c = 8.200 (2) Å | T = 273 K |
V = 1267.0 (7) Å3 | Block, red |
Z = 4 | 0.3 × 0.22 × 0.16 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 1299 independent reflections |
Radiation source: fine-focus sealed tube | 1238 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
φ and ω scans | θmax = 26.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −15→14 |
Tmin = 0.043, Tmax = 0.141 | k = −15→13 |
6226 measured reflections | l = −10→9 |
Refinement top
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)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0442P)2 + 3.0733P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
1299 reflections | Δρmax = 1.50 e Å−3 |
83 parameters | Δρmin = −1.61 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0010 (3) |
Special details top
Experimental. Spectroscopic analysis: 1H NMR (CD3SOCD3, δ, p.p.m.): 8.71 (d, 2H, J =
6.3 Hz), 8.26 (t, 2H, J = 7.7 Hz), 7.60 (d, 2H, J = 8.3 Hz), 7.54 (t, 2H, J =
6.73 Hz). ESI–MS (+P) m/z = 438.1. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Au1 | −0.01457 (3) | 0.2500 | 0.79814 (3) | 0.02216 (17) | |
C1 | 0.0959 (4) | 0.3501 (5) | 0.5219 (6) | 0.0231 (11) | |
C2 | 0.1337 (5) | 0.4368 (5) | 0.4301 (7) | 0.0258 (12) | |
H2 | 0.1439 | 0.4291 | 0.3184 | 0.031* | |
C3 | 0.1556 (5) | 0.5327 (6) | 0.5041 (8) | 0.0340 (14) | |
H3 | 0.1813 | 0.5909 | 0.4434 | 0.041* | |
C4 | 0.1394 (5) | 0.5437 (5) | 0.6725 (8) | 0.0307 (14) | |
H4 | 0.1567 | 0.6080 | 0.7259 | 0.037* | |
C5 | 0.0978 (5) | 0.4580 (5) | 0.7559 (7) | 0.0291 (13) | |
H5 | 0.0853 | 0.4652 | 0.8672 | 0.035* | |
Cl1 | −0.12404 (13) | 0.12231 (13) | 0.90454 (19) | 0.0383 (4) | |
Cl2 | 0.1445 (2) | 0.2500 | 0.0773 (2) | 0.0397 (6) | |
N1 | 0.0739 (4) | 0.3627 (4) | 0.6822 (5) | 0.0216 (10) | |
N2 | 0.0787 (6) | 0.2500 | 0.4496 (8) | 0.0284 (16) | |
H2B | 0.1199 | 0.2500 | 0.3598 | 0.034* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Au1 | 0.0196 (2) | 0.0282 (2) | 0.0187 (2) | 0.000 | 0.00364 (10) | 0.000 |
C1 | 0.017 (3) | 0.030 (3) | 0.022 (2) | 0.006 (2) | 0.000 (2) | 0.000 (2) |
C2 | 0.020 (3) | 0.033 (3) | 0.024 (3) | 0.003 (2) | 0.004 (2) | 0.004 (2) |
C3 | 0.020 (3) | 0.039 (3) | 0.043 (4) | 0.000 (3) | 0.002 (3) | 0.010 (3) |
C4 | 0.029 (4) | 0.027 (3) | 0.036 (3) | −0.003 (3) | −0.005 (3) | 0.001 (2) |
C5 | 0.028 (3) | 0.035 (3) | 0.025 (3) | 0.003 (3) | −0.005 (3) | −0.007 (2) |
Cl1 | 0.0358 (9) | 0.0430 (9) | 0.0360 (8) | −0.0094 (7) | 0.0116 (7) | 0.0051 (7) |
Cl2 | 0.0456 (14) | 0.0499 (13) | 0.0235 (10) | 0.000 | −0.0025 (9) | 0.000 |
N1 | 0.017 (2) | 0.028 (2) | 0.021 (2) | −0.001 (2) | 0.0027 (18) | 0.0026 (18) |
N2 | 0.035 (4) | 0.029 (4) | 0.021 (3) | 0.000 | 0.006 (3) | 0.000 |
Geometric parameters (Å, º) top
Au1—N1i | 2.015 (5) | C2—H2 | 0.9300 |
Au1—N1 | 2.015 (5) | C3—C4 | 1.403 (9) |
Au1—Cl1 | 2.2628 (16) | C3—H3 | 0.9300 |
Au1—Cl1i | 2.2628 (16) | C4—C5 | 1.362 (9) |
Au1—Cl2ii | 3.037 (2) | C4—H4 | 0.9300 |
C1—N1 | 1.352 (7) | C5—N1 | 1.354 (8) |
C1—N2 | 1.385 (6) | C5—H5 | 0.9300 |
C1—C2 | 1.390 (8) | N2—C1i | 1.385 (6) |
C2—C3 | 1.355 (9) | N2—H2B | 0.9000 |
| | | |
N1i—Au1—N1 | 87.0 (3) | C2—C3—C4 | 119.7 (6) |
N1i—Au1—Cl1 | 92.18 (15) | C2—C3—H3 | 120.1 |
N1—Au1—Cl1 | 174.11 (13) | C4—C3—H3 | 120.1 |
N1i—Au1—Cl1i | 174.11 (13) | C5—C4—C3 | 118.3 (6) |
N1—Au1—Cl1i | 92.18 (15) | C5—C4—H4 | 120.8 |
Cl1—Au1—Cl1i | 88.02 (9) | C3—C4—H4 | 120.8 |
N1i—Au1—Cl2ii | 89.61 (14) | N1—C5—C4 | 122.2 (5) |
N1—Au1—Cl2ii | 89.61 (14) | N1—C5—H5 | 118.9 |
Cl1—Au1—Cl2ii | 96.22 (6) | C4—C5—H5 | 118.9 |
Cl1i—Au1—Cl2ii | 96.22 (6) | C5—N1—C1 | 119.2 (5) |
N1—C1—N2 | 119.1 (5) | C5—N1—Au1 | 120.6 (4) |
N1—C1—C2 | 120.5 (5) | C1—N1—Au1 | 119.5 (4) |
N2—C1—C2 | 120.3 (5) | C1—N2—C1i | 125.7 (6) |
C3—C2—C1 | 119.7 (5) | C1—N2—H2B | 105.1 |
C3—C2—H2 | 120.1 | C1i—N2—H2B | 105.1 |
C1—C2—H2 | 120.1 | | |
| | | |
N1—C1—C2—C3 | 4.5 (9) | C2—C1—N1—Au1 | 164.4 (4) |
N2—C1—C2—C3 | −176.5 (6) | N1i—Au1—N1—C5 | −145.9 (4) |
C1—C2—C3—C4 | −0.3 (9) | Cl1i—Au1—N1—C5 | 39.9 (5) |
C2—C3—C4—C5 | −2.6 (10) | Cl2ii—Au1—N1—C5 | −56.3 (4) |
C3—C4—C5—N1 | 1.4 (10) | N1i—Au1—N1—C1 | 44.1 (5) |
C4—C5—N1—C1 | 2.7 (9) | Cl1i—Au1—N1—C1 | −130.0 (4) |
C4—C5—N1—Au1 | −167.3 (5) | Cl2ii—Au1—N1—C1 | 133.7 (4) |
N2—C1—N1—C5 | 175.4 (6) | N1—C1—N2—C1i | −36.9 (12) |
C2—C1—N1—C5 | −5.7 (8) | C2—C1—N2—C1i | 144.1 (6) |
N2—C1—N1—Au1 | −14.5 (8) | | |
Symmetry codes: (i) x, −y+1/2, z; (ii) x, y, z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···Cl2 | 0.90 | 2.34 | 3.162 (7) | 153 |
C5—H5···Cl1iii | 0.93 | 2.74 | 3.457 (6) | 135 |
Symmetry code: (iii) −x, y+1/2, −z+2. |