Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043668/zl2064sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043668/zl2064Isup2.hkl |
CCDC reference: 663759
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.051
- wR factor = 0.109
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT601_ALERT_2_A Structure Contains Solvent Accessible VOIDS of . 251.00 A 3
Author Response: The voids of structure were filled with diffuse solvate molecules. The diffuse electron density within these areas using the Program Platon by A. Spek (Spek, 1999) (See Squeeze results appended to this cif file). |
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 40 Perc. PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.99 PLAT230_ALERT_2_C Hirshfeld Test Diff for P1 - C23 .. 6.56 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C29 - C34 .. 5.70 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C37 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT480_ALERT_4_C Long H...A H-Bond Reported H22B .. BR1 .. 2.98 Ang.
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 7
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 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 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Czerwinski (1986, 2004); Ponnuswamy & Czerwinski (1986); Schubert et al. (2006); Tessore et al. (2005).
The title compound was prepared as described previously (Tessore et al., 2005). A solution of triphenylphosphine (0.26 g, 1 mmol) and 4'-(phenyl-p-bromomethyl)-2,2':6',2"-terpyridine (0.401 g, 1 mmol) in toluene (10 ml) was refluxed for 4 h under magnetic stirring. During this time a white solid precipitate formed. The reaction mixture was cooled with an ice bath and the solid was collected by filtration. The residue was recrystallized from toluene/methanol/water (1:4:1, 6 ml), yielding colorless blocky single crystals.
Large voids filled with diffuse solvent molecules of two times 252.5 Å3 were found in the unit cell of the compound (13.9% of the unit cell volume). Due to the amorphous nature of the solvent molecules, possibly water or methanol, no individual atom positions could be identified and thus the dataset was corrected for the contributions of the diffuse solvent using the Squeeze procedure implemented in the molecular geometry program PLATON (Spek, 2003). The R values improved from 0.0693 to 0.0513 and 0.2299 to 0.1095 for R1 and wR2, respectively, after application of the correction.
Carbon atoms C29 and C34 showed unusually asymmetric anistropic displacement parameters and were subjected to a rigid bond restraint, i.e. the components of the anisotropic displacement parameters in the direction of the bonds were restrained to be equal within standard deviations of 0.02 for bonds and 0.01 for 1,3 distances (DELU restraint in SHELXTL). The ADPs were also restrained to have the same Uij components as the neighboring atoms within standard deviations of 0.02 and 0.01 for s and st (SIMU restraint in SHELXTL).
Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 or 0.97 Å and with Uiso(H) = 1.2 Ueq(C), respectively.
Terpyridines are a family of widely used functional ligands (Schubert et al., 2006). In this paper, we descibe the crystal structure of the title compound, a cationic and potentially trichelating terpyridine ligand.
The atom labeling and displacement ellipsoids of the title compound are shown in Fig. 1. The 4'-(4-benzyl)-2,2':6',2"-terpyridine moiety, which is attached via the terminal C atom of the benzyl group to the P atom, is in a slightly twisted conformation. The dihedral angle between the benzyl ring and the plane of the central pyridyl ring of the terpyridine moiety is 28.87 (5) °. The three pyridyl rings are located almost within the same plane with dihedral angles of 4.04 (4) and 7.17 (5)° between the two outer and the inner pyridyl rings, respectively. The phenyl substituents of the triphenylphosphonium moiety are in a propeller configuration typical for this type of compounds (Czerwinski, 1986, 2004; Ponnuswamy & Czerwinski, 1986).
The title compound exhibits large voids filled with diffuse solvent molecules of 252.5 Å3 (13.9% of the unit cell volume) which stretch as channels parallel to the c axis, and the dataset was corrected for the contributions of the diffuse solvent using PLATON (Spek, 2003; see the experimental section for details). The packing of the structural components is governed by C—H···Br hydrogen bonds, and C—H···π as well as π-π stacking interactions to form a three-dimensional supramolecular structure (Fig. 2). The C—H···Br hydrogen bonds are given in the hydrogen-bond geometry table. Short C—H···π contacts are found for C40—H···Cg1 (2.85 (2) Å) and C39—H···Cg2ii (2.73 (4) Å). The molecules also exhibit π-π stacking interactions, the closest centroid to centroid distance is found for Cg1—Cg3iii (3.843 (2) Å). [Cg1 = Ring (C16—C21); Cg2 = Ring (C23—C28); Cg3 = Ring (N1, C1—C5); (ii): -x, 1 - y, -z; (iii): 1 - x, 1 - y, -z].
For related literature, see: Czerwinski (1986, 2004); Ponnuswamy & Czerwinski (1986); Schubert et al. (2006); Tessore et al. (2005).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004) and PLATON (Spek, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2004).
C40H31N3P+·Br− | F(000) = 1368 |
Mr = 664.56 | Dx = 1.215 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6500 reflections |
a = 12.7721 (3) Å | θ = 1.4–28.0° |
b = 12.5364 (3) Å | µ = 1.21 mm−1 |
c = 23.3622 (6) Å | T = 293 K |
β = 103.874 (2)° | Block, colorless |
V = 3631.53 (15) Å3 | 0.30 × 0.29 × 0.23 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 6392 independent reflections |
Radiation source: fine-focus sealed tube | 2543 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
φ and ω scan | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→8 |
Tmin = 0.714, Tmax = 0.769 | k = −14→11 |
20487 measured reflections | l = −25→27 |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.83 | w = 1/[σ2(Fo2) + (0.0449P)2] where P = (Fo2 + 2Fc2)/3 |
6392 reflections | (Δ/σ)max < 0.001 |
406 parameters | Δρmax = 0.26 e Å−3 |
7 restraints | Δρmin = −0.22 e Å−3 |
C40H31N3P+·Br− | V = 3631.53 (15) Å3 |
Mr = 664.56 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.7721 (3) Å | µ = 1.21 mm−1 |
b = 12.5364 (3) Å | T = 293 K |
c = 23.3622 (6) Å | 0.30 × 0.29 × 0.23 mm |
β = 103.874 (2)° |
Bruker APEXII area-detector diffractometer | 6392 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2543 reflections with I > 2σ(I) |
Tmin = 0.714, Tmax = 0.769 | Rint = 0.061 |
20487 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 7 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.83 | Δρmax = 0.26 e Å−3 |
6392 reflections | Δρmin = −0.22 e Å−3 |
406 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 | ||
Br1 | 0.14824 (3) | 0.03312 (4) | 0.21079 (2) | 0.0791 (2) | |
C1 | 0.4092 (4) | 0.7413 (4) | −0.1284 (3) | 0.0893 (16) | |
H1 | 0.3845 | 0.8047 | −0.1155 | 0.107* | |
C2 | 0.4580 (4) | 0.7468 (5) | −0.1753 (2) | 0.0850 (16) | |
H2 | 0.4655 | 0.8116 | −0.1932 | 0.102* | |
C3 | 0.4944 (3) | 0.6547 (5) | −0.1942 (2) | 0.0773 (14) | |
H3 | 0.5277 | 0.6548 | −0.2255 | 0.093* | |
C4 | 0.4810 (3) | 0.5615 (4) | −0.16598 (19) | 0.0607 (12) | |
H4 | 0.5048 | 0.4974 | −0.1783 | 0.073* | |
C5 | 0.4320 (3) | 0.5628 (4) | −0.11921 (19) | 0.0513 (11) | |
C6 | 0.4219 (3) | 0.4655 (4) | −0.08609 (16) | 0.0411 (10) | |
C7 | 0.3655 (3) | 0.4635 (3) | −0.04207 (16) | 0.0476 (10) | |
H7 | 0.3325 | 0.5253 | −0.0331 | 0.057* | |
C8 | 0.3581 (3) | 0.3695 (3) | −0.01107 (17) | 0.0451 (10) | |
C9 | 0.4096 (3) | 0.2803 (3) | −0.02670 (16) | 0.0490 (11) | |
H9 | 0.4069 | 0.2159 | −0.0074 | 0.059* | |
C10 | 0.4654 (3) | 0.2867 (4) | −0.07129 (18) | 0.0476 (11) | |
C11 | 0.5220 (3) | 0.1930 (4) | −0.08802 (18) | 0.0507 (11) | |
C12 | 0.5833 (3) | 0.1995 (4) | −0.12916 (18) | 0.0612 (12) | |
H12 | 0.5903 | 0.2640 | −0.1475 | 0.073* | |
C13 | 0.6338 (3) | 0.1095 (5) | −0.1427 (2) | 0.0744 (14) | |
H13 | 0.6755 | 0.1126 | −0.1703 | 0.089* | |
C14 | 0.6226 (4) | 0.0160 (5) | −0.1154 (2) | 0.0884 (16) | |
H14 | 0.6556 | −0.0460 | −0.1240 | 0.106* | |
C15 | 0.5613 (4) | 0.0161 (4) | −0.0749 (2) | 0.0991 (18) | |
H15 | 0.5548 | −0.0477 | −0.0558 | 0.119* | |
C16 | 0.2999 (3) | 0.3639 (3) | 0.03712 (16) | 0.0437 (10) | |
C17 | 0.2908 (3) | 0.4522 (3) | 0.07130 (18) | 0.0518 (11) | |
H17 | 0.3181 | 0.5175 | 0.0627 | 0.062* | |
C18 | 0.2419 (3) | 0.4450 (3) | 0.11786 (17) | 0.0521 (11) | |
H18 | 0.2393 | 0.5045 | 0.1413 | 0.062* | |
C19 | 0.1968 (3) | 0.3502 (4) | 0.12970 (16) | 0.0457 (10) | |
C20 | 0.2052 (3) | 0.2611 (3) | 0.09625 (19) | 0.0572 (12) | |
H20 | 0.1767 | 0.1963 | 0.1046 | 0.069* | |
C21 | 0.2560 (3) | 0.2685 (3) | 0.05018 (17) | 0.0543 (11) | |
H21 | 0.2607 | 0.2083 | 0.0276 | 0.065* | |
C22 | 0.1367 (3) | 0.3417 (3) | 0.17850 (16) | 0.0505 (11) | |
H22A | 0.1766 | 0.3805 | 0.2128 | 0.061* | |
H22B | 0.1341 | 0.2674 | 0.1897 | 0.061* | |
C23 | 0.0014 (4) | 0.5363 (3) | 0.15640 (18) | 0.0500 (11) | |
C24 | 0.0839 (4) | 0.5943 (5) | 0.19176 (19) | 0.0668 (13) | |
H24 | 0.1414 | 0.5597 | 0.2168 | 0.080* | |
C25 | 0.0802 (4) | 0.7036 (5) | 0.1895 (2) | 0.0796 (15) | |
H25 | 0.1371 | 0.7425 | 0.2123 | 0.096* | |
C26 | −0.0058 (6) | 0.7574 (4) | 0.1543 (3) | 0.0902 (16) | |
H26 | −0.0067 | 0.8316 | 0.1532 | 0.108* | |
C27 | −0.0901 (4) | 0.6999 (5) | 0.1208 (2) | 0.0849 (15) | |
H27 | −0.1497 | 0.7351 | 0.0978 | 0.102* | |
C28 | −0.0863 (3) | 0.5905 (4) | 0.12108 (18) | 0.0658 (13) | |
H28 | −0.1428 | 0.5520 | 0.0975 | 0.079* | |
C29 | −0.0731 (3) | 0.3506 (4) | 0.20963 (17) | 0.0582 (12) | |
C30 | −0.1347 (3) | 0.4209 (4) | 0.23347 (19) | 0.0801 (14) | |
H30 | −0.1342 | 0.4931 | 0.2246 | 0.096* | |
C31 | −0.1971 (4) | 0.3847 (6) | 0.2704 (2) | 0.102 (2) | |
H31 | −0.2381 | 0.4324 | 0.2865 | 0.122* | |
C32 | −0.1981 (4) | 0.2801 (6) | 0.2830 (2) | 0.098 (2) | |
H32 | −0.2403 | 0.2565 | 0.3078 | 0.118* | |
C33 | −0.1386 (4) | 0.2068 (4) | 0.2601 (2) | 0.0864 (16) | |
H33 | −0.1407 | 0.1345 | 0.2688 | 0.104* | |
C34 | −0.0751 (3) | 0.2450 (4) | 0.22351 (18) | 0.0723 (13) | |
H34 | −0.0332 | 0.1972 | 0.2082 | 0.087* | |
C35 | −0.0673 (3) | 0.3479 (3) | 0.08584 (16) | 0.0471 (10) | |
C36 | −0.1589 (4) | 0.2867 (4) | 0.0772 (2) | 0.0750 (14) | |
H36 | −0.1867 | 0.2683 | 0.1092 | 0.090* | |
C37 | −0.2107 (4) | 0.2520 (4) | 0.0210 (3) | 0.0937 (16) | |
H37 | −0.2724 | 0.2101 | 0.0157 | 0.112* | |
C38 | −0.1717 (4) | 0.2788 (4) | −0.0257 (2) | 0.0771 (14) | |
H38 | −0.2058 | 0.2544 | −0.0632 | 0.093* | |
C39 | −0.0824 (4) | 0.3418 (3) | −0.01822 (19) | 0.0704 (13) | |
H39 | −0.0563 | 0.3609 | −0.0507 | 0.085* | |
C40 | −0.0307 (3) | 0.3771 (3) | 0.03710 (19) | 0.0606 (12) | |
H40 | 0.0294 | 0.4210 | 0.0417 | 0.073* | |
N1 | 0.3952 (3) | 0.6523 (4) | −0.10053 (15) | 0.0709 (11) | |
N2 | 0.4714 (2) | 0.3785 (3) | −0.10008 (13) | 0.0473 (9) | |
N3 | 0.5100 (3) | 0.1016 (4) | −0.06086 (17) | 0.0832 (12) | |
P1 | −0.00022 (8) | 0.39351 (9) | 0.15776 (4) | 0.0518 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0646 (3) | 0.0886 (4) | 0.0834 (4) | −0.0003 (3) | 0.0167 (3) | 0.0069 (3) |
C1 | 0.096 (4) | 0.061 (4) | 0.117 (5) | 0.010 (3) | 0.037 (4) | 0.010 (4) |
C2 | 0.082 (4) | 0.081 (5) | 0.094 (5) | 0.001 (3) | 0.025 (3) | 0.036 (3) |
C3 | 0.073 (3) | 0.085 (5) | 0.075 (4) | 0.005 (3) | 0.019 (3) | 0.025 (4) |
C4 | 0.060 (3) | 0.067 (4) | 0.057 (3) | 0.000 (2) | 0.020 (2) | 0.007 (3) |
C5 | 0.042 (3) | 0.058 (4) | 0.051 (3) | −0.002 (2) | 0.004 (2) | 0.007 (3) |
C6 | 0.035 (2) | 0.051 (3) | 0.036 (3) | 0.004 (2) | 0.0080 (19) | 0.000 (2) |
C7 | 0.042 (3) | 0.052 (3) | 0.047 (3) | 0.005 (2) | 0.007 (2) | −0.001 (2) |
C8 | 0.043 (3) | 0.049 (3) | 0.044 (3) | 0.006 (2) | 0.010 (2) | −0.002 (2) |
C9 | 0.047 (3) | 0.051 (3) | 0.052 (3) | 0.003 (2) | 0.017 (2) | 0.008 (2) |
C10 | 0.045 (3) | 0.055 (3) | 0.043 (3) | 0.005 (2) | 0.011 (2) | −0.002 (2) |
C11 | 0.055 (3) | 0.055 (4) | 0.042 (3) | 0.009 (3) | 0.011 (2) | 0.000 (2) |
C12 | 0.057 (3) | 0.075 (4) | 0.053 (3) | 0.012 (3) | 0.015 (2) | −0.006 (2) |
C13 | 0.070 (3) | 0.091 (5) | 0.064 (4) | 0.019 (3) | 0.018 (3) | −0.013 (3) |
C14 | 0.098 (4) | 0.085 (5) | 0.085 (4) | 0.030 (3) | 0.026 (3) | −0.015 (3) |
C15 | 0.133 (5) | 0.067 (4) | 0.113 (5) | 0.039 (3) | 0.059 (4) | 0.017 (3) |
C16 | 0.040 (3) | 0.050 (3) | 0.045 (3) | 0.002 (2) | 0.018 (2) | 0.004 (2) |
C17 | 0.049 (3) | 0.053 (3) | 0.057 (3) | 0.001 (2) | 0.019 (2) | −0.008 (2) |
C18 | 0.042 (3) | 0.062 (3) | 0.058 (3) | 0.001 (2) | 0.022 (2) | −0.007 (2) |
C19 | 0.035 (2) | 0.061 (3) | 0.045 (3) | 0.007 (2) | 0.019 (2) | 0.003 (2) |
C20 | 0.063 (3) | 0.049 (3) | 0.067 (3) | 0.002 (2) | 0.031 (3) | 0.001 (3) |
C21 | 0.060 (3) | 0.048 (3) | 0.061 (3) | −0.002 (2) | 0.029 (2) | −0.007 (2) |
C22 | 0.045 (3) | 0.064 (3) | 0.043 (3) | 0.007 (2) | 0.011 (2) | 0.006 (2) |
C23 | 0.051 (3) | 0.054 (3) | 0.048 (3) | 0.010 (3) | 0.017 (2) | −0.006 (3) |
C24 | 0.062 (4) | 0.079 (4) | 0.060 (3) | 0.008 (3) | 0.015 (3) | −0.020 (3) |
C25 | 0.070 (4) | 0.100 (5) | 0.070 (4) | −0.008 (4) | 0.020 (3) | −0.035 (4) |
C26 | 0.132 (5) | 0.066 (4) | 0.078 (4) | 0.000 (4) | 0.036 (4) | −0.023 (3) |
C27 | 0.099 (4) | 0.075 (5) | 0.076 (4) | 0.025 (4) | 0.011 (3) | −0.015 (3) |
C28 | 0.062 (3) | 0.066 (4) | 0.062 (3) | 0.009 (3) | 0.001 (3) | −0.011 (3) |
C29 | 0.049 (3) | 0.081 (4) | 0.047 (3) | 0.013 (3) | 0.017 (2) | 0.009 (3) |
C30 | 0.069 (3) | 0.111 (4) | 0.070 (4) | 0.015 (3) | 0.035 (3) | 0.004 (3) |
C31 | 0.080 (4) | 0.160 (6) | 0.081 (4) | 0.025 (4) | 0.050 (3) | 0.010 (4) |
C32 | 0.067 (4) | 0.169 (7) | 0.063 (4) | 0.001 (4) | 0.025 (3) | 0.035 (4) |
C33 | 0.074 (4) | 0.118 (5) | 0.067 (4) | −0.006 (3) | 0.016 (3) | 0.025 (3) |
C34 | 0.051 (3) | 0.113 (4) | 0.055 (3) | 0.004 (3) | 0.018 (2) | 0.014 (3) |
C35 | 0.041 (3) | 0.067 (3) | 0.036 (3) | 0.003 (2) | 0.014 (2) | −0.002 (2) |
C36 | 0.066 (3) | 0.109 (4) | 0.054 (4) | −0.015 (3) | 0.022 (3) | 0.004 (3) |
C37 | 0.088 (4) | 0.120 (4) | 0.068 (4) | −0.051 (3) | 0.010 (3) | −0.008 (3) |
C38 | 0.085 (4) | 0.085 (4) | 0.052 (4) | −0.013 (3) | −0.001 (3) | −0.009 (3) |
C39 | 0.082 (4) | 0.086 (4) | 0.045 (3) | −0.013 (3) | 0.018 (3) | −0.006 (3) |
C40 | 0.065 (3) | 0.077 (3) | 0.040 (3) | −0.014 (2) | 0.012 (2) | −0.011 (2) |
N1 | 0.082 (3) | 0.064 (3) | 0.071 (3) | −0.004 (2) | 0.026 (2) | 0.014 (3) |
N2 | 0.043 (2) | 0.054 (3) | 0.045 (2) | 0.0026 (19) | 0.0108 (17) | 0.001 (2) |
N3 | 0.102 (3) | 0.069 (3) | 0.093 (3) | 0.028 (3) | 0.049 (3) | 0.013 (3) |
P1 | 0.0418 (7) | 0.0747 (10) | 0.0410 (7) | 0.0074 (6) | 0.0141 (5) | 0.0003 (6) |
C1—N1 | 1.325 (5) | C21—H21 | 0.9300 |
C1—C2 | 1.386 (6) | C22—P1 | 1.818 (3) |
C1—H1 | 0.9300 | C22—H22A | 0.9700 |
C2—C3 | 1.358 (6) | C22—H22B | 0.9700 |
C2—H2 | 0.9300 | C23—C24 | 1.380 (5) |
C3—C4 | 1.373 (5) | C23—C28 | 1.399 (5) |
C3—H3 | 0.9300 | C23—P1 | 1.790 (4) |
C4—C5 | 1.383 (5) | C24—C25 | 1.372 (5) |
C4—H4 | 0.9300 | C24—H24 | 0.9300 |
C5—N1 | 1.330 (4) | C25—C26 | 1.381 (6) |
C5—C6 | 1.467 (5) | C25—H25 | 0.9300 |
C6—N2 | 1.341 (4) | C26—C27 | 1.374 (6) |
C6—C7 | 1.389 (4) | C26—H26 | 0.9300 |
C7—C8 | 1.398 (4) | C27—C28 | 1.372 (5) |
C7—H7 | 0.9300 | C27—H27 | 0.9300 |
C8—C9 | 1.390 (4) | C28—H28 | 0.9300 |
C8—C16 | 1.492 (5) | C29—C34 | 1.365 (5) |
C9—C10 | 1.399 (4) | C29—C30 | 1.384 (5) |
C9—H9 | 0.9300 | C29—P1 | 1.779 (4) |
C10—N2 | 1.344 (4) | C30—C31 | 1.385 (6) |
C10—C11 | 1.480 (5) | C30—H30 | 0.9300 |
C11—N3 | 1.336 (4) | C31—C32 | 1.344 (6) |
C11—C12 | 1.380 (5) | C31—H31 | 0.9300 |
C12—C13 | 1.373 (5) | C32—C33 | 1.379 (6) |
C12—H12 | 0.9300 | C32—H32 | 0.9300 |
C13—C14 | 1.358 (5) | C33—C34 | 1.397 (5) |
C13—H13 | 0.9300 | C33—H33 | 0.9300 |
C14—C15 | 1.364 (6) | C34—H34 | 0.9300 |
C14—H14 | 0.9300 | C35—C36 | 1.373 (5) |
C15—N3 | 1.338 (5) | C35—C40 | 1.380 (4) |
C15—H15 | 0.9300 | C35—P1 | 1.787 (4) |
C16—C21 | 1.385 (4) | C36—C37 | 1.390 (5) |
C16—C17 | 1.386 (4) | C36—H36 | 0.9300 |
C17—C18 | 1.381 (4) | C37—C38 | 1.346 (5) |
C17—H17 | 0.9300 | C37—H37 | 0.9300 |
C18—C19 | 1.377 (4) | C38—C39 | 1.364 (5) |
C18—H18 | 0.9300 | C38—H38 | 0.9300 |
C19—C20 | 1.382 (5) | C39—C40 | 1.376 (5) |
C19—C22 | 1.524 (4) | C39—H39 | 0.9300 |
C20—C21 | 1.387 (5) | C40—H40 | 0.9300 |
C20—H20 | 0.9300 | ||
N1—C1—C2 | 124.6 (5) | C19—C22—H22B | 108.8 |
N1—C1—H1 | 117.7 | P1—C22—H22B | 108.8 |
C2—C1—H1 | 117.7 | H22A—C22—H22B | 107.7 |
C3—C2—C1 | 118.1 (5) | C24—C23—C28 | 119.1 (4) |
C3—C2—H2 | 121.0 | C24—C23—P1 | 121.8 (4) |
C1—C2—H2 | 121.0 | C28—C23—P1 | 119.0 (4) |
C2—C3—C4 | 118.3 (5) | C25—C24—C23 | 119.3 (5) |
C2—C3—H3 | 120.8 | C25—C24—H24 | 120.4 |
C4—C3—H3 | 120.8 | C23—C24—H24 | 120.4 |
C3—C4—C5 | 120.1 (5) | C24—C25—C26 | 121.7 (5) |
C3—C4—H4 | 120.0 | C24—C25—H25 | 119.1 |
C5—C4—H4 | 120.0 | C26—C25—H25 | 119.1 |
N1—C5—C4 | 122.1 (4) | C27—C26—C25 | 119.1 (5) |
N1—C5—C6 | 116.5 (4) | C27—C26—H26 | 120.5 |
C4—C5—C6 | 121.4 (5) | C25—C26—H26 | 120.5 |
N2—C6—C7 | 121.6 (4) | C28—C27—C26 | 120.0 (5) |
N2—C6—C5 | 116.2 (4) | C28—C27—H27 | 120.0 |
C7—C6—C5 | 122.2 (4) | C26—C27—H27 | 120.0 |
C6—C7—C8 | 120.7 (4) | C27—C28—C23 | 120.8 (4) |
C6—C7—H7 | 119.7 | C27—C28—H28 | 119.6 |
C8—C7—H7 | 119.7 | C23—C28—H28 | 119.6 |
C9—C8—C7 | 116.5 (4) | C34—C29—C30 | 118.4 (4) |
C9—C8—C16 | 120.8 (4) | C34—C29—P1 | 119.9 (3) |
C7—C8—C16 | 122.6 (4) | C30—C29—P1 | 121.5 (4) |
C8—C9—C10 | 120.5 (4) | C29—C30—C31 | 120.7 (5) |
C8—C9—H9 | 119.8 | C29—C30—H30 | 119.6 |
C10—C9—H9 | 119.8 | C31—C30—H30 | 119.6 |
N2—C10—C9 | 121.4 (4) | C32—C31—C30 | 119.5 (5) |
N2—C10—C11 | 117.2 (4) | C32—C31—H31 | 120.3 |
C9—C10—C11 | 121.3 (4) | C30—C31—H31 | 120.3 |
N3—C11—C12 | 122.0 (4) | C31—C32—C33 | 122.1 (5) |
N3—C11—C10 | 115.8 (4) | C31—C32—H32 | 118.9 |
C12—C11—C10 | 122.1 (4) | C33—C32—H32 | 118.9 |
C13—C12—C11 | 119.2 (4) | C32—C33—C34 | 117.6 (5) |
C13—C12—H12 | 120.4 | C32—C33—H33 | 121.2 |
C11—C12—H12 | 120.4 | C34—C33—H33 | 121.2 |
C14—C13—C12 | 119.5 (5) | C29—C34—C33 | 121.7 (4) |
C14—C13—H13 | 120.2 | C29—C34—H34 | 119.2 |
C12—C13—H13 | 120.2 | C33—C34—H34 | 119.2 |
C13—C14—C15 | 117.9 (5) | C36—C35—C40 | 118.2 (4) |
C13—C14—H14 | 121.1 | C36—C35—P1 | 121.1 (3) |
C15—C14—H14 | 121.1 | C40—C35—P1 | 120.7 (3) |
N3—C15—C14 | 124.5 (5) | C35—C36—C37 | 120.6 (4) |
N3—C15—H15 | 117.7 | C35—C36—H36 | 119.7 |
C14—C15—H15 | 117.7 | C37—C36—H36 | 119.7 |
C21—C16—C17 | 117.9 (4) | C38—C37—C36 | 120.2 (5) |
C21—C16—C8 | 120.6 (4) | C38—C37—H37 | 119.9 |
C17—C16—C8 | 121.5 (4) | C36—C37—H37 | 119.9 |
C18—C17—C16 | 121.2 (4) | C37—C38—C39 | 120.0 (4) |
C18—C17—H17 | 119.4 | C37—C38—H38 | 120.0 |
C16—C17—H17 | 119.4 | C39—C38—H38 | 120.0 |
C19—C18—C17 | 120.3 (4) | C38—C39—C40 | 120.4 (4) |
C19—C18—H18 | 119.9 | C38—C39—H39 | 119.8 |
C17—C18—H18 | 119.9 | C40—C39—H39 | 119.8 |
C18—C19—C20 | 119.4 (4) | C39—C40—C35 | 120.6 (4) |
C18—C19—C22 | 121.3 (4) | C39—C40—H40 | 119.7 |
C20—C19—C22 | 119.2 (4) | C35—C40—H40 | 119.7 |
C19—C20—C21 | 119.9 (4) | C1—N1—C5 | 116.7 (4) |
C19—C20—H20 | 120.0 | C6—N2—C10 | 119.2 (4) |
C21—C20—H20 | 120.0 | C11—N3—C15 | 116.8 (4) |
C16—C21—C20 | 121.2 (4) | C29—P1—C35 | 109.4 (2) |
C16—C21—H21 | 119.4 | C29—P1—C23 | 108.95 (19) |
C20—C21—H21 | 119.4 | C35—P1—C23 | 107.97 (19) |
C19—C22—P1 | 113.6 (2) | C29—P1—C22 | 109.69 (18) |
C19—C22—H22A | 108.8 | C35—P1—C22 | 110.46 (17) |
P1—C22—H22A | 108.8 | C23—P1—C22 | 110.30 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22B···Br1 | 0.97 | 2.98 | 3.938 (4) | 171 |
C24—H24···Br1i | 0.93 | 2.83 | 3.707 (5) | 158 |
Symmetry code: (i) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C40H31N3P+·Br− |
Mr | 664.56 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 12.7721 (3), 12.5364 (3), 23.3622 (6) |
β (°) | 103.874 (2) |
V (Å3) | 3631.53 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.21 |
Crystal size (mm) | 0.30 × 0.29 × 0.23 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.714, 0.769 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20487, 6392, 2543 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.110, 0.83 |
No. of reflections | 6392 |
No. of parameters | 406 |
No. of restraints | 7 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.22 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004) and PLATON (Spek, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22B···Br1 | 0.97 | 2.98 | 3.938 (4) | 171.0 |
C24—H24···Br1i | 0.93 | 2.83 | 3.707 (5) | 157.6 |
Symmetry code: (i) −x+1/2, y+1/2, −z+1/2. |
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Terpyridines are a family of widely used functional ligands (Schubert et al., 2006). In this paper, we descibe the crystal structure of the title compound, a cationic and potentially trichelating terpyridine ligand.
The atom labeling and displacement ellipsoids of the title compound are shown in Fig. 1. The 4'-(4-benzyl)-2,2':6',2"-terpyridine moiety, which is attached via the terminal C atom of the benzyl group to the P atom, is in a slightly twisted conformation. The dihedral angle between the benzyl ring and the plane of the central pyridyl ring of the terpyridine moiety is 28.87 (5) °. The three pyridyl rings are located almost within the same plane with dihedral angles of 4.04 (4) and 7.17 (5)° between the two outer and the inner pyridyl rings, respectively. The phenyl substituents of the triphenylphosphonium moiety are in a propeller configuration typical for this type of compounds (Czerwinski, 1986, 2004; Ponnuswamy & Czerwinski, 1986).
The title compound exhibits large voids filled with diffuse solvent molecules of 252.5 Å3 (13.9% of the unit cell volume) which stretch as channels parallel to the c axis, and the dataset was corrected for the contributions of the diffuse solvent using PLATON (Spek, 2003; see the experimental section for details). The packing of the structural components is governed by C—H···Br hydrogen bonds, and C—H···π as well as π-π stacking interactions to form a three-dimensional supramolecular structure (Fig. 2). The C—H···Br hydrogen bonds are given in the hydrogen-bond geometry table. Short C—H···π contacts are found for C40—H···Cg1 (2.85 (2) Å) and C39—H···Cg2ii (2.73 (4) Å). The molecules also exhibit π-π stacking interactions, the closest centroid to centroid distance is found for Cg1—Cg3iii (3.843 (2) Å). [Cg1 = Ring (C16—C21); Cg2 = Ring (C23—C28); Cg3 = Ring (N1, C1—C5); (ii): -x, 1 - y, -z; (iii): 1 - x, 1 - y, -z].