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Acta Cryst. (2010). E66, m549-m550    [ doi:10.1107/S1600536810013899 ]

(Sulfasalazinato-[kappa]O)bis(triphenylphosphine-[kappa]P)copper(I)

K.-B. Huang, Y.-S. Tan, X.-Y. Song, Y.-C. Liu and Z.-F. Chen

Abstract top

The title mixed-ligand copper(I) complex, [Cu(C18H13N4O5S)(C18H15P)2], was synthesized via solvothermal reaction of [Cu(PPh3)2(MeCN)2]ClO4 and sulfasalazine [systematic name: 2-hydroxy-5-(2-{4-[(2-pyridylamino)sulfonyl]phenyl}diazenyl)benzoic acid]. The mononuclear complex displays a trigonal coordination geometry for the Cu(I) atom, which is surrounded by two P-atom donors from two different PPh3 ligands and one O-atom donor from the monodentate carboxylate group of the sulfasalazinate ligand. The latter ligand is found in a zwitterionic form, with a deprotonated amine N atom and a protonated pyridine N atom. Such a feature was previously described for free sulfasalazine. The crystal structure is stabilized by C-H...O, C-H...N, N-H...N and O-H...O hydrogen bonds.

Comment top

Sulfasalazine (systematic name: 2-hydroxy-5-[2-[4-[(2-pyridinylamino)sulfonyl]phenyl]diazenyl]-benzoic acid) is a drug used in treatment of joint diseases such as rheumatoid arthritis and spondyloarthropathies (Neva et al., 2000), as well as in inflammatory bowel diseases (Mansfield et al., 2002). Several crystal structures of metal complexes with sulfasalazine have been reported, with the sulfasalazine exhibiting diversity in its coordination behavior, giving rise to the formation of both monomeric and polymeric structures (Chen et al., 2003, 2008; Kang et al., 2006, 2008a,b; Wang et al., 2005; Yuan et al., 2006).

The copper ion in the title complex displays a trigonal geometry, being linked to two P atoms of two PPh3 ligands, and one O atom of the sulfasalazine ligand (Fig. 1), Due to the great steric effect of the bulky PPh3 ligands, there is a weak bond Cu1—O2 [2.624 (2)Å]. The geometric parameters of sulfasalazine are as expected, and comparable to the reported values (Chen et al., 2008). They also compare well with those of free sulfasalazine (van der Sluis & Spek, 1990) and ethyl-3-[4,5]-dimethoxy-2-(4-methyl-2-pyridylsulphamoyl)phenyl]propionate (Eliopoulos et al., 1983). The sulfasalazine ligand displays a zwitterionic form, with a deprotonated N atom (N3) and a protonated N atom (N4), which is further supported by a strong peak at 1525 cm-1 in the infrared spectrum of the complex (Franklin & Richardson 1980). The crystal structure is stabilized by C—H···O, C—H···N, N—H···N, and O—H···O hydrogen bonds (Table 1 and Fig. 2).

Related literature top

For applications of sulfasalazine, see: Neva et al. (2000); Mansfield et al. (2002). For crystal structures of metal complexes with sulfasalazine, see: Chen et al. (2003, 2008); Kang et al. (2006, 2008a,b); Wang et al. (2005); Yuan et al. (2006). For the crystal structure of free sulfasalazine, see: van der Sluis & Spek (1990). For the structure of a zwitterion related to sulfasalazine, see: Eliopoulos et al. (1983). For spectroscopic evidences supporting the presence of a protonated pyridine, see: Franklin & Richardson (1980).

Experimental top

Samples of [Cu(PPh3)2(MeCN)2]ClO4 (0.1 mmol) and sulfasalazine (0.1 mmol) were placed in a thick-walled Pyrex tube (ca 20 cm long). After addition of CHCl3 (1 ml), the tube was frozen with liquid nitrogen, evacuated under vacuum and sealed with a torch. The tube was heated at 353 K for 2 days and then was slowly cooled down to room temperature. Orange-red block crystals were obtained. Yield: 45%. IR (KBr, cm-1): 3444(m), 3050(m), 1627(s), 1586(s), 1525(m), 1463(m), 1434(m), 1362(m), 1291(m), 1269(m), 1198(w), 1169(m), 1135(s), 1083(m), 1002(m), 963(m), 930(w), 848(m), 805(m), 772(m), 746(s), 695(s), 645(w), 610(s), 582(m), 565(m), 510(m).

Refinement top

H atoms bonded to C atoms were positioned geometrically and refined using a riding model with Uiso(H) = 1.2Ueq(C) (C—H = 0.95 Å). The hydroxyl H atom H3 was placed in calculated position, with O—H distance of 0.84 Å, and Uiso(H3) = 1.5Ueq(O3). H atom attached to N4 in the pyridine ring (H1) was located in a difference map and refined freely.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram of the title complex. Some Hydrogen bonds are shown as dashed lines.
[2-hydroxy-5-(2-{4-[(2-pyridylamino)sulfonyl]phenyl}diazenyl)benzoato- κO]bis(triphenylphosphine-κP)copper(I) top
Crystal data top
[Cu(C18H13N4O5S)(C18H15P)2]Z = 2
Mr = 985.46F(000) = 1020
Triclinic, P1Dx = 1.359 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71070 Å
a = 14.0126 (5) ÅCell parameters from 8593 reflections
b = 14.2236 (12) Åθ = 3.0–25.3°
c = 14.2302 (4) ŵ = 0.62 mm−1
α = 81.068 (11)°T = 193 K
β = 61.606 (7)°Block, orange-red
γ = 75.011 (10)°0.40 × 0.30 × 0.10 mm
V = 2408.4 (2) Å3
Data collection top
Rigaku Mercury CCD
diffractometer		8763 independent reflections
Radiation source: fine-focus sealed tube6866 reflections with I > 2σ(I)
graphiteRint = 0.044
Detector resolution: 7.31 pixels mm-1θmax = 25.4°, θmin = 3.0°
ω scansh = −15→16
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)		k = −16→17
Tmin = 0.791, Tmax = 0.941l = −17→17
24096 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0333P)2 + 1.5872P]
where P = (Fo2 + 2Fc2)/3
8763 reflections(Δ/σ)max < 0.001
610 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.33 e Å−3
0 constraints
Crystal data top
[Cu(C18H13N4O5S)(C18H15P)2]γ = 75.011 (10)°
Mr = 985.46V = 2408.4 (2) Å3
Triclinic, P1Z = 2
a = 14.0126 (5) ÅMo Kα radiation
b = 14.2236 (12) ŵ = 0.62 mm−1
c = 14.2302 (4) ÅT = 193 K
α = 81.068 (11)°0.40 × 0.30 × 0.10 mm
β = 61.606 (7)°
Data collection top
Rigaku Mercury CCD
diffractometer		8763 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)		6866 reflections with I > 2σ(I)
Tmin = 0.791, Tmax = 0.941Rint = 0.044
24096 measured reflectionsθmax = 25.4°
Refinement top
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109Δρmax = 0.31 e Å−3
S = 1.10Δρmin = −0.33 e Å−3
8763 reflectionsAbsolute structure: ?
610 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.45981 (3)0.41881 (3)0.23424 (3)0.03507 (12)
S10.98672 (7)1.04661 (6)0.28783 (6)0.0347 (2)
P10.59805 (6)0.29238 (6)0.21974 (6)0.0316 (2)
P20.28157 (6)0.44685 (6)0.35221 (6)0.02895 (19)
O10.50582 (17)0.52994 (15)0.12432 (17)0.0374 (5)
O20.52453 (19)0.56619 (17)0.25992 (18)0.0449 (6)
O30.58620 (19)0.61550 (17)−0.05550 (17)0.0419 (6)
H30.55130.5767−0.00850.063*
O40.89660 (19)1.12476 (16)0.34663 (18)0.0444 (6)
O51.07566 (18)1.07320 (17)0.18968 (17)0.0425 (6)
N10.7910 (2)0.80601 (18)0.0838 (2)0.0321 (6)
N20.7683 (2)0.80115 (19)0.1806 (2)0.0346 (6)
N31.0242 (2)0.98829 (19)0.3734 (2)0.0344 (6)
N41.1440 (2)0.8879 (2)0.4284 (2)0.0379 (7)
C10.5420 (2)0.5779 (2)0.1661 (3)0.0332 (7)
C20.6124 (2)0.6470 (2)0.0913 (2)0.0284 (7)
C30.6324 (2)0.6610 (2)−0.0162 (2)0.0323 (7)
C40.7023 (2)0.7211 (2)−0.0851 (2)0.0350 (8)
H40.71520.7306−0.15740.042*
C50.7531 (2)0.7671 (2)−0.0491 (2)0.0341 (7)
H50.80140.8080−0.09700.041*
C60.7343 (2)0.7543 (2)0.0566 (2)0.0297 (7)
C70.6634 (2)0.6941 (2)0.1270 (2)0.0306 (7)
H70.65010.68550.19940.037*
C80.8276 (2)0.8567 (2)0.2012 (2)0.0305 (7)
C90.9189 (3)0.8911 (2)0.1218 (2)0.0378 (8)
H90.94760.87530.04950.045*
C100.9677 (3)0.9485 (2)0.1486 (2)0.0369 (8)
H101.02920.97330.09430.044*
C110.9274 (2)0.9699 (2)0.2542 (2)0.0296 (7)
C120.8391 (3)0.9323 (2)0.3337 (3)0.0385 (8)
H120.81250.94570.40630.046*
C130.7897 (3)0.8750 (2)0.3071 (3)0.0396 (8)
H130.72990.84840.36170.047*
C141.1221 (3)0.9230 (2)0.3448 (3)0.0357 (8)
C151.2032 (3)0.8868 (3)0.2444 (3)0.0481 (9)
H151.19420.91060.18230.058*
C161.2944 (3)0.8177 (3)0.2358 (3)0.0588 (11)
H161.34790.79350.16750.071*
C171.3108 (3)0.7820 (3)0.3245 (3)0.0590 (11)
H171.37410.73310.31790.071*
C181.2341 (3)0.8186 (3)0.4208 (3)0.0516 (10)
H181.24340.79580.48290.062*
C190.7369 (2)0.3189 (2)0.1587 (2)0.0342 (7)
C200.8185 (3)0.2702 (3)0.1884 (3)0.0436 (8)
H200.80270.22210.24490.052*
C210.9230 (3)0.2918 (3)0.1358 (3)0.0513 (10)
H210.97910.25760.15540.062*
C220.9461 (3)0.3628 (3)0.0550 (3)0.0499 (9)
H221.01800.37720.01890.060*
C230.8649 (3)0.4125 (3)0.0266 (3)0.0484 (9)
H230.88060.4618−0.02870.058*
C240.7604 (3)0.3910 (2)0.0784 (3)0.0391 (8)
H240.70450.42600.05880.047*
C250.6144 (2)0.1902 (2)0.1472 (2)0.0333 (7)
C260.5200 (3)0.1771 (3)0.1471 (3)0.0573 (11)
H260.45210.22300.18020.069*
C270.5235 (4)0.0976 (3)0.0991 (4)0.0774 (15)
H270.45780.08850.10080.093*
C280.6225 (3)0.0317 (3)0.0489 (3)0.0606 (11)
H280.6252−0.02300.01630.073*
C290.7160 (3)0.0456 (3)0.0462 (3)0.0461 (9)
H290.78440.00090.01030.055*
C300.7131 (3)0.1236 (2)0.0949 (3)0.0415 (8)
H300.77930.13180.09250.050*
C310.5741 (2)0.2396 (2)0.3525 (2)0.0354 (8)
C320.5958 (3)0.1413 (3)0.3768 (3)0.0493 (9)
H320.63050.09600.32140.059*
C330.5671 (3)0.1079 (3)0.4819 (3)0.0630 (11)
H330.58210.04000.49810.076*
C340.5173 (3)0.1727 (4)0.5624 (3)0.0656 (12)
H340.49720.14950.63420.079*
C350.4962 (3)0.2710 (4)0.5395 (3)0.0643 (12)
H350.46340.31600.59490.077*
C360.5230 (3)0.3039 (3)0.4354 (3)0.0487 (9)
H360.50640.37180.42000.058*
C370.2514 (2)0.4620 (2)0.4891 (2)0.0325 (7)
C380.3070 (3)0.5206 (3)0.5054 (3)0.0524 (10)
H380.35880.55180.44610.063*
C390.2872 (4)0.5338 (3)0.6076 (3)0.0711 (13)
H390.32480.57480.61810.085*
C400.2139 (4)0.4884 (3)0.6943 (3)0.0626 (11)
H400.20150.49720.76440.075*
C410.1589 (3)0.4301 (3)0.6788 (3)0.0601 (11)
H410.10800.39850.73830.072*
C420.1772 (3)0.4175 (3)0.5771 (3)0.0481 (9)
H420.13810.37740.56740.058*
C430.2143 (2)0.3488 (2)0.3632 (2)0.0335 (7)
C440.2645 (3)0.2546 (2)0.3810 (3)0.0430 (8)
H440.32800.24430.39240.052*
C450.2232 (4)0.1755 (3)0.3823 (3)0.0581 (11)
H450.25790.11140.39480.070*
C460.1319 (4)0.1906 (4)0.3653 (3)0.0652 (13)
H460.10380.13650.36550.078*
C470.0804 (3)0.2830 (4)0.3478 (3)0.0592 (12)
H470.01670.29260.33670.071*
C480.1219 (3)0.3628 (3)0.3463 (3)0.0449 (9)
H480.08680.42680.33380.054*
C490.1983 (2)0.5553 (2)0.3211 (2)0.0330 (7)
C500.2246 (3)0.5793 (3)0.2144 (3)0.0470 (9)
H500.28660.54080.15990.056*
C510.1603 (3)0.6595 (3)0.1876 (3)0.0589 (11)
H510.17810.67530.11460.071*
C520.0713 (3)0.7161 (3)0.2654 (3)0.0510 (9)
H520.02660.77000.24640.061*
C530.0469 (3)0.6953 (3)0.3702 (3)0.0462 (9)
H53−0.01340.73610.42370.055*
C540.1094 (3)0.6151 (2)0.3990 (3)0.0397 (8)
H540.09160.60100.47220.048*
H11.094 (3)0.918 (3)0.491 (3)0.056 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0288 (2)0.0294 (2)0.0395 (2)−0.00721 (16)−0.01025 (17)0.00251 (17)
S10.0439 (5)0.0330 (5)0.0374 (4)−0.0145 (4)−0.0237 (4)−0.0004 (4)
P10.0293 (4)0.0304 (5)0.0331 (4)−0.0045 (3)−0.0130 (3)−0.0025 (4)
P20.0279 (4)0.0282 (4)0.0317 (4)−0.0079 (3)−0.0129 (3)−0.0027 (3)
O10.0399 (13)0.0356 (13)0.0462 (13)−0.0202 (10)−0.0229 (11)0.0044 (10)
O20.0499 (14)0.0508 (15)0.0358 (13)−0.0267 (12)−0.0155 (11)0.0071 (11)
O30.0508 (14)0.0491 (15)0.0378 (13)−0.0297 (11)−0.0201 (11)−0.0023 (11)
O40.0574 (15)0.0357 (13)0.0475 (14)−0.0035 (11)−0.0314 (12)−0.0068 (11)
O50.0503 (14)0.0466 (14)0.0415 (13)−0.0276 (11)−0.0231 (11)0.0060 (11)
N10.0330 (14)0.0349 (15)0.0330 (15)−0.0133 (11)−0.0163 (12)0.0007 (12)
N20.0392 (15)0.0382 (16)0.0343 (15)−0.0168 (12)−0.0196 (12)0.0009 (12)
N30.0380 (15)0.0386 (16)0.0373 (15)−0.0115 (12)−0.0236 (12)−0.0023 (12)
N40.0391 (16)0.0434 (18)0.0375 (16)−0.0070 (13)−0.0223 (14)−0.0051 (14)
C10.0295 (17)0.0315 (18)0.0385 (19)−0.0083 (13)−0.0144 (14)−0.0015 (15)
C20.0245 (15)0.0286 (17)0.0318 (16)−0.0101 (12)−0.0103 (13)−0.0014 (13)
C30.0292 (16)0.0333 (18)0.0362 (17)−0.0114 (13)−0.0125 (14)−0.0071 (14)
C40.0361 (18)0.047 (2)0.0249 (16)−0.0219 (15)−0.0100 (14)−0.0003 (14)
C50.0332 (17)0.042 (2)0.0287 (17)−0.0184 (14)−0.0114 (14)0.0030 (14)
C60.0311 (16)0.0277 (17)0.0365 (17)−0.0111 (13)−0.0173 (14)−0.0032 (14)
C70.0321 (17)0.0306 (17)0.0297 (16)−0.0104 (13)−0.0123 (13)−0.0020 (13)
C80.0328 (17)0.0316 (18)0.0356 (18)−0.0123 (13)−0.0208 (14)0.0021 (14)
C90.0432 (19)0.050 (2)0.0280 (17)−0.0198 (16)−0.0181 (15)0.0000 (15)
C100.0378 (18)0.049 (2)0.0329 (18)−0.0209 (15)−0.0192 (15)0.0046 (15)
C110.0326 (17)0.0302 (17)0.0337 (17)−0.0098 (13)−0.0203 (14)0.0006 (14)
C120.0395 (19)0.048 (2)0.0298 (17)−0.0129 (16)−0.0140 (15)−0.0076 (15)
C130.0406 (19)0.049 (2)0.0352 (18)−0.0226 (16)−0.0170 (15)0.0018 (16)
C140.0416 (19)0.039 (2)0.0388 (19)−0.0188 (15)−0.0224 (16)−0.0017 (15)
C150.050 (2)0.060 (3)0.038 (2)−0.0110 (19)−0.0214 (17)−0.0101 (18)
C160.047 (2)0.073 (3)0.050 (2)0.001 (2)−0.0186 (19)−0.023 (2)
C170.050 (2)0.065 (3)0.066 (3)0.0062 (19)−0.033 (2)−0.023 (2)
C180.051 (2)0.056 (2)0.054 (2)−0.0009 (19)−0.0325 (19)−0.0096 (19)
C190.0291 (17)0.0357 (19)0.0352 (17)−0.0036 (14)−0.0123 (14)−0.0079 (15)
C200.0372 (19)0.040 (2)0.055 (2)−0.0057 (15)−0.0233 (17)0.0008 (17)
C210.034 (2)0.055 (2)0.068 (3)−0.0056 (17)−0.0276 (18)−0.005 (2)
C220.0301 (19)0.057 (3)0.058 (2)−0.0124 (17)−0.0122 (17)−0.010 (2)
C230.043 (2)0.049 (2)0.044 (2)−0.0169 (17)−0.0096 (17)−0.0014 (17)
C240.0353 (19)0.042 (2)0.0374 (18)−0.0070 (15)−0.0150 (15)−0.0028 (16)
C250.0344 (18)0.0316 (18)0.0309 (17)−0.0025 (14)−0.0143 (14)−0.0027 (14)
C260.040 (2)0.061 (3)0.078 (3)0.0046 (18)−0.031 (2)−0.031 (2)
C270.058 (3)0.079 (3)0.118 (4)0.001 (2)−0.053 (3)−0.051 (3)
C280.066 (3)0.049 (2)0.074 (3)0.003 (2)−0.038 (2)−0.026 (2)
C290.043 (2)0.040 (2)0.049 (2)−0.0020 (16)−0.0175 (17)−0.0120 (17)
C300.0349 (18)0.037 (2)0.048 (2)−0.0036 (15)−0.0163 (16)−0.0066 (16)
C310.0283 (17)0.042 (2)0.0374 (18)−0.0084 (14)−0.0158 (14)−0.0012 (15)
C320.057 (2)0.051 (2)0.041 (2)−0.0156 (18)−0.0222 (18)0.0023 (18)
C330.071 (3)0.067 (3)0.055 (3)−0.029 (2)−0.031 (2)0.019 (2)
C340.052 (2)0.107 (4)0.039 (2)−0.028 (2)−0.0208 (19)0.012 (3)
C350.055 (2)0.099 (4)0.039 (2)−0.004 (2)−0.0241 (19)−0.015 (2)
C360.046 (2)0.058 (2)0.043 (2)−0.0033 (18)−0.0228 (17)−0.0108 (18)
C370.0315 (17)0.0336 (18)0.0336 (17)−0.0065 (14)−0.0145 (14)−0.0062 (14)
C380.056 (2)0.060 (3)0.046 (2)−0.0306 (19)−0.0154 (18)−0.0124 (19)
C390.081 (3)0.090 (3)0.061 (3)−0.036 (3)−0.031 (2)−0.027 (3)
C400.083 (3)0.070 (3)0.041 (2)−0.012 (2)−0.032 (2)−0.015 (2)
C410.081 (3)0.064 (3)0.031 (2)−0.027 (2)−0.0165 (19)−0.0024 (19)
C420.058 (2)0.052 (2)0.040 (2)−0.0225 (18)−0.0208 (18)−0.0043 (17)
C430.0325 (17)0.041 (2)0.0241 (16)−0.0152 (14)−0.0051 (13)−0.0076 (14)
C440.052 (2)0.038 (2)0.0399 (19)−0.0180 (17)−0.0166 (16)−0.0037 (16)
C450.077 (3)0.047 (2)0.042 (2)−0.033 (2)−0.010 (2)−0.0018 (18)
C460.078 (3)0.074 (3)0.043 (2)−0.054 (3)−0.005 (2)−0.014 (2)
C470.047 (2)0.094 (4)0.043 (2)−0.040 (2)−0.0090 (18)−0.018 (2)
C480.0364 (19)0.061 (2)0.0383 (19)−0.0210 (17)−0.0097 (15)−0.0118 (17)
C490.0312 (17)0.0326 (18)0.0395 (18)−0.0074 (13)−0.0187 (14)−0.0033 (15)
C500.057 (2)0.046 (2)0.0367 (19)0.0030 (17)−0.0245 (17)−0.0105 (17)
C510.079 (3)0.053 (3)0.045 (2)0.011 (2)−0.039 (2)−0.0075 (19)
C520.054 (2)0.039 (2)0.067 (3)−0.0006 (17)−0.037 (2)−0.0041 (19)
C530.0342 (19)0.040 (2)0.055 (2)0.0007 (15)−0.0155 (17)−0.0071 (18)
C540.0338 (18)0.040 (2)0.0388 (19)−0.0051 (15)−0.0129 (15)−0.0001 (16)
Geometric parameters (Å, °) top
Cu1—O12.040 (2)C22—H220.9500
Cu1—P22.2181 (9)C23—C241.384 (5)
Cu1—P12.2276 (9)C23—H230.9500
Cu1—O22.624 (2)C24—H240.9500
S1—O51.439 (2)C25—C261.383 (5)
S1—O41.445 (2)C25—C301.388 (4)
S1—N31.587 (3)C26—C271.389 (5)
S1—C111.766 (3)C26—H260.9500
P1—C251.816 (3)C27—C281.380 (5)
P1—C311.825 (3)C27—H270.9500
P1—C191.831 (3)C28—C291.357 (5)
P2—C491.812 (3)C28—H280.9500
P2—C371.822 (3)C29—C301.379 (5)
P2—C431.825 (3)C29—H290.9500
O1—C11.292 (4)C30—H300.9500
O2—C11.229 (4)C31—C321.378 (5)
O3—C31.351 (3)C31—C361.390 (5)
O3—H30.8400C32—C331.390 (5)
N1—N21.253 (3)C32—H320.9500
N1—C61.414 (4)C33—C341.372 (6)
N2—C81.430 (4)C33—H330.9500
N3—C141.355 (4)C34—C351.373 (6)
N4—C181.354 (4)C34—H340.9500
N4—C141.359 (4)C35—C361.378 (5)
N4—H10.91 (4)C35—H350.9500
C1—C21.500 (4)C36—H360.9500
C2—C71.384 (4)C37—C421.380 (4)
C2—C31.409 (4)C37—C381.389 (4)
C3—C41.383 (4)C38—C391.378 (5)
C4—C51.374 (4)C38—H380.9500
C4—H40.9500C39—C401.373 (6)
C5—C61.390 (4)C39—H390.9500
C5—H50.9500C40—C411.371 (5)
C6—C71.396 (4)C40—H400.9500
C7—H70.9500C41—C421.377 (5)
C8—C131.383 (4)C41—H410.9500
C8—C91.389 (4)C42—H420.9500
C9—C101.384 (4)C43—C481.386 (4)
C9—H90.9500C43—C441.388 (5)
C10—C111.384 (4)C44—C451.387 (5)
C10—H100.9500C44—H440.9500
C11—C121.386 (4)C45—C461.370 (6)
C12—C131.386 (4)C45—H450.9500
C12—H120.9500C46—C471.375 (6)
C13—H130.9500C46—H460.9500
C14—C151.407 (4)C47—C481.396 (5)
C15—C161.361 (5)C47—H470.9500
C15—H150.9500C48—H480.9500
C16—C171.386 (5)C49—C501.389 (4)
C16—H160.9500C49—C541.391 (4)
C17—C181.356 (5)C50—C511.385 (5)
C17—H170.9500C50—H500.9500
C18—H180.9500C51—C521.369 (5)
C19—C241.385 (4)C51—H510.9500
C19—C201.388 (4)C52—C531.362 (5)
C20—C211.385 (5)C52—H520.9500
C20—H200.9500C53—C541.384 (5)
C21—C221.378 (5)C53—H530.9500
C21—H210.9500C54—H540.9500
C22—C231.374 (5)
O1—Cu1—P2114.45 (7)C21—C22—H22120.1
O1—Cu1—P1114.67 (7)C22—C23—C24120.2 (3)
P2—Cu1—P1130.83 (4)C22—C23—H23119.9
O1—Cu1—O255.07 (8)C24—C23—H23119.9
P2—Cu1—O2102.07 (6)C23—C24—C19120.4 (3)
P1—Cu1—O2103.67 (6)C23—C24—H24119.8
O5—S1—O4117.01 (14)C19—C24—H24119.8
O5—S1—N3114.63 (14)C26—C25—C30118.1 (3)
O4—S1—N3104.26 (14)C26—C25—P1116.8 (2)
O5—S1—C11106.82 (14)C30—C25—P1125.0 (2)
O4—S1—C11106.23 (14)C25—C26—C27120.8 (3)
N3—S1—C11107.27 (14)C25—C26—H26119.6
C25—P1—C31103.77 (15)C27—C26—H26119.6
C25—P1—C19104.45 (14)C28—C27—C26119.9 (4)
C31—P1—C19105.45 (14)C28—C27—H27120.1
C25—P1—Cu1116.38 (10)C26—C27—H27120.1
C31—P1—Cu1109.53 (10)C29—C28—C27119.7 (4)
C19—P1—Cu1116.06 (11)C29—C28—H28120.2
C49—P2—C37104.22 (14)C27—C28—H28120.2
C49—P2—C43104.55 (15)C28—C29—C30120.9 (3)
C37—P2—C43104.23 (14)C28—C29—H29119.6
C49—P2—Cu1114.07 (10)C30—C29—H29119.6
C37—P2—Cu1115.74 (10)C29—C30—C25120.7 (3)
C43—P2—Cu1112.85 (10)C29—C30—H30119.6
C1—O1—Cu1102.76 (19)C25—C30—H30119.6
C1—O2—Cu177.43 (18)C32—C31—C36118.4 (3)
C3—O3—H3109.5C32—C31—P1124.7 (3)
N2—N1—C6115.7 (2)C36—C31—P1116.7 (3)
N1—N2—C8112.0 (2)C31—C32—C33120.3 (4)
C14—N3—S1122.1 (2)C31—C32—H32119.8
C18—N4—C14124.2 (3)C33—C32—H32119.8
C18—N4—H1123 (2)C34—C33—C32120.2 (4)
C14—N4—H1113 (2)C34—C33—H33119.9
O2—C1—O1123.2 (3)C32—C33—H33119.9
O2—C1—C2121.0 (3)C33—C34—C35120.2 (4)
O1—C1—C2115.7 (3)C33—C34—H34119.9
C7—C2—C3119.2 (3)C35—C34—H34119.9
C7—C2—C1119.4 (3)C34—C35—C36119.4 (4)
C3—C2—C1121.3 (3)C34—C35—H35120.3
O3—C3—C4118.1 (3)C36—C35—H35120.3
O3—C3—C2121.6 (3)C35—C36—C31121.3 (4)
C4—C3—C2120.3 (3)C35—C36—H36119.3
C5—C4—C3120.1 (3)C31—C36—H36119.3
C5—C4—H4120.0C42—C37—C38118.3 (3)
C3—C4—H4120.0C42—C37—P2123.6 (2)
C4—C5—C6120.5 (3)C38—C37—P2118.1 (3)
C4—C5—H5119.7C39—C38—C37120.1 (4)
C6—C5—H5119.7C39—C38—H38120.0
C5—C6—C7119.8 (3)C37—C38—H38120.0
C5—C6—N1115.0 (3)C40—C39—C38121.0 (4)
C7—C6—N1125.2 (3)C40—C39—H39119.5
C2—C7—C6120.1 (3)C38—C39—H39119.5
C2—C7—H7119.9C41—C40—C39119.3 (4)
C6—C7—H7119.9C41—C40—H40120.3
C13—C8—C9120.1 (3)C39—C40—H40120.3
C13—C8—N2116.2 (3)C40—C41—C42120.2 (4)
C9—C8—N2123.7 (3)C40—C41—H41119.9
C10—C9—C8119.7 (3)C42—C41—H41119.9
C10—C9—H9120.2C41—C42—C37121.2 (3)
C8—C9—H9120.2C41—C42—H42119.4
C9—C10—C11120.2 (3)C37—C42—H42119.4
C9—C10—H10119.9C48—C43—C44119.0 (3)
C11—C10—H10119.9C48—C43—P2123.3 (3)
C10—C11—C12120.0 (3)C44—C43—P2117.5 (2)
C10—C11—S1120.2 (2)C45—C44—C43120.9 (4)
C12—C11—S1119.8 (2)C45—C44—H44119.5
C11—C12—C13120.0 (3)C43—C44—H44119.5
C11—C12—H12120.0C46—C45—C44119.4 (4)
C13—C12—H12120.0C46—C45—H45120.3
C8—C13—C12119.9 (3)C44—C45—H45120.3
C8—C13—H13120.0C45—C46—C47121.0 (4)
C12—C13—H13120.0C45—C46—H46119.5
N3—C14—N4113.2 (3)C47—C46—H46119.5
N3—C14—C15131.0 (3)C46—C47—C48119.8 (4)
N4—C14—C15115.8 (3)C46—C47—H47120.1
C16—C15—C14120.4 (3)C48—C47—H47120.1
C16—C15—H15119.8C43—C48—C47120.0 (4)
C14—C15—H15119.8C43—C48—H48120.0
C15—C16—C17121.4 (3)C47—C48—H48120.0
C15—C16—H16119.3C50—C49—C54118.7 (3)
C17—C16—H16119.3C50—C49—P2118.2 (2)
C18—C17—C16118.3 (4)C54—C49—P2123.1 (2)
C18—C17—H17120.9C51—C50—C49120.0 (3)
C16—C17—H17120.9C51—C50—H50120.0
N4—C18—C17119.9 (4)C49—C50—H50120.0
N4—C18—H18120.1C52—C51—C50120.5 (3)
C17—C18—H18120.1C52—C51—H51119.7
C24—C19—C20119.2 (3)C50—C51—H51119.7
C24—C19—P1117.5 (2)C53—C52—C51120.1 (3)
C20—C19—P1123.3 (3)C53—C52—H52120.0
C21—C20—C19120.0 (3)C51—C52—H52120.0
C21—C20—H20120.0C52—C53—C54120.4 (3)
C19—C20—H20120.0C52—C53—H53119.8
C22—C21—C20120.4 (3)C54—C53—H53119.8
C22—C21—H21119.8C53—C54—C49120.3 (3)
C20—C21—H21119.8C53—C54—H54119.9
C23—C22—C21119.8 (3)C49—C54—H54119.9
C23—C22—H22120.1
O1—Cu1—P1—C25−97.32 (13)C25—P1—C19—C20−84.2 (3)
P2—Cu1—P1—C2585.50 (12)C31—P1—C19—C2024.9 (3)
O2—Cu1—P1—C25−154.86 (12)Cu1—P1—C19—C20146.3 (2)
O1—Cu1—P1—C31145.44 (13)C24—C19—C20—C21−2.0 (5)
P2—Cu1—P1—C31−31.74 (12)P1—C19—C20—C21177.5 (3)
O2—Cu1—P1—C3187.90 (12)C19—C20—C21—C221.1 (5)
O1—Cu1—P1—C1926.23 (14)C20—C21—C22—C230.2 (6)
P2—Cu1—P1—C19−150.95 (11)C21—C22—C23—C24−0.5 (5)
O2—Cu1—P1—C19−31.31 (13)C22—C23—C24—C19−0.4 (5)
O1—Cu1—P2—C499.54 (13)C20—C19—C24—C231.6 (5)
P1—Cu1—P2—C49−173.28 (11)P1—C19—C24—C23−177.9 (3)
O2—Cu1—P2—C4966.45 (12)C31—P1—C25—C2693.1 (3)
O1—Cu1—P2—C37−111.38 (13)C19—P1—C25—C26−156.7 (3)
P1—Cu1—P2—C3765.80 (13)Cu1—P1—C25—C26−27.3 (3)
O2—Cu1—P2—C37−54.47 (13)C31—P1—C25—C30−85.2 (3)
O1—Cu1—P2—C43128.67 (13)C19—P1—C25—C3025.1 (3)
P1—Cu1—P2—C43−54.15 (13)Cu1—P1—C25—C30154.4 (3)
O2—Cu1—P2—C43−174.42 (13)C30—C25—C26—C272.2 (6)
P2—Cu1—O1—C194.71 (18)P1—C25—C26—C27−176.1 (4)
P1—Cu1—O1—C1−82.94 (18)C25—C26—C27—C28−1.4 (7)
O2—Cu1—O1—C16.85 (17)C26—C27—C28—C29−0.4 (7)
O1—Cu1—O2—C1−7.20 (18)C27—C28—C29—C301.3 (6)
P2—Cu1—O2—C1−118.72 (18)C28—C29—C30—C25−0.4 (6)
P1—Cu1—O2—C1103.55 (18)C26—C25—C30—C29−1.4 (5)
C6—N1—N2—C8−179.0 (2)P1—C25—C30—C29176.9 (3)
O5—S1—N3—C14−35.7 (3)C25—P1—C31—C3215.9 (3)
O4—S1—N3—C14−164.9 (2)C19—P1—C31—C32−93.6 (3)
C11—S1—N3—C1482.7 (3)Cu1—P1—C31—C32140.8 (3)
Cu1—O2—C1—O111.2 (3)C25—P1—C31—C36−159.4 (3)
Cu1—O2—C1—C2−165.9 (3)C19—P1—C31—C3691.1 (3)
Cu1—O1—C1—O2−14.5 (4)Cu1—P1—C31—C36−34.5 (3)
Cu1—O1—C1—C2162.8 (2)C36—C31—C32—C33−0.1 (5)
O2—C1—C2—C73.6 (4)P1—C31—C32—C33−175.3 (3)
O1—C1—C2—C7−173.7 (3)C31—C32—C33—C34−0.2 (6)
O2—C1—C2—C3−179.8 (3)C32—C33—C34—C35−0.6 (6)
O1—C1—C2—C32.8 (4)C33—C34—C35—C361.6 (6)
C7—C2—C3—O3178.9 (3)C34—C35—C36—C31−1.9 (6)
C1—C2—C3—O32.3 (4)C32—C31—C36—C351.1 (5)
C7—C2—C3—C40.0 (4)P1—C31—C36—C35176.7 (3)
C1—C2—C3—C4−176.6 (3)C49—P2—C37—C4299.5 (3)
O3—C3—C4—C5−178.6 (3)C43—P2—C37—C42−9.9 (3)
C2—C3—C4—C50.4 (5)Cu1—P2—C37—C42−134.4 (3)
C3—C4—C5—C6−0.4 (5)C49—P2—C37—C38−81.2 (3)
C4—C5—C6—C70.0 (5)C43—P2—C37—C38169.4 (3)
C4—C5—C6—N1−179.7 (3)Cu1—P2—C37—C3844.9 (3)
N2—N1—C6—C5174.7 (3)C42—C37—C38—C39−0.3 (6)
N2—N1—C6—C7−5.0 (4)P2—C37—C38—C39−179.7 (3)
C3—C2—C7—C6−0.3 (4)C37—C38—C39—C401.0 (7)
C1—C2—C7—C6176.3 (3)C38—C39—C40—C41−0.8 (7)
C5—C6—C7—C20.3 (4)C39—C40—C41—C420.0 (7)
N1—C6—C7—C2180.0 (3)C40—C41—C42—C370.6 (6)
N1—N2—C8—C13165.2 (3)C38—C37—C42—C41−0.4 (5)
N1—N2—C8—C9−15.2 (4)P2—C37—C42—C41178.9 (3)
C13—C8—C9—C10−3.7 (5)C49—P2—C43—C481.7 (3)
N2—C8—C9—C10176.7 (3)C37—P2—C43—C48110.9 (3)
C8—C9—C10—C111.3 (5)Cu1—P2—C43—C48−122.8 (2)
C9—C10—C11—C121.2 (5)C49—P2—C43—C44176.5 (2)
C9—C10—C11—S1−177.9 (3)C37—P2—C43—C44−74.4 (3)
O5—S1—C11—C10−1.2 (3)Cu1—P2—C43—C4451.9 (3)
O4—S1—C11—C10124.4 (3)C48—C43—C44—C45−0.2 (5)
N3—S1—C11—C10−124.5 (3)P2—C43—C44—C45−175.1 (3)
O5—S1—C11—C12179.7 (3)C43—C44—C45—C460.3 (5)
O4—S1—C11—C12−54.7 (3)C44—C45—C46—C47−0.5 (6)
N3—S1—C11—C1256.4 (3)C45—C46—C47—C480.6 (6)
C10—C11—C12—C13−1.4 (5)C44—C43—C48—C470.2 (5)
S1—C11—C12—C13177.6 (3)P2—C43—C48—C47174.9 (2)
C9—C8—C13—C123.5 (5)C46—C47—C48—C43−0.4 (5)
N2—C8—C13—C12−176.9 (3)C37—P2—C49—C50162.7 (3)
C11—C12—C13—C8−0.9 (5)C43—P2—C49—C50−88.2 (3)
S1—N3—C14—N4173.9 (2)Cu1—P2—C49—C5035.5 (3)
S1—N3—C14—C15−5.7 (5)C37—P2—C49—C54−17.5 (3)
C18—N4—C14—N3176.8 (3)C43—P2—C49—C5491.7 (3)
C18—N4—C14—C15−3.4 (5)Cu1—P2—C49—C54−144.6 (2)
N3—C14—C15—C16−177.6 (3)C54—C49—C50—C51−2.4 (5)
N4—C14—C15—C162.8 (5)P2—C49—C50—C51177.5 (3)
C14—C15—C16—C17−0.7 (6)C49—C50—C51—C520.7 (6)
C15—C16—C17—C18−1.0 (6)C50—C51—C52—C531.6 (6)
C14—N4—C18—C171.9 (5)C51—C52—C53—C54−2.1 (6)
C16—C17—C18—N40.4 (6)C52—C53—C54—C490.3 (5)
C25—P1—C19—C2495.4 (3)C50—C49—C54—C531.9 (5)
C31—P1—C19—C24−155.6 (2)P2—C49—C54—C53−178.0 (3)
Cu1—P1—C19—C24−34.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C46—H46···N3i0.952.593.542 (5)178
C18—H18···O4ii0.952.493.042 (4)117
C5—H5···O5iii0.952.493.429 (4)169
N4—H1···O4ii0.91 (4)2.36 (4)2.957 (4)123 (3)
N4—H1···N3ii0.91 (4)2.20 (4)3.112 (4)171 (3)
O3—H3···O10.841.762.510 (3)147
Symmetry codes: (i) x−1, y−1, z; (ii) −x+2, −y+2, −z+1; (iii) −x+2, −y+2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C46—H46···N3i0.952.593.542 (5)178
C5—H5···O5ii0.952.493.429 (4)169
N4—H1···N3iii0.91 (4)2.20 (4)3.112 (4)171 (3)
O3—H3···O10.841.762.510 (3)147
Symmetry codes: (i) x−1, y−1, z; (ii) −x+2, −y+2, −z; (iii) −x+2, −y+2, −z+1.
Acknowledgements top

The authors thank the Natural Science Foundation of Guangxi of China (No. 0991003,0991012Z) and the Open Foundation of the Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), for financial support.

references
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