Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812050970/zl2525sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536812050970/zl2525Isup2.hkl |
CCDC reference: 920201
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.007 Å
- Disorder in solvent or counterion
- R factor = 0.046
- wR factor = 0.101
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT911_ALERT_3_B Missing # FCF Refl Between THmin & STh/L= 0.600 2851 PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers . 1
Alert level C PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.9 Ratio PLAT480_ALERT_4_C Long H...A H-Bond Reported H63 .. S1 .. 2.95 Ang. PLAT481_ALERT_4_C Long D...A H-Bond Reported C14 .. CG1 .. 4.08 Ang. PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 41 A 3 PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 6.211 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 1
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 5 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF ? PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ ? PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I1 -- Cu1 .. 9.0 su PLAT244_ALERT_4_G Low 'Solvent' Ueq as Compared to Neighbors of C8 PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ................... 33 Perc. PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3 PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 371
0 ALERT level A = Most likely a serious problem - resolve or explain 2 ALERT level B = A potentially serious problem, consider carefully 7 ALERT level C = Check. Ensure it is not caused by an omission or oversight 9 ALERT level G = General information/check it is not something unexpected 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
1-Ethylthiourea, ettu, (0.03 g, 0.29 mmol) was dissolved in 30 cm3 of acetonitrile at 348 K and then CuI (0.05 g, 0.26 mmol) was added. The mixture was stirred for 4 h and then bis(diphenylphosphanyl)methane, dppm, (0.1 g, 0.26 mmol) was added and the new reaction mixture was heated under reflux for 12 h where upon the precipitate gradually disappeared. The resulting clear solution was filtered off and left to evaporate at room temperature. The crystalline complex, which was deposited upon standing for several days, was filtered off and dried in vacuo (0.12 g, yield 67%). Mp = 531–533 K. Analysis found: C 47.77, H 4.02, N 3.68, S 2.26%; calculated for C112H113Cu4IN7P8S2: C 51.09, H 4.29, N 3.72, S 2.43%.
The H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 with Uiso(H) = 1.2 Ueq(C) for H atoms on C(sp2) and 0.98–0.99 Å with Uiso(H) = 1.5 Ueq(C) for H atoms on C(sp3). All H atoms bonded to N atoms were located in a difference Fourier map and refined isotropically, with N—H distances restrained to 0.87 (2) Å with Uiso(H) = 1.2Ueq(N). One of the acetonitrile molecules is disordered in a 1:1 ratio across a crystallographic inversion center and was refined anisotropically.
Metal(I) complexes with mixed phosphine and sulfur donor ligands have attracted much attention in recent years because of various applications based on e.g. their luminescent properties (Safin et al., 2010) or antimicrobial activities (Isab et al., 2010). CuI ions functioning as Lewis acids tend to form covalent bonds with soft ligands and can make close Cu···Cu contacts, features that can promote uncommon bonding, reactivity and catalytic properties of multinuclear copper complexes. Bis(diphenylphosphanyl)methane (dppm), for example, has been reported on multiple occasions to be a diphosphine ligands that is able to lock two metal atoms together in close proximity (Yang et al., 2000; Liaw et al., 2005; Jin et al., 2009). Copper complexes of thiourea ligands such as 1-ethylthiourea (ettu), on the other hand have been of increasing interest due to the variety of their structures and their similarity to metallothioneines, i.e. they contain coordinated Cu—S moieties which play an important role in animals and plants. Herein, the crystal structure of a dinuclear copper(I) iodode complex containing both dppm and ettu is described.
The molecular structure of the dinuclear title compound is shown in Fig. 1. Each CuI ion displays a distorted tetrahedral coordination geometry with internal angles in the range 97.00 (4)–119.56 (4)°. The dppm ligand and the bridging S atom of the ettu ligand force the two copper atoms into close proximity, leading to the formation of a close intramolecular Cu···Cu contact [3.3747 (17) Å]. The Cu—P distances vary from 2.2563 (10) to 2.2786 (11) Å, which are quite similar to those observed in related copper(I) complexes containing the dppm ligand (Yam et al., 2001; Zhou et al., 2001). The Cu—S bond lengths (Cu1—S1 = 2.3450 (11), Cu2—S1 = 2.3493 (11) Å) are shorter than that found in for example [Cu2(µ-HL1)2(µ-dppm)(η1-dppm)2] (H2L1 = 8-mercaptotheophylline), which are 2.392 (5)–2.410 (6) Å (Colacio et al., 1997). The terminal Cu—I bond distances (Cu1—I1 = 2.6694 (6) and Cu2—I2 = 2.6690 (5) Å), are in their typical ranges [see e.g. Nimthong et al., 2008; Pakawatchai et al., 2012]. The conformation of the dinuclear complex is such that the two dppm ligands are located on one side of the metal complex, while the two iodine atoms are pointed towards the other side of the complex. This conformation is stabilized by two intramolecular N—H···I hydrogen bonds between the ettu NH2 and NHEt moieties and the iodine atoms with N···H distances of 3.796 (4) (for N1···I2) and 3.563 (4) Å (for N2···I1), respectively (Table 1). In the crystal, the N and I atoms are also involved in intramolecular N—H···I hydrogen bonds to form dimers across an inversion center (symmetry code: -x, -y, -z + 1) (Table 1, Fig. 2). The dimers are in turn connected with each other and with the interstitial acetonitrile solvate molecules via a range of weaker C—H···I and C—H···S interactions (Table 1) and through a weak C(sp2)—H···π interaction [C14—H14···Cg1iv, with H14···Cg1iv = 3.38 (3) Å, C14···Cg1iv = 4.09 (3) Å and C14—H14···Cg1iv = 129.4 (4)°, Cg1 = C41—C42—C43—C44—C45—C46 ring, symmetry code: (iv) -x+1/2, y-1/2, -z+1] leading to the formation of a three-dimensional network, Fig. 3 and Table 1. One of the solvent acetonitrile molecules is disordered in a 1:1 ratio across a crystallographic inversion center.
For potential applications of related complexes, see: Isab et al. (2010); Safin et al. (2010). For examples of dppm as a chelating ligand, see: Yang et al. (2000); Liaw et al. (2005); Jin et al. (2009). For relevant examples of discrete complexes, see: Colacio et al. (1997); Yam et al. (2001); Zhou et al. (2001); Nimthong et al. (2008); Pakawatchai et al. (2012).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
[Cu2I2(C3H8N2S)(C25H22P2)2]·1.5C2H3N | F(000) = 2628 |
Mr = 1315.37 | Dx = 1.546 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9510 reflections |
a = 13.7751 (6) Å | θ = 2.3–28.3° |
b = 24.5147 (11) Å | µ = 2.03 mm−1 |
c = 18.0172 (8) Å | T = 100 K |
β = 111.720 (1)° | Hexagon, colorless |
V = 5652.3 (4) Å3 | 0.28 × 0.17 × 0.10 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 10863 independent reflections |
Radiation source: fine-focus sealed tube | 9108 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
phi and ω scans | θmax = 28.3°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −18→18 |
Tmin = 0.670, Tmax = 0.821 | k = −32→32 |
53066 measured reflections | l = −24→24 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0416P)2] where P = (Fo2 + 2Fc2)/3 |
10863 reflections | (Δ/σ)max = 0.001 |
643 parameters | Δρmax = 0.84 e Å−3 |
3 restraints | Δρmin = −0.55 e Å−3 |
[Cu2I2(C3H8N2S)(C25H22P2)2]·1.5C2H3N | V = 5652.3 (4) Å3 |
Mr = 1315.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.7751 (6) Å | µ = 2.03 mm−1 |
b = 24.5147 (11) Å | T = 100 K |
c = 18.0172 (8) Å | 0.28 × 0.17 × 0.10 mm |
β = 111.720 (1)° |
Bruker SMART CCD diffractometer | 10863 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 9108 reflections with I > 2σ(I) |
Tmin = 0.670, Tmax = 0.821 | Rint = 0.054 |
53066 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 3 restraints |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.84 e Å−3 |
10863 reflections | Δρmin = −0.55 e Å−3 |
643 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.0596 (3) | 0.11641 (17) | 0.4430 (2) | 0.0175 (8) | |
C2 | −0.1075 (4) | 0.1437 (2) | 0.3356 (3) | 0.0345 (12) | |
H2A | −0.1447 | 0.1791 | 0.3243 | 0.041* | |
H2B | −0.1444 | 0.1196 | 0.3606 | 0.041* | |
C3 | −0.1131 (5) | 0.1191 (3) | 0.2594 (4) | 0.0556 (17) | |
H3A | −0.0782 | 0.1431 | 0.2334 | 0.067* | |
H3B | −0.1864 | 0.1144 | 0.2243 | 0.067* | |
H3C | −0.0782 | 0.0835 | 0.2697 | 0.067* | |
C4 | 0.1919 (3) | 0.19363 (16) | 0.7423 (2) | 0.0156 (8) | |
H4A | 0.2645 | 0.2063 | 0.7704 | 0.019* | |
H4B | 0.1533 | 0.1998 | 0.7783 | 0.019* | |
C5 | 0.4659 (3) | 0.18775 (15) | 0.6705 (2) | 0.0145 (8) | |
H5A | 0.4682 | 0.1968 | 0.7246 | 0.017* | |
H5B | 0.5376 | 0.1922 | 0.6710 | 0.017* | |
C6 | 0.7716 (5) | 0.3044 (3) | 0.3672 (5) | 0.0482 (16) | |
C7 | 0.8360 (5) | 0.3346 (3) | 0.4376 (4) | 0.0517 (16) | |
H7A | 0.9098 | 0.3304 | 0.4449 | 0.078* | |
H7B | 0.8248 | 0.3204 | 0.4846 | 0.078* | |
H7C | 0.8170 | 0.3733 | 0.4306 | 0.078* | |
C8 | 0.0220 (10) | 0.0485 (5) | 0.9548 (7) | 0.042 (3) | 0.50 |
C9 | 0.1316 (8) | 0.0558 (4) | 0.9733 (7) | 0.032 (2) | 0.50 |
H9A | 0.1710 | 0.0383 | 1.0245 | 0.048* | 0.50 |
H9B | 0.1477 | 0.0949 | 0.9769 | 0.048* | 0.50 |
H9C | 0.1509 | 0.0394 | 0.9312 | 0.048* | 0.50 |
N4 | −0.0633 (9) | 0.0414 (6) | 0.9455 (8) | 0.085 (5) | 0.50 |
C11 | 0.4225 (3) | 0.30180 (16) | 0.6545 (2) | 0.0158 (8) | |
C12 | 0.5229 (4) | 0.31089 (18) | 0.7102 (3) | 0.0224 (9) | |
H12 | 0.5727 | 0.2821 | 0.7243 | 0.027* | |
C13 | 0.5504 (4) | 0.3625 (2) | 0.7455 (3) | 0.0307 (11) | |
H13 | 0.6185 | 0.3685 | 0.7840 | 0.037* | |
C14 | 0.4789 (5) | 0.40422 (19) | 0.7242 (3) | 0.0321 (12) | |
H14 | 0.4987 | 0.4396 | 0.7460 | 0.039* | |
C15 | 0.3780 (4) | 0.39475 (18) | 0.6712 (3) | 0.0300 (11) | |
H15 | 0.3277 | 0.4232 | 0.6585 | 0.036* | |
C16 | 0.3505 (4) | 0.34411 (18) | 0.6368 (3) | 0.0237 (9) | |
H16 | 0.2811 | 0.3380 | 0.6003 | 0.028* | |
C21 | 0.4350 (3) | 0.24310 (16) | 0.5205 (2) | 0.0156 (8) | |
C22 | 0.5175 (4) | 0.27774 (17) | 0.5271 (3) | 0.0219 (9) | |
H22 | 0.5478 | 0.2997 | 0.5734 | 0.026* | |
C23 | 0.5555 (4) | 0.28020 (18) | 0.4661 (3) | 0.0243 (10) | |
H23 | 0.6100 | 0.3051 | 0.4701 | 0.029* | |
C24 | 0.5159 (4) | 0.24728 (19) | 0.3998 (3) | 0.0228 (9) | |
H24 | 0.5443 | 0.2485 | 0.3591 | 0.027* | |
C25 | 0.4335 (4) | 0.21213 (19) | 0.3930 (3) | 0.0236 (10) | |
H25 | 0.4051 | 0.1893 | 0.3475 | 0.028* | |
C26 | 0.3930 (4) | 0.21056 (17) | 0.4533 (3) | 0.0197 (9) | |
H26 | 0.3362 | 0.1870 | 0.4483 | 0.024* | |
C31 | 0.4709 (3) | 0.09683 (16) | 0.5689 (2) | 0.0172 (8) | |
C32 | 0.5688 (4) | 0.11185 (18) | 0.5680 (3) | 0.0220 (9) | |
H32 | 0.6162 | 0.1320 | 0.6113 | 0.026* | |
C33 | 0.5963 (4) | 0.09741 (19) | 0.5043 (3) | 0.0256 (10) | |
H33 | 0.6629 | 0.1073 | 0.5041 | 0.031* | |
C34 | 0.5263 (4) | 0.06833 (18) | 0.4403 (3) | 0.0240 (10) | |
H34 | 0.5450 | 0.0585 | 0.3964 | 0.029* | |
C35 | 0.4305 (4) | 0.05394 (18) | 0.4409 (3) | 0.0221 (9) | |
H35 | 0.3824 | 0.0348 | 0.3967 | 0.027* | |
C36 | 0.4028 (3) | 0.06715 (17) | 0.5057 (3) | 0.0179 (8) | |
H36 | 0.3372 | 0.0558 | 0.5065 | 0.022* | |
C41 | 0.5279 (3) | 0.08573 (16) | 0.7403 (2) | 0.0156 (8) | |
C42 | 0.6097 (4) | 0.05246 (17) | 0.7397 (3) | 0.0200 (9) | |
H42 | 0.6153 | 0.0433 | 0.6902 | 0.024* | |
C43 | 0.6820 (4) | 0.03278 (19) | 0.8094 (3) | 0.0253 (10) | |
H43 | 0.7378 | 0.0106 | 0.8080 | 0.030* | |
C44 | 0.6741 (4) | 0.04503 (19) | 0.8823 (3) | 0.0259 (10) | |
H44 | 0.7247 | 0.0317 | 0.9306 | 0.031* | |
C45 | 0.5915 (4) | 0.07692 (19) | 0.8837 (3) | 0.0264 (10) | |
H45 | 0.5842 | 0.0846 | 0.9330 | 0.032* | |
C46 | 0.5206 (4) | 0.09737 (18) | 0.8140 (3) | 0.0213 (9) | |
H46 | 0.4654 | 0.1199 | 0.8158 | 0.026* | |
C51 | −0.0082 (3) | 0.22244 (16) | 0.6224 (3) | 0.0168 (8) | |
C52 | −0.0682 (4) | 0.20973 (19) | 0.5442 (3) | 0.0243 (10) | |
H52 | −0.0361 | 0.2066 | 0.5060 | 0.029* | |
C53 | −0.1756 (4) | 0.2015 (2) | 0.5208 (3) | 0.0332 (11) | |
H53 | −0.2159 | 0.1917 | 0.4671 | 0.040* | |
C54 | −0.2232 (4) | 0.20746 (19) | 0.5747 (3) | 0.0300 (11) | |
H54 | −0.2967 | 0.2029 | 0.5580 | 0.036* | |
C55 | −0.1650 (4) | 0.2200 (2) | 0.6533 (4) | 0.0392 (14) | |
H55 | −0.1984 | 0.2240 | 0.6906 | 0.047* | |
C56 | −0.0563 (4) | 0.2270 (2) | 0.6783 (3) | 0.0348 (12) | |
H56 | −0.0158 | 0.2347 | 0.7326 | 0.042* | |
C61 | 0.1374 (3) | 0.30465 (16) | 0.6903 (3) | 0.0171 (8) | |
C62 | 0.1786 (3) | 0.31816 (17) | 0.7703 (3) | 0.0183 (8) | |
H62 | 0.2064 | 0.2904 | 0.8093 | 0.022* | |
C63 | 0.1796 (4) | 0.37259 (18) | 0.7944 (3) | 0.0245 (10) | |
H63 | 0.2093 | 0.3816 | 0.8496 | 0.029* | |
C64 | 0.1379 (4) | 0.41329 (18) | 0.7387 (3) | 0.0262 (10) | |
H64 | 0.1385 | 0.4501 | 0.7553 | 0.031* | |
C65 | 0.0951 (5) | 0.39985 (19) | 0.6582 (3) | 0.0330 (12) | |
H65 | 0.0655 | 0.4275 | 0.6195 | 0.040* | |
C66 | 0.0955 (4) | 0.34600 (19) | 0.6340 (3) | 0.0288 (11) | |
H66 | 0.0671 | 0.3372 | 0.5787 | 0.035* | |
C71 | 0.2684 (3) | 0.09250 (16) | 0.8223 (2) | 0.0159 (8) | |
C72 | 0.3174 (3) | 0.12398 (17) | 0.8905 (2) | 0.0189 (9) | |
H72 | 0.3117 | 0.1626 | 0.8877 | 0.023* | |
C73 | 0.3747 (4) | 0.09874 (19) | 0.9631 (3) | 0.0233 (9) | |
H73 | 0.4077 | 0.1206 | 1.0092 | 0.028* | |
C74 | 0.3843 (4) | 0.04333 (19) | 0.9690 (3) | 0.0246 (10) | |
H74 | 0.4231 | 0.0266 | 1.0188 | 0.030* | |
C75 | 0.3364 (4) | 0.01183 (18) | 0.9014 (3) | 0.0300 (11) | |
H75 | 0.3436 | −0.0267 | 0.9049 | 0.036* | |
C76 | 0.2784 (4) | 0.03575 (17) | 0.8289 (3) | 0.0226 (9) | |
H76 | 0.2450 | 0.0135 | 0.7834 | 0.027* | |
C81 | 0.0611 (3) | 0.09752 (16) | 0.7085 (3) | 0.0163 (8) | |
C82 | −0.0038 (4) | 0.07981 (18) | 0.6340 (3) | 0.0230 (9) | |
H82 | 0.0212 | 0.0787 | 0.5915 | 0.028* | |
C83 | −0.1055 (4) | 0.0635 (2) | 0.6206 (3) | 0.0265 (10) | |
H83 | −0.1497 | 0.0513 | 0.5691 | 0.032* | |
C84 | −0.1423 (4) | 0.06518 (19) | 0.6821 (3) | 0.0286 (11) | |
H84 | −0.2120 | 0.0544 | 0.6730 | 0.034* | |
C85 | −0.0776 (4) | 0.0824 (2) | 0.7568 (3) | 0.0378 (14) | |
H85 | −0.1029 | 0.0836 | 0.7991 | 0.045* | |
C86 | 0.0249 (4) | 0.0982 (2) | 0.7706 (3) | 0.0339 (13) | |
H86 | 0.0697 | 0.1094 | 0.8225 | 0.041* | |
N1 | 0.0293 (3) | 0.06564 (16) | 0.4455 (2) | 0.0234 (8) | |
N2 | −0.0010 (3) | 0.15260 (15) | 0.3924 (2) | 0.0218 (8) | |
N3 | 0.7233 (5) | 0.2815 (3) | 0.3116 (4) | 0.0662 (18) | |
P1 | 0.38018 (8) | 0.23788 (4) | 0.59951 (6) | 0.0136 (2) | |
P2 | 0.42899 (8) | 0.11516 (4) | 0.65079 (6) | 0.0130 (2) | |
P3 | 0.13118 (8) | 0.23514 (4) | 0.65131 (6) | 0.0130 (2) | |
P4 | 0.19412 (8) | 0.12008 (4) | 0.72331 (6) | 0.0132 (2) | |
S1 | 0.18473 (8) | 0.13532 (4) | 0.50372 (6) | 0.01496 (19) | |
Cu1 | 0.20473 (4) | 0.223317 (19) | 0.55840 (3) | 0.01406 (11) | |
Cu2 | 0.25996 (4) | 0.095310 (19) | 0.63076 (3) | 0.01382 (11) | |
I1 | 0.10743 (2) | 0.286304 (11) | 0.431721 (16) | 0.01865 (7) | |
I2 | 0.23544 (2) | −0.012447 (10) | 0.611802 (17) | 0.01886 (7) | |
H1A | −0.032 (2) | 0.0543 (19) | 0.414 (2) | 0.023* | |
H1B | 0.073 (3) | 0.0450 (17) | 0.479 (2) | 0.023* | |
H2 | 0.024 (4) | 0.1856 (11) | 0.394 (3) | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.016 (2) | 0.024 (2) | 0.014 (2) | −0.0039 (16) | 0.0078 (18) | −0.0042 (16) |
C2 | 0.022 (3) | 0.044 (3) | 0.028 (3) | −0.005 (2) | −0.001 (2) | 0.008 (2) |
C3 | 0.042 (4) | 0.077 (5) | 0.040 (4) | −0.007 (3) | 0.006 (3) | −0.002 (3) |
C4 | 0.018 (2) | 0.0165 (18) | 0.0123 (19) | 0.0002 (16) | 0.0052 (17) | −0.0003 (15) |
C5 | 0.0133 (19) | 0.0162 (18) | 0.0129 (19) | −0.0033 (15) | 0.0036 (17) | −0.0029 (15) |
C6 | 0.028 (3) | 0.063 (4) | 0.058 (4) | 0.011 (3) | 0.022 (3) | 0.017 (4) |
C7 | 0.044 (4) | 0.049 (4) | 0.058 (4) | 0.022 (3) | 0.014 (3) | 0.002 (3) |
C8 | 0.050 (7) | 0.042 (6) | 0.044 (7) | 0.000 (5) | 0.029 (6) | −0.014 (5) |
C9 | 0.030 (5) | 0.026 (5) | 0.041 (6) | 0.017 (4) | 0.016 (5) | 0.020 (4) |
N4 | 0.039 (7) | 0.148 (13) | 0.081 (9) | −0.055 (8) | 0.038 (7) | −0.071 (9) |
C11 | 0.020 (2) | 0.0127 (17) | 0.017 (2) | −0.0039 (16) | 0.0096 (18) | 0.0000 (15) |
C12 | 0.024 (2) | 0.021 (2) | 0.023 (2) | −0.0022 (18) | 0.009 (2) | −0.0027 (17) |
C13 | 0.038 (3) | 0.029 (3) | 0.023 (2) | −0.012 (2) | 0.008 (2) | −0.006 (2) |
C14 | 0.054 (4) | 0.018 (2) | 0.026 (3) | −0.009 (2) | 0.017 (3) | −0.0102 (19) |
C15 | 0.045 (3) | 0.017 (2) | 0.028 (3) | 0.003 (2) | 0.015 (3) | −0.0036 (19) |
C16 | 0.028 (2) | 0.022 (2) | 0.020 (2) | −0.0013 (18) | 0.007 (2) | −0.0024 (17) |
C21 | 0.0149 (19) | 0.0188 (19) | 0.016 (2) | 0.0000 (16) | 0.0091 (18) | 0.0010 (16) |
C22 | 0.021 (2) | 0.022 (2) | 0.021 (2) | −0.0024 (17) | 0.007 (2) | −0.0010 (17) |
C23 | 0.019 (2) | 0.030 (2) | 0.028 (3) | 0.0000 (18) | 0.013 (2) | 0.0094 (19) |
C24 | 0.022 (2) | 0.031 (2) | 0.020 (2) | 0.0058 (19) | 0.013 (2) | 0.0085 (18) |
C25 | 0.023 (2) | 0.032 (2) | 0.018 (2) | 0.0013 (19) | 0.010 (2) | −0.0020 (18) |
C26 | 0.023 (2) | 0.021 (2) | 0.017 (2) | −0.0019 (17) | 0.009 (2) | 0.0020 (16) |
C31 | 0.020 (2) | 0.0180 (19) | 0.017 (2) | 0.0019 (16) | 0.0103 (19) | −0.0006 (16) |
C32 | 0.022 (2) | 0.023 (2) | 0.025 (2) | −0.0018 (17) | 0.014 (2) | 0.0014 (18) |
C33 | 0.025 (2) | 0.030 (2) | 0.029 (3) | 0.0041 (19) | 0.019 (2) | 0.006 (2) |
C34 | 0.030 (3) | 0.029 (2) | 0.019 (2) | 0.013 (2) | 0.015 (2) | 0.0040 (18) |
C35 | 0.024 (2) | 0.026 (2) | 0.015 (2) | 0.0069 (18) | 0.0054 (19) | −0.0045 (17) |
C36 | 0.015 (2) | 0.021 (2) | 0.020 (2) | 0.0043 (16) | 0.0093 (19) | −0.0015 (17) |
C41 | 0.015 (2) | 0.0137 (18) | 0.017 (2) | −0.0038 (15) | 0.0047 (18) | −0.0006 (15) |
C42 | 0.024 (2) | 0.020 (2) | 0.020 (2) | −0.0036 (17) | 0.013 (2) | −0.0036 (17) |
C43 | 0.018 (2) | 0.027 (2) | 0.032 (3) | −0.0002 (18) | 0.010 (2) | 0.005 (2) |
C44 | 0.021 (2) | 0.033 (3) | 0.018 (2) | −0.0037 (19) | 0.001 (2) | 0.0081 (19) |
C45 | 0.030 (3) | 0.030 (2) | 0.018 (2) | −0.005 (2) | 0.008 (2) | 0.0009 (19) |
C46 | 0.021 (2) | 0.024 (2) | 0.021 (2) | 0.0013 (18) | 0.010 (2) | 0.0021 (17) |
C51 | 0.013 (2) | 0.0173 (19) | 0.019 (2) | 0.0024 (15) | 0.0053 (18) | 0.0031 (16) |
C52 | 0.019 (2) | 0.035 (3) | 0.018 (2) | −0.0011 (19) | 0.005 (2) | 0.0028 (19) |
C53 | 0.014 (2) | 0.046 (3) | 0.033 (3) | −0.004 (2) | 0.001 (2) | 0.004 (2) |
C54 | 0.016 (2) | 0.031 (3) | 0.042 (3) | 0.0027 (19) | 0.010 (2) | 0.012 (2) |
C55 | 0.022 (3) | 0.059 (4) | 0.044 (4) | 0.000 (2) | 0.020 (3) | 0.003 (3) |
C56 | 0.028 (3) | 0.054 (3) | 0.029 (3) | −0.004 (2) | 0.018 (3) | −0.008 (2) |
C61 | 0.022 (2) | 0.0138 (18) | 0.020 (2) | −0.0007 (16) | 0.0127 (19) | 0.0000 (16) |
C62 | 0.023 (2) | 0.0181 (19) | 0.016 (2) | 0.0002 (16) | 0.0093 (19) | 0.0021 (16) |
C63 | 0.036 (3) | 0.022 (2) | 0.019 (2) | −0.0058 (19) | 0.014 (2) | −0.0056 (17) |
C64 | 0.040 (3) | 0.016 (2) | 0.028 (3) | 0.0005 (19) | 0.019 (2) | −0.0014 (18) |
C65 | 0.055 (4) | 0.018 (2) | 0.028 (3) | 0.010 (2) | 0.017 (3) | 0.0045 (19) |
C66 | 0.044 (3) | 0.025 (2) | 0.017 (2) | 0.007 (2) | 0.010 (2) | 0.0011 (18) |
C71 | 0.019 (2) | 0.0151 (18) | 0.018 (2) | 0.0009 (15) | 0.0109 (18) | 0.0031 (15) |
C72 | 0.023 (2) | 0.0176 (19) | 0.019 (2) | 0.0007 (17) | 0.012 (2) | 0.0007 (16) |
C73 | 0.023 (2) | 0.032 (2) | 0.015 (2) | 0.0041 (19) | 0.008 (2) | 0.0042 (18) |
C74 | 0.023 (2) | 0.031 (2) | 0.020 (2) | 0.0088 (19) | 0.007 (2) | 0.0080 (19) |
C75 | 0.039 (3) | 0.016 (2) | 0.032 (3) | 0.005 (2) | 0.010 (3) | 0.0057 (19) |
C76 | 0.031 (3) | 0.0145 (19) | 0.021 (2) | 0.0004 (18) | 0.008 (2) | −0.0010 (17) |
C81 | 0.017 (2) | 0.0123 (18) | 0.023 (2) | −0.0026 (15) | 0.0116 (19) | −0.0014 (15) |
C82 | 0.022 (2) | 0.029 (2) | 0.020 (2) | −0.0004 (18) | 0.011 (2) | −0.0019 (18) |
C83 | 0.019 (2) | 0.032 (2) | 0.027 (3) | −0.0050 (19) | 0.006 (2) | −0.005 (2) |
C84 | 0.024 (2) | 0.023 (2) | 0.046 (3) | −0.0044 (19) | 0.021 (2) | −0.003 (2) |
C85 | 0.037 (3) | 0.049 (3) | 0.039 (3) | −0.022 (3) | 0.027 (3) | −0.019 (3) |
C86 | 0.039 (3) | 0.043 (3) | 0.031 (3) | −0.021 (2) | 0.026 (3) | −0.018 (2) |
N1 | 0.0152 (19) | 0.024 (2) | 0.024 (2) | −0.0025 (16) | −0.0004 (17) | 0.0010 (16) |
N2 | 0.0161 (18) | 0.0247 (19) | 0.0180 (19) | −0.0041 (15) | −0.0014 (16) | 0.0031 (15) |
N3 | 0.040 (3) | 0.101 (5) | 0.053 (4) | −0.004 (3) | 0.012 (3) | 0.002 (4) |
P1 | 0.0149 (5) | 0.0143 (5) | 0.0130 (5) | −0.0025 (4) | 0.0067 (4) | −0.0017 (4) |
P2 | 0.0130 (5) | 0.0146 (5) | 0.0132 (5) | −0.0014 (4) | 0.0071 (4) | −0.0021 (4) |
P3 | 0.0143 (5) | 0.0143 (5) | 0.0117 (5) | 0.0007 (4) | 0.0064 (4) | 0.0003 (4) |
P4 | 0.0158 (5) | 0.0129 (5) | 0.0134 (5) | −0.0008 (4) | 0.0084 (4) | −0.0002 (4) |
S1 | 0.0141 (5) | 0.0169 (5) | 0.0137 (5) | −0.0016 (4) | 0.0051 (4) | −0.0014 (4) |
Cu1 | 0.0151 (2) | 0.0159 (2) | 0.0129 (2) | −0.00091 (19) | 0.0072 (2) | −0.00045 (18) |
Cu2 | 0.0135 (2) | 0.0153 (2) | 0.0147 (2) | −0.00164 (18) | 0.0076 (2) | −0.00205 (18) |
I1 | 0.02440 (15) | 0.01919 (13) | 0.01354 (14) | 0.00084 (10) | 0.00841 (12) | 0.00374 (10) |
I2 | 0.01749 (14) | 0.01558 (13) | 0.02425 (15) | −0.00252 (10) | 0.00860 (12) | −0.00355 (10) |
C1—N1 | 1.319 (5) | C42—H42 | 0.9500 |
C1—N2 | 1.323 (6) | C43—C44 | 1.389 (6) |
C1—S1 | 1.729 (4) | C43—H43 | 0.9500 |
C2—N2 | 1.462 (6) | C44—C45 | 1.388 (7) |
C2—C3 | 1.476 (8) | C44—H44 | 0.9500 |
C2—H2A | 0.9900 | C45—C46 | 1.369 (6) |
C2—H2B | 0.9900 | C45—H45 | 0.9500 |
C3—H3A | 0.9800 | C46—H46 | 0.9500 |
C3—H3B | 0.9800 | C51—C52 | 1.380 (6) |
C3—H3C | 0.9800 | C51—C56 | 1.399 (6) |
C4—P4 | 1.838 (4) | C51—P3 | 1.821 (4) |
C4—P3 | 1.846 (4) | C52—C53 | 1.395 (7) |
C4—H4A | 0.9900 | C52—H52 | 0.9500 |
C4—H4B | 0.9900 | C53—C54 | 1.365 (7) |
C5—P1 | 1.850 (4) | C53—H53 | 0.9500 |
C5—P2 | 1.849 (4) | C54—C55 | 1.380 (8) |
C5—H5A | 0.9900 | C54—H54 | 0.9500 |
C5—H5B | 0.9900 | C55—C56 | 1.404 (7) |
C6—N3 | 1.125 (9) | C55—H55 | 0.9500 |
C6—C7 | 1.453 (10) | C56—H56 | 0.9500 |
C7—H7A | 0.9800 | C61—C62 | 1.380 (6) |
C7—H7B | 0.9800 | C61—C66 | 1.399 (6) |
C7—H7C | 0.9800 | C61—P3 | 1.833 (4) |
C8—N4 | 1.138 (16) | C62—C63 | 1.402 (6) |
C8—C9 | 1.431 (16) | C62—H62 | 0.9500 |
C9—H9A | 0.9800 | C63—C64 | 1.381 (7) |
C9—H9B | 0.9800 | C63—H63 | 0.9500 |
C9—H9C | 0.9800 | C64—C65 | 1.388 (7) |
C11—C16 | 1.389 (6) | C64—H64 | 0.9500 |
C11—C12 | 1.393 (6) | C65—C66 | 1.391 (6) |
C11—P1 | 1.830 (4) | C65—H65 | 0.9500 |
C12—C13 | 1.403 (6) | C66—H66 | 0.9500 |
C12—H12 | 0.9500 | C71—C72 | 1.396 (6) |
C13—C14 | 1.373 (8) | C71—C76 | 1.399 (5) |
C13—H13 | 0.9500 | C71—P4 | 1.826 (4) |
C14—C15 | 1.384 (8) | C72—C73 | 1.397 (6) |
C14—H14 | 0.9500 | C72—H72 | 0.9500 |
C15—C16 | 1.377 (6) | C73—C74 | 1.365 (6) |
C15—H15 | 0.9500 | C73—H73 | 0.9500 |
C16—H16 | 0.9500 | C74—C75 | 1.386 (7) |
C21—C26 | 1.385 (6) | C74—H74 | 0.9500 |
C21—C22 | 1.388 (6) | C75—C76 | 1.384 (7) |
C21—P1 | 1.847 (4) | C75—H75 | 0.9500 |
C22—C23 | 1.382 (6) | C76—H76 | 0.9500 |
C22—H22 | 0.9500 | C81—C82 | 1.378 (6) |
C23—C24 | 1.376 (7) | C81—C86 | 1.384 (6) |
C23—H23 | 0.9500 | C81—P4 | 1.837 (4) |
C24—C25 | 1.394 (6) | C82—C83 | 1.390 (6) |
C24—H24 | 0.9500 | C82—H82 | 0.9500 |
C25—C26 | 1.392 (6) | C83—C84 | 1.379 (6) |
C25—H25 | 0.9500 | C83—H83 | 0.9500 |
C26—H26 | 0.9500 | C84—C85 | 1.377 (7) |
C31—C36 | 1.384 (6) | C84—H84 | 0.9500 |
C31—C32 | 1.404 (6) | C85—C86 | 1.394 (7) |
C31—P2 | 1.828 (4) | C85—H85 | 0.9500 |
C32—C33 | 1.381 (6) | C86—H86 | 0.9500 |
C32—H32 | 0.9500 | N1—H1A | 0.873 (19) |
C33—C34 | 1.395 (7) | N1—H1B | 0.841 (19) |
C33—H33 | 0.9500 | N2—H2 | 0.875 (19) |
C34—C35 | 1.370 (7) | P1—Cu1 | 2.2786 (11) |
C34—H34 | 0.9500 | P2—Cu2 | 2.2730 (11) |
C35—C36 | 1.394 (5) | P3—Cu1 | 2.2733 (10) |
C35—H35 | 0.9500 | P4—Cu2 | 2.2563 (10) |
C36—H36 | 0.9500 | S1—Cu1 | 2.3450 (11) |
C41—C42 | 1.394 (6) | S1—Cu2 | 2.3493 (11) |
C41—C46 | 1.397 (6) | Cu1—I1 | 2.6694 (6) |
C41—P2 | 1.831 (4) | Cu2—I2 | 2.6690 (5) |
C42—C43 | 1.370 (7) | ||
N1—C1—N2 | 122.0 (4) | C56—C51—P3 | 120.7 (4) |
N1—C1—S1 | 119.0 (3) | C51—C52—C53 | 120.6 (4) |
N2—C1—S1 | 118.9 (3) | C51—C52—H52 | 119.7 |
N2—C2—C3 | 114.0 (5) | C53—C52—H52 | 119.7 |
N2—C2—H2A | 108.8 | C54—C53—C52 | 120.2 (5) |
C3—C2—H2A | 108.8 | C54—C53—H53 | 119.9 |
N2—C2—H2B | 108.8 | C52—C53—H53 | 119.9 |
C3—C2—H2B | 108.8 | C53—C54—C55 | 120.3 (5) |
H2A—C2—H2B | 107.7 | C53—C54—H54 | 119.8 |
C2—C3—H3A | 109.5 | C55—C54—H54 | 119.8 |
C2—C3—H3B | 109.5 | C54—C55—C56 | 120.1 (5) |
H3A—C3—H3B | 109.5 | C54—C55—H55 | 120.0 |
C2—C3—H3C | 109.5 | C56—C55—H55 | 120.0 |
H3A—C3—H3C | 109.5 | C51—C56—C55 | 119.5 (5) |
H3B—C3—H3C | 109.5 | C51—C56—H56 | 120.2 |
P4—C4—P3 | 114.1 (2) | C55—C56—H56 | 120.2 |
P4—C4—H4A | 108.7 | C62—C61—C66 | 118.9 (4) |
P3—C4—H4A | 108.7 | C62—C61—P3 | 124.5 (3) |
P4—C4—H4B | 108.7 | C66—C61—P3 | 116.6 (3) |
P3—C4—H4B | 108.7 | C61—C62—C63 | 120.3 (4) |
H4A—C4—H4B | 107.6 | C61—C62—H62 | 119.8 |
P1—C5—P2 | 116.5 (2) | C63—C62—H62 | 119.8 |
P1—C5—H5A | 108.2 | C64—C63—C62 | 120.6 (4) |
P2—C5—H5A | 108.2 | C64—C63—H63 | 119.7 |
P1—C5—H5B | 108.2 | C62—C63—H63 | 119.7 |
P2—C5—H5B | 108.2 | C63—C64—C65 | 119.3 (4) |
H5A—C5—H5B | 107.3 | C63—C64—H64 | 120.3 |
N3—C6—C7 | 178.1 (7) | C65—C64—H64 | 120.3 |
C6—C7—H7A | 109.5 | C66—C65—C64 | 120.2 (4) |
C6—C7—H7B | 109.5 | C66—C65—H65 | 119.9 |
H7A—C7—H7B | 109.5 | C64—C65—H65 | 119.9 |
C6—C7—H7C | 109.5 | C65—C66—C61 | 120.6 (4) |
H7A—C7—H7C | 109.5 | C65—C66—H66 | 119.7 |
H7B—C7—H7C | 109.5 | C61—C66—H66 | 119.7 |
N4—C8—C9 | 175.2 (15) | C72—C71—C76 | 118.3 (4) |
C8—C9—H9A | 109.5 | C72—C71—P4 | 124.7 (3) |
C8—C9—H9B | 109.5 | C76—C71—P4 | 117.0 (3) |
H9A—C9—H9B | 109.5 | C73—C72—C71 | 120.1 (4) |
C8—C9—H9C | 109.5 | C73—C72—H72 | 120.0 |
H9A—C9—H9C | 109.5 | C71—C72—H72 | 120.0 |
H9B—C9—H9C | 109.5 | C74—C73—C72 | 121.3 (4) |
C16—C11—C12 | 118.7 (4) | C74—C73—H73 | 119.4 |
C16—C11—P1 | 117.2 (3) | C72—C73—H73 | 119.4 |
C12—C11—P1 | 124.0 (3) | C73—C74—C75 | 119.0 (4) |
C11—C12—C13 | 120.0 (4) | C73—C74—H74 | 120.5 |
C11—C12—H12 | 120.0 | C75—C74—H74 | 120.5 |
C13—C12—H12 | 120.0 | C76—C75—C74 | 121.0 (4) |
C14—C13—C12 | 120.0 (5) | C76—C75—H75 | 119.5 |
C14—C13—H13 | 120.0 | C74—C75—H75 | 119.5 |
C12—C13—H13 | 120.0 | C75—C76—C71 | 120.4 (4) |
C13—C14—C15 | 120.0 (4) | C75—C76—H76 | 119.8 |
C13—C14—H14 | 120.0 | C71—C76—H76 | 119.8 |
C15—C14—H14 | 120.0 | C82—C81—C86 | 119.6 (4) |
C14—C15—C16 | 120.1 (5) | C82—C81—P4 | 119.3 (3) |
C14—C15—H15 | 120.0 | C86—C81—P4 | 121.1 (4) |
C16—C15—H15 | 120.0 | C81—C82—C83 | 120.6 (4) |
C15—C16—C11 | 121.1 (5) | C81—C82—H82 | 119.7 |
C15—C16—H16 | 119.5 | C83—C82—H82 | 119.7 |
C11—C16—H16 | 119.5 | C84—C83—C82 | 119.9 (5) |
C26—C21—C22 | 119.5 (4) | C84—C83—H83 | 120.0 |
C26—C21—P1 | 118.4 (3) | C82—C83—H83 | 120.0 |
C22—C21—P1 | 122.1 (3) | C83—C84—C85 | 119.8 (4) |
C23—C22—C21 | 119.8 (4) | C83—C84—H84 | 120.1 |
C23—C22—H22 | 120.1 | C85—C84—H84 | 120.1 |
C21—C22—H22 | 120.1 | C84—C85—C86 | 120.5 (4) |
C24—C23—C22 | 121.3 (4) | C84—C85—H85 | 119.8 |
C24—C23—H23 | 119.3 | C86—C85—H85 | 119.8 |
C22—C23—H23 | 119.3 | C81—C86—C85 | 119.7 (5) |
C23—C24—C25 | 119.1 (4) | C81—C86—H86 | 120.2 |
C23—C24—H24 | 120.4 | C85—C86—H86 | 120.2 |
C25—C24—H24 | 120.4 | C1—N1—H1A | 122 (3) |
C26—C25—C24 | 119.8 (4) | C1—N1—H1B | 116 (4) |
C26—C25—H25 | 120.1 | H1A—N1—H1B | 122 (5) |
C24—C25—H25 | 120.1 | C1—N2—C2 | 126.6 (4) |
C21—C26—C25 | 120.4 (4) | C1—N2—H2 | 117 (3) |
C21—C26—H26 | 119.8 | C2—N2—H2 | 116 (3) |
C25—C26—H26 | 119.8 | C11—P1—C21 | 102.63 (18) |
C36—C31—C32 | 119.3 (4) | C11—P1—C5 | 101.56 (19) |
C36—C31—P2 | 118.2 (3) | C21—P1—C5 | 103.90 (18) |
C32—C31—P2 | 122.5 (3) | C11—P1—Cu1 | 113.42 (14) |
C33—C32—C31 | 120.2 (4) | C21—P1—Cu1 | 116.59 (14) |
C33—C32—H32 | 119.9 | C5—P1—Cu1 | 116.72 (13) |
C31—C32—H32 | 119.9 | C31—P2—C41 | 105.06 (19) |
C32—C33—C34 | 119.9 (4) | C31—P2—C5 | 104.17 (18) |
C32—C33—H33 | 120.0 | C41—P2—C5 | 98.51 (18) |
C34—C33—H33 | 120.0 | C31—P2—Cu2 | 115.48 (15) |
C35—C34—C33 | 119.9 (4) | C41—P2—Cu2 | 116.10 (13) |
C35—C34—H34 | 120.0 | C5—P2—Cu2 | 115.44 (13) |
C33—C34—H34 | 120.0 | C51—P3—C61 | 99.41 (19) |
C34—C35—C36 | 120.7 (4) | C51—P3—C4 | 104.06 (19) |
C34—C35—H35 | 119.7 | C61—P3—C4 | 103.32 (19) |
C36—C35—H35 | 119.7 | C51—P3—Cu1 | 118.56 (14) |
C31—C36—C35 | 119.9 (4) | C61—P3—Cu1 | 115.48 (12) |
C31—C36—H36 | 120.0 | C4—P3—Cu1 | 113.87 (13) |
C35—C36—H36 | 120.0 | C71—P4—C81 | 101.49 (19) |
C42—C41—C46 | 118.0 (4) | C71—P4—C4 | 102.91 (18) |
C42—C41—P2 | 124.3 (3) | C81—P4—C4 | 103.77 (18) |
C46—C41—P2 | 117.7 (3) | C71—P4—Cu2 | 112.88 (13) |
C43—C42—C41 | 120.9 (4) | C81—P4—Cu2 | 117.63 (13) |
C43—C42—H42 | 119.5 | C4—P4—Cu2 | 116.13 (12) |
C41—C42—H42 | 119.5 | C1—S1—Cu1 | 116.57 (15) |
C42—C43—C44 | 120.4 (4) | C1—S1—Cu2 | 118.81 (14) |
C42—C43—H43 | 119.8 | Cu1—S1—Cu2 | 91.94 (4) |
C44—C43—H43 | 119.8 | P3—Cu1—P1 | 116.67 (4) |
C45—C44—C43 | 119.3 (4) | P3—Cu1—S1 | 114.30 (4) |
C45—C44—H44 | 120.3 | P1—Cu1—S1 | 103.08 (4) |
C43—C44—H44 | 120.3 | P3—Cu1—I1 | 109.65 (3) |
C46—C45—C44 | 120.1 (4) | P1—Cu1—I1 | 108.89 (3) |
C46—C45—H45 | 120.0 | S1—Cu1—I1 | 103.25 (3) |
C44—C45—H45 | 120.0 | P4—Cu2—P2 | 119.56 (4) |
C45—C46—C41 | 121.2 (4) | P4—Cu2—S1 | 117.04 (4) |
C45—C46—H46 | 119.4 | P2—Cu2—S1 | 97.00 (4) |
C41—C46—H46 | 119.4 | P4—Cu2—I2 | 107.13 (3) |
C52—C51—C56 | 119.2 (4) | P2—Cu2—I2 | 107.81 (3) |
C52—C51—P3 | 120.0 (3) | S1—Cu2—I2 | 107.41 (3) |
C16—C11—C12—C13 | −1.9 (6) | C42—C41—P2—C5 | −112.7 (4) |
P1—C11—C12—C13 | 175.6 (3) | C46—C41—P2—C5 | 67.4 (3) |
C11—C12—C13—C14 | −0.9 (7) | C42—C41—P2—Cu2 | 123.4 (3) |
C12—C13—C14—C15 | 3.4 (7) | C46—C41—P2—Cu2 | −56.4 (4) |
C13—C14—C15—C16 | −3.0 (7) | P1—C5—P2—C31 | 77.2 (2) |
C14—C15—C16—C11 | 0.2 (7) | P1—C5—P2—C41 | −174.8 (2) |
C12—C11—C16—C15 | 2.2 (6) | P1—C5—P2—Cu2 | −50.5 (2) |
P1—C11—C16—C15 | −175.4 (3) | C52—C51—P3—C61 | 121.4 (4) |
C26—C21—C22—C23 | 1.3 (7) | C56—C51—P3—C61 | −56.7 (4) |
P1—C21—C22—C23 | −179.8 (3) | C52—C51—P3—C4 | −132.2 (4) |
C21—C22—C23—C24 | −2.6 (7) | C56—C51—P3—C4 | 49.7 (4) |
C22—C23—C24—C25 | 2.2 (7) | C52—C51—P3—Cu1 | −4.5 (4) |
C23—C24—C25—C26 | −0.3 (7) | C56—C51—P3—Cu1 | 177.4 (4) |
C22—C21—C26—C25 | 0.5 (7) | C62—C61—P3—C51 | 106.4 (4) |
P1—C21—C26—C25 | −178.4 (3) | C66—C61—P3—C51 | −72.5 (4) |
C24—C25—C26—C21 | −1.0 (7) | C62—C61—P3—C4 | −0.6 (4) |
C36—C31—C32—C33 | 0.4 (7) | C66—C61—P3—C4 | −179.5 (3) |
P2—C31—C32—C33 | −179.4 (3) | C62—C61—P3—Cu1 | −125.6 (3) |
C31—C32—C33—C34 | 0.7 (7) | C66—C61—P3—Cu1 | 55.5 (4) |
C32—C33—C34—C35 | −0.3 (7) | P4—C4—P3—C51 | 74.8 (2) |
C33—C34—C35—C36 | −1.3 (7) | P4—C4—P3—C61 | 178.3 (2) |
C32—C31—C36—C35 | −2.0 (6) | P4—C4—P3—Cu1 | −55.7 (2) |
P2—C31—C36—C35 | 177.9 (3) | C72—C71—P4—C81 | −112.8 (4) |
C34—C35—C36—C31 | 2.4 (7) | C76—C71—P4—C81 | 68.8 (3) |
C46—C41—C42—C43 | −1.4 (6) | C72—C71—P4—C4 | −5.6 (4) |
P2—C41—C42—C43 | 178.7 (3) | C76—C71—P4—C4 | 176.0 (3) |
C41—C42—C43—C44 | 1.0 (7) | C72—C71—P4—Cu2 | 120.4 (3) |
C42—C43—C44—C45 | 0.7 (7) | C76—C71—P4—Cu2 | −58.1 (3) |
C43—C44—C45—C46 | −2.0 (7) | C82—C81—P4—C71 | −141.0 (3) |
C44—C45—C46—C41 | 1.6 (7) | C86—C81—P4—C71 | 39.3 (4) |
C42—C41—C46—C45 | 0.1 (6) | C82—C81—P4—C4 | 112.5 (4) |
P2—C41—C46—C45 | −180.0 (3) | C86—C81—P4—C4 | −67.2 (4) |
C56—C51—C52—C53 | 0.0 (7) | C82—C81—P4—Cu2 | −17.3 (4) |
P3—C51—C52—C53 | −178.1 (4) | C86—C81—P4—Cu2 | 163.0 (4) |
C51—C52—C53—C54 | 1.9 (8) | P3—C4—P4—C71 | 175.0 (2) |
C52—C53—C54—C55 | −2.0 (8) | P3—C4—P4—C81 | −79.6 (2) |
C53—C54—C55—C56 | 0.2 (8) | P3—C4—P4—Cu2 | 51.1 (3) |
C52—C51—C56—C55 | −1.8 (8) | N1—C1—S1—Cu1 | −143.2 (3) |
P3—C51—C56—C55 | 176.3 (4) | N2—C1—S1—Cu1 | 40.2 (4) |
C54—C55—C56—C51 | 1.7 (8) | N1—C1—S1—Cu2 | −34.7 (4) |
C66—C61—C62—C63 | −0.9 (6) | N2—C1—S1—Cu2 | 148.8 (3) |
P3—C61—C62—C63 | −179.8 (3) | C51—P3—Cu1—P1 | −178.53 (15) |
C61—C62—C63—C64 | 1.1 (7) | C61—P3—Cu1—P1 | 63.72 (17) |
C62—C63—C64—C65 | −0.3 (7) | C4—P3—Cu1—P1 | −55.62 (15) |
C63—C64—C65—C66 | −0.8 (8) | C51—P3—Cu1—S1 | −58.22 (16) |
C64—C65—C66—C61 | 1.0 (8) | C61—P3—Cu1—S1 | −175.97 (16) |
C62—C61—C66—C65 | −0.2 (7) | C4—P3—Cu1—S1 | 64.68 (15) |
P3—C61—C66—C65 | 178.8 (4) | C51—P3—Cu1—I1 | 57.13 (15) |
C76—C71—C72—C73 | 0.1 (6) | C61—P3—Cu1—I1 | −60.62 (17) |
P4—C71—C72—C73 | −178.3 (3) | C4—P3—Cu1—I1 | −179.96 (14) |
C71—C72—C73—C74 | 0.0 (6) | C11—P1—Cu1—P3 | −48.21 (15) |
C72—C73—C74—C75 | 0.4 (7) | C21—P1—Cu1—P3 | −167.11 (15) |
C73—C74—C75—C76 | −1.0 (7) | C5—P1—Cu1—P3 | 69.35 (14) |
C74—C75—C76—C71 | 1.1 (7) | C11—P1—Cu1—S1 | −174.32 (14) |
C72—C71—C76—C75 | −0.7 (6) | C21—P1—Cu1—S1 | 66.78 (15) |
P4—C71—C76—C75 | 177.8 (4) | C5—P1—Cu1—S1 | −56.77 (14) |
C86—C81—C82—C83 | 1.0 (7) | C11—P1—Cu1—I1 | 76.52 (14) |
P4—C81—C82—C83 | −178.7 (4) | C21—P1—Cu1—I1 | −42.38 (15) |
C81—C82—C83—C84 | 0.1 (7) | C5—P1—Cu1—I1 | −165.93 (14) |
C82—C83—C84—C85 | −0.6 (8) | C1—S1—Cu1—P3 | 68.75 (16) |
C83—C84—C85—C86 | 0.0 (8) | Cu2—S1—Cu1—P3 | −55.03 (5) |
C82—C81—C86—C85 | −1.7 (8) | C1—S1—Cu1—P1 | −163.63 (15) |
P4—C81—C86—C85 | 178.0 (4) | Cu2—S1—Cu1—P1 | 72.59 (4) |
C84—C85—C86—C81 | 1.2 (9) | C1—S1—Cu1—I1 | −50.29 (15) |
N1—C1—N2—C2 | 2.2 (7) | Cu2—S1—Cu1—I1 | −174.07 (3) |
S1—C1—N2—C2 | 178.6 (4) | C71—P4—Cu2—P2 | −56.81 (15) |
C3—C2—N2—C1 | −84.3 (6) | C81—P4—Cu2—P2 | −174.52 (15) |
C16—C11—P1—C21 | 98.8 (3) | C4—P4—Cu2—P2 | 61.69 (16) |
C12—C11—P1—C21 | −78.7 (4) | C71—P4—Cu2—S1 | −173.35 (14) |
C16—C11—P1—C5 | −153.9 (3) | C81—P4—Cu2—S1 | 68.94 (16) |
C12—C11—P1—C5 | 28.5 (4) | C4—P4—Cu2—S1 | −54.85 (16) |
C16—C11—P1—Cu1 | −27.9 (3) | C71—P4—Cu2—I2 | 66.06 (15) |
C12—C11—P1—Cu1 | 154.6 (3) | C81—P4—Cu2—I2 | −51.64 (16) |
C26—C21—P1—C11 | −160.4 (4) | C4—P4—Cu2—I2 | −175.44 (15) |
C22—C21—P1—C11 | 20.6 (4) | C31—P2—Cu2—P4 | −176.36 (15) |
C26—C21—P1—C5 | 94.1 (4) | C41—P2—Cu2—P4 | 59.99 (15) |
C22—C21—P1—C5 | −84.8 (4) | C5—P2—Cu2—P4 | −54.57 (15) |
C26—C21—P1—Cu1 | −35.9 (4) | C31—P2—Cu2—S1 | −49.76 (15) |
C22—C21—P1—Cu1 | 145.2 (3) | C41—P2—Cu2—S1 | −173.40 (14) |
P2—C5—P1—C11 | 165.5 (2) | C5—P2—Cu2—S1 | 72.04 (15) |
P2—C5—P1—C21 | −88.2 (2) | C31—P2—Cu2—I2 | 61.10 (15) |
P2—C5—P1—Cu1 | 41.6 (2) | C41—P2—Cu2—I2 | −62.55 (15) |
C36—C31—P2—C41 | 122.1 (3) | C5—P2—Cu2—I2 | −177.11 (14) |
C32—C31—P2—C41 | −58.1 (4) | C1—S1—Cu2—P4 | −70.66 (16) |
C36—C31—P2—C5 | −134.9 (3) | Cu1—S1—Cu2—P4 | 51.30 (5) |
C32—C31—P2—C5 | 45.0 (4) | C1—S1—Cu2—P2 | 160.97 (16) |
C36—C31—P2—Cu2 | −7.2 (4) | Cu1—S1—Cu2—P2 | −77.07 (4) |
C32—C31—P2—Cu2 | 172.6 (3) | C1—S1—Cu2—I2 | 49.77 (16) |
C42—C41—P2—C31 | −5.5 (4) | Cu1—S1—Cu2—I2 | 171.74 (3) |
C46—C41—P2—C31 | 174.7 (3) |
Cg1 is the centroid of the C41–C46 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I2i | 0.87 (2) | 2.85 (3) | 3.645 (4) | 152 (4) |
N1—H1B···I2 | 0.84 (2) | 2.96 (2) | 3.796 (4) | 171 (5) |
N2—H2···I1 | 0.88 (2) | 2.70 (2) | 3.563 (4) | 168 (4) |
C63—H63···S1ii | 0.95 | 2.95 | 3.751 (5) | 143 |
C7—H7A···I1iii | 0.98 | 3.02 | 3.961 (7) | 161 |
C14—H14···Cg1iv | 0.95 | 3.37 (1) | 4.08 | 130 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x+1, y, z; (iv) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu2I2(C3H8N2S)(C25H22P2)2]·1.5C2H3N |
Mr | 1315.37 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 13.7751 (6), 24.5147 (11), 18.0172 (8) |
β (°) | 111.720 (1) |
V (Å3) | 5652.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.03 |
Crystal size (mm) | 0.28 × 0.17 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.670, 0.821 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 53066, 10863, 9108 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.101, 1.05 |
No. of reflections | 10863 |
No. of parameters | 643 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.84, −0.55 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
Cg1 is the centroid of the C41–C46 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I2i | 0.873 (19) | 2.85 (3) | 3.645 (4) | 152 (4) |
N1—H1B···I2 | 0.841 (19) | 2.96 (2) | 3.796 (4) | 171 (5) |
N2—H2···I1 | 0.875 (19) | 2.70 (2) | 3.563 (4) | 168 (4) |
C63—H63···S1ii | 0.95 | 2.948 | 3.751 (5) | 142.6 |
C7—H7A···I1iii | 0.98 | 3.019 | 3.961 (7) | 161 |
C14—H14···Cg1iv | 0.95 | 3.367 (14) | 4.08 | 129.8 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x+1, y, z; (iv) −x+1, y+1/2, −z+3/2. |
Metal(I) complexes with mixed phosphine and sulfur donor ligands have attracted much attention in recent years because of various applications based on e.g. their luminescent properties (Safin et al., 2010) or antimicrobial activities (Isab et al., 2010). CuI ions functioning as Lewis acids tend to form covalent bonds with soft ligands and can make close Cu···Cu contacts, features that can promote uncommon bonding, reactivity and catalytic properties of multinuclear copper complexes. Bis(diphenylphosphanyl)methane (dppm), for example, has been reported on multiple occasions to be a diphosphine ligands that is able to lock two metal atoms together in close proximity (Yang et al., 2000; Liaw et al., 2005; Jin et al., 2009). Copper complexes of thiourea ligands such as 1-ethylthiourea (ettu), on the other hand have been of increasing interest due to the variety of their structures and their similarity to metallothioneines, i.e. they contain coordinated Cu—S moieties which play an important role in animals and plants. Herein, the crystal structure of a dinuclear copper(I) iodode complex containing both dppm and ettu is described.
The molecular structure of the dinuclear title compound is shown in Fig. 1. Each CuI ion displays a distorted tetrahedral coordination geometry with internal angles in the range 97.00 (4)–119.56 (4)°. The dppm ligand and the bridging S atom of the ettu ligand force the two copper atoms into close proximity, leading to the formation of a close intramolecular Cu···Cu contact [3.3747 (17) Å]. The Cu—P distances vary from 2.2563 (10) to 2.2786 (11) Å, which are quite similar to those observed in related copper(I) complexes containing the dppm ligand (Yam et al., 2001; Zhou et al., 2001). The Cu—S bond lengths (Cu1—S1 = 2.3450 (11), Cu2—S1 = 2.3493 (11) Å) are shorter than that found in for example [Cu2(µ-HL1)2(µ-dppm)(η1-dppm)2] (H2L1 = 8-mercaptotheophylline), which are 2.392 (5)–2.410 (6) Å (Colacio et al., 1997). The terminal Cu—I bond distances (Cu1—I1 = 2.6694 (6) and Cu2—I2 = 2.6690 (5) Å), are in their typical ranges [see e.g. Nimthong et al., 2008; Pakawatchai et al., 2012]. The conformation of the dinuclear complex is such that the two dppm ligands are located on one side of the metal complex, while the two iodine atoms are pointed towards the other side of the complex. This conformation is stabilized by two intramolecular N—H···I hydrogen bonds between the ettu NH2 and NHEt moieties and the iodine atoms with N···H distances of 3.796 (4) (for N1···I2) and 3.563 (4) Å (for N2···I1), respectively (Table 1). In the crystal, the N and I atoms are also involved in intramolecular N—H···I hydrogen bonds to form dimers across an inversion center (symmetry code: -x, -y, -z + 1) (Table 1, Fig. 2). The dimers are in turn connected with each other and with the interstitial acetonitrile solvate molecules via a range of weaker C—H···I and C—H···S interactions (Table 1) and through a weak C(sp2)—H···π interaction [C14—H14···Cg1iv, with H14···Cg1iv = 3.38 (3) Å, C14···Cg1iv = 4.09 (3) Å and C14—H14···Cg1iv = 129.4 (4)°, Cg1 = C41—C42—C43—C44—C45—C46 ring, symmetry code: (iv) -x+1/2, y-1/2, -z+1] leading to the formation of a three-dimensional network, Fig. 3 and Table 1. One of the solvent acetonitrile molecules is disordered in a 1:1 ratio across a crystallographic inversion center.