Structural and luminescent properties of co-crystals of tetra­iodo­ethyl­ene with two aza­phenanthrenes

Cui, Y.-J.; Su, F.; Jin, W.-J.

doi:10.1107/S2056989020002182

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 76| Part 3| March 2020| Pages 438-442

https://doi.org/10.1107/S2056989020002182

Open

access

Structural and luminescent properties of co-crystals of tetraiodoethylene with two azaphenanthrenes

Yu-Jin Cui,^a Feng Su ^a and Wei-Jun Jin ^b ^*

^aDepartment of Chemistry, Changzhi University, Changzhi 046011, People's Republic of China, and ^bKey Laboratory Chemical Biology and Molecular Engineering, Education Ministry, People's Republic of China
^*Correspondence e-mail: 250951251@qq.com

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 28 November 2019; accepted 17 February 2020; online 25 February 2020)

Two new co-crystals, tetraiodoethylene–phenanthridine (1/2), 0.5C₂I₄·C₁₃H₉N (1) and tetraiodoethylene–benzo[f]quinoline (1/2), 0.5C₂I₄·C₁₃H₉N (2), were obtained from tetraiodoethylene and azaphenanthrenes, and characterized by IR and fluorescence spectroscopy, elemental analysis and X-ray crystallography. In the crystal structures, C—I⋯π and C—I⋯N halogen bonds link the independent molecules into one-dimensional chains and two-dimensional networks with subloops. In addition, the planar azaphenanthrenes lend themselves to π–π stacking and C—H⋯π interactions, leading to a diversity of supramolecular three-dimensional structural motifs being formed by these interactions. Luminescence studies show that co-crystals 1 and 2 exhibit distinctly different luminescence properties in the solid state at room temperature.

Keywords: co-crystallized molecules; crystal structure; tetraiodoethylene; azaphenanthrenes; luminescence.

CCDC references: 1899078; 1899077

1. Chemical context

A halogen bond is an attractive non-covalent interaction between an electrophilic region in a covalently bonded halogen atom and a Lewis base. Halogen bonding (XB) is a powerful tool to assemble supramolecular materials and to promote chemical or biological molecular recognition (Desiraju et al., 2013 ; Cavallo et al., 2016 ; Gilday et al., 2015 ; Wang et al., 2016 ). Over the past few years, XB has been used successfully to assemble luminescent co-crystals (Liu et al., 2017a ; d'Agostino et al., 2015 ; Ventura et al., 2014 ; Bolton et al., 2011 ). XB can play multiple roles in co-crystals, for example, as cement to assemble XB donors and acceptors together (Metrangolo et al., 2005 ), and, importantly, as a heavy-atom source to enhance phosphorescence or delayed fluorescence by efficient spin-orbital coupling (Gao et al., 2012 ). Phosphorescence or delayed fluorescence materials are very popular for preparing light devices because of the higher internal quantum efficiency of triplet excitons (Brown et al., 1993 ; Baldo et al., 1999 ).

Nitrogen heteroaromatic rings are a common type of luminescence or luminescent precursor materials. However, in general, it is difficult to use them to generate phosphorescence or delayed fluorescence. Haloperfluorobenzenes, as XB donors, have been used in attempts to assemble luminescence co-crystals with azaphenanthrenes (Gao et al., 2017 ; Wang et al., 2014 , 2016; Wang & Jin, 2017 ; Liu et al., 2017b ). We report herein the use of tetraiodoethylene (TIE) as a new XB donor in the assembly of co-crystals with two different azaphenanthrenes, namely phenanthridine (PHN) and benzo[f]quinoline (BfQ), which is expected to tune their luminescence behaviour via a change of the co-crystal structures. Single crystal X-ray diffraction (XRD) data reveal that the two co-crystals of TIE with PHN and BfQ reported here have interesting structural properties and exhibit different luminescence behaviour from previous reports. TIE as a quadridentate XB donor allows the formation of three-dimensional halogen-bonded networks with XB acceptors, PHN and BfQ. Using the conventional solution-based method, yellow co-crystals suitable for XRD measurement were obtained. The crystal structures of the co-crystals are mainly constructed by C—I⋯π and C—I⋯N halogen bonds. Other multiple intermolecular interactions, such as π–π stacking, C—H⋯π, C—H⋯I as well as C—H⋯H—C interactions, are also observed in the co-crystals.

2. Structural commentary

The asymmetric units of co-crystals 1 and 2 each comprise one half TIE molecule lying about an inversion centre and one PHN or BfQ molecule in a general position, hence the co-crystals have a 1:2 stoichiometry (Fig. 1). Co-crystal 1 crystallizes in the monoclinic space group C2/c while 2 crystallizes in the triclinic space group P $[\overline{1}]$ .

Figure 1
The molecular structures of co-crystals 1 and 2, showing the atom-labelling scheme and displacement ellipsoids at the 30% probability level [Symmetry codes: (i) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1 for co-crystal 1; (i) −x, −y + 1, −z + 2 for co-crystal 2].

3. Supramolecular features

In the crystal of 1, C—I⋯N, C—I⋯C and C—I⋯π halogen bonds lead to the formation of a two-dimensional network structure in which the rectangular motif has a D⋯2A⋯D⋯2A arrangement, as shown in Fig. 2a. The I1 atom of the TIE molecule interacts with the N1 atom of a PHN molecule, forming a C1—I1⋯N1 halogen bond (Fig. 2b). The I1⋯N1ⁱ distance is 2.864 (7) Å and the corresponding C14–I1⋯N1ⁱ angle is 172.8 (2)° [symmetry code: (i) x, y + 1, z]. The strong C14—I1⋯N1 halogen bond results in a I1⋯C13ⁱ distance [3.553 (8) Å] shorter than the sum of the van der Waals radii, which indicates a C1—I1⋯C13 halogen interaction. In addition, the C14—I2⋯C9ⁱⁱ/C10ⁱⁱ C—I⋯π separations [Fig. 2b; symmetry code: (ii) $[1\over2]$ − x, $[1\over2]$ − y, z] are 3.432 (9) and 3.612 (8) Å, and the corresponding bond angles are 165.6 (2) and 156.7 (2)°, respectively. Furthermore, π–π stacking [Fig. 2c; Cg1⋯Cg2ⁱⁱⁱ = 3.692 (4) Å, Cg3⋯Cg2ⁱⁱⁱ = 3.626 (4) Å; Cg1, Cg2 and Cg3 are the centroids of rings C1–C6, C7–C12 and N1/C1/C6/C7/C12/C13, respectively; symmetry code: (iii) x, −1 + y, z] and C—H⋯H—C interactions between two adjacent PHN molecules contribute to the extension of the two-dimensional network into a three-dimensional supramolecular structure (Fig. 3).

Figure 2
Crystal packing of 1. (a) The two-dimensional network structure formed by C—I⋯N, C—I⋯C and C—I⋯π halogen bonds. (b) The structural motif extracted from the two-dimensional network. (c) The π–π stacking interactions extracted from the three-dimensional structure.

Figure 3
Crystal packing of 1. (a) The two-dimensional network extends along the a- and c-axis directions, and two directions connect by C—H⋯H—C interactions. (b) The two-dimensional networks connected by π–π stacking and C—H⋯H—C interactions to form a three-dimensional structure.

The two-dimensional network of co-crystal 2 is similar to that of 1, as shown in Fig. 4a. Both of them are constructed by the same halogen-bonded synthon, i.e., C—I⋯N, C—I⋯C and C—I⋯π halogen bonds, but the bonding characteristics are slightly different. In general, the distances of the C—I⋯N, C—I⋯C and C—I⋯π interactions [I1⋯N1 = 2.901 (4), I1⋯C1 = 3.641 (5), I2⋯C13(−x, 1 − y, 1 − z) = 3.436 (5) and I2⋯C8(−x, 1 − y, 1 − z) = 3.733 (4) Å, respectively] in co-crystal 2 are all a little longer (0.004–0.121 Å) than in 1 (Fig. 4b). In addition, the two-dimensional network (Fig. 5) is extended to a three-dimensional supramolecular structure by π–π stacking (Fig. 4c and 5; Cg1⋯Cg1ⁱ = 3.562 (3) Å, Cg1⋯Cg2ⁱⁱ = 3.963 (2) Å, Cg1⋯Cg3ⁱⁱ = 3.746 (3) Å, Cg2⋯Cg2ⁱⁱ = 3.768 (2) Å; Cg1, Cg2 and Cg3 are the centroids of rings N1/C1–C5, C4–C9 and C8–C13, respectively; symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1 − x, −y, 1 − z] and C—H⋯I hydrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °) for (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯I2ⁱ	0.93	3.16	4.019 (5)	155
C6—H6⋯I1	0.93	3.31	3.945 (4)	127
Symmetry code: (i) x+1, y, z.

Figure 4
Crystal packing of 2. (a) The two-dimensional network structure formed by C—I⋯N and C—I⋯π halogen bonds. (b) The structural motif of the two-dimensional network. (c) The π–π stacking interactions in the three-dimensional structure.

Figure 5
Crystal packing of 2. The two-dimensional network extends along two directions, by C—I2⋯H7 interactions and π–π stacking in one direction, and by C—I2⋯H1 interactions and π–π stacking in the other.

4. Powder X-ray diffraction pattern

The powder X-ray diffraction (PXRD) experiments were carried out for the title co-crystals using a Bruker D8-ADVANCE X-ray diffractometer (Cu Kα, λ = 1.5418 Å) in the 2θ range of 5 to 50°. As shown in Fig. 6, the experimental patterns for 1 and 2 match well with the spectra simulated from the XRD data, which confirms the purity of 1 and 2.

Figure 6
Powder X-ray diffraction pattern of co-crystals (a) 1 and (b) 2.

5. Luminescence behavior of co-crystals 1 and 2

As shown in Fig. 7, the two co-crystals fluoresce with some vibrational fine structure (see also spectroscopic data in Table 2). The two co-crystals also show delayed fluorescence (Fig. 8). For both co-crystals, the emission bands in the region of 450–480 nm should be relative to the π–π stacking patterns. Luminescence from the excimer is possible because of the close π–π stacking distances as shown in Figs. 2–5 , besides luminescence from a monomer. Furthermore, TIE–PHN and TIE–BfQ produce weak phosphorescence. The strong XB interaction between the iodine atoms of TIE and the non-bonding orbitals of the azaphenanthrene N atoms should cause the energy of the lowest ¹(n, π*) state to drop below that of the ³(π, π*) state. It is supposed that for the singlet states the 0–0 transition of emitters in co-crystals is localized at 375 nm and 450 nm, respectively, and for triplet states the 0–0 transition is at about 600 nm. The energy gap between S₁ and T₁ is largely greater than 20 kJ mol⁻¹, so the delayed fluorescence most likely originates from the triplet–triplet annihilation process, named P-type delayed fluorescence (P-DF). Both delayed fluorescence and phosphorescence are relative to triplet states, so they should be significant for improving the exciton emission efficiency of luminescence materials (Adachi et al., 2001 ).

Table 2
Phosphorescent characteristics of co-crystals at room temperature

		TIE–PHN	TIE–BfQ
Total luminescent spectra	λ_ex/nm	300	300
	λ_em /nm	375, 484, 578	368, 438, 452, 480
	τ_average/ ns	11.49	9.29

DF and phosphorescent spectra	λ_ex/nm	330	330
	λ_em /nm	375, 489, 600	430, 489, 596, 654
	τ_average/ µs	4.36	6.45

Figure 7
Total luminescence spectra of co-crystals (a) 1 and (b) 2 (excitation at 300 nm) measured under fluorescence mode.

Figure 8
Luminescence spectra of co-crystals (a) 1 and (b) 2 (excitation at 330 nm) measured under phosphorescence mode.

For the luminescence decay, all singlet state decay lifetimes (11.49 ns for 1 and 9.29 ns for 2) are about 10 ns, while the delayed fluorescence lifetime (4.36 µs for 1 and 6.45 µs for 2) is less than the 10 µs level because of the strong heavy-atom effect leading to a faster decay of the triplet state. Additionally, the phosphorescence is too weak to measure its decay lifetime. However, the phosphorescence lifetime can be estimated to be about 20 µs based on the relationship between P-DF and the accompanying phosphorescence (Parker et al., 1962 , 1965 ).

6. Synthesis and crystallization

0.1 mmol of PHN/BfQ and 0.05 mmol of TIE were dissolved in an acetone/chloroform (2:1) mixture in a glass vial. Well–formed co-crystals 1 and 2 suitable for single-crystal X–ray diffraction (XRD) measurements were obtained by slow evaporation of the solvent at room temperature after about two weeks. Elemental analysis (%, EA) calculated for C₁₄H₉NI₂ (445.02): C 37.78, H 2.04, N 3.15. Found: C 37.54, H 2.31, N 3.26. For co-crystal 1, and C 37.85, H 2.16, N 3.04 for co-crystal 2. IR (KBr, ν, cm⁻¹) For 1: 3048(w), 1603(w), 1572(w), 1494(m), 1446(w), 1382(m), 1293(m), 1267(m), 1189(m), 1089(m), 948(m), 870(s), 832(s), 802(s), 749(s), 707(s), 615(m), 538(m), 487(m), 435(m). For 2: 3048(w), 1611(w), 1576(s), 1522(w), 1486(w), 1458(m), 1440(m), 1238(m), 1132(m), 1032(m), 953(m), 924(m), 889(s), 745(s), 714(s), 610(m), 552(m), 448(m), 423(m).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms attached to C atoms were positioned geometrically and refined as riding on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

	1	2
Crystal data
Chemical formula	0.5C₂I₄·C₁₃H₉N	0.5C₂I₄·C₁₃H₉N
M_r	445.02	445.02
Crystal system, space group	Monoclinic, C2/c	Triclinic, P $[\overline{1}]$
Temperature (K)	296	296
a, b, c (Å)	24.2920 (18), 4.8348 (4), 24.8761 (16)	7.3179 (4), 8.1089 (5), 11.3252 (7)
α, β, γ (°)	90, 116.272 (2), 90	97.050 (2), 92.059 (2), 95.579 (2)
V (Å³)	2619.8 (3)	663.02 (7)
Z	8	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	4.78	4.72
Crystal size (mm)	0.30 × 0.25 × 0.25	0.35 × 0.32 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )	Multi-scan (SADABS; Bruker, 2012)
T_min, T_max	0.489, 0.745	0.638, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	12094, 2635, 1782	8567, 2701, 2099
R_int	0.045	0.026
(sin θ/λ)_max (Å⁻¹)	0.624	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.078, 1.03	0.028, 0.058, 1.08
No. of reflections	2635	2701
No. of parameters	154	154
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.08, −0.62	0.80, −0.74
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), (Sheldrick, 2008), DIAMOND (Brandenburg, 2005 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1899078; 1899077

Crystal structure: contains datablocks 1, 2. DOI: https://doi.org/10.1107/S2056989020002182/vm2225sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989020002182/vm22251sup4.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989020002182/vm22252sup5.hkl

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015). Molecular graphics: SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2005) for (1); SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2005), for (2). For both structures, software used to prepare material for publication: publCIF (Westrip, 2010).

Tetraiodoethylene–phenanthridine (1/2) (1) top

Crystal data top

0.5C₂I₄·C₁₃H₉N	F(000) = 1648
M_r = 445.02	D_x = 2.257 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.2920 (18) Å	Cell parameters from 5311 reflections
b = 4.8348 (4) Å	θ = 3.1–26.3°
c = 24.8761 (16) Å	µ = 4.78 mm⁻¹
β = 116.272 (2)°	T = 296 K
V = 2619.8 (3) Å³	Block, yellow
Z = 8	0.30 × 0.25 × 0.25 mm

Data collection top

Bruker APEXII CCD diffractometer	1782 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.045
φ and ω scans	θ_max = 26.3°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −30→29
T_min = 0.489, T_max = 0.745	k = −6→6
12094 measured reflections	l = −31→30
2635 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0187P)² + 28.9715P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2635 reflections	Δρ_max = 1.08 e Å⁻³
154 parameters	Δρ_min = −0.61 e Å⁻³

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

	x	y	z	U_iso*/U_eq
I1	0.70990 (2)	0.95088 (10)	0.57060 (2)	0.04011 (16)
I2	0.85225 (2)	0.96131 (11)	0.56611 (2)	0.04316 (16)
N1	0.6417 (3)	0.1927 (12)	0.6276 (2)	0.0377 (14)
C1	0.6440 (3)	0.1453 (14)	0.6836 (3)	0.0339 (16)
C2	0.6849 (3)	−0.0548 (15)	0.7193 (3)	0.0442 (18)
H2	0.708323	−0.152775	0.704671	0.053*
C3	0.6910 (4)	−0.1093 (16)	0.7755 (3)	0.053 (2)
H3	0.719345	−0.239978	0.799494	0.064*
C4	0.6547 (4)	0.0319 (17)	0.7965 (3)	0.054 (2)
H4	0.658318	−0.006933	0.834537	0.065*
C5	0.6141 (3)	0.2253 (16)	0.7623 (3)	0.0452 (19)
H5	0.590382	0.318582	0.777344	0.054*
C6	0.6070 (3)	0.2880 (14)	0.7044 (3)	0.0328 (16)
C7	0.5640 (3)	0.4901 (13)	0.6650 (3)	0.0342 (16)
C8	0.5240 (3)	0.6464 (16)	0.6801 (3)	0.0475 (19)
H8	0.524161	0.622630	0.717264	0.057*
C9	0.4853 (3)	0.8313 (17)	0.6406 (4)	0.054 (2)
H9	0.459174	0.933001	0.651309	0.065*
C10	0.4834 (3)	0.8741 (16)	0.5846 (4)	0.051 (2)
H10	0.456128	1.001451	0.558148	0.061*
C11	0.5219 (3)	0.7271 (15)	0.5691 (3)	0.0455 (19)
H11	0.521208	0.755053	0.531834	0.055*
C12	0.5627 (3)	0.5329 (14)	0.6091 (3)	0.0345 (16)
C13	0.6035 (3)	0.3779 (15)	0.5941 (3)	0.0405 (18)
H13	0.602707	0.412409	0.557015	0.049*
C14	0.7603 (3)	0.8233 (15)	0.5244 (3)	0.0411 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0411 (3)	0.0521 (3)	0.0327 (3)	0.0057 (2)	0.0213 (2)	−0.0022 (2)
I2	0.0332 (3)	0.0582 (3)	0.0364 (3)	−0.0048 (2)	0.0139 (2)	−0.0059 (2)
N1	0.034 (3)	0.046 (4)	0.037 (3)	0.000 (3)	0.019 (3)	−0.004 (3)
C1	0.034 (4)	0.036 (4)	0.033 (4)	−0.005 (3)	0.016 (3)	−0.005 (3)
C2	0.042 (4)	0.043 (4)	0.046 (4)	0.001 (4)	0.018 (4)	0.001 (4)
C3	0.060 (5)	0.049 (5)	0.041 (5)	0.000 (4)	0.013 (4)	0.011 (4)
C4	0.067 (6)	0.066 (6)	0.027 (4)	−0.015 (5)	0.019 (4)	−0.001 (4)
C5	0.048 (5)	0.053 (5)	0.041 (4)	−0.010 (4)	0.026 (4)	−0.008 (4)
C6	0.031 (4)	0.038 (4)	0.030 (4)	−0.008 (3)	0.014 (3)	−0.007 (3)
C7	0.032 (4)	0.034 (4)	0.041 (4)	−0.006 (3)	0.020 (3)	−0.008 (3)
C8	0.045 (5)	0.053 (5)	0.049 (5)	−0.002 (4)	0.026 (4)	−0.005 (4)
C9	0.031 (5)	0.051 (5)	0.081 (6)	−0.003 (4)	0.025 (4)	−0.015 (5)
C10	0.038 (5)	0.040 (5)	0.070 (6)	0.006 (4)	0.019 (4)	0.005 (4)
C11	0.042 (5)	0.049 (5)	0.039 (4)	−0.012 (4)	0.012 (4)	−0.003 (4)
C12	0.030 (4)	0.036 (4)	0.033 (4)	−0.003 (3)	0.010 (3)	−0.001 (3)
C13	0.046 (5)	0.052 (5)	0.030 (4)	−0.005 (4)	0.023 (4)	−0.002 (4)
C14	0.045 (5)	0.044 (5)	0.043 (4)	0.007 (4)	0.028 (4)	0.003 (3)

Geometric parameters (Å, º) top

I1—C14	2.108 (6)	C6—C7	1.449 (9)
I2—C14	2.111 (7)	C7—C12	1.394 (9)
N1—C13	1.293 (8)	C7—C8	1.406 (9)
N1—C1	1.390 (8)	C8—C9	1.353 (10)
C1—C2	1.389 (9)	C8—H8	0.9300
C1—C6	1.400 (9)	C9—C10	1.387 (11)
C2—C3	1.364 (10)	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.360 (10)
C3—C4	1.389 (11)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.408 (9)
C4—C5	1.352 (10)	C11—H11	0.9300
C4—H4	0.9300	C12—C13	1.416 (9)
C5—C6	1.406 (9)	C13—H13	0.9300
C5—H5	0.9300	C14—C14ⁱ	1.301 (13)

C13—N1—C1	117.3 (6)	C9—C8—C7	120.1 (7)
N1—C1—C2	117.1 (6)	C9—C8—H8	120.0
N1—C1—C6	122.8 (6)	C7—C8—H8	120.0
C2—C1—C6	120.1 (6)	C8—C9—C10	122.1 (7)
C3—C2—C1	120.8 (7)	C8—C9—H9	119.0
C3—C2—H2	119.6	C10—C9—H9	119.0
C1—C2—H2	119.6	C11—C10—C9	119.0 (7)
C2—C3—C4	119.4 (7)	C11—C10—H10	120.5
C2—C3—H3	120.3	C9—C10—H10	120.5
C4—C3—H3	120.3	C10—C11—C12	120.4 (7)
C5—C4—C3	120.8 (7)	C10—C11—H11	119.8
C5—C4—H4	119.6	C12—C11—H11	119.8
C3—C4—H4	119.6	C7—C12—C11	120.1 (6)
C4—C5—C6	121.2 (7)	C7—C12—C13	118.4 (6)
C4—C5—H5	119.4	C11—C12—C13	121.6 (6)
C6—C5—H5	119.4	N1—C13—C12	125.7 (6)
C1—C6—C5	117.7 (6)	N1—C13—H13	117.1
C1—C6—C7	118.1 (6)	C12—C13—H13	117.1
C5—C6—C7	124.2 (6)	C14ⁱ—C14—I2	121.2 (7)
C12—C7—C8	118.3 (7)	C14ⁱ—C14—I1	126.2 (7)
C12—C7—C6	117.7 (6)	I2—C14—I1	112.5 (3)
C8—C7—C6	124.0 (6)

C13—N1—C1—C2	179.7 (6)	C5—C6—C7—C8	−0.3 (11)
C13—N1—C1—C6	0.2 (10)	C12—C7—C8—C9	0.5 (11)
N1—C1—C2—C3	178.4 (7)	C6—C7—C8—C9	179.9 (7)
C6—C1—C2—C3	−2.1 (11)	C7—C8—C9—C10	0.0 (12)
C1—C2—C3—C4	1.8 (12)	C8—C9—C10—C11	−0.5 (12)
C2—C3—C4—C5	−1.0 (12)	C9—C10—C11—C12	0.5 (11)
C3—C4—C5—C6	0.5 (12)	C8—C7—C12—C11	−0.5 (10)
N1—C1—C6—C5	−179.0 (6)	C6—C7—C12—C11	−179.9 (6)
C2—C1—C6—C5	1.5 (10)	C8—C7—C12—C13	179.3 (6)
N1—C1—C6—C7	1.0 (10)	C6—C7—C12—C13	−0.2 (10)
C2—C1—C6—C7	−178.5 (6)	C10—C11—C12—C7	0.0 (10)
C4—C5—C6—C1	−0.7 (10)	C10—C11—C12—C13	−179.7 (7)
C4—C5—C6—C7	179.3 (7)	C1—N1—C13—C12	−1.4 (10)
C1—C6—C7—C12	−0.9 (9)	C7—C12—C13—N1	1.5 (11)
C5—C6—C7—C12	179.1 (7)	C11—C12—C13—N1	−178.8 (7)
C1—C6—C7—C8	179.7 (6)

Symmetry code: (i) −x+3/2, −y+3/2, −z+1.

Tetraiodoethylene–benzo[f]quinoline (1/2) (2) top

Crystal data top

0.5C₂I₄·C₁₃H₉N	Z = 2
M_r = 445.02	F(000) = 412
Triclinic, P1	D_x = 2.229 Mg m⁻³
a = 7.3179 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1089 (5) Å	Cell parameters from 4699 reflections
c = 11.3252 (7) Å	θ = 2.8–26.4°
α = 97.050 (2)°	µ = 4.72 mm⁻¹
β = 92.059 (2)°	T = 296 K
γ = 95.579 (2)°	Block, yellow
V = 663.02 (7) Å³	0.35 × 0.32 × 0.30 mm

Data collection top

Bruker APEXII CCD diffractometer	2099 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.026
φ and ω scans	θ_max = 26.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −9→9
T_min = 0.638, T_max = 0.745	k = −10→10
8567 measured reflections	l = −14→14
2701 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.0189P)² + 0.7413P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2701 reflections	Δρ_max = 0.80 e Å⁻³
154 parameters	Δρ_min = −0.74 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.20988 (4)	0.45307 (3)	0.82595 (2)	0.04767 (10)
I2	−0.08934 (4)	0.75374 (3)	0.91391 (3)	0.05167 (11)
N1	0.4565 (5)	0.3596 (5)	0.6400 (3)	0.0518 (9)
C1	0.6267 (7)	0.4270 (6)	0.6615 (4)	0.0597 (13)
H1	0.655445	0.495377	0.733212	0.072*
C2	0.7655 (7)	0.4022 (6)	0.5841 (5)	0.0613 (13)
H2	0.883874	0.453358	0.603495	0.074*
C3	0.7274 (6)	0.3026 (6)	0.4794 (5)	0.0541 (12)
H3	0.819507	0.286190	0.425958	0.065*
C4	0.5492 (5)	0.2240 (5)	0.4514 (4)	0.0399 (10)
C5	0.4171 (5)	0.2587 (5)	0.5350 (4)	0.0389 (9)
C6	0.2327 (6)	0.1869 (5)	0.5119 (4)	0.0470 (11)
H6	0.144788	0.211154	0.566982	0.056*
C7	0.1844 (6)	0.0845 (5)	0.4114 (4)	0.0471 (11)
H7	0.062732	0.038787	0.398340	0.057*
C8	0.3128 (6)	0.0431 (5)	0.3238 (4)	0.0424 (10)
C9	0.4960 (6)	0.1144 (5)	0.3424 (4)	0.0418 (10)
C10	0.6199 (7)	0.0731 (6)	0.2544 (4)	0.0561 (12)
H10	0.741510	0.119847	0.264207	0.067*
C11	0.5643 (9)	−0.0348 (7)	0.1546 (5)	0.0730 (16)
H11	0.648615	−0.060734	0.097457	0.088*
C12	0.3842 (9)	−0.1063 (7)	0.1373 (4)	0.0716 (16)
H12	0.347907	−0.180218	0.069304	0.086*
C13	0.2612 (7)	−0.0676 (6)	0.2203 (4)	0.0555 (12)
H13	0.140145	−0.115380	0.208420	0.067*
C14	0.0238 (6)	0.5360 (5)	0.9536 (4)	0.0449 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0579 (2)	0.04585 (18)	0.04064 (16)	0.01385 (14)	0.01030 (14)	0.00193 (12)
I2	0.0700 (2)	0.04158 (18)	0.04756 (18)	0.02041 (15)	0.00980 (15)	0.00849 (13)
N1	0.058 (3)	0.051 (2)	0.049 (2)	0.0117 (19)	0.003 (2)	0.0083 (18)
C1	0.068 (3)	0.052 (3)	0.058 (3)	0.007 (3)	−0.016 (3)	0.006 (2)
C2	0.042 (3)	0.067 (3)	0.076 (4)	−0.002 (2)	−0.010 (3)	0.024 (3)
C3	0.039 (3)	0.055 (3)	0.073 (3)	0.006 (2)	0.013 (2)	0.026 (3)
C4	0.036 (2)	0.041 (2)	0.049 (2)	0.0109 (18)	0.008 (2)	0.0221 (19)
C5	0.041 (2)	0.036 (2)	0.043 (2)	0.0108 (18)	0.0065 (19)	0.0135 (18)
C6	0.042 (2)	0.054 (3)	0.048 (3)	0.008 (2)	0.015 (2)	0.009 (2)
C7	0.036 (2)	0.051 (3)	0.056 (3)	0.003 (2)	0.006 (2)	0.016 (2)
C8	0.051 (3)	0.036 (2)	0.044 (2)	0.0087 (19)	0.006 (2)	0.0144 (18)
C9	0.046 (2)	0.042 (2)	0.044 (2)	0.0161 (19)	0.014 (2)	0.0199 (19)
C10	0.059 (3)	0.066 (3)	0.052 (3)	0.023 (2)	0.021 (2)	0.022 (2)
C11	0.099 (5)	0.080 (4)	0.051 (3)	0.043 (4)	0.031 (3)	0.018 (3)
C12	0.115 (5)	0.059 (3)	0.044 (3)	0.025 (3)	0.007 (3)	0.004 (2)
C13	0.072 (3)	0.047 (3)	0.049 (3)	0.009 (2)	−0.003 (3)	0.010 (2)
C14	0.054 (3)	0.039 (2)	0.041 (2)	0.011 (2)	0.002 (2)	−0.0017 (18)

Geometric parameters (Å, º) top

I1—C14	2.116 (4)	C6—H6	0.9300
I2—C14	2.111 (4)	C7—C8	1.423 (6)
N1—C1	1.313 (6)	C7—H7	0.9300
N1—C5	1.363 (5)	C8—C13	1.402 (6)
C1—C2	1.379 (7)	C8—C9	1.405 (6)
C1—H1	0.9300	C9—C10	1.403 (6)
C2—C3	1.354 (7)	C10—C11	1.365 (7)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.402 (6)	C11—C12	1.384 (8)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.401 (5)	C12—C13	1.355 (7)
C4—C9	1.448 (6)	C12—H12	0.9300
C5—C6	1.418 (6)	C13—H13	0.9300
C6—C7	1.339 (6)	C14—C14ⁱ	1.305 (8)

C1—N1—C5	117.4 (4)	C13—C8—C9	119.4 (4)
N1—C1—C2	123.8 (5)	C13—C8—C7	121.7 (4)
N1—C1—H1	118.1	C9—C8—C7	118.9 (4)
C2—C1—H1	118.1	C10—C9—C8	118.0 (4)
C3—C2—C1	119.2 (4)	C10—C9—C4	123.0 (4)
C3—C2—H2	120.4	C8—C9—C4	119.0 (4)
C1—C2—H2	120.4	C11—C10—C9	120.9 (5)
C2—C3—C4	120.1 (4)	C11—C10—H10	119.6
C2—C3—H3	120.0	C9—C10—H10	119.6
C4—C3—H3	120.0	C10—C11—C12	121.0 (5)
C3—C4—C5	116.5 (4)	C10—C11—H11	119.5
C3—C4—C9	124.0 (4)	C12—C11—H11	119.5
C5—C4—C9	119.5 (4)	C13—C12—C11	119.5 (5)
N1—C5—C4	123.0 (4)	C13—C12—H12	120.3
N1—C5—C6	117.1 (4)	C11—C12—H12	120.3
C4—C5—C6	119.9 (4)	C12—C13—C8	121.3 (5)
C7—C6—C5	120.4 (4)	C12—C13—H13	119.4
C7—C6—H6	119.8	C8—C13—H13	119.4
C5—C6—H6	119.8	C14ⁱ—C14—I2	121.4 (4)
C6—C7—C8	122.3 (4)	C14ⁱ—C14—I1	126.2 (4)
C6—C7—H7	118.9	I2—C14—I1	112.33 (18)
C8—C7—H7	118.9

C5—N1—C1—C2	0.5 (7)	C13—C8—C9—C10	1.1 (6)
N1—C1—C2—C3	−0.3 (8)	C7—C8—C9—C10	−179.4 (4)
C1—C2—C3—C4	−0.9 (7)	C13—C8—C9—C4	−177.9 (4)
C2—C3—C4—C5	1.7 (6)	C7—C8—C9—C4	1.6 (6)
C2—C3—C4—C9	−179.4 (4)	C3—C4—C9—C10	1.3 (6)
C1—N1—C5—C4	0.5 (6)	C5—C4—C9—C10	−179.8 (4)
C1—N1—C5—C6	−179.7 (4)	C3—C4—C9—C8	−179.7 (4)
C3—C4—C5—N1	−1.6 (6)	C5—C4—C9—C8	−0.9 (6)
C9—C4—C5—N1	179.5 (4)	C8—C9—C10—C11	−0.9 (6)
C3—C4—C5—C6	178.6 (4)	C4—C9—C10—C11	178.1 (4)
C9—C4—C5—C6	−0.3 (6)	C9—C10—C11—C12	0.1 (8)
N1—C5—C6—C7	−179.0 (4)	C10—C11—C12—C13	0.4 (8)
C4—C5—C6—C7	0.8 (6)	C11—C12—C13—C8	−0.2 (7)
C5—C6—C7—C8	−0.1 (7)	C9—C8—C13—C12	−0.5 (6)
C6—C7—C8—C13	178.4 (4)	C7—C8—C13—C12	180.0 (4)
C6—C7—C8—C9	−1.1 (6)

Symmetry code: (i) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···I2ⁱⁱ	0.93	3.16	4.019 (5)	155
C6—H6···I1	0.93	3.31	3.945 (4)	127

Symmetry code: (ii) x+1, y, z.

Phosphorescent characteristics of co-crystals at room temperature top

		TIE–PHN	TIE–BfQ
Total luminescent spectra	λ_ex/nm	300	300
	λ_em /nm	375, 484, 578	368, 452, 480
	τ_average/ ns	11.49	9.29

DF and phosphorescent spectra	λ_ex/nm	330	330
	λ_em /nm	375, 489, 600	430, 489, 596
	τ_average/ µs	4.36	6.45

Funding information

The authors are grateful for support by the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi Province (grant No. 2019L0895) and the Undergraduate Innovation and Entrepreneurship Project of Changzhi University (award No. zz201814).

References

Adachi, C., Baldo, M. A., Thompson, M. E. & Forrest, S. R. (2001). J. Appl. Phys. 90, 5048–5051. Web of Science CrossRef CAS Google Scholar
Agostino, S. d', Grepioni, F., Braga, D. & Ventura, B. (2015). Cryst. Growth Des. 15, 2039–2045. Google Scholar
Baldo, M. A., O'Brien, D. F., Thompson, M. E. & Forrest, S. R. (1999). Phys. Rev. B, 60, 14422–14428. Web of Science CrossRef CAS Google Scholar
Bolton, O., Lee, K., Kim, H. J., Lin, K. Y. & Kim, J. (2011). Nat. Chem. 3, 205–210. CSD CrossRef CAS PubMed Google Scholar
Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brown, A. R., Pichler, K., Greenham, N. C., Bradley, D. D. C., Friend, R. H. & Holmes, A. B. (1993). Chem. Phys. Lett. 210, 61–66. CrossRef CAS Web of Science Google Scholar
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cavallo, G., Metrangolo, P., Milani, R., Pilati, T., Priimagi, A., Resnati, G. & Terraneo, G. (2016). Chem. Rev. 116, 2478–2601. Web of Science CrossRef CAS PubMed Google Scholar
Desiraju, G. R., Ho, P. S., Kloo, L., Legon, A. C., Marquardt, R., Metrangolo, P., Politzer, P., Resnati, G. & Rissanen, K. (2013). Pure Appl. Chem. 85, 1711–1713. Web of Science CrossRef CAS Google Scholar
Gao, H. Y., Shen, Q. J., Zhao, X. R., Yan, X. Q., Pang, X. & Jin, W. J. (2012). J. Mater. Chem. 22, 5336–5343. Web of Science CSD CrossRef CAS Google Scholar
Gao, Y. J., Li, C., Liu, R. & Jin, W. J. (2017). Spectrochim. Acta A, 173, 792–799. Web of Science CSD CrossRef CAS Google Scholar
Gilday, L. C., Robinson, S. W., Barendt, T. A., Langton, M. J., Mullaney, B. R. & Beer, P. D. (2015). Chem. Rev. 115, 7118–7195. Web of Science CrossRef CAS PubMed Google Scholar
Liu, R., Gao, Y. J. & Jin, W. J. (2017a). Acta Cryst. B73, 247–254. CSD CrossRef IUCr Journals Google Scholar
Liu, R., Wang, H. & Jin, W. J. (2017b). Cryst. Growth Des. 17, 3331–3337. CSD CrossRef CAS Google Scholar
Metrangolo, P., Neukirch, H., Pilati, T. & Resnati, G. (2005). Acc. Chem. Res. 38, 386–395. Web of Science CrossRef PubMed CAS Google Scholar
Parker, C. A. & Hatchard, C. G. (1962). Proc. Roy. Soc. A, 269, 574–584. Google Scholar
Parker, C. A., Hatchard, C. G. & Joyce, T. A. (1965). Nature, 205, 1282–1284. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Ventura, B., Bertocco, A., Braga, D., Catalano, L., d'Agostino, S., Grepioni, F. & Taddei, P. (2014). J. Phys. Chem. C, 118, 18646–18658. Web of Science CrossRef CAS Google Scholar
Wang, H., Hu, R. X., Pang, X., Gao, H. Y. & Jin, W. J. (2014). CrystEngComm, 16, 7942–7948. Web of Science CSD CrossRef CAS Google Scholar
Wang, H. & Jin, W. J. (2017). Acta Cryst. B73, 210–216. CSD CrossRef IUCr Journals Google Scholar
Wang, H., Wang, W. & Jin, W. J. (2016). Chem. Rev. 116, 5072–5104. Web of Science CrossRef CAS PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 76| Part 3| March 2020| Pages 438-442

https://doi.org/10.1107/S2056989020002182

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Structural and luminescent properties of co-crystals of tetra­iodo­ethyl­ene with two aza­phenanthrenes

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Powder X-ray diffraction pattern

5. Luminescence behavior of co-crystals 1 and 2

6. Synthesis and crystallization

7. Refinement

Supporting information

Funding information

References

research communications

Structural and luminescent properties of co-crystals of tetraiodoethylene with two azaphenanthrenes

3. Supramolecular features