metal-organic compounds
cis-Diammine[3-(3-chloro-7-methoxy-9,10-dihydroacridin-9-ylideneamino)propan-1-amine-κ2N,N′]platinum(II) dinitrate
aDivision of Chemical Biology & Medicinal Chemistry, College of Pharmacy, University of Texas at Austin, Austin, Texas 78712, USA
*Correspondence e-mail: seongminlee@austin.utexas.edu
The title complex salt, [Pt(C16H17N3)(NH3)2](NO3)2, is of interest with respect to anticancer activity. The secondary amine of 9-aminoacridine coordinates with the platinum(II) atom, leading to imine–platinum complex cation formation. The displays extensive N—H⋯O and N—H⋯N hydrogen bonding and weak C—H⋯Cl and C—H⋯O hydrogen bonding.
Keywords: crystal structure; platinum ammine complex; 9-aminoacridine; 9,10-dihydroacridin-9-imine.
CCDC reference: 1469909
Structure description
Platinum has been widely used for chemotherapy since cisplatin was approved by the US Food and Drug Administration in 1978 (Galanski et al., 2005). Unfortunately, due to the widespread use of platinum drugs, patients began to develop drug resistance (Shen et al., 2012). Non-classical platinum drugs, for example, platinum-intercalator conjugates are thought to be an alternative solution to overcome cisplatin resistance (Johnstone et al., 2014; Baruah et al., 2004; Martins et al., 2001). We attempted to synthesize a 9-aminoacridine derivative linked with monofunctional platinum via a three-carbon alkyl chain. During the platination reaction between the primary amine and cis-[Pt(NH3)2(O-donor)Cl]+ (O-donor = O1-DMF and NO3−), an unexpected product formed predominantly. We grew crystals of the compound to investigate the structure via X-ray diffraction of the crystal.
The secondary amine of 9-aminoacridine replaced the chloride to form a platinum–nitrogen complex. The platinum complex (Fig. 1) has a square-planar geometry and the three-carbon alkyl chain became part of a newly formed six-membered ring with Pt, N13 and N9. The longer bond lengths of N13—Pt [2.053 (9) Å] and N9—Pt [1.993 (8) Å] appears to compensate for the smaller bond angle of N13—Pt—N9 [87.3 (3)°], allowing the six-membered ring to adopt a conformation similar to a chair conformation. The bond length of N9—C9 [1.293 (13) Å], 120° bond angles around N9 and C9, and the protonation of N10 suggest the formation of an imine and proton rearrangement (Fig. 2). The resulting acridin-imine is strained around C9. The C1—C9A—C9—N9 torsion angle is 33 (1)° and C8—C8A-–C9—N9 is −35 (2)°. The ring is bent approximately 15°, resembling a bow when viewed from the side.
There are two nitrate ions present in the crystal. One nitrate can form hydrogen bonds (Table 1) with H10 [H10—O19B = 2.20 (12) Å] and H13C (H13C–O19A = 2.059 Å), and the other can form a hydrogen bond with H13D (H13D—O18A = 2.03 Å). The packing is illustrated in Fig. 3.
Synthesis and crystallization
cis-[Pt(NH3)2(Od)Cl]+ (Od = O1-DMF and NO3−) was prepared from cisplatin (45 mg, 0.15 mmol) and silver nitrate (26 mg, 0.15 mmol) in N,N-dimethylformamide at 55°C in the dark for 1–3 days (Hollis et al., 1989). The title compound was prepared by mixing N1-(6-chloro-2-methoxyacridin-9-yl)propane-1,3-diamine (32 mg, 0.1 mmol) and cis-[Pt(NH3)2(Od)Cl]+ in DMF at 55°C in the dark for 24 h. DMF was removed under high vacuum and the crude mixture was dissolved in methanol (4 ml). Any undissolved solids were removed via filtration. Cold diethyl ether (60 ml) was poured to the filtrate, resulting in precipitation of the desired product. The fine precipitates were collected with EMD Millipore HNWP grade 0.45 µm nylon membrane filter (37 mg, 0.042 mmol, 42% yield). Yellow, thin-needle crystals of the title compound were obtained from vapor diffusion between methanol and diethyl ether.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
|
Structural data
CCDC reference: 1469909
10.1107/S2414314616004818/xu4005sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616004818/xu4005Isup2.hkl
Platinum has been widely used for chemotherapy since cisplatin was approved by US Food and Drug Administration in 1978 (Galanski et al., 2005). Unfortunately due to the widespread use of platinum drugs, patients began to develop drug resistance (Shen et al., 2012). Non-classical platinum drugs, for example, platinum-intercalator conjugates are thought to be an alternative solution to overcome cisplatin resistance (Johnstone et al., 2014; Baruah et al., 2004; Martins et al., 2001). We attempted to synthesize a 9-aminoacridine derivative linked with monofunctional platinum via 3-carbon alkyl chain. During the platination reaction between the primary amine and cis-[Pt(NH3)2(N-donor)Cl]+ (N-donor = O1-DMF and NO3-), an unexpected product formed predominantly. We grew crystals of the compound to investigate the structure via X-ray diffraction of the crystal.
The secondary amine of 9-aminoacridine replaced the chloride to form a platinum-nitrogen complex. The platinum-nitrogen complex has a square planar geometry and the 3-carbon alkyl chain became part of a newly formed 6-membered ring of Pt, N13 and N9. The longer bond lengths of N13–Pt [2.054 (9) Å] and N9–Pt [1.993 (8) Å] appears to compensate for the smaller bond angle of N13–Pt–N9 [87.3 (3)°], allowing the 6-membered ring to adopt a conformation similar to chair conformation. The bond length of N9–C9 [1.29 (1) Å], ~120° bond angles around N9 and C9, and the protonation of N10 suggest the formation of imine and proton rearrangement (Figure 3). The resulting acridin-imine is strained around C9. The torsion angle of C1–C9A–C9–N9 is 33 (1)° and C8–C8A–C9–N9 is -35 (2)°. The ring is bent approximately 15°, resembling a bow when viewed from the side.
There are two nitrate ions present in the crystal. One nitrate can form hydrogen bonds with H10 [H10–O19B 2.2 (1) Å] and H13C (H13C–O19A 2.059 Å), and the other can form a hydrogen bond with H13D (H13D–O18A 2.02 Å).
cis-[Pt(NH3)2(Od)Cl]+ (Od = O1-DMF and NO3-) was prepared from cisplatin (45 mg, 0.15 mmol) and silver nitrate (26 mg, 0.15 mmol) in N,N-dimethylformamide at 55 °C in the dark for 1–3 days (Hollis et al., 1989). The title compound was prepared by mixing N1-(6-chloro-2-methoxyacridin-9-yl)propane-1,3-diamine (32mg, 0.1 mmol) and cis-[Pt(NH3)2(Od)Cl]+ in DMF at 55 °C in the dark for 24 hours. DMF was removed under high vacuum and the crude mixture was dissolved in methanol (4 mL). Any undissolved solids were removed via filtration. Cold diethyl ether (60 mL) was poured to the filtrate, resulting in precipitations of the desired product. The fine precipitates were collected with EMD Millipore HNWP grade 0.45 µm nylon membrane filter (37 mg, 0.042 mmol, 42% yield). Yellow, thin needle crystals of the title compound were obtained from vapor diffusion between methanol and diethyl ether.
Crystal data, data collection and structure
details are summarized in Table 1. The hydrogen atoms were calculated in ideal positions with isotropic displacement parameters set to 1.2 times Ueq of the attached atom (1.5 times Ueq for methyl hydrogen atoms). The hydrogen atom bound to N10 was calculated in an idealized position but was allowed to refine with its isotropic displacement parameter set to 1.2 times Ueq of N10.cis-[Pt(NH3)2(Od)Cl]+ (Od = O1-DMF and NO3-) was prepared from cisplatin (45 mg, 0.15 mmol) and silver nitrate (26 mg, 0.15 mmol) in N,N-dimethylformamide at 55°C in the dark for 1–3 days (Hollis et al., 1989). The title compound was prepared by mixing N1-(6-chloro-2-methoxyacridin-9-yl)propane-1,3-diamine (32 mg, 0.1 mmol) and cis-[Pt(NH3)2(Od)Cl]+ in DMF at 55°C in the dark for 24 h. DMF was removed under high vacuum and the crude mixture was dissolved in methanol (4 ml). Any undissolved solids were removed via filtration. Cold diethyl ether (60 ml) was poured to the filtrate, resulting in precipitation of the desired product. The fine precipitates were collected with EMD Millipore HNWP grade 0.45 µm nylon membrane filter (37 mg, 0.042 mmol, 42% yield). Yellow, thin-needle crystals of the title compound were obtained from vapor diffusion between methanol and diethyl ether.
Platinum has been widely used for chemotherapy since cisplatin was approved by the US Food and Drug Administration in 1978 (Galanski et al., 2005). Unfortunately, due to the widespread use of platinum drugs, patients began to develop drug resistance (Shen et al., 2012). Non-classical platinum drugs, for example, platinum-intercalator conjugates are thought to be an alternative solution to overcome cisplatin resistance (Johnstone et al., 2014; Baruah et al., 2004; Martins et al., 2001). We attempted to synthesize a 9-aminoacridine derivative linked with monofunctional platinum via a three-carbon alkyl chain. During the platination reaction between the primary amine and cis-[Pt(NH3)2(N-donor)Cl]+ (N-donor = O1-DMF and NO3-), an unexpected product formed predominantly. We grew crystals of the compound to investigate the structure via X-ray diffraction of the crystal.
The secondary amine of 9-aminoacridine replaced the chloride to form a platinum–nitrogen complex. The platinum–nitrogen complex (Fig. 1)has a square-planar geometry and the three-carbon alkyl chain became part of a newly formed six-membered ring of Pt, N13 and N9. The longer bond lengths of N13—Pt [2.053 (9) Å] and N9—Pt [1.993 (8) Å] appears to compensate for the smaller bond angle of N13—Pt—N9 [87.3 (3)°], allowing the six-membered ring to adopt a conformation similar to chair conformation. The bond length of N9—C9 [1.293 (13) Å], ~120° bond angles around N9 and C9, and the protonation of N10 suggest the formation of an imine and proton rearrangement (Fig. 2). The resulting acridin-imine is strained around C9. The C1—C9A—C9—N9 torsion angle is 33 (1)° and C8—C8A-–C9—N9 is -35 (2)°. The ring is bent approximately 15°, resembling a bow when viewed from the side.
There are two nitrate ions present in the crystal. One nitrate can form hydrogen bonds (Table 1) with H10 [H10—O19B = 2.20 (12) Å] and H13C (H13C–O19A = 2.059 Å), and the other can form a hydrogen bond with H13D (H13D—O18A = 2.03 Å). The packing is illustrated in Fig. 3.
Data collection: CrysAlis PRO (Agilent, 2013); cell
CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids for the non-H atoms at the 50% probability level. Nitrate counter-ions have been omitted for clarity. | |
Fig. 2. Potential mechanism of the formation of the title compound. | |
Fig. 3. Packing plot of the title compound. |
[Pt(C16H18N3)(NH3)2](NO3)2 | F(000) = 1304 |
Mr = 668.97 | Dx = 2.068 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 7.6398 (3) Å | Cell parameters from 2416 reflections |
b = 10.8372 (11) Å | θ = 3.4–72.7° |
c = 25.982 (4) Å | µ = 13.87 mm−1 |
β = 92.478 (5)° | T = 100 K |
V = 2149.1 (4) Å3 | Needle, yellow |
Z = 4 | 0.13 × 0.02 × 0.02 mm |
Agilent SuperNova with AtlasS2 CCD diffractometer | 3105 reflections with I > 2σ(I) |
Radiation source: sealed microfocus tube | Rint = 0.066 |
ω–scans | θmax = 75.2°, θmin = 3.4° |
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2013) | h = −9→5 |
Tmin = 0.503, Tmax = 1.00 | k = −13→7 |
8178 measured reflections | l = −30→31 |
4158 independent reflections |
Refinement on F2 | 444 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.059 | Only H-atom coordinates refined |
wR(F2) = 0.155 | w = 1/[σ2(Fo2) + (0.0625P)2 + 7.5338P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
4158 reflections | Δρmax = 2.22 e Å−3 |
304 parameters | Δρmin = −3.37 e Å−3 |
[Pt(C16H18N3)(NH3)2](NO3)2 | V = 2149.1 (4) Å3 |
Mr = 668.97 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 7.6398 (3) Å | µ = 13.87 mm−1 |
b = 10.8372 (11) Å | T = 100 K |
c = 25.982 (4) Å | 0.13 × 0.02 × 0.02 mm |
β = 92.478 (5)° |
Agilent SuperNova with AtlasS2 CCD diffractometer | 4158 independent reflections |
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2013) | 3105 reflections with I > 2σ(I) |
Tmin = 0.503, Tmax = 1.00 | Rint = 0.066 |
8178 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 444 restraints |
wR(F2) = 0.155 | Only H-atom coordinates refined |
S = 1.04 | Δρmax = 2.22 e Å−3 |
4158 reflections | Δρmin = −3.37 e Å−3 |
304 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C13 | 0.5794 (15) | 1.0413 (10) | 0.6474 (4) | 0.024 (2) | |
H13A | 0.6710 | 1.0710 | 0.6725 | 0.028* | |
H13B | 0.4831 | 1.1025 | 0.6463 | 0.028* | |
C12 | 0.6562 (15) | 1.0332 (10) | 0.5942 (4) | 0.024 (2) | |
H12A | 0.5618 | 1.0093 | 0.5689 | 0.029* | |
H12B | 0.6978 | 1.1162 | 0.5845 | 0.029* | |
C11 | 0.8071 (15) | 0.9424 (10) | 0.5904 (5) | 0.025 (2) | |
H11A | 0.8578 | 0.9494 | 0.5561 | 0.029* | |
H11B | 0.9000 | 0.9621 | 0.6169 | 0.029* | |
C9 | 0.7168 (13) | 0.7372 (9) | 0.5604 (4) | 0.0181 (18) | |
C8A | 0.7632 (13) | 0.7546 (9) | 0.5058 (4) | 0.0187 (19) | |
C8 | 0.7575 (13) | 0.8684 (10) | 0.4799 (4) | 0.022 (2) | |
H8 | 0.7111 | 0.9386 | 0.4965 | 0.026* | |
C7 | 0.8178 (14) | 0.8798 (11) | 0.4312 (4) | 0.026 (2) | |
H7 | 0.8093 | 0.9563 | 0.4135 | 0.031* | |
C6 | 0.8915 (14) | 0.7780 (11) | 0.4084 (4) | 0.025 (2) | |
C5 | 0.8907 (13) | 0.6629 (11) | 0.4302 (4) | 0.024 (2) | |
H5 | 0.9377 | 0.5937 | 0.4131 | 0.029* | |
C4B | 0.8181 (13) | 0.6505 (10) | 0.4788 (4) | 0.022 (2) | |
C4A | 0.7001 (14) | 0.5117 (10) | 0.5402 (4) | 0.020 (2) | |
C4 | 0.6508 (14) | 0.3901 (10) | 0.5529 (4) | 0.023 (2) | |
H4 | 0.6940 | 0.3219 | 0.5343 | 0.027* | |
C3 | 0.5401 (15) | 0.3714 (11) | 0.5923 (4) | 0.025 (2) | |
H3 | 0.5032 | 0.2900 | 0.5998 | 0.030* | |
C2 | 0.4806 (14) | 0.4694 (10) | 0.6216 (4) | 0.024 (2) | |
C1 | 0.5295 (13) | 0.5870 (9) | 0.6094 (4) | 0.0181 (19) | |
H1 | 0.4828 | 0.6545 | 0.6277 | 0.022* | |
C9A | 0.6466 (13) | 0.6103 (9) | 0.5707 (4) | 0.0180 (19) | |
C17 | 0.3137 (15) | 0.5425 (11) | 0.6906 (4) | 0.028 (2) | |
H17A | 0.4163 | 0.5799 | 0.7083 | 0.042* | |
H17B | 0.2330 | 0.5124 | 0.7161 | 0.042* | |
H17C | 0.2542 | 0.6042 | 0.6685 | 0.042* | |
N13 | 0.5114 (12) | 0.9219 (8) | 0.6653 (4) | 0.0247 (19) | |
H13C | 0.4258 | 0.8952 | 0.6425 | 0.030* | |
H13D | 0.4625 | 0.9330 | 0.6963 | 0.030* | |
N9 | 0.7426 (10) | 0.8136 (7) | 0.5982 (3) | 0.0131 (15) | |
N10 | 0.8018 (12) | 0.5329 (9) | 0.4987 (4) | 0.0224 (19) | |
N15 | 0.9092 (13) | 0.6683 (9) | 0.6799 (4) | 0.028 (2) | |
H15A | 0.9869 | 0.6955 | 0.7049 | 0.042* | |
H15B | 0.9632 | 0.6636 | 0.6494 | 0.042* | |
H15C | 0.8693 | 0.5923 | 0.6885 | 0.042* | |
N14 | 0.6630 (14) | 0.7624 (9) | 0.7488 (3) | 0.030 (2) | |
H14A | 0.6614 | 0.6801 | 0.7557 | 0.045* | |
H14B | 0.5588 | 0.7965 | 0.7569 | 0.045* | |
H14C | 0.7512 | 0.7988 | 0.7680 | 0.045* | |
N18 | 0.1917 (13) | 0.8899 (10) | 0.7529 (4) | 0.031 (2) | |
N19 | 1.1839 (13) | 0.7603 (9) | 0.5780 (4) | 0.0285 (19) | |
O1 | 0.3694 (10) | 0.4397 (7) | 0.6591 (3) | 0.0281 (17) | |
O18C | 0.2424 (13) | 0.7816 (9) | 0.7465 (4) | 0.046 (2) | |
O18B | 0.0363 (12) | 0.9147 (10) | 0.7567 (4) | 0.052 (3) | |
O18A | 0.3072 (12) | 0.9761 (9) | 0.7549 (4) | 0.039 (2) | |
O19A | 1.1896 (10) | 0.8149 (7) | 0.6210 (3) | 0.0280 (17) | |
O19B | 1.1044 (11) | 0.6585 (7) | 0.5742 (3) | 0.0304 (18) | |
O19C | 1.2554 (14) | 0.8075 (8) | 0.5413 (4) | 0.047 (2) | |
Cl6 | 0.9803 (4) | 0.7921 (3) | 0.34724 (11) | 0.0360 (7) | |
Pt | 0.70226 (6) | 0.78889 (4) | 0.67275 (2) | 0.02123 (16) | |
H10 | 0.816 (17) | 0.483 (12) | 0.481 (5) | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C13 | 0.025 (4) | 0.013 (4) | 0.034 (5) | 0.005 (3) | 0.009 (4) | 0.002 (3) |
C12 | 0.027 (4) | 0.013 (4) | 0.033 (5) | 0.004 (4) | 0.008 (4) | −0.001 (3) |
C11 | 0.025 (4) | 0.012 (4) | 0.037 (5) | 0.000 (3) | 0.012 (4) | −0.002 (3) |
C9 | 0.017 (4) | 0.014 (3) | 0.024 (3) | −0.002 (3) | 0.005 (3) | 0.003 (3) |
C8A | 0.018 (4) | 0.014 (3) | 0.024 (3) | −0.001 (3) | 0.005 (3) | −0.001 (3) |
C8 | 0.019 (4) | 0.017 (4) | 0.029 (4) | 0.001 (3) | 0.002 (3) | 0.000 (3) |
C7 | 0.025 (5) | 0.024 (4) | 0.028 (4) | 0.000 (4) | 0.005 (3) | 0.002 (3) |
C6 | 0.020 (4) | 0.027 (4) | 0.029 (4) | −0.004 (3) | 0.007 (3) | 0.000 (3) |
C5 | 0.018 (4) | 0.024 (4) | 0.030 (4) | 0.003 (3) | 0.007 (3) | −0.001 (3) |
C4B | 0.019 (4) | 0.018 (4) | 0.029 (4) | 0.000 (3) | 0.007 (3) | −0.002 (3) |
C4A | 0.022 (4) | 0.014 (3) | 0.026 (4) | −0.002 (3) | 0.002 (3) | 0.001 (3) |
C4 | 0.024 (4) | 0.013 (4) | 0.031 (4) | −0.002 (3) | 0.002 (4) | 0.001 (3) |
C3 | 0.029 (4) | 0.015 (4) | 0.032 (4) | −0.005 (3) | 0.004 (4) | 0.003 (3) |
C2 | 0.025 (4) | 0.018 (4) | 0.029 (4) | −0.008 (3) | 0.004 (4) | −0.002 (3) |
C1 | 0.015 (4) | 0.014 (4) | 0.024 (4) | 0.001 (3) | 0.001 (3) | −0.001 (3) |
C9A | 0.019 (4) | 0.010 (3) | 0.025 (4) | −0.002 (3) | 0.004 (3) | −0.002 (3) |
C17 | 0.028 (5) | 0.027 (5) | 0.031 (5) | 0.006 (4) | 0.011 (4) | 0.002 (4) |
N13 | 0.027 (4) | 0.019 (4) | 0.029 (4) | −0.002 (3) | 0.005 (3) | 0.001 (3) |
N9 | 0.016 (3) | 0.012 (3) | 0.011 (3) | −0.003 (3) | 0.004 (2) | 0.003 (2) |
N10 | 0.022 (4) | 0.015 (3) | 0.031 (4) | −0.002 (3) | 0.008 (3) | −0.001 (3) |
N15 | 0.034 (4) | 0.025 (5) | 0.025 (5) | 0.000 (4) | 0.000 (4) | 0.005 (4) |
N14 | 0.045 (5) | 0.033 (5) | 0.012 (4) | 0.001 (4) | 0.002 (3) | −0.001 (3) |
N18 | 0.029 (4) | 0.036 (4) | 0.028 (5) | 0.003 (3) | 0.011 (3) | −0.006 (3) |
N19 | 0.029 (4) | 0.022 (4) | 0.035 (4) | 0.007 (3) | 0.005 (3) | 0.001 (3) |
O1 | 0.030 (4) | 0.023 (4) | 0.033 (4) | −0.004 (3) | 0.012 (3) | 0.000 (3) |
O18C | 0.051 (5) | 0.036 (4) | 0.051 (6) | 0.006 (4) | 0.013 (4) | −0.010 (4) |
O18B | 0.031 (4) | 0.054 (6) | 0.072 (7) | 0.004 (4) | 0.017 (4) | 0.006 (5) |
O18A | 0.037 (4) | 0.037 (4) | 0.046 (5) | −0.005 (3) | 0.012 (4) | −0.014 (4) |
O19A | 0.023 (4) | 0.026 (4) | 0.035 (4) | 0.005 (3) | 0.007 (3) | −0.002 (3) |
O19B | 0.029 (4) | 0.019 (3) | 0.044 (5) | 0.004 (3) | 0.006 (3) | −0.004 (3) |
O19C | 0.065 (6) | 0.032 (5) | 0.044 (4) | −0.004 (4) | 0.025 (4) | 0.001 (4) |
Cl6 | 0.0408 (15) | 0.0412 (17) | 0.0271 (14) | −0.0127 (15) | 0.0124 (12) | −0.0027 (13) |
Pt | 0.0231 (2) | 0.0156 (2) | 0.0255 (3) | 0.0002 (2) | 0.00693 (17) | 0.0003 (2) |
C13—H13A | 0.9900 | C3—H3 | 0.9500 |
C13—H13B | 0.9900 | C3—C2 | 1.393 (16) |
C13—C12 | 1.527 (14) | C2—C1 | 1.370 (15) |
C13—N13 | 1.477 (13) | C2—O1 | 1.359 (13) |
C12—H12A | 0.9900 | C1—H1 | 0.9500 |
C12—H12B | 0.9900 | C1—C9A | 1.398 (13) |
C12—C11 | 1.522 (14) | C17—H17A | 0.9800 |
C11—H11A | 0.9900 | C17—H17B | 0.9800 |
C11—H11B | 0.9900 | C17—H17C | 0.9800 |
C11—N9 | 1.497 (12) | C17—O1 | 1.457 (13) |
C9—C8A | 1.489 (14) | N13—H13C | 0.9100 |
C9—C9A | 1.504 (14) | N13—H13D | 0.9100 |
C9—N9 | 1.293 (13) | N13—Pt | 2.053 (9) |
C8A—C8 | 1.404 (15) | N9—Pt | 1.993 (8) |
C8A—C4B | 1.402 (14) | N10—H10 | 0.72 (12) |
C8—H8 | 0.9500 | N15—H15A | 0.9100 |
C8—C7 | 1.371 (14) | N15—H15B | 0.9100 |
C7—H7 | 0.9500 | N15—H15C | 0.9100 |
C7—C6 | 1.384 (16) | N15—Pt | 2.053 (10) |
C6—C5 | 1.371 (16) | N14—H14A | 0.9100 |
C6—Cl6 | 1.760 (11) | N14—H14B | 0.9100 |
C5—H5 | 0.9500 | N14—H14C | 0.9100 |
C5—C4B | 1.407 (14) | N14—Pt | 2.033 (9) |
C4B—N10 | 1.383 (14) | N18—O18C | 1.249 (13) |
C4A—C4 | 1.414 (14) | N18—O18B | 1.225 (13) |
C4A—C9A | 1.402 (14) | N18—O18A | 1.284 (13) |
C4A—N10 | 1.374 (14) | N19—O19A | 1.262 (12) |
C4—H4 | 0.9500 | N19—O19B | 1.261 (13) |
C4—C3 | 1.370 (15) | N19—O19C | 1.231 (13) |
H13A—C13—H13B | 107.8 | O1—C2—C1 | 124.8 (10) |
C12—C13—H13A | 109.0 | C2—C1—H1 | 119.2 |
C12—C13—H13B | 109.0 | C2—C1—C9A | 121.6 (10) |
N13—C13—H13A | 109.0 | C9A—C1—H1 | 119.2 |
N13—C13—H13B | 109.0 | C4A—C9A—C9 | 118.8 (9) |
N13—C13—C12 | 112.9 (9) | C1—C9A—C9 | 122.4 (9) |
C13—C12—H12A | 108.6 | C1—C9A—C4A | 118.8 (9) |
C13—C12—H12B | 108.6 | H17A—C17—H17B | 109.5 |
H12A—C12—H12B | 107.6 | H17A—C17—H17C | 109.5 |
C11—C12—C13 | 114.7 (9) | H17B—C17—H17C | 109.5 |
C11—C12—H12A | 108.6 | O1—C17—H17A | 109.5 |
C11—C12—H12B | 108.6 | O1—C17—H17B | 109.5 |
C12—C11—H11A | 109.7 | O1—C17—H17C | 109.5 |
C12—C11—H11B | 109.7 | C13—N13—H13C | 109.0 |
H11A—C11—H11B | 108.2 | C13—N13—H13D | 109.0 |
N9—C11—C12 | 109.8 (9) | C13—N13—Pt | 112.8 (7) |
N9—C11—H11A | 109.7 | H13C—N13—H13D | 107.8 |
N9—C11—H11B | 109.7 | Pt—N13—H13C | 109.0 |
C8A—C9—C9A | 112.7 (9) | Pt—N13—H13D | 109.0 |
N9—C9—C8A | 127.4 (9) | C11—N9—Pt | 108.8 (6) |
N9—C9—C9A | 119.7 (9) | C9—N9—C11 | 122.3 (8) |
C8—C8A—C9 | 124.3 (9) | C9—N9—Pt | 128.8 (7) |
C8—C8A—C4B | 118.1 (10) | C4B—N10—H10 | 115 (10) |
C4B—C8A—C9 | 117.6 (9) | C4A—N10—C4B | 120.7 (9) |
C8A—C8—H8 | 119.5 | C4A—N10—H10 | 119 (10) |
C7—C8—C8A | 121.1 (10) | H15A—N15—H15B | 109.5 |
C7—C8—H8 | 119.5 | H15A—N15—H15C | 109.5 |
C8—C7—H7 | 120.5 | H15B—N15—H15C | 109.5 |
C8—C7—C6 | 118.9 (11) | Pt—N15—H15A | 109.5 |
C6—C7—H7 | 120.5 | Pt—N15—H15B | 109.5 |
C7—C6—Cl6 | 119.9 (9) | Pt—N15—H15C | 109.5 |
C5—C6—C7 | 122.5 (10) | H14A—N14—H14B | 109.5 |
C5—C6—Cl6 | 117.5 (9) | H14A—N14—H14C | 109.5 |
C6—C5—H5 | 121.1 | H14B—N14—H14C | 109.5 |
C6—C5—C4B | 117.9 (10) | Pt—N14—H14A | 109.5 |
C4B—C5—H5 | 121.1 | Pt—N14—H14B | 109.5 |
C8A—C4B—C5 | 120.7 (10) | Pt—N14—H14C | 109.5 |
N10—C4B—C8A | 121.3 (10) | O18C—N18—O18A | 118.2 (10) |
N10—C4B—C5 | 117.9 (10) | O18B—N18—O18C | 121.6 (11) |
C9A—C4A—C4 | 119.3 (10) | O18B—N18—O18A | 120.2 (11) |
N10—C4A—C4 | 120.3 (10) | O19B—N19—O19A | 118.6 (10) |
N10—C4A—C9A | 120.3 (9) | O19C—N19—O19A | 119.3 (10) |
C4A—C4—H4 | 120.3 | O19C—N19—O19B | 122.0 (11) |
C3—C4—C4A | 119.5 (10) | C2—O1—C17 | 115.4 (9) |
C3—C4—H4 | 120.3 | N9—Pt—N13 | 87.3 (3) |
C4—C3—H3 | 119.3 | N9—Pt—N15 | 91.3 (4) |
C4—C3—C2 | 121.5 (10) | N9—Pt—N14 | 179.5 (4) |
C2—C3—H3 | 119.3 | N15—Pt—N13 | 174.9 (4) |
C1—C2—C3 | 119.0 (10) | N14—Pt—N13 | 93.3 (4) |
O1—C2—C3 | 116.1 (10) | N14—Pt—N15 | 88.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H10···O19Bi | 0.72 (12) | 2.20 (12) | 2.919 (12) | 172 (14) |
N13—H13C···O19Aii | 0.91 | 2.06 | 2.910 (13) | 155 |
N13—H13D···N18 | 0.91 | 2.63 | 3.428 (13) | 147 |
N13—H13D···O18A | 0.91 | 2.03 | 2.918 (13) | 166 |
N14—H14A···O18Aiii | 0.91 | 2.24 | 3.113 (14) | 160 |
N14—H14B···O18C | 0.91 | 2.43 | 3.218 (15) | 146 |
N14—H14C···O18Biv | 0.91 | 2.54 | 3.294 (15) | 140 |
N14—H14C···Cl6v | 0.91 | 2.82 | 3.497 (10) | 132 |
N15—H15A···O18Civ | 0.91 | 2.38 | 3.257 (15) | 162 |
N15—H15B···O19A | 0.91 | 2.52 | 3.120 (13) | 124 |
N15—H15B···O19B | 0.91 | 2.27 | 3.183 (13) | 178 |
N15—H15C···O18Biii | 0.91 | 2.48 | 3.223 (14) | 139 |
N15—H15C···O18Aiii | 0.91 | 2.40 | 3.192 (13) | 146 |
C4—H4···O19Ci | 0.95 | 2.46 | 3.354 (14) | 157 |
C7—H7···O19Avi | 0.95 | 2.64 | 3.576 (14) | 170 |
C11—H11B···Cl6vi | 0.99 | 2.95 | 3.649 (12) | 128 |
C17—H17A···O18Aiii | 0.98 | 2.54 | 3.250 (15) | 129 |
C17—H17B···O18Bvii | 0.98 | 2.45 | 3.356 (15) | 154 |
C17—H17C···O19Aii | 0.98 | 2.63 | 3.568 (14) | 160 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z+3/2; (iv) x+1, y, z; (v) x, −y+3/2, z+1/2; (vi) −x+2, −y+2, −z+1; (vii) −x, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H10···O19Bi | 0.72 (12) | 2.20 (12) | 2.919 (12) | 172 (14) |
N13—H13C···O19Aii | 0.91 | 2.06 | 2.910 (13) | 155.2 |
N13—H13D···N18 | 0.91 | 2.63 | 3.428 (13) | 146.6 |
N13—H13D···O18A | 0.91 | 2.03 | 2.918 (13) | 166.4 |
N14—H14A···O18Aiii | 0.91 | 2.24 | 3.113 (14) | 160.0 |
N14—H14B···O18C | 0.91 | 2.43 | 3.218 (15) | 145.6 |
N14—H14C···O18Biv | 0.91 | 2.54 | 3.294 (15) | 140.3 |
N14—H14C···Cl6v | 0.91 | 2.82 | 3.497 (10) | 132.0 |
N15—H15A···O18Civ | 0.91 | 2.38 | 3.257 (15) | 161.5 |
N15—H15B···O19A | 0.91 | 2.52 | 3.120 (13) | 124.2 |
N15—H15B···O19B | 0.91 | 2.27 | 3.183 (13) | 177.7 |
N15—H15C···O18Biii | 0.91 | 2.48 | 3.223 (14) | 138.7 |
N15—H15C···O18Aiii | 0.91 | 2.40 | 3.192 (13) | 146.2 |
C4—H4···O19Ci | 0.95 | 2.46 | 3.354 (14) | 157.0 |
C7—H7···O19Avi | 0.95 | 2.64 | 3.576 (14) | 170.1 |
C11—H11B···Cl6vi | 0.99 | 2.95 | 3.649 (12) | 128.1 |
C17—H17A···O18Aiii | 0.98 | 2.54 | 3.250 (15) | 128.9 |
C17—H17B···O18Bvii | 0.98 | 2.45 | 3.356 (15) | 154.3 |
C17—H17C···O19Aii | 0.98 | 2.63 | 3.568 (14) | 160.0 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z+3/2; (iv) x+1, y, z; (v) x, −y+3/2, z+1/2; (vi) −x+2, −y+2, −z+1; (vii) −x, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Pt(C16H18N3)(NH3)2](NO3)2 |
Mr | 668.97 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 7.6398 (3), 10.8372 (11), 25.982 (4) |
β (°) | 92.478 (5) |
V (Å3) | 2149.1 (4) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 13.87 |
Crystal size (mm) | 0.13 × 0.02 × 0.02 |
Data collection | |
Diffractometer | Agilent SuperNova with AtlasS2 CCD |
Absorption correction | Gaussian (CrysAlis PRO; Agilent, 2013) |
Tmin, Tmax | 0.503, 1.00 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8178, 4158, 3105 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.155, 1.04 |
No. of reflections | 4158 |
No. of parameters | 304 |
No. of restraints | 444 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 2.22, −3.37 |
Computer programs: CrysAlis PRO (Agilent, 2013), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors thank Dr Vincent Lynch at University of Texas X-ray Diffraction Lab for the data acquisition and valuable advice. This work was supported by the Robert A. Welch Foundation (F-1741).
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