metal-organic compounds
Iodido[1-(propan-2-ylidene)thiosemicarbazide-κS]bis(triphenylphosphane-κP)copper(I)
aDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai 90112, Thailand, and bDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
*Correspondence e-mail: yupa.t@psu.ac.th
In the mononuclear title complex, [CuI(C4H9N3S)(C18H15P)2], the CuI ion displays a distorted tetrahedral coordination geometry involving two P atoms of two triphenylphosphane molecules, one S atom of a 1-(propan-2-ylidene)thiosemicarbazide molecule and one iodide ion. In the crystal, C—H⋯π interactions [C—H⋯centroid distances = 3.443 (3) and 3.788 (3) Å] and N—H⋯S hydrogen bonds form layers parallel to (100). An intramolecular N—H⋯I hydrogen bond is also observed.
Related literature
For the potential applications of related complexes, see: Matesanz et al. (1999); Konstantinović et al. (2008); Zhang et al. (2008). For relevant examples of related discrete complexes, see: Cox et al. (2000); Nimthong et al. (2008); Pakawatchai et al. (2012).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1998); cell SAINT (Bruker, 2003); data reduction: SAINT; 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 and publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812044066/zb2025sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044066/zb2025Isup2.hkl
Triphenylphosphane (0.28 g, 1.07 mmol) was dissolved in 30 cm3 of acetone at 338 K and then CuI (0.10 g, 0.53 mmol) was added. The mixture was stirred for 2 h and then thiosemicarbazide (0.05 g, 0.55 mmol) was added and the new reaction mixture was heated under reflux for 5 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.
The H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 with Uiso(H) = 1.2 Ueq(C) and 0.96 Å with Uiso(H) = 1.5 Ueq(C) for for H atoms on C(sp2) and C(sp3), respectively. All H atoms bonded to N atoms were located in a difference Fourier map and refined isotropically.
Data collection: SMART (Bruker, 1998); cell
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: SHEXTl97 (Sheldrick, 2008) and publCIF (Westrip, 2010).[CuI(C4H9N3S)(C18H15P)2] | Z = 2 |
Mr = 846.18 | F(000) = 856 |
Triclinic, P1 | Dx = 1.477 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8832 (6) Å | Cell parameters from 7509 reflections |
b = 12.5712 (7) Å | θ = 2.2–26.4° |
c = 16.0206 (8) Å | µ = 1.56 mm−1 |
α = 98.867 (1)° | T = 293 K |
β = 100.517 (1)° | Plate, colourless |
γ = 114.056 (1)° | 0.26 × 0.21 × 0.04 mm |
V = 1903.04 (18) Å3 |
Bruker SMART CCD area-detector diffractometer | 9206 independent reflections |
Radiation source: fine-focus sealed tube | 7690 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Frames, each covering 0.3 ° in ω scans | θmax = 28.1°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −14→14 |
Tmin = 0.682, Tmax = 0.940 | k = −16→16 |
26251 measured reflections | l = −21→21 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0373P)2 + 0.6367P] where P = (Fo2 + 2Fc2)/3 |
9206 reflections | (Δ/σ)max = 0.002 |
444 parameters | Δρmax = 0.66 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
[CuI(C4H9N3S)(C18H15P)2] | γ = 114.056 (1)° |
Mr = 846.18 | V = 1903.04 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.8832 (6) Å | Mo Kα radiation |
b = 12.5712 (7) Å | µ = 1.56 mm−1 |
c = 16.0206 (8) Å | T = 293 K |
α = 98.867 (1)° | 0.26 × 0.21 × 0.04 mm |
β = 100.517 (1)° |
Bruker SMART CCD area-detector diffractometer | 9206 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 7690 reflections with I > 2σ(I) |
Tmin = 0.682, Tmax = 0.940 | Rint = 0.033 |
26251 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.66 e Å−3 |
9206 reflections | Δρmin = −0.27 e Å−3 |
444 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 | ||
C1 | 0.9764 (3) | 0.3109 (2) | 0.05375 (16) | 0.0384 (5) | |
C2 | 0.8564 (3) | 0.2797 (3) | −0.01226 (18) | 0.0496 (7) | |
H2 | 0.7874 | 0.2998 | 0.0006 | 0.060* | |
C3 | 0.8377 (4) | 0.2189 (3) | −0.0971 (2) | 0.0630 (8) | |
H3 | 0.7560 | 0.1977 | −0.1402 | 0.076* | |
C4 | 0.9382 (4) | 0.1899 (3) | −0.1178 (2) | 0.0627 (9) | |
H4 | 0.9261 | 0.1508 | −0.1751 | 0.075* | |
C5 | 1.0567 (4) | 0.2185 (3) | −0.05395 (19) | 0.0544 (7) | |
H5 | 1.1252 | 0.1987 | −0.0680 | 0.065* | |
C6 | 1.0759 (3) | 0.2770 (2) | 0.03164 (17) | 0.0435 (6) | |
H6 | 1.1559 | 0.2939 | 0.0747 | 0.052* | |
C7 | 1.1523 (3) | 0.5247 (2) | 0.20007 (17) | 0.0402 (6) | |
C8 | 1.2636 (3) | 0.5503 (3) | 0.1635 (2) | 0.0606 (8) | |
H8 | 1.2571 | 0.4948 | 0.1151 | 0.073* | |
C9 | 1.3843 (3) | 0.6576 (3) | 0.1979 (3) | 0.0781 (11) | |
H9 | 1.4586 | 0.6733 | 0.1730 | 0.094* | |
C10 | 1.3953 (4) | 0.7406 (3) | 0.2683 (3) | 0.0765 (11) | |
H10 | 1.4773 | 0.8121 | 0.2918 | 0.092* | |
C11 | 1.2856 (4) | 0.7183 (3) | 0.3039 (2) | 0.0780 (11) | |
H11 | 1.2919 | 0.7758 | 0.3509 | 0.094* | |
C12 | 1.1647 (4) | 0.6105 (3) | 0.2707 (2) | 0.0606 (8) | |
H12 | 1.0910 | 0.5957 | 0.2961 | 0.073* | |
C13 | 0.8550 (3) | 0.4181 (2) | 0.16390 (16) | 0.0371 (5) | |
C14 | 0.7594 (3) | 0.3687 (2) | 0.21055 (18) | 0.0435 (6) | |
H14 | 0.7732 | 0.3200 | 0.2457 | 0.052* | |
C15 | 0.6439 (3) | 0.3907 (3) | 0.2057 (2) | 0.0526 (7) | |
H15 | 0.5804 | 0.3565 | 0.2371 | 0.063* | |
C16 | 0.6236 (3) | 0.4628 (3) | 0.1546 (2) | 0.0594 (8) | |
H16 | 0.5453 | 0.4767 | 0.1505 | 0.071* | |
C17 | 0.7184 (3) | 0.5151 (3) | 0.1092 (2) | 0.0590 (8) | |
H17 | 0.7041 | 0.5645 | 0.0749 | 0.071* | |
C18 | 0.8342 (3) | 0.4947 (2) | 0.11416 (19) | 0.0487 (6) | |
H18 | 0.8989 | 0.5319 | 0.0844 | 0.058* | |
C19 | 0.7536 (2) | −0.0101 (2) | 0.13076 (15) | 0.0360 (5) | |
C20 | 0.6175 (3) | −0.1014 (3) | 0.10113 (19) | 0.0613 (9) | |
H20 | 0.5629 | −0.1203 | 0.1401 | 0.074* | |
C21 | 0.5629 (3) | −0.1644 (3) | 0.0135 (2) | 0.0762 (11) | |
H21 | 0.4716 | −0.2255 | −0.0060 | 0.091* | |
C22 | 0.6418 (3) | −0.1376 (3) | −0.04459 (19) | 0.0640 (9) | |
H22 | 0.6039 | −0.1794 | −0.1035 | 0.077* | |
C23 | 0.7762 (3) | −0.0493 (3) | −0.01590 (18) | 0.0511 (7) | |
H23 | 0.8309 | −0.0322 | −0.0550 | 0.061* | |
C24 | 0.8314 (3) | 0.0147 (2) | 0.07120 (16) | 0.0404 (6) | |
H24 | 0.9227 | 0.0758 | 0.0899 | 0.048* | |
C25 | 0.7027 (3) | 0.0710 (2) | 0.29446 (17) | 0.0377 (5) | |
C26 | 0.7158 (3) | 0.0687 (3) | 0.38138 (19) | 0.0557 (7) | |
H26 | 0.7923 | 0.0628 | 0.4131 | 0.067* | |
C27 | 0.6157 (5) | 0.0750 (3) | 0.4216 (3) | 0.0819 (12) | |
H27 | 0.6256 | 0.0734 | 0.4803 | 0.098* | |
C28 | 0.5032 (5) | 0.0836 (4) | 0.3762 (4) | 0.0937 (15) | |
H28 | 0.4363 | 0.0875 | 0.4035 | 0.112* | |
C29 | 0.4888 (4) | 0.0864 (4) | 0.2902 (3) | 0.0862 (13) | |
H29 | 0.4114 | 0.0915 | 0.2589 | 0.103* | |
C30 | 0.5887 (3) | 0.0819 (3) | 0.2494 (2) | 0.0592 (8) | |
H30 | 0.5793 | 0.0861 | 0.1913 | 0.071* | |
C31 | 0.8974 (2) | −0.0266 (2) | 0.29335 (15) | 0.0340 (5) | |
C32 | 1.0122 (3) | 0.0236 (3) | 0.3647 (2) | 0.0566 (8) | |
H32 | 1.0604 | 0.1069 | 0.3858 | 0.068* | |
C33 | 1.0572 (4) | −0.0485 (3) | 0.4057 (2) | 0.0738 (10) | |
H33 | 1.1339 | −0.0134 | 0.4549 | 0.089* | |
C34 | 0.9894 (4) | −0.1706 (3) | 0.3743 (2) | 0.0640 (9) | |
H34 | 1.0204 | −0.2188 | 0.4015 | 0.077* | |
C35 | 0.8769 (4) | −0.2213 (3) | 0.3035 (2) | 0.0599 (8) | |
H35 | 0.8305 | −0.3047 | 0.2823 | 0.072* | |
C36 | 0.8299 (3) | −0.1508 (2) | 0.26227 (18) | 0.0478 (6) | |
H36 | 0.7527 | −0.1870 | 0.2134 | 0.057* | |
C37 | 1.1977 (3) | 0.4956 (2) | 0.45169 (16) | 0.0399 (5) | |
C38 | 1.5399 (3) | 0.6307 (2) | 0.43728 (17) | 0.0436 (6) | |
C39 | 1.5519 (3) | 0.5446 (3) | 0.3685 (2) | 0.0624 (8) | |
H39A | 1.5303 | 0.4699 | 0.3847 | 0.094* | |
H39B | 1.6455 | 0.5777 | 0.3627 | 0.094* | |
H39C | 1.4875 | 0.5304 | 0.3135 | 0.094* | |
C40 | 1.6672 (3) | 0.7473 (3) | 0.4791 (2) | 0.0663 (9) | |
H40A | 1.6877 | 0.7931 | 0.4363 | 0.099* | |
H40B | 1.7449 | 0.7321 | 0.5013 | 0.099* | |
H40C | 1.6511 | 0.7921 | 0.5265 | 0.099* | |
N1 | 1.3115 (2) | 0.5081 (2) | 0.42585 (14) | 0.0410 (5) | |
N2 | 1.4325 (2) | 0.6151 (2) | 0.46382 (14) | 0.0467 (5) | |
N3 | 1.2117 (3) | 0.5846 (2) | 0.51463 (18) | 0.0631 (8) | |
P1 | 0.99834 (6) | 0.37784 (5) | 0.16846 (4) | 0.03298 (13) | |
P2 | 0.84194 (6) | 0.07508 (5) | 0.24472 (4) | 0.03094 (13) | |
S1 | 1.04319 (6) | 0.36891 (6) | 0.40876 (4) | 0.04410 (16) | |
Cu1 | 1.01628 (3) | 0.26360 (2) | 0.264156 (18) | 0.03273 (8) | |
I1 | 1.243129 (17) | 0.239385 (16) | 0.254284 (11) | 0.04628 (7) | |
H1 | 1.304 (3) | 0.454 (3) | 0.388 (2) | 0.056* | |
H3A | 1.140 (3) | 0.583 (3) | 0.529 (2) | 0.056* | |
H3B | 1.290 (3) | 0.643 (3) | 0.535 (2) | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0453 (14) | 0.0323 (12) | 0.0416 (13) | 0.0173 (11) | 0.0158 (11) | 0.0157 (10) |
C2 | 0.0542 (16) | 0.0495 (16) | 0.0475 (15) | 0.0279 (14) | 0.0099 (13) | 0.0100 (13) |
C3 | 0.077 (2) | 0.065 (2) | 0.0428 (16) | 0.0356 (18) | 0.0025 (15) | 0.0104 (14) |
C4 | 0.099 (3) | 0.0581 (19) | 0.0399 (16) | 0.0413 (19) | 0.0238 (17) | 0.0133 (14) |
C5 | 0.081 (2) | 0.0505 (17) | 0.0540 (17) | 0.0397 (16) | 0.0368 (16) | 0.0217 (14) |
C6 | 0.0530 (15) | 0.0426 (14) | 0.0453 (14) | 0.0258 (13) | 0.0202 (12) | 0.0184 (12) |
C7 | 0.0381 (13) | 0.0318 (12) | 0.0475 (14) | 0.0119 (11) | 0.0078 (11) | 0.0167 (11) |
C8 | 0.0480 (16) | 0.0408 (16) | 0.095 (2) | 0.0169 (13) | 0.0287 (17) | 0.0216 (16) |
C9 | 0.0428 (17) | 0.052 (2) | 0.136 (4) | 0.0129 (15) | 0.027 (2) | 0.035 (2) |
C10 | 0.055 (2) | 0.0445 (19) | 0.093 (3) | −0.0013 (15) | −0.0123 (19) | 0.0233 (19) |
C11 | 0.095 (3) | 0.0460 (19) | 0.0530 (19) | 0.0045 (18) | 0.0016 (19) | 0.0034 (15) |
C12 | 0.068 (2) | 0.0408 (16) | 0.0518 (17) | 0.0064 (14) | 0.0162 (15) | 0.0069 (13) |
C13 | 0.0378 (13) | 0.0306 (12) | 0.0417 (13) | 0.0153 (10) | 0.0112 (10) | 0.0059 (10) |
C14 | 0.0414 (14) | 0.0405 (14) | 0.0468 (15) | 0.0174 (12) | 0.0136 (12) | 0.0067 (12) |
C15 | 0.0418 (15) | 0.0529 (17) | 0.0617 (18) | 0.0217 (13) | 0.0204 (13) | 0.0019 (14) |
C16 | 0.0450 (16) | 0.0563 (18) | 0.073 (2) | 0.0301 (15) | 0.0085 (15) | −0.0055 (16) |
C17 | 0.0617 (19) | 0.0519 (18) | 0.071 (2) | 0.0360 (16) | 0.0111 (16) | 0.0134 (15) |
C18 | 0.0525 (16) | 0.0418 (15) | 0.0600 (17) | 0.0255 (13) | 0.0207 (14) | 0.0167 (13) |
C19 | 0.0371 (12) | 0.0321 (12) | 0.0308 (12) | 0.0103 (10) | 0.0050 (10) | 0.0060 (10) |
C20 | 0.0433 (16) | 0.069 (2) | 0.0416 (15) | 0.0014 (14) | 0.0107 (12) | −0.0001 (14) |
C21 | 0.0442 (17) | 0.085 (3) | 0.0500 (18) | −0.0024 (16) | 0.0006 (14) | −0.0140 (17) |
C22 | 0.064 (2) | 0.071 (2) | 0.0333 (14) | 0.0187 (17) | 0.0003 (14) | −0.0025 (14) |
C23 | 0.0654 (18) | 0.0476 (16) | 0.0367 (14) | 0.0218 (14) | 0.0157 (13) | 0.0088 (12) |
C24 | 0.0442 (14) | 0.0317 (12) | 0.0387 (13) | 0.0120 (11) | 0.0105 (11) | 0.0066 (10) |
C25 | 0.0365 (12) | 0.0275 (12) | 0.0487 (14) | 0.0112 (10) | 0.0176 (11) | 0.0105 (10) |
C26 | 0.0610 (18) | 0.0609 (19) | 0.0456 (16) | 0.0255 (15) | 0.0230 (14) | 0.0098 (14) |
C27 | 0.098 (3) | 0.080 (3) | 0.076 (2) | 0.035 (2) | 0.057 (2) | 0.014 (2) |
C28 | 0.094 (3) | 0.074 (3) | 0.147 (4) | 0.048 (2) | 0.086 (3) | 0.027 (3) |
C29 | 0.067 (2) | 0.082 (3) | 0.154 (4) | 0.055 (2) | 0.060 (3) | 0.056 (3) |
C30 | 0.0519 (17) | 0.0611 (19) | 0.078 (2) | 0.0312 (15) | 0.0245 (16) | 0.0308 (17) |
C31 | 0.0380 (12) | 0.0302 (12) | 0.0339 (12) | 0.0143 (10) | 0.0117 (10) | 0.0094 (9) |
C32 | 0.0561 (17) | 0.0380 (15) | 0.0565 (17) | 0.0128 (13) | −0.0086 (14) | 0.0119 (13) |
C33 | 0.068 (2) | 0.062 (2) | 0.074 (2) | 0.0213 (17) | −0.0143 (17) | 0.0292 (18) |
C34 | 0.072 (2) | 0.064 (2) | 0.076 (2) | 0.0413 (18) | 0.0230 (18) | 0.0379 (18) |
C35 | 0.079 (2) | 0.0348 (15) | 0.067 (2) | 0.0246 (15) | 0.0236 (17) | 0.0146 (14) |
C36 | 0.0530 (16) | 0.0369 (14) | 0.0439 (15) | 0.0144 (12) | 0.0090 (12) | 0.0050 (11) |
C37 | 0.0336 (12) | 0.0422 (14) | 0.0366 (13) | 0.0154 (11) | 0.0074 (10) | −0.0022 (11) |
C38 | 0.0346 (13) | 0.0481 (15) | 0.0378 (13) | 0.0128 (11) | 0.0067 (10) | 0.0030 (11) |
C39 | 0.0486 (16) | 0.062 (2) | 0.065 (2) | 0.0165 (15) | 0.0251 (15) | −0.0037 (16) |
C40 | 0.0389 (15) | 0.059 (2) | 0.070 (2) | 0.0033 (14) | 0.0133 (15) | −0.0095 (16) |
N1 | 0.0322 (10) | 0.0391 (12) | 0.0392 (12) | 0.0109 (9) | 0.0082 (9) | −0.0073 (9) |
N2 | 0.0338 (11) | 0.0459 (13) | 0.0429 (12) | 0.0089 (10) | 0.0072 (9) | −0.0067 (10) |
N3 | 0.0371 (13) | 0.0562 (16) | 0.0702 (18) | 0.0093 (12) | 0.0176 (13) | −0.0246 (13) |
P1 | 0.0333 (3) | 0.0291 (3) | 0.0381 (3) | 0.0134 (2) | 0.0130 (3) | 0.0103 (2) |
P2 | 0.0305 (3) | 0.0283 (3) | 0.0281 (3) | 0.0090 (2) | 0.0061 (2) | 0.0057 (2) |
S1 | 0.0330 (3) | 0.0448 (4) | 0.0415 (3) | 0.0101 (3) | 0.0127 (3) | −0.0064 (3) |
Cu1 | 0.03092 (14) | 0.02914 (15) | 0.03466 (15) | 0.01103 (12) | 0.00811 (11) | 0.00656 (12) |
I1 | 0.03963 (10) | 0.05671 (12) | 0.04491 (11) | 0.02808 (9) | 0.01026 (7) | 0.00238 (8) |
C1—C2 | 1.389 (4) | C23—H23 | 0.9300 |
C1—C6 | 1.395 (4) | C24—H24 | 0.9300 |
C1—P1 | 1.828 (3) | C25—C26 | 1.380 (4) |
C2—C3 | 1.387 (4) | C25—C30 | 1.385 (4) |
C2—H2 | 0.9300 | C25—P2 | 1.824 (2) |
C3—C4 | 1.364 (5) | C26—C27 | 1.386 (4) |
C3—H3 | 0.9300 | C26—H26 | 0.9300 |
C4—C5 | 1.366 (5) | C27—C28 | 1.359 (6) |
C4—H4 | 0.9300 | C27—H27 | 0.9300 |
C5—C6 | 1.387 (4) | C28—C29 | 1.365 (6) |
C5—H5 | 0.9300 | C28—H28 | 0.9300 |
C6—H6 | 0.9300 | C29—C30 | 1.382 (5) |
C7—C12 | 1.383 (4) | C29—H29 | 0.9300 |
C7—C8 | 1.383 (4) | C30—H30 | 0.9300 |
C7—P1 | 1.831 (2) | C31—C32 | 1.370 (4) |
C8—C9 | 1.382 (4) | C31—C36 | 1.384 (3) |
C8—H8 | 0.9300 | C31—P2 | 1.836 (2) |
C9—C10 | 1.364 (6) | C32—C33 | 1.387 (4) |
C9—H9 | 0.9300 | C32—H32 | 0.9300 |
C10—C11 | 1.362 (5) | C33—C34 | 1.362 (5) |
C10—H10 | 0.9300 | C33—H33 | 0.9300 |
C11—C12 | 1.386 (4) | C34—C35 | 1.351 (4) |
C11—H11 | 0.9300 | C34—H34 | 0.9300 |
C12—H12 | 0.9300 | C35—C36 | 1.382 (4) |
C13—C14 | 1.388 (3) | C35—H35 | 0.9300 |
C13—C18 | 1.401 (4) | C36—H36 | 0.9300 |
C13—P1 | 1.819 (3) | C37—N3 | 1.323 (3) |
C14—C15 | 1.384 (4) | C37—N1 | 1.334 (3) |
C14—H14 | 0.9300 | C37—S1 | 1.701 (3) |
C15—C16 | 1.367 (4) | C38—N2 | 1.267 (3) |
C15—H15 | 0.9300 | C38—C39 | 1.484 (4) |
C16—C17 | 1.377 (5) | C38—C40 | 1.490 (4) |
C16—H16 | 0.9300 | C39—H39A | 0.9600 |
C17—C18 | 1.376 (4) | C39—H39B | 0.9600 |
C17—H17 | 0.9300 | C39—H39C | 0.9600 |
C18—H18 | 0.9300 | C40—H40A | 0.9600 |
C19—C24 | 1.377 (3) | C40—H40B | 0.9600 |
C19—C20 | 1.388 (4) | C40—H40C | 0.9600 |
C19—P2 | 1.823 (2) | N1—N2 | 1.388 (3) |
C20—C21 | 1.385 (4) | N1—H1 | 0.80 (3) |
C20—H20 | 0.9300 | N3—H3A | 0.85 (3) |
C21—C22 | 1.368 (4) | N3—H3B | 0.83 (3) |
C21—H21 | 0.9300 | P1—Cu1 | 2.2910 (7) |
C22—C23 | 1.362 (4) | P2—Cu1 | 2.2814 (6) |
C22—H22 | 0.9300 | S1—Cu1 | 2.3866 (7) |
C23—C24 | 1.382 (4) | Cu1—I1 | 2.6369 (3) |
C2—C1—C6 | 117.4 (2) | C25—C26—H26 | 119.8 |
C2—C1—P1 | 122.6 (2) | C27—C26—H26 | 119.8 |
C6—C1—P1 | 119.7 (2) | C28—C27—C26 | 120.5 (4) |
C3—C2—C1 | 121.0 (3) | C28—C27—H27 | 119.7 |
C3—C2—H2 | 119.5 | C26—C27—H27 | 119.7 |
C1—C2—H2 | 119.5 | C27—C28—C29 | 119.8 (3) |
C4—C3—C2 | 120.6 (3) | C27—C28—H28 | 120.1 |
C4—C3—H3 | 119.7 | C29—C28—H28 | 120.1 |
C2—C3—H3 | 119.7 | C28—C29—C30 | 120.4 (4) |
C3—C4—C5 | 119.6 (3) | C28—C29—H29 | 119.8 |
C3—C4—H4 | 120.2 | C30—C29—H29 | 119.8 |
C5—C4—H4 | 120.2 | C29—C30—C25 | 120.5 (3) |
C4—C5—C6 | 120.7 (3) | C29—C30—H30 | 119.8 |
C4—C5—H5 | 119.7 | C25—C30—H30 | 119.8 |
C6—C5—H5 | 119.7 | C32—C31—C36 | 118.3 (2) |
C5—C6—C1 | 120.7 (3) | C32—C31—P2 | 117.90 (19) |
C5—C6—H6 | 119.6 | C36—C31—P2 | 123.84 (19) |
C1—C6—H6 | 119.6 | C31—C32—C33 | 120.7 (3) |
C12—C7—C8 | 118.0 (3) | C31—C32—H32 | 119.7 |
C12—C7—P1 | 118.0 (2) | C33—C32—H32 | 119.7 |
C8—C7—P1 | 123.7 (2) | C34—C33—C32 | 120.3 (3) |
C9—C8—C7 | 120.7 (3) | C34—C33—H33 | 119.9 |
C9—C8—H8 | 119.7 | C32—C33—H33 | 119.9 |
C7—C8—H8 | 119.7 | C35—C34—C33 | 119.7 (3) |
C10—C9—C8 | 120.5 (3) | C35—C34—H34 | 120.1 |
C10—C9—H9 | 119.7 | C33—C34—H34 | 120.1 |
C8—C9—H9 | 119.7 | C34—C35—C36 | 120.8 (3) |
C11—C10—C9 | 119.7 (3) | C34—C35—H35 | 119.6 |
C11—C10—H10 | 120.2 | C36—C35—H35 | 119.6 |
C9—C10—H10 | 120.2 | C35—C36—C31 | 120.3 (3) |
C10—C11—C12 | 120.4 (4) | C35—C36—H36 | 119.8 |
C10—C11—H11 | 119.8 | C31—C36—H36 | 119.8 |
C12—C11—H11 | 119.8 | N3—C37—N1 | 116.9 (2) |
C7—C12—C11 | 120.7 (3) | N3—C37—S1 | 121.4 (2) |
C7—C12—H12 | 119.6 | N1—C37—S1 | 121.72 (19) |
C11—C12—H12 | 119.6 | N2—C38—C39 | 126.6 (2) |
C14—C13—C18 | 118.1 (2) | N2—C38—C40 | 116.9 (2) |
C14—C13—P1 | 118.57 (19) | C39—C38—C40 | 116.5 (2) |
C18—C13—P1 | 123.3 (2) | C38—C39—H39A | 109.5 |
C15—C14—C13 | 121.2 (3) | C38—C39—H39B | 109.5 |
C15—C14—H14 | 119.4 | H39A—C39—H39B | 109.5 |
C13—C14—H14 | 119.4 | C38—C39—H39C | 109.5 |
C16—C15—C14 | 119.6 (3) | H39A—C39—H39C | 109.5 |
C16—C15—H15 | 120.2 | H39B—C39—H39C | 109.5 |
C14—C15—H15 | 120.2 | C38—C40—H40A | 109.5 |
C15—C16—C17 | 120.4 (3) | C38—C40—H40B | 109.5 |
C15—C16—H16 | 119.8 | H40A—C40—H40B | 109.5 |
C17—C16—H16 | 119.8 | C38—C40—H40C | 109.5 |
C18—C17—C16 | 120.5 (3) | H40A—C40—H40C | 109.5 |
C18—C17—H17 | 119.8 | H40B—C40—H40C | 109.5 |
C16—C17—H17 | 119.8 | C37—N1—N2 | 117.7 (2) |
C17—C18—C13 | 120.2 (3) | C37—N1—H1 | 117 (2) |
C17—C18—H18 | 119.9 | N2—N1—H1 | 125 (2) |
C13—C18—H18 | 119.9 | C38—N2—N1 | 118.6 (2) |
C24—C19—C20 | 118.3 (2) | C37—N3—H3A | 119 (2) |
C24—C19—P2 | 116.79 (18) | C37—N3—H3B | 118 (2) |
C20—C19—P2 | 124.8 (2) | H3A—N3—H3B | 123 (3) |
C21—C20—C19 | 120.0 (3) | C13—P1—C1 | 103.89 (11) |
C21—C20—H20 | 120.0 | C13—P1—C7 | 102.85 (11) |
C19—C20—H20 | 120.0 | C1—P1—C7 | 106.61 (12) |
C22—C21—C20 | 120.7 (3) | C13—P1—Cu1 | 115.50 (8) |
C22—C21—H21 | 119.7 | C1—P1—Cu1 | 115.50 (8) |
C20—C21—H21 | 119.7 | C7—P1—Cu1 | 111.31 (8) |
C23—C22—C21 | 119.8 (3) | C19—P2—C25 | 105.23 (12) |
C23—C22—H22 | 120.1 | C19—P2—C31 | 103.20 (11) |
C21—C22—H22 | 120.1 | C25—P2—C31 | 102.33 (11) |
C22—C23—C24 | 120.0 (3) | C19—P2—Cu1 | 115.17 (8) |
C22—C23—H23 | 120.0 | C25—P2—Cu1 | 114.47 (8) |
C24—C23—H23 | 120.0 | C31—P2—Cu1 | 114.92 (8) |
C19—C24—C23 | 121.2 (2) | C37—S1—Cu1 | 113.83 (9) |
C19—C24—H24 | 119.4 | P2—Cu1—P1 | 120.68 (2) |
C23—C24—H24 | 119.4 | P2—Cu1—S1 | 104.67 (2) |
C26—C25—C30 | 118.3 (3) | P1—Cu1—S1 | 109.32 (3) |
C26—C25—P2 | 120.0 (2) | P2—Cu1—I1 | 106.92 (2) |
C30—C25—P2 | 121.4 (2) | P1—Cu1—I1 | 104.358 (19) |
C25—C26—C27 | 120.4 (3) | S1—Cu1—I1 | 110.821 (19) |
C6—C1—C2—C3 | −1.0 (4) | C18—C13—P1—C7 | 53.7 (2) |
P1—C1—C2—C3 | −173.9 (2) | C14—C13—P1—Cu1 | −6.2 (2) |
C1—C2—C3—C4 | −0.9 (5) | C18—C13—P1—Cu1 | 175.13 (19) |
C2—C3—C4—C5 | 1.5 (5) | C2—C1—P1—C13 | −11.9 (2) |
C3—C4—C5—C6 | −0.1 (5) | C6—C1—P1—C13 | 175.3 (2) |
C4—C5—C6—C1 | −1.9 (4) | C2—C1—P1—C7 | −120.1 (2) |
C2—C1—C6—C5 | 2.4 (4) | C6—C1—P1—C7 | 67.1 (2) |
P1—C1—C6—C5 | 175.5 (2) | C2—C1—P1—Cu1 | 115.6 (2) |
C12—C7—C8—C9 | 1.3 (5) | C6—C1—P1—Cu1 | −57.2 (2) |
P1—C7—C8—C9 | −171.6 (3) | C12—C7—P1—C13 | 48.9 (2) |
C7—C8—C9—C10 | −0.6 (5) | C8—C7—P1—C13 | −138.1 (2) |
C8—C9—C10—C11 | −1.0 (6) | C12—C7—P1—C1 | 157.9 (2) |
C9—C10—C11—C12 | 1.8 (6) | C8—C7—P1—C1 | −29.1 (3) |
C8—C7—C12—C11 | −0.6 (5) | C12—C7—P1—Cu1 | −75.3 (2) |
P1—C7—C12—C11 | 172.8 (3) | C8—C7—P1—Cu1 | 97.6 (2) |
C10—C11—C12—C7 | −1.0 (5) | C24—C19—P2—C25 | 156.56 (19) |
C18—C13—C14—C15 | 2.4 (4) | C20—C19—P2—C25 | −26.9 (3) |
P1—C13—C14—C15 | −176.4 (2) | C24—C19—P2—C31 | −96.5 (2) |
C13—C14—C15—C16 | −0.4 (4) | C20—C19—P2—C31 | 80.0 (3) |
C14—C15—C16—C17 | −1.0 (4) | C24—C19—P2—Cu1 | 29.5 (2) |
C15—C16—C17—C18 | 0.5 (5) | C20—C19—P2—Cu1 | −154.0 (2) |
C16—C17—C18—C13 | 1.5 (5) | C26—C25—P2—C19 | 146.5 (2) |
C14—C13—C18—C17 | −2.9 (4) | C30—C25—P2—C19 | −39.7 (2) |
P1—C13—C18—C17 | 175.7 (2) | C26—C25—P2—C31 | 39.0 (2) |
C24—C19—C20—C21 | −0.4 (5) | C30—C25—P2—C31 | −147.3 (2) |
P2—C19—C20—C21 | −176.8 (3) | C26—C25—P2—Cu1 | −86.0 (2) |
C19—C20—C21—C22 | −0.1 (6) | C30—C25—P2—Cu1 | 87.8 (2) |
C20—C21—C22—C23 | 1.0 (6) | C32—C31—P2—C19 | 153.3 (2) |
C21—C22—C23—C24 | −1.6 (5) | C36—C31—P2—C19 | −26.8 (2) |
C20—C19—C24—C23 | −0.2 (4) | C32—C31—P2—C25 | −97.5 (2) |
P2—C19—C24—C23 | 176.6 (2) | C36—C31—P2—C25 | 82.4 (2) |
C22—C23—C24—C19 | 1.1 (4) | C32—C31—P2—Cu1 | 27.1 (2) |
C30—C25—C26—C27 | 1.0 (4) | C36—C31—P2—Cu1 | −153.0 (2) |
P2—C25—C26—C27 | 175.0 (3) | N3—C37—S1—Cu1 | 156.4 (2) |
C25—C26—C27—C28 | 0.0 (6) | N1—C37—S1—Cu1 | −26.1 (3) |
C26—C27—C28—C29 | −0.3 (6) | C19—P2—Cu1—P1 | 35.40 (10) |
C27—C28—C29—C30 | −0.6 (6) | C25—P2—Cu1—P1 | −86.79 (10) |
C28—C29—C30—C25 | 1.7 (6) | C31—P2—Cu1—P1 | 155.17 (8) |
C26—C25—C30—C29 | −1.9 (5) | C19—P2—Cu1—S1 | 158.97 (9) |
P2—C25—C30—C29 | −175.8 (3) | C25—P2—Cu1—S1 | 36.78 (10) |
C36—C31—C32—C33 | −1.5 (5) | C31—P2—Cu1—S1 | −81.26 (9) |
P2—C31—C32—C33 | 178.4 (3) | C19—P2—Cu1—I1 | −83.40 (9) |
C31—C32—C33—C34 | 1.4 (6) | C25—P2—Cu1—I1 | 154.41 (9) |
C32—C33—C34—C35 | −0.8 (6) | C31—P2—Cu1—I1 | 36.36 (9) |
C33—C34—C35—C36 | 0.3 (5) | C13—P1—Cu1—P2 | 63.00 (9) |
C34—C35—C36—C31 | −0.4 (5) | C1—P1—Cu1—P2 | −58.48 (10) |
C32—C31—C36—C35 | 1.0 (4) | C7—P1—Cu1—P2 | 179.78 (10) |
P2—C31—C36—C35 | −178.9 (2) | C13—P1—Cu1—S1 | −58.33 (9) |
N3—C37—N1—N2 | −3.0 (4) | C1—P1—Cu1—S1 | −179.81 (9) |
S1—C37—N1—N2 | 179.31 (19) | C7—P1—Cu1—S1 | 58.45 (10) |
C39—C38—N2—N1 | −0.5 (5) | C13—P1—Cu1—I1 | −176.92 (9) |
C40—C38—N2—N1 | 179.4 (3) | C1—P1—Cu1—I1 | 61.60 (9) |
C37—N1—N2—C38 | −176.9 (3) | C7—P1—Cu1—I1 | −60.14 (10) |
C14—C13—P1—C1 | 121.3 (2) | C37—S1—Cu1—P2 | 161.89 (10) |
C18—C13—P1—C1 | −57.3 (2) | C37—S1—Cu1—P1 | −67.52 (11) |
C14—C13—P1—C7 | −127.7 (2) | C37—S1—Cu1—I1 | 46.97 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···S1i | 0.85 (3) | 2.62 (3) | 3.447 (3) | 166 (3) |
N1—H1···I1 | 0.80 (3) | 2.93 (3) | 3.723 (2) | 173 (3) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [CuI(C4H9N3S)(C18H15P)2] |
Mr | 846.18 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.8832 (6), 12.5712 (7), 16.0206 (8) |
α, β, γ (°) | 98.867 (1), 100.517 (1), 114.056 (1) |
V (Å3) | 1903.04 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.56 |
Crystal size (mm) | 0.26 × 0.21 × 0.04 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.682, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26251, 9206, 7690 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.084, 1.02 |
No. of reflections | 9206 |
No. of parameters | 444 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.66, −0.27 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHEXTl97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···S1i | 0.85 (3) | 2.62 (3) | 3.447 (3) | 166 (3) |
N1—H1···I1 | 0.80 (3) | 2.93 (3) | 3.723 (2) | 173 (3) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Acknowledgements
Financial support from the Center of Excellence for Innovation in Chemistry (PERCH–CIC), Office of the Higher Education Commission, Ministry of Education and Department of Chemistry, Prince of Songkla University, is gratefully acknowledged.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Thiosemicarbazones and thiosemicarbazone derivatives as well as their complexes have been receiving more attention, because of their potentially beneficial biochemical properties, such as antimicrobial activity (Konstantinović et al., 2008), anticancer activity on cisplatin-resistant neuroblastoma cells (Zhang et al., 2008), important antitumor properties and DNA binding (Matesanz et al., 1999).
The molecular structure of the title compound displays the distorted tetrahedral coordination of the CuI center. (Fig. 1) The arrangement is considerably distorted since the phosphorous angle at metal site, P2—Cu1—P1 with a value of 120.68 (2)°, is much larger than the tetrahedral value 109.5°, This higher angle is counterbalanced by the bond angles of P1—Cu1—I1, P2—Cu1—I1, P1—Cu1—S1 and P2—Cu1—S1 whose values are 104.358 (19)°, 106.92 (2)°, 109.32 (3)° and 104.67 (2)°, respectively. The tetrahedral distortion is due to steric imposition of the bulky of phosphane ligands and was observed previously in analogous complex. For instance, the P—Cu—P angles of 118.63 (5)° in [CuI(C7H8N2S)(C18H15P)2]. (Nimthong et al., 2008). The two Cu1—P1 and Cu1—P2 bond distances of 2.2910 (7) Å and 2.2814 (6) Å are comparable to these in CuI(C6H8N2S)(C18H15P)2 (2.2897 (5)–2.3047 (5) Å) (Pakawatchai et al., 2012). The Cu1—S1 bond distance of 2.3866 (7) Å, which is larger than the value observed in tetrahedrally coordinated copper(I) halide complexes with S donors such as [CuBr(dppe)(py2SH)]2 with Cu—S bond distance of 2.3456 (13) Å (Cox et al., 2000). The non-bonding distance in the molecule, N1—H1···I1, can be accepted as an intramolecular hydrogen bond with the geometry N1···I1 = 3.723 (2) Å. In the crystal packing, the C5(sp2)—H5···π interactions [H5···Cg1 = 2.948 (3) Å, C5(sp2)—H5···Cg1 = 3.788 (3) Å and C5(sp2)—H5···Cg1 = 134.62 (8)°, Cg1 = C19—C20—C21—C22—C23—C24 ring] and N3—H3A···S1 hydrogen bonds can be linked each molecule forming one dimensional chain. In addition, chains are connected through C3(sp2)—H3···π interactions [H3···Cg2 = 2.870 (3) Å, C3(sp2)—H3···Cg2 = 3.443 (3) Å and C3(sp2)—H3···Cg2 = 138.54 (7)°, Cg2 = C7—C8—C9—C10—C11—C12 ring] forming the two-dimensional layer networks (see Table 1 and Fig. 2).