A new substance,
cis-amminedibromido(2-methylpyridine-κ
N)platinum(II),
cis-[PtBr
2(C
6H
7N)(NH
3)], which is a potential platinum-based antineoplastic agent for the treatment of patients with solid tumors, has been synthesized and structurally characterized. There is one molecule in the asymmetric unit and molecules are linked
via two symmetry-independent N—H
Br hydrogen bonds into zigzag chains running parallel to the
c axis. C—H
Br hydrogen bonds crosslink these chains to give a layer parallel to (010). N—H
Br hydrogen bonds and π–π stacking interactions between pairs of pyridine rings stack the layers along
b.
Supporting information
CCDC reference: 934593
Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: JANA2006 (Petříček et al., 2006).
cis-amminedibromido(2-methylpyridine-
κN)platinum(II)
top
Crystal data top
[PtBr2(C6H7N)(NH3)] | F(000) = 832 |
Mr = 465 | Dx = 3.018 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: -P 2ybc | Cell parameters from 13149 reflections |
a = 10.0371 (3) Å | θ = 4.5–77.0° |
b = 9.0733 (3) Å | µ = 34.36 mm−1 |
c = 11.4901 (4) Å | T = 190 K |
β = 102.120 (3)° | Block, yellow |
V = 1023.07 (6) Å3 | 0.23 × 0.17 × 0.10 mm |
Z = 4 | |
Data collection top
Oxford Diffraction Xcalibur diffractometer with an Onyx detector | 2148 independent reflections |
Radiation source: Enhance (Cu) X-ray Source | 1822 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.090 |
Detector resolution: 8.1917 pixels mm-1 | θmax = 77.3°, θmin = 4.5° |
ω scans | h = −12→12 |
Absorption correction: multi-scan [CrysAlis PRO (Agilent, 2011) using spherical harminics] | k = −11→11 |
Tmin = 0.212, Tmax = 1 | l = −14→14 |
25523 measured reflections | |
Refinement top
Refinement on F | 40 constraints |
R[F > 3σ(F)] = 0.030 | H-atom parameters constrained |
wR(F) = 0.036 | Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0001F2) |
S = 1.69 | (Δ/σ)max = 0.013 |
2148 reflections | Δρmax = 1.35 e Å−3 |
100 parameters | Δρmin = −2.43 e Å−3 |
0 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.37243 (3) | 0.67977 (3) | 0.19269 (2) | 0.01751 (9) | |
Br1 | 0.25429 (7) | 0.54401 (9) | 0.32423 (7) | 0.0241 (2) | |
Br2 | 0.58974 (7) | 0.67033 (10) | 0.33290 (7) | 0.0292 (2) | |
N1 | 0.1947 (6) | 0.6881 (6) | 0.0673 (5) | 0.0197 (17) | |
N2 | 0.4656 (7) | 0.8066 (7) | 0.0871 (6) | 0.031 (2) | |
C2 | −0.0253 (8) | 0.7924 (10) | 0.0069 (8) | 0.037 (3) | |
C4 | 0.0498 (7) | 0.6082 (9) | −0.1112 (7) | 0.026 (2) | |
C6 | 0.2841 (8) | 0.5045 (9) | −0.0506 (7) | 0.033 (3) | |
C3 | −0.0517 (8) | 0.7047 (9) | −0.0912 (8) | 0.037 (3) | |
C5 | 0.1741 (7) | 0.6022 (8) | −0.0307 (6) | 0.022 (2) | |
C1 | 0.0980 (8) | 0.7816 (9) | 0.0853 (7) | 0.033 (3) | |
H1c2 | −0.09248 | 0.861425 | 0.02128 | 0.0444* | |
H1c4 | 0.033681 | 0.546279 | −0.180466 | 0.0312* | |
H1c6 | 0.246621 | 0.428601 | −0.106109 | 0.0395* | |
H3c6 | 0.349494 | 0.560623 | −0.082071 | 0.0395* | |
H2c6 | 0.327947 | 0.460325 | 0.023537 | 0.0395* | |
H1c3 | −0.138423 | 0.708938 | −0.145711 | 0.0443* | |
H1c1 | 0.115307 | 0.842899 | 0.154975 | 0.0396* | |
H1n2 | 0.496737 | 0.750471 | 0.037425 | 0.0377* | |
H3n2 | 0.407211 | 0.868809 | 0.047642 | 0.0377* | |
H2n2 | 0.532822 | 0.854564 | 0.131117 | 0.0377* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.01468 (14) | 0.02128 (15) | 0.01572 (16) | −0.00189 (12) | 0.00125 (10) | −0.00082 (12) |
Br1 | 0.0180 (3) | 0.0318 (4) | 0.0222 (4) | −0.0043 (3) | 0.0033 (3) | 0.0025 (3) |
Br2 | 0.0171 (3) | 0.0461 (5) | 0.0218 (4) | −0.0092 (3) | −0.0018 (3) | 0.0026 (4) |
N1 | 0.023 (3) | 0.018 (3) | 0.018 (3) | 0.003 (2) | 0.003 (2) | 0.002 (2) |
N2 | 0.031 (3) | 0.035 (4) | 0.028 (4) | −0.008 (3) | 0.005 (3) | 0.007 (3) |
C2 | 0.020 (4) | 0.041 (5) | 0.049 (5) | 0.013 (4) | 0.006 (4) | 0.002 (4) |
C4 | 0.017 (3) | 0.036 (4) | 0.024 (4) | −0.007 (3) | 0.003 (3) | 0.004 (3) |
C6 | 0.032 (4) | 0.032 (4) | 0.034 (5) | 0.008 (4) | 0.005 (4) | −0.008 (4) |
C3 | 0.020 (4) | 0.041 (5) | 0.046 (5) | −0.002 (3) | 0.000 (4) | 0.010 (4) |
C5 | 0.023 (3) | 0.025 (4) | 0.018 (3) | −0.002 (3) | 0.004 (3) | −0.003 (3) |
C1 | 0.032 (4) | 0.035 (4) | 0.031 (4) | 0.013 (4) | 0.005 (3) | −0.003 (4) |
Geometric parameters (Å, º) top
Pt1—Br1 | 2.4414 (9) | N2—H2n2 | 0.87 |
Pt1—Br2 | 2.4258 (7) | C2—C3 | 1.360 (13) |
Pt1—N1 | 2.045 (5) | C2—C1 | 1.373 (11) |
Pt1—N2 | 2.037 (7) | C2—H1c2 | 0.96 |
Br1—N1 | 3.169 (6) | C4—C3 | 1.399 (12) |
Br1—N2i | 3.518 (7) | C4—C5 | 1.389 (9) |
Br1—N2ii | 3.574 (6) | C4—H1c4 | 0.96 |
Br2—N2 | 3.095 (6) | C6—C5 | 1.471 (12) |
Br2—N2i | 3.502 (7) | C6—H1c6 | 0.96 |
Br2—N2ii | 3.414 (7) | C6—H3c6 | 0.96 |
N1—C5 | 1.349 (9) | C6—H2c6 | 0.96 |
N1—C1 | 1.338 (11) | C3—H1c3 | 0.96 |
N2—H1n2 | 0.87 | C1—H1c1 | 0.96 |
N2—H3n2 | 0.87 | | |
| | | |
Br1—Pt1—Br2 | 93.26 (3) | Br1iv—N2—Br2iv | 60.79 (11) |
Br1—Pt1—N1 | 89.42 (18) | Br1iv—N2—H1n2 | 84.17 |
Br1—Pt1—N2 | 175.9 (2) | Br1iv—N2—H3n2 | 25.53 |
Br2—Pt1—N1 | 176.94 (18) | Br1iv—N2—H2n2 | 123.47 |
Br2—Pt1—N2 | 87.37 (18) | Br2—N2—Br2iii | 101.10 (18) |
N1—Pt1—N2 | 90.1 (2) | Br2—N2—Br2iv | 131.0 (2) |
Pt1—Br1—N1 | 40.20 (11) | Br2—N2—H1n2 | 103.53 |
Pt1—Br1—N2i | 91.48 (12) | Br2—N2—H3n2 | 146.4 |
Pt1—Br1—N2ii | 93.01 (12) | Br2—N2—H2n2 | 63.59 |
N1—Br1—N2i | 120.35 (16) | Br2iii—N2—Br2iv | 105.86 (18) |
N1—Br1—N2ii | 126.39 (15) | Br2iii—N2—H1n2 | 145.3 |
N2i—Br1—N2ii | 72.01 (15) | Br2iii—N2—H3n2 | 52.99 |
Pt1—Br2—N2 | 41.10 (13) | Br2iii—N2—H2n2 | 61.44 |
Pt1—Br2—N2i | 92.15 (11) | Br2iv—N2—H1n2 | 39.57 |
Pt1—Br2—N2ii | 97.31 (11) | Br2iv—N2—H3n2 | 80.88 |
N2—Br2—N2i | 124.08 (16) | Br2iv—N2—H2n2 | 95.12 |
N2—Br2—N2ii | 127.37 (18) | H1n2—N2—H3n2 | 109.47 |
N2i—Br2—N2ii | 74.14 (16) | H1n2—N2—H2n2 | 109.47 |
Pt1—N1—Br1 | 50.38 (12) | H3n2—N2—H2n2 | 109.47 |
Pt1—N1—C5 | 121.7 (5) | C3—C2—C1 | 119.7 (8) |
Pt1—N1—C1 | 117.9 (5) | C3—C2—H1c2 | 120.17 |
Br1—N1—C5 | 120.3 (4) | C1—C2—H1c2 | 120.17 |
Br1—N1—C1 | 96.8 (5) | C3—C4—C5 | 119.9 (7) |
C5—N1—C1 | 120.4 (6) | C3—C4—H1c4 | 120.04 |
Pt1—N2—Br1iii | 127.8 (3) | C5—C4—H1c4 | 120.03 |
Pt1—N2—Br1iv | 116.9 (3) | C5—C6—H1c6 | 109.47 |
Pt1—N2—Br2 | 51.53 (14) | C5—C6—H3c6 | 109.47 |
Pt1—N2—Br2iii | 104.9 (3) | C5—C6—H2c6 | 109.47 |
Pt1—N2—Br2iv | 147.2 (3) | H1c6—C6—H3c6 | 109.47 |
Pt1—N2—H1n2 | 109.47 | H1c6—C6—H2c6 | 109.47 |
Pt1—N2—H3n2 | 109.47 | H3c6—C6—H2c6 | 109.47 |
Pt1—N2—H2n2 | 109.47 | C2—C3—C4 | 118.7 (7) |
Br1iii—N2—Br1iv | 107.99 (18) | C2—C3—H1c3 | 120.66 |
Br1iii—N2—Br2 | 80.58 (14) | C4—C3—H1c3 | 120.66 |
Br1iii—N2—Br2iii | 60.53 (11) | N1—C5—C4 | 119.5 (7) |
Br1iii—N2—Br2iv | 78.31 (16) | N1—C5—C6 | 119.3 (6) |
Br1iii—N2—H1n2 | 99.98 | C4—C5—C6 | 121.3 (7) |
Br1iii—N2—H3n2 | 99.42 | N1—C1—C2 | 121.8 (8) |
Br1iii—N2—H2n2 | 18.3 | N1—C1—H1c1 | 119.1 |
Br1iv—N2—Br2 | 167.6 (3) | C2—C1—H1c1 | 119.1 |
Br1iv—N2—Br2iii | 76.44 (13) | | |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+3/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···Br2iv | 0.87 | 2.80 | 3.414 (7) | 129 |
N2—H3N2···Br1iv | 0.87 | 2.81 | 3.574 (6) | 147 |
C3—H1C3···Br2v | 0.96 | 2.90 | 3.698 (8) | 141 |
N2—H3N2···Br2iii | 0.87 | 3.06 | 3.502 (7) | 114 |
N2—H2N2···Br1iii | 0.87 | 2.71 | 3.518 (7) | 156 |
Symmetry codes: (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z−1/2; (v) x−1, −y+3/2, z−1/2. |