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The synthesis, crystal structure and Hirshfeld surface analysis of a new PdII cinnamaldehyde 4-thio­semicarbazone homoleptic complex is reported. As a result of H...S intra­molecular inter­actions, graph-set motif S(5), the coordination sphere resembles a hydrogen-bonded macrocyclic environment-type. In the crystal, the mol­ecules are linked by H...S inter­actions, with graph-set motifs R_{2}^{2}(8), forming a mono-periodic hydrogen-bonded polymer along [001].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989023008654/zn2032sup1.cif
Contains datablocks I, publication_text

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989023008654/zn2032Isup2.hkl
Contains datablock I

CCDC reference: 2163054

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2006), CrystalExplorer (Wolff et al., 2012); software used to prepare material for publication: WinGX (Farrugia, 2012), publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

trans-Bis{(2E)-N-phenyl-2-[(2E)-3-phenyl-2-propen-1-ylidene]hydrazinecarbothioamidato-κ2N1,S}palladium(II) top
Crystal data top
[Pd(C16H14N3S)2]F(000) = 1360
Mr = 667.12Dx = 1.505 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 15.084 (5) ÅCell parameters from 9138 reflections
b = 11.418 (4) Åθ = 2.2–28.3°
c = 17.097 (6) ŵ = 0.81 mm1
β = 91.097 (9)°T = 299 K
V = 2944.0 (16) Å3Block, orange
Z = 40.25 × 0.18 × 0.11 mm
Data collection top
Bruker D8 Venture Photon 100 area detector
diffractometer
6204 reflections with I > 2σ(I)
Radiation source: microfocus X ray tubeRint = 0.042
φ and ω scansθmax = 28.4°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
h = 2020
Tmin = 0.699, Tmax = 0.746k = 1515
87933 measured reflectionsl = 2222
7344 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.063 w = 1/[σ2(Fo2) + (0.0241P)2 + 1.5227P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.003
7344 reflectionsΔρmax = 0.34 e Å3
370 parametersΔρmin = 0.50 e Å3
0 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.93114 (12)0.25646 (18)0.41478 (10)0.0408 (4)
H10.9113570.2227550.3680990.049*
C21.02188 (12)0.29262 (18)0.41878 (11)0.0429 (4)
H21.0423220.3344030.4621900.052*
C31.07777 (12)0.26780 (19)0.36174 (11)0.0434 (4)
H31.0547150.2286560.3181960.052*
C41.17186 (12)0.29659 (18)0.36156 (11)0.0436 (4)
C51.20873 (15)0.3801 (2)0.41107 (14)0.0566 (5)
H41.1726340.4229240.4440570.068*
C61.29897 (17)0.4000 (3)0.41148 (17)0.0738 (8)
H51.3231350.4572060.4441830.089*
C71.35360 (16)0.3362 (3)0.36419 (19)0.0765 (8)
H61.4145320.3486170.3661630.092*
C81.31865 (17)0.2555 (3)0.31492 (18)0.0745 (8)
H71.3554930.2129550.2824400.089*
C91.22814 (15)0.2358 (2)0.31256 (14)0.0613 (6)
H81.2045910.1811270.2776380.074*
C100.85343 (12)0.31504 (17)0.59615 (10)0.0377 (4)
C110.95766 (12)0.42049 (17)0.68829 (10)0.0397 (4)
C120.95571 (14)0.48633 (19)0.75646 (11)0.0466 (5)
H90.9040120.4893770.7851750.056*
C131.02970 (15)0.5473 (2)0.78205 (13)0.0559 (5)
H101.0273080.5913070.8277310.067*
C141.10674 (15)0.5437 (2)0.74084 (14)0.0584 (6)
H111.1565120.5851260.7579690.070*
C151.10894 (14)0.4777 (2)0.67371 (14)0.0597 (6)
H121.1610630.4744070.6456100.072*
C161.03566 (13)0.4160 (2)0.64695 (12)0.0516 (5)
H131.0386710.3716770.6014300.062*
C170.55839 (12)0.16720 (18)0.50233 (11)0.0416 (4)
H140.5789170.1855240.5524910.050*
C180.46597 (12)0.14045 (18)0.49358 (11)0.0429 (4)
H150.4445660.1151830.4450710.052*
C190.40947 (13)0.15030 (19)0.55209 (12)0.0472 (5)
H160.4333160.1727550.6003610.057*
C200.31419 (13)0.12958 (18)0.54837 (12)0.0454 (4)
C210.27211 (14)0.0746 (2)0.48604 (13)0.0513 (5)
H170.3051740.0477970.4443120.062*
C220.18134 (15)0.0590 (2)0.48519 (16)0.0644 (6)
H180.1539340.0215360.4429350.077*
C230.13142 (16)0.0979 (3)0.54540 (18)0.0713 (8)
H190.0702930.0871730.5442120.086*
C240.17159 (17)0.1526 (3)0.60741 (18)0.0739 (8)
H200.1376280.1801990.6483390.089*
C250.26240 (16)0.1673 (2)0.60978 (15)0.0653 (6)
H210.2892720.2029280.6530320.078*
C260.63696 (12)0.14116 (18)0.31857 (11)0.0406 (4)
C270.52836 (12)0.06730 (19)0.21755 (12)0.0456 (5)
C280.50883 (17)0.0809 (2)0.13948 (14)0.0657 (7)
H220.5475690.1218320.1078270.079*
C290.4319 (2)0.0341 (3)0.10764 (19)0.0878 (10)
H230.4186570.0448460.0547720.105*
C300.37560 (18)0.0272 (3)0.1525 (2)0.0837 (9)
H240.3238550.0584960.1306980.100*
C310.39511 (18)0.0431 (3)0.23033 (19)0.0803 (8)
H250.3565850.0859450.2610470.096*
C320.47140 (16)0.0038 (2)0.26388 (15)0.0633 (6)
H260.4842280.0070870.3168030.076*
N10.87363 (10)0.26614 (14)0.47008 (8)0.0375 (3)
N20.90767 (10)0.31587 (16)0.53850 (9)0.0428 (4)
N30.87873 (10)0.36111 (16)0.66658 (9)0.0442 (4)
H270.8410820.3528420.7033130.053*
N40.61600 (10)0.16837 (14)0.44748 (9)0.0383 (3)
N50.58090 (10)0.13619 (16)0.37463 (9)0.0437 (4)
N60.61038 (11)0.11296 (18)0.24427 (9)0.0521 (5)
H280.6490000.1246270.2087500.063*
Pd10.74528 (2)0.21629 (2)0.46039 (2)0.03379 (5)
S10.74605 (3)0.25655 (5)0.59231 (3)0.04797 (12)
S20.74676 (3)0.18416 (6)0.32859 (3)0.04861 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0320 (9)0.0589 (11)0.0314 (9)0.0018 (8)0.0020 (7)0.0014 (8)
C20.0327 (9)0.0625 (12)0.0337 (9)0.0045 (8)0.0002 (7)0.0005 (8)
C30.0337 (9)0.0606 (12)0.0358 (9)0.0037 (9)0.0015 (7)0.0006 (9)
C40.0326 (9)0.0575 (12)0.0407 (10)0.0026 (8)0.0018 (7)0.0101 (9)
C50.0445 (12)0.0656 (14)0.0596 (13)0.0060 (10)0.0040 (10)0.0032 (11)
C60.0551 (15)0.0816 (18)0.0838 (18)0.0223 (14)0.0209 (14)0.0151 (15)
C70.0348 (12)0.094 (2)0.100 (2)0.0080 (13)0.0040 (13)0.0419 (18)
C80.0416 (13)0.097 (2)0.0858 (19)0.0078 (13)0.0206 (13)0.0207 (17)
C90.0445 (12)0.0805 (17)0.0594 (14)0.0030 (11)0.0151 (10)0.0011 (12)
C100.0314 (9)0.0475 (10)0.0343 (9)0.0002 (7)0.0017 (7)0.0005 (7)
C110.0351 (9)0.0486 (10)0.0354 (9)0.0000 (8)0.0029 (7)0.0001 (8)
C120.0446 (11)0.0557 (12)0.0396 (10)0.0024 (9)0.0016 (8)0.0032 (9)
C130.0578 (13)0.0596 (13)0.0499 (12)0.0054 (11)0.0067 (10)0.0103 (10)
C140.0443 (12)0.0655 (14)0.0650 (14)0.0103 (10)0.0128 (10)0.0005 (11)
C150.0341 (10)0.0826 (17)0.0624 (14)0.0034 (11)0.0010 (10)0.0032 (12)
C160.0361 (10)0.0735 (14)0.0453 (11)0.0009 (10)0.0016 (8)0.0096 (10)
C170.0360 (9)0.0542 (11)0.0347 (9)0.0016 (8)0.0036 (7)0.0037 (8)
C180.0356 (9)0.0542 (11)0.0392 (10)0.0007 (8)0.0053 (8)0.0008 (8)
C190.0413 (10)0.0586 (12)0.0420 (10)0.0018 (9)0.0078 (8)0.0009 (9)
C200.0390 (10)0.0505 (11)0.0471 (11)0.0018 (8)0.0116 (8)0.0071 (9)
C210.0415 (11)0.0609 (13)0.0516 (12)0.0024 (10)0.0072 (9)0.0081 (10)
C220.0468 (13)0.0740 (16)0.0722 (16)0.0050 (12)0.0071 (11)0.0167 (13)
C230.0379 (12)0.0804 (18)0.096 (2)0.0040 (12)0.0149 (13)0.0283 (16)
C240.0539 (14)0.0804 (18)0.089 (2)0.0055 (13)0.0362 (14)0.0086 (16)
C250.0539 (14)0.0782 (16)0.0645 (15)0.0027 (12)0.0246 (11)0.0050 (13)
C260.0315 (9)0.0554 (11)0.0351 (9)0.0013 (8)0.0021 (7)0.0016 (8)
C270.0323 (9)0.0553 (12)0.0488 (11)0.0009 (8)0.0040 (8)0.0101 (9)
C280.0631 (15)0.0751 (16)0.0582 (14)0.0127 (13)0.0205 (12)0.0074 (12)
C290.084 (2)0.095 (2)0.083 (2)0.0132 (18)0.0477 (17)0.0046 (17)
C300.0520 (15)0.089 (2)0.109 (2)0.0128 (14)0.0269 (16)0.0201 (18)
C310.0566 (15)0.087 (2)0.098 (2)0.0283 (14)0.0074 (15)0.0243 (17)
C320.0520 (13)0.0787 (16)0.0592 (14)0.0154 (12)0.0031 (11)0.0121 (12)
N10.0299 (7)0.0523 (9)0.0303 (7)0.0014 (6)0.0009 (6)0.0023 (6)
N20.0324 (8)0.0645 (10)0.0316 (8)0.0058 (7)0.0017 (6)0.0059 (7)
N30.0348 (8)0.0659 (11)0.0319 (8)0.0070 (8)0.0045 (6)0.0067 (7)
N40.0304 (7)0.0496 (9)0.0349 (8)0.0023 (7)0.0030 (6)0.0023 (7)
N50.0322 (8)0.0646 (11)0.0342 (8)0.0057 (7)0.0027 (6)0.0055 (7)
N60.0341 (8)0.0878 (14)0.0346 (8)0.0110 (9)0.0028 (7)0.0081 (8)
Pd10.02574 (7)0.04563 (8)0.03007 (7)0.00040 (5)0.00212 (5)0.00124 (5)
S10.0344 (2)0.0749 (3)0.0349 (2)0.0119 (2)0.00699 (18)0.0100 (2)
S20.0275 (2)0.0866 (4)0.0319 (2)0.0068 (2)0.00370 (17)0.0071 (2)
Geometric parameters (Å, º) top
C1—N11.300 (2)C18—H150.9300
C1—C21.430 (3)C19—C201.457 (3)
C1—H10.9300C19—H160.9300
C2—C31.332 (3)C20—C211.381 (3)
C2—H20.9300C20—C251.389 (3)
C3—C41.457 (3)C21—C221.380 (3)
C3—H30.9300C21—H170.9300
C4—C51.385 (3)C22—C231.361 (4)
C4—C91.389 (3)C22—H180.9300
C5—C61.380 (3)C23—C241.363 (4)
C5—H40.9300C23—H190.9300
C6—C71.374 (4)C24—C251.380 (3)
C6—H50.9300C24—H200.9300
C7—C81.349 (4)C25—H210.9300
C7—H60.9300C26—N51.291 (2)
C8—C91.383 (3)C26—N61.363 (2)
C8—H70.9300C26—S21.7328 (19)
C9—H80.9300C27—C281.370 (3)
C10—N21.293 (2)C27—C321.384 (3)
C10—N31.362 (2)C27—N61.410 (2)
C10—S11.7520 (19)C28—C291.380 (3)
C11—C161.385 (3)C28—H220.9300
C11—C121.388 (3)C29—C301.351 (4)
C11—N31.413 (2)C29—H230.9300
C12—C131.380 (3)C30—C311.369 (4)
C12—H90.9300C30—H240.9300
C13—C141.371 (3)C31—C321.384 (3)
C13—H100.9300C31—H250.9300
C14—C151.374 (3)C32—H260.9300
C14—H110.9300N1—N21.390 (2)
C15—C161.381 (3)N1—Pd12.0217 (16)
C15—H120.9300N3—H270.8600
C16—H130.9300N4—N51.393 (2)
C17—N41.291 (2)N4—Pd12.0333 (16)
C17—C181.432 (3)N6—H280.8600
C17—H140.9300Pd1—S22.2836 (9)
C18—C191.331 (3)Pd1—S12.3016 (9)
N1—C1—C2126.30 (17)C25—C20—C19119.0 (2)
N1—C1—H1116.8C22—C21—C20120.5 (2)
C2—C1—H1116.8C22—C21—H17119.7
C3—C2—C1121.49 (18)C20—C21—H17119.7
C3—C2—H2119.3C23—C22—C21120.9 (3)
C1—C2—H2119.3C23—C22—H18119.6
C2—C3—C4125.73 (19)C21—C22—H18119.6
C2—C3—H3117.1C22—C23—C24119.6 (2)
C4—C3—H3117.1C22—C23—H19120.2
C5—C4—C9118.0 (2)C24—C23—H19120.2
C5—C4—C3122.27 (19)C23—C24—C25120.3 (2)
C9—C4—C3119.7 (2)C23—C24—H20119.8
C6—C5—C4120.0 (2)C25—C24—H20119.8
C6—C5—H4120.0C24—C25—C20120.8 (3)
C4—C5—H4120.0C24—C25—H21119.6
C7—C6—C5120.8 (3)C20—C25—H21119.6
C7—C6—H5119.6N5—C26—N6119.74 (17)
C5—C6—H5119.6N5—C26—S2125.25 (14)
C8—C7—C6119.9 (2)N6—C26—S2115.00 (13)
C8—C7—H6120.1C28—C27—C32119.5 (2)
C6—C7—H6120.1C28—C27—N6116.4 (2)
C7—C8—C9120.2 (3)C32—C27—N6123.9 (2)
C7—C8—H7119.9C27—C28—C29120.3 (3)
C9—C8—H7119.9C27—C28—H22119.9
C8—C9—C4121.0 (3)C29—C28—H22119.9
C8—C9—H8119.5C30—C29—C28120.6 (3)
C4—C9—H8119.5C30—C29—H23119.7
N2—C10—N3120.03 (17)C28—C29—H23119.7
N2—C10—S1124.91 (14)C29—C30—C31119.7 (2)
N3—C10—S1115.06 (13)C29—C30—H24120.2
C16—C11—C12118.73 (18)C31—C30—H24120.2
C16—C11—N3124.58 (18)C30—C31—C32120.9 (3)
C12—C11—N3116.68 (17)C30—C31—H25119.6
C13—C12—C11120.6 (2)C32—C31—H25119.6
C13—C12—H9119.7C31—C32—C27119.0 (2)
C11—C12—H9119.7C31—C32—H26120.5
C14—C13—C12120.7 (2)C27—C32—H26120.5
C14—C13—H10119.7C1—N1—N2113.95 (15)
C12—C13—H10119.7C1—N1—Pd1124.60 (13)
C13—C14—C15118.7 (2)N2—N1—Pd1121.45 (11)
C13—C14—H11120.7C10—N2—N1114.18 (15)
C15—C14—H11120.7C10—N3—C11129.63 (16)
C14—C15—C16121.6 (2)C10—N3—H27115.2
C14—C15—H12119.2C11—N3—H27115.2
C16—C15—H12119.2C17—N4—N5113.40 (15)
C15—C16—C11119.6 (2)C17—N4—Pd1125.56 (13)
C15—C16—H13120.2N5—N4—Pd1121.01 (11)
C11—C16—H13120.2C26—N5—N4114.13 (15)
N4—C17—C18126.43 (17)C26—N6—C27129.03 (17)
N4—C17—H14116.8C26—N6—H28115.5
C18—C17—H14116.8C27—N6—H28115.5
C19—C18—C17122.63 (19)N1—Pd1—N4178.31 (6)
C19—C18—H15118.7N1—Pd1—S295.66 (4)
C17—C18—H15118.7N4—Pd1—S282.94 (4)
C18—C19—C20126.8 (2)N1—Pd1—S182.92 (4)
C18—C19—H16116.6N4—Pd1—S198.45 (4)
C20—C19—H16116.6S2—Pd1—S1177.57 (2)
C21—C20—C25117.9 (2)C10—S1—Pd195.74 (6)
C21—C20—C19123.10 (18)C26—S2—Pd196.65 (6)
N1—C1—C2—C3172.9 (2)C32—C27—C28—C291.5 (4)
C1—C2—C3—C4177.50 (19)N6—C27—C28—C29177.0 (3)
C2—C3—C4—C517.8 (3)C27—C28—C29—C301.1 (5)
C2—C3—C4—C9159.6 (2)C28—C29—C30—C310.0 (5)
C9—C4—C5—C60.8 (3)C29—C30—C31—C320.6 (5)
C3—C4—C5—C6176.7 (2)C30—C31—C32—C270.1 (4)
C4—C5—C6—C71.2 (4)C28—C27—C32—C310.9 (4)
C5—C6—C7—C82.0 (4)N6—C27—C32—C31176.0 (2)
C6—C7—C8—C90.8 (4)C2—C1—N1—N20.7 (3)
C7—C8—C9—C41.3 (4)C2—C1—N1—Pd1178.74 (16)
C5—C4—C9—C82.0 (4)N3—C10—N2—N1179.95 (17)
C3—C4—C9—C8175.5 (2)S1—C10—N2—N10.6 (3)
C16—C11—C12—C130.8 (3)C1—N1—N2—C10173.45 (18)
N3—C11—C12—C13179.92 (19)Pd1—N1—N2—C107.1 (2)
C11—C12—C13—C140.3 (3)N2—C10—N3—C114.6 (3)
C12—C13—C14—C150.3 (4)S1—C10—N3—C11175.92 (16)
C13—C14—C15—C160.4 (4)C16—C11—N3—C1018.5 (3)
C14—C15—C16—C110.2 (4)C12—C11—N3—C10162.2 (2)
C12—C11—C16—C150.7 (3)C18—C17—N4—N52.1 (3)
N3—C11—C16—C15180.0 (2)C18—C17—N4—Pd1176.05 (16)
N4—C17—C18—C19174.5 (2)N6—C26—N5—N4179.31 (18)
C17—C18—C19—C20177.5 (2)S2—C26—N5—N40.4 (3)
C18—C19—C20—C2113.0 (4)C17—N4—N5—C26177.55 (18)
C18—C19—C20—C25166.5 (2)Pd1—N4—N5—C260.7 (2)
C25—C20—C21—C220.5 (3)N5—C26—N6—C276.0 (4)
C19—C20—C21—C22178.9 (2)S2—C26—N6—C27175.02 (18)
C20—C21—C22—C230.3 (4)C28—C27—N6—C26160.2 (2)
C21—C22—C23—C240.2 (4)C32—C27—N6—C2624.6 (4)
C22—C23—C24—C250.8 (4)N2—C10—S1—Pd16.03 (18)
C23—C24—C25—C201.7 (4)N3—C10—S1—Pd1174.54 (14)
C21—C20—C25—C241.5 (4)N5—C26—S2—Pd11.1 (2)
C19—C20—C25—C24178.0 (2)N6—C26—S2—Pd1179.99 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···S20.932.603.230 (2)126
C16—H13···N20.932.322.887 (3)119
C17—H14···S10.932.723.355 (2)126
C32—H26···N50.932.392.911 (3)115
N3—H27···S2i0.862.633.4805 (18)171
N6—H28···S1ii0.862.843.6554 (19)159
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.
Bond lengths (Å) for the N—N—C—S entities in cinnamaldehyde-4-phenylthiosemicarbazone structures: as a neutral molecule and as an anionic ligand top
N—NN—CC—S
C16H15N3Sa,c1.369 (2)1.354 (2)1.6704 (19)
Ni(C16H14N3S)2b,c1.405 (5)1.301 (6)1.730 (5)
Pd(C16H14N3S)2b,d1.390 (2)1.293 (2)1.7520 (19)
1.393 (2)1.291 (2)1.7328 (19)
Notes: (a) Neutral, non-coordinated form of the cinnamaldehyde 4-phenylthiosemicarbazone; (b) anionic, coordinated form of the cinnamaldehyde 4-phenylthiosemicarbazone; (c) Song et al. (2014); (d) this work.
 

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