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The mol­ecule of the title NCNHCS pincer N-heterocyclic carbene palladium(II) complex, [PdBr(C21H25N3S)]Br, exhibits a slightly distorted square-planar coordination at the palladium(II) atom, with the five-membered chelate ring nearly planar. The six-membered chelate ring adopts an envelope conformation. Upon chelation, the sulfur atom becomes a stereogenic centre with an RS configuration induced by the chiral carbon of the precursor imidazolium salt. There are intra­molecular C—H...Br—Pd hydrogen bonds in the structure. The two inter­stitial Br atoms, as the counter-anion of the structure, are both located on crystallographic twofold axes and are connected to the complex cations via C—H...·Br hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2414314624003602/zl4070sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2414314624003602/zl4070Isup3.hkl
Contains datablock I

CCDC reference: 2312031

Key indicators

Structure: I
  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.012 Å
  • R factor = 0.030
  • wR factor = 0.072
  • Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT196_ALERT_1_B No TEMP record and _measurement_temperature .NE. 293 Degree
Alert level C PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.01176 Ang. PLAT915_ALERT_3_C No Flack x Check Done: Low Friedel Pair Coverage 79 %
Alert level G PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ..... (K) 293 Check PLAT304_ALERT_4_G Non-Integer Number of Atoms in ..... (Resd 2) 0.50 Check PLAT304_ALERT_4_G Non-Integer Number of Atoms in ..... (Resd 3) 0.50 Check PLAT480_ALERT_4_G Long H...A H-Bond Reported H16 ..BR3 . 3.11 Ang. PLAT484_ALERT_4_G Round D-H..A Angle Rep for C1 ..BR1 . 124 Degree PLAT484_ALERT_4_G Round D-H..A Angle Rep for C6 ..BR2 . 173 Degree PLAT484_ALERT_4_G Round D-H..A Angle Rep for C10 ..BR3 . 144 Degree PLAT794_ALERT_5_G Tentative Bond Valency for Pd1 (II) . 2.13 Info PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters 1 Info PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min). 1 Note 0 0 1, PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 16 Note PLAT969_ALERT_5_G The 'Henn et al.' R-Factor-gap value ........... 1.91 Note Predicted wR2: Based on SigI   2 3.79 or SHELX Weight 7.22 PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density. 0 Info
0 ALERT level A = Most likely a serious problem - resolve or explain 1 ALERT level B = A potentially serious problem, consider carefully 2 ALERT level C = Check. Ensure it is not caused by an omission or oversight 14 ALERT level G = General information/check it is not something unexpected 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 8 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check

Computing details top

(SC,RS)-Bromido(N-{4-methyl-1-[(4-methylphenyl)sulfanyl]pentan-2-yl}-N'-(pyridin-2-yl)imidazol-2-ylidene)palladium(II) bromide top
Crystal data top
[PdBr(C21H25N3S)]BrF(000) = 1216
Mr = 617.72Dx = 1.785 Mg m3
Monoclinic, C2Cu Kα radiation, λ = 1.54184 Å
a = 25.8993 (7) ÅCell parameters from 8595 reflections
b = 6.6206 (2) Åθ = 4.5–70.1°
c = 13.4938 (3) ŵ = 11.52 mm1
β = 96.425 (2)°T = 293 K
V = 2299.23 (12) Å3Plate, colourless
Z = 40.14 × 0.1 × 0.03 mm
Data collection top
Xcalibur, Eos, Gemini
diffractometer
3950 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source3693 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
Detector resolution: 16.2312 pixels mm-1θmax = 70.5°, θmin = 3.4°
ω scansh = 3131
Absorption correction: multi-scan
(CrysAlisPro; Rigaku OD, 2023)
k = 86
Tmin = 0.419, Tmax = 1.000l = 1616
20069 measured reflections
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.033P)2 + 2.7656P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.030(Δ/σ)max < 0.001
wR(F2) = 0.072Δρmax = 0.36 e Å3
S = 1.04Δρmin = 0.38 e Å3
3950 reflectionsExtinction correction: SHELXL-2014/7 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
258 parametersExtinction coefficient: 0.00034 (4)
1 restraintAbsolute structure: Flack x determined using 1371 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.030 (7)
Hydrogen site location: inferred from neighbouring sites
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.

Refinement. The H atoms on the carbons were positioned geometrically and constrained to ride on their parent atoms. C—H bond distances were constrained to 0.93 Å for aromatic and alkene C—H moieties, and to 0.98, 0.91 and 0.96 Å for aliphatic C—H, CH2 and CH3 moieties, respectively. Methyl CH3 H atoms were allowed to rotate but not to tip to best fit the experimental electron density. Uiso(H) values were set to a multiple of Ueq(C) with 1.5 for CH3, and 1.2 for C—H and CH2 units, respectively.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd10.37598 (2)0.06095 (8)0.28758 (3)0.03701 (15)
S10.40637 (6)0.0902 (3)0.15555 (12)0.0381 (4)
N10.3574 (2)0.2356 (11)0.4079 (4)0.0443 (16)
N20.4255 (2)0.4165 (10)0.3607 (4)0.0413 (14)
N30.4680 (2)0.3203 (10)0.2419 (4)0.0381 (13)
C10.3187 (3)0.2026 (16)0.4635 (6)0.057 (2)
H10.29720.09120.45010.069*
C20.3100 (4)0.3329 (18)0.5414 (7)0.069 (3)
H20.28320.30850.58040.083*
C30.3414 (4)0.4954 (18)0.5587 (7)0.074 (3)
H30.33590.58400.60990.089*
C40.3813 (3)0.5318 (18)0.5021 (6)0.061 (2)
H40.40330.64220.51440.073*
C50.3873 (3)0.3975 (13)0.4263 (5)0.0450 (18)
C60.4650 (3)0.5562 (15)0.3556 (5)0.0478 (16)
H60.47190.66860.39630.057*
C70.4911 (3)0.4978 (13)0.2812 (6)0.049 (2)
H70.51950.56320.25930.059*
C80.4280 (2)0.2737 (13)0.2911 (5)0.0393 (16)
C90.4434 (2)0.1033 (12)0.0964 (5)0.0415 (18)
H9A0.45740.04390.03940.050*
H9B0.41990.21080.07200.050*
C100.4877 (3)0.1938 (11)0.1649 (5)0.0366 (15)
H100.50720.28210.12420.044*
C110.5255 (2)0.0360 (13)0.2122 (5)0.0397 (16)
H11A0.53250.05990.16100.048*
H11B0.50850.03730.26170.048*
C120.5777 (3)0.1161 (12)0.2623 (5)0.0441 (19)
H120.57070.21090.31500.053*
C130.6081 (3)0.0612 (16)0.3099 (7)0.065 (3)
H13A0.58920.12080.35980.097*
H13B0.64130.01500.34040.097*
H13C0.61320.15990.25980.097*
C140.6090 (3)0.2258 (18)0.1894 (7)0.072 (3)
H14A0.60920.14670.12980.108*
H14B0.64400.24480.21960.108*
H14C0.59350.35490.17290.108*
C150.3558 (3)0.1214 (13)0.0549 (5)0.0428 (18)
C160.3572 (3)0.2944 (13)0.0012 (6)0.0494 (19)
H160.38140.39490.01740.059*
C170.3221 (3)0.3171 (14)0.0853 (6)0.054 (2)
H170.32250.43530.12240.064*
C180.2862 (3)0.1665 (14)0.1157 (5)0.048 (2)
C190.2848 (3)0.0021 (14)0.0560 (5)0.051 (2)
H190.26010.10150.07340.061*
C200.3190 (3)0.0263 (14)0.0282 (5)0.049 (2)
H200.31760.14150.06720.059*
C210.2512 (3)0.1845 (17)0.2126 (6)0.067 (3)
H21A0.26840.12900.26590.101*
H21B0.21950.11160.20750.101*
H21C0.24330.32420.22610.101*
Br10.30979 (4)0.20451 (15)0.29589 (7)0.0603 (3)
Br20.50000.0140 (2)0.50000.0609 (4)
Br30.50000.61892 (17)0.00000.0480 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0397 (2)0.0390 (3)0.0327 (2)0.0004 (2)0.00594 (15)0.0005 (2)
S10.0391 (8)0.0388 (11)0.0362 (8)0.0001 (7)0.0032 (6)0.0042 (8)
N10.050 (3)0.054 (5)0.030 (3)0.012 (3)0.009 (2)0.007 (3)
N20.050 (3)0.036 (4)0.038 (3)0.007 (3)0.003 (2)0.007 (3)
N30.042 (3)0.031 (4)0.042 (3)0.003 (3)0.006 (2)0.002 (3)
C10.054 (4)0.073 (7)0.047 (4)0.009 (4)0.015 (3)0.002 (4)
C20.063 (5)0.091 (9)0.055 (5)0.018 (5)0.019 (4)0.003 (5)
C30.089 (7)0.087 (9)0.050 (4)0.020 (6)0.019 (4)0.017 (5)
C40.071 (5)0.058 (7)0.054 (4)0.012 (5)0.010 (3)0.019 (5)
C50.051 (4)0.043 (5)0.038 (4)0.010 (4)0.006 (3)0.007 (4)
C60.061 (4)0.030 (4)0.050 (4)0.001 (4)0.001 (3)0.008 (4)
C70.052 (4)0.038 (5)0.055 (4)0.011 (3)0.003 (3)0.000 (4)
C80.042 (3)0.037 (5)0.036 (3)0.005 (3)0.003 (3)0.002 (3)
C90.042 (3)0.047 (6)0.035 (3)0.001 (3)0.003 (2)0.001 (3)
C100.045 (3)0.031 (4)0.034 (3)0.002 (3)0.008 (3)0.001 (3)
C110.049 (3)0.032 (4)0.039 (3)0.002 (3)0.009 (2)0.000 (4)
C120.043 (3)0.048 (6)0.041 (3)0.005 (3)0.004 (3)0.001 (3)
C130.051 (4)0.073 (7)0.068 (5)0.007 (4)0.005 (4)0.010 (5)
C140.051 (5)0.096 (9)0.069 (6)0.019 (5)0.006 (4)0.022 (6)
C150.038 (3)0.051 (5)0.039 (3)0.001 (3)0.003 (3)0.009 (4)
C160.047 (4)0.038 (5)0.062 (5)0.003 (3)0.001 (3)0.009 (4)
C170.056 (4)0.051 (6)0.051 (4)0.001 (4)0.006 (3)0.020 (4)
C180.036 (3)0.058 (6)0.048 (4)0.011 (3)0.004 (3)0.006 (4)
C190.042 (4)0.060 (7)0.050 (4)0.007 (3)0.002 (3)0.000 (4)
C200.051 (4)0.046 (6)0.051 (4)0.014 (4)0.004 (3)0.011 (4)
C210.058 (5)0.079 (8)0.061 (5)0.003 (5)0.014 (4)0.006 (5)
Br10.0612 (5)0.0547 (7)0.0674 (5)0.0142 (4)0.0173 (4)0.0042 (5)
Br20.0953 (9)0.0421 (9)0.0444 (5)0.0000.0037 (5)0.000
Br30.0607 (6)0.0392 (8)0.0460 (5)0.0000.0141 (4)0.000
Geometric parameters (Å, º) top
Pd1—S12.2603 (17)C10—H100.9800
Pd1—N12.093 (6)C10—C111.522 (10)
Pd1—C81.946 (8)C11—H11A0.9700
Pd1—Br12.4663 (10)C11—H11B0.9700
S1—C91.836 (7)C11—C121.537 (9)
S1—C151.789 (7)C12—H120.9800
N1—C11.335 (9)C12—C131.517 (11)
N1—C51.330 (10)C12—C141.527 (10)
N2—C51.405 (9)C13—H13A0.9600
N2—C61.387 (10)C13—H13B0.9600
N2—C81.340 (9)C13—H13C0.9600
N3—C71.396 (10)C14—H14A0.9600
N3—C81.328 (9)C14—H14B0.9600
N3—C101.470 (9)C14—H14C0.9600
C1—H10.9300C15—C161.376 (11)
C1—C21.397 (13)C15—C201.384 (11)
C2—H20.9300C16—H160.9300
C2—C31.354 (15)C16—C171.380 (11)
C3—H30.9300C17—H170.9300
C3—C41.373 (12)C17—C181.393 (12)
C4—H40.9300C18—C191.379 (11)
C4—C51.376 (11)C18—C211.511 (10)
C6—H60.9300C19—H190.9300
C6—C71.329 (10)C19—C201.370 (10)
C7—H70.9300C20—H200.9300
C9—H9A0.9700C21—H21A0.9600
C9—H9B0.9700C21—H21B0.9600
C9—C101.513 (9)C21—H21C0.9600
S1—Pd1—Br191.46 (5)C9—C10—H10107.3
N1—Pd1—S1170.64 (19)C9—C10—C11113.1 (6)
N1—Pd1—Br197.90 (19)C11—C10—H10107.3
C8—Pd1—S192.2 (2)C10—C11—H11A108.3
C8—Pd1—N178.4 (3)C10—C11—H11B108.3
C8—Pd1—Br1175.9 (2)C10—C11—C12116.1 (7)
C9—S1—Pd1106.2 (2)H11A—C11—H11B107.4
C15—S1—Pd1111.0 (2)C12—C11—H11A108.3
C15—S1—C997.2 (3)C12—C11—H11B108.3
C1—N1—Pd1126.7 (6)C11—C12—H12108.5
C5—N1—Pd1114.3 (5)C13—C12—C11108.0 (7)
C5—N1—C1119.0 (7)C13—C12—H12108.5
C6—N2—C5131.8 (6)C13—C12—C14110.6 (7)
C8—N2—C5118.1 (7)C14—C12—C11112.7 (6)
C8—N2—C6110.0 (6)C14—C12—H12108.5
C7—N3—C10125.5 (6)C12—C13—H13A109.5
C8—N3—C7109.3 (6)C12—C13—H13B109.5
C8—N3—C10124.9 (6)C12—C13—H13C109.5
N1—C1—H1119.5H13A—C13—H13B109.5
N1—C1—C2121.1 (9)H13A—C13—H13C109.5
C2—C1—H1119.5H13B—C13—H13C109.5
C1—C2—H2120.8C12—C14—H14A109.5
C3—C2—C1118.4 (8)C12—C14—H14B109.5
C3—C2—H2120.8C12—C14—H14C109.5
C2—C3—H3119.4H14A—C14—H14B109.5
C2—C3—C4121.3 (9)H14A—C14—H14C109.5
C4—C3—H3119.4H14B—C14—H14C109.5
C3—C4—H4121.5C16—C15—S1116.9 (6)
C3—C4—C5117.0 (10)C16—C15—C20120.2 (7)
C5—C4—H4121.5C20—C15—S1122.7 (6)
N1—C5—N2113.0 (6)C15—C16—H16120.4
N1—C5—C4123.2 (8)C15—C16—C17119.2 (8)
C4—C5—N2123.8 (8)C17—C16—H16120.4
N2—C6—H6126.8C16—C17—H17119.3
C7—C6—N2106.5 (7)C16—C17—C18121.4 (8)
C7—C6—H6126.8C18—C17—H17119.3
N3—C7—H7126.3C17—C18—C21121.0 (8)
C6—C7—N3107.4 (7)C19—C18—C17117.9 (7)
C6—C7—H7126.3C19—C18—C21121.1 (8)
N2—C8—Pd1116.1 (5)C18—C19—H19119.3
N3—C8—Pd1137.2 (6)C20—C19—C18121.5 (8)
N3—C8—N2106.7 (7)C20—C19—H19119.3
S1—C9—H9A108.7C15—C20—H20120.1
S1—C9—H9B108.7C19—C20—C15119.7 (8)
H9A—C9—H9B107.6C19—C20—H20120.1
C10—C9—S1114.1 (5)C18—C21—H21A109.5
C10—C9—H9A108.7C18—C21—H21B109.5
C10—C9—H9B108.7C18—C21—H21C109.5
N3—C10—C9111.0 (5)H21A—C21—H21B109.5
N3—C10—H10107.3H21A—C21—H21C109.5
N3—C10—C11110.6 (5)H21B—C21—H21C109.5
Pd1—S1—C9—C1058.1 (5)C7—N3—C8—Pd1179.7 (6)
Pd1—S1—C15—C16143.9 (5)C7—N3—C8—N20.4 (8)
Pd1—S1—C15—C2041.2 (7)C7—N3—C10—C9144.6 (7)
Pd1—N1—C1—C2179.1 (6)C7—N3—C10—C1189.0 (8)
Pd1—N1—C5—N20.3 (8)C8—N2—C5—N11.1 (9)
Pd1—N1—C5—C4179.8 (6)C8—N2—C5—C4178.8 (8)
S1—C9—C10—N369.7 (7)C8—N2—C6—C70.8 (9)
S1—C9—C10—C1155.2 (7)C8—N3—C7—C60.9 (9)
S1—C15—C16—C17173.9 (6)C8—N3—C10—C941.5 (9)
S1—C15—C20—C19173.0 (6)C8—N3—C10—C1184.8 (8)
N1—C1—C2—C30.7 (14)C9—S1—C15—C16105.7 (6)
N2—C6—C7—N31.0 (9)C9—S1—C15—C2069.3 (7)
N3—C10—C11—C1268.7 (7)C9—C10—C11—C12166.1 (5)
C1—N1—C5—N2178.3 (7)C10—N3—C7—C6173.7 (7)
C1—N1—C5—C41.8 (12)C10—N3—C8—Pd15.0 (11)
C1—C2—C3—C40.5 (15)C10—N3—C8—N2174.3 (6)
C2—C3—C4—C50.9 (15)C10—C11—C12—C13176.6 (6)
C3—C4—C5—N11.6 (13)C10—C11—C12—C1460.9 (9)
C3—C4—C5—N2178.6 (8)C15—S1—C9—C10172.5 (5)
C5—N1—C1—C21.3 (12)C15—C16—C17—C181.5 (13)
C5—N2—C6—C7177.4 (7)C16—C15—C20—C191.8 (12)
C5—N2—C8—Pd12.0 (8)C16—C17—C18—C193.5 (12)
C5—N2—C8—N3177.4 (6)C16—C17—C18—C21174.6 (8)
C6—N2—C5—N1177.5 (7)C17—C18—C19—C202.9 (12)
C6—N2—C5—C42.4 (13)C18—C19—C20—C150.3 (12)
C6—N2—C8—Pd1179.2 (5)C20—C15—C16—C171.2 (12)
C6—N2—C8—N30.2 (8)C21—C18—C19—C20175.2 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···Br10.932.903.510 (10)124
C6—H6···Br2i0.932.743.661 (9)173
C10—H10···Br30.982.783.624 (7)144
C16—H16···Br3ii0.933.113.742 (7)127
Symmetry codes: (i) x, y+1, z; (ii) x, y1, z.
 

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