Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035398/rn2022sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035398/rn2022Isup2.hkl |
CCDC reference: 657845
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.002 Å
- R factor = 0.045
- wR factor = 0.126
- Data-to-parameter ratio = 15.2
checkCIF/PLATON results
No syntax errors found
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.112 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.11 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.12 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Phenyl terpyridine was prepared according to the method described in the literature (Constable et al., 1992). Then oxygenation of the phenyl terpyridine was carried out by the following way: the 3-chloroperbenzoic acid (1.7257 g, 10 mmol, 60% pure) was added to a mixture of 4'-phenyl-2':6',2"- terpyridine (1.0315 g, 3 mmol) and CH2Cl2 (50 ml). After stirring overnight, the mixture was washed with 10% Na2CO3 solution (twice with 30 ml) and water (30 ml), dried (MgSO4) and evaporated yielding phenylterpyridine dioxide as a white compound (Thummel & Jahng, 1985). The phenylterpyridine dioxide powder was dissolved in boiling absolute ethanol, concentrated and left for crystallization. Colorless crystals were obtained after one week.
The H atoms were geometrically placed (C—H = 0.95 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier). The mosaicity of the crystal was high and it did not diffract well so the Rint is high.
The title molecule lies on a crystallographic twofold axis which passes through N(2), C(8), C(9) and C(12) atoms (see Fig. 1). The compound contains weak intermolecular C—H···O hydrogen bonds which are gaining more attention in the field of crystal engineering and their significance has been reported for numerous crystal structures (Green, 1974; Taylor & Kennard, 1982; Desiraju, 1996; Steiner, 1997; McKay et al., 2004).
The aryl H atoms participate in C—H···O hydrogen bonds because of the electronic influence of the corresponding sp2 Caryl atom. The crystal structure of the compound was analysed to understand the hydrogen-bond preferences of C—H···O—N interactions. Terpyridine compounds are well represented in the Cambridge Structural Database (Allen, 2002), due to their excellent chelating and favorable hydrogen-bond-acceptor ability. Introduction of two N-oxide functionalities to the phenylterpyridine framework, provides an opportunity to explore the interdependency of two strong acceptors and molecular alignment.
The compound adopts a conformation that results from the twist about each pyridine–pyridine bond [N1—C5—C6—N2 = 128.91 (12)°]. This conformation is less skewed than that in the terpyridine trioxide [76.8 (2)°] (McKay et al., 2004), presumably due to a more sterically favorable environment of the central pyridine fragment. Other selected geometric parameters are given in Table 1.
The supramolecular motifs observed in the structure of (I) are influenced by the construction of non-bonded contacts (Table 2) as the edges of the compound (I) are constituted exclusively with O atoms and C—H groups and it is to be expected that weak C—H···O hydrogen bonds will be present in the crystal structure (Steiner, 1997; Desiraju & Steiner, 1999). In the compound, C2 and C10 form these hydrogen bonds with O1 and C—H···.O1—N1 contacts link neighboring terpyridine molecules (see Fig. 2).
For general background, see: Green (1974); Desiraju (1996); McKay et al. (2004); Steiner (1997); Taylor & Kennard (1982). For related structures, see: Constable et al. (1992); Thummel & Jahng (1985). For structure analysis tools used, see: Farrugia (1997, 1999); Nonius (1997, 2000); Otwinowski & Minor (1997); Sheldrick (1990, 1997).
For related literature, see: Allen (2002).
Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C21H15N3O2 | F(000) = 712 |
Mr = 341.36 | Dx = 1.402 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1843 reflections |
a = 19.1173 (8) Å | θ = 2.9–27.5° |
b = 10.9251 (5) Å | µ = 0.09 mm−1 |
c = 7.7581 (3) Å | T = 120 K |
β = 93.416 (2)° | Block, colorless |
V = 1617.47 (12) Å3 | 0.10 × 0.08 × 0.05 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 1843 independent reflections |
Radiation source: fine-focus sealed tube | 1329 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.112 |
ω and φ scans | θmax = 27.5°, θmin = 3.4° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −24→24 |
Tmin = 0.991, Tmax = 0.995 | k = −14→13 |
7527 measured reflections | l = −10→10 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0586P)2 + 0.3346P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
1843 reflections | Δρmax = 0.26 e Å−3 |
121 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0051 (11) |
C21H15N3O2 | V = 1617.47 (12) Å3 |
Mr = 341.36 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.1173 (8) Å | µ = 0.09 mm−1 |
b = 10.9251 (5) Å | T = 120 K |
c = 7.7581 (3) Å | 0.10 × 0.08 × 0.05 mm |
β = 93.416 (2)° |
Nonius KappaCCD diffractometer | 1843 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1329 reflections with I > 2σ(I) |
Tmin = 0.991, Tmax = 0.995 | Rint = 0.112 |
7527 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.26 e Å−3 |
1843 reflections | Δρmin = −0.28 e Å−3 |
121 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 | ||
O1 | 0.18038 (6) | 0.62710 (9) | 0.09623 (13) | 0.0263 (3) | |
N1 | 0.18001 (6) | 0.71228 (11) | 0.21502 (15) | 0.0208 (3) | |
N2 | 0.0000 | 0.71614 (14) | 0.2500 | 0.0185 (4) | |
C1 | 0.23682 (8) | 0.78705 (14) | 0.2399 (2) | 0.0256 (4) | |
H1 | 0.2760 | 0.7756 | 0.1718 | 0.031* | |
C2 | 0.23843 (8) | 0.87827 (14) | 0.3610 (2) | 0.0288 (4) | |
H2 | 0.2784 | 0.9297 | 0.3761 | 0.035* | |
C3 | 0.18193 (9) | 0.89553 (13) | 0.4611 (2) | 0.0285 (4) | |
H3 | 0.1830 | 0.9568 | 0.5481 | 0.034* | |
C4 | 0.12369 (8) | 0.82145 (13) | 0.43189 (19) | 0.0240 (4) | |
H4 | 0.0838 | 0.8338 | 0.4972 | 0.029* | |
C5 | 0.12276 (7) | 0.72989 (13) | 0.30924 (18) | 0.0193 (4) | |
C6 | 0.05943 (7) | 0.65209 (13) | 0.27456 (16) | 0.0185 (3) | |
C7 | 0.06210 (7) | 0.52497 (12) | 0.27623 (17) | 0.0187 (3) | |
H7 | 0.1057 | 0.4838 | 0.2950 | 0.022* | |
C8 | 0.0000 | 0.45848 (18) | 0.2500 | 0.0179 (4) | |
C9 | 0.0000 | 0.32240 (18) | 0.2500 | 0.0193 (5) | |
C10 | −0.05106 (8) | 0.25744 (13) | 0.15219 (18) | 0.0223 (4) | |
H10 | −0.0866 | 0.3003 | 0.0860 | 0.027* | |
C11 | −0.05025 (8) | 0.13022 (13) | 0.15108 (19) | 0.0259 (4) | |
H11 | −0.0846 | 0.0869 | 0.0816 | 0.031* | |
C12 | 0.0000 | 0.0657 (2) | 0.2500 | 0.0282 (5) | |
H12 | 0.0000 | −0.0213 | 0.2500 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0277 (7) | 0.0246 (6) | 0.0269 (6) | 0.0017 (4) | 0.0051 (4) | −0.0043 (4) |
N1 | 0.0209 (7) | 0.0194 (7) | 0.0219 (6) | 0.0004 (5) | −0.0004 (5) | 0.0039 (5) |
N2 | 0.0182 (9) | 0.0199 (9) | 0.0171 (8) | 0.000 | 0.0001 (7) | 0.000 |
C1 | 0.0195 (8) | 0.0278 (9) | 0.0294 (8) | −0.0031 (6) | −0.0003 (6) | 0.0076 (7) |
C2 | 0.0252 (9) | 0.0247 (8) | 0.0353 (9) | −0.0066 (6) | −0.0084 (7) | 0.0082 (7) |
C3 | 0.0318 (10) | 0.0197 (8) | 0.0329 (8) | −0.0008 (6) | −0.0080 (7) | −0.0013 (7) |
C4 | 0.0240 (8) | 0.0220 (8) | 0.0258 (8) | 0.0024 (6) | −0.0014 (6) | −0.0005 (6) |
C5 | 0.0185 (8) | 0.0177 (7) | 0.0213 (7) | 0.0011 (6) | −0.0013 (6) | 0.0043 (6) |
C6 | 0.0203 (8) | 0.0186 (7) | 0.0168 (7) | 0.0001 (6) | 0.0020 (5) | 0.0001 (6) |
C7 | 0.0178 (8) | 0.0192 (7) | 0.0191 (7) | 0.0024 (5) | 0.0011 (5) | 0.0011 (5) |
C8 | 0.0208 (11) | 0.0182 (10) | 0.0148 (9) | 0.000 | 0.0023 (7) | 0.000 |
C9 | 0.0237 (11) | 0.0163 (10) | 0.0184 (9) | 0.000 | 0.0055 (8) | 0.000 |
C10 | 0.0252 (9) | 0.0205 (8) | 0.0214 (8) | 0.0009 (6) | 0.0024 (6) | 0.0005 (6) |
C11 | 0.0309 (9) | 0.0217 (8) | 0.0254 (8) | −0.0058 (6) | 0.0029 (6) | −0.0035 (6) |
C12 | 0.0372 (14) | 0.0170 (10) | 0.0312 (11) | 0.000 | 0.0097 (10) | 0.000 |
O1—N1 | 1.3100 (15) | C6—C7 | 1.3897 (19) |
N1—C1 | 1.3634 (19) | C7—C8 | 1.3963 (17) |
N1—C5 | 1.3655 (19) | C7—H7 | 0.9500 |
N2—C6 | 1.3383 (16) | C8—C7i | 1.3963 (17) |
N2—C6i | 1.3384 (16) | C8—C9 | 1.487 (3) |
C1—C2 | 1.369 (2) | C9—C10 | 1.3943 (18) |
C1—H1 | 0.9500 | C9—C10i | 1.3943 (18) |
C2—C3 | 1.381 (2) | C10—C11 | 1.390 (2) |
C2—H2 | 0.9500 | C10—H10 | 0.9500 |
C3—C4 | 1.384 (2) | C11—C12 | 1.3861 (19) |
C3—H3 | 0.9500 | C11—H11 | 0.9500 |
C4—C5 | 1.380 (2) | C12—C11i | 1.3861 (19) |
C4—H4 | 0.9500 | C12—H12 | 0.9500 |
C5—C6 | 1.4905 (19) | ||
O1—N1—C1 | 119.17 (13) | N2—C6—C5 | 113.65 (12) |
O1—N1—C5 | 120.98 (12) | C7—C6—C5 | 122.63 (12) |
C1—N1—C5 | 119.81 (13) | C6—C7—C8 | 119.22 (13) |
C6—N2—C6i | 116.95 (16) | C6—C7—H7 | 120.4 |
N1—C1—C2 | 121.22 (15) | C8—C7—H7 | 120.4 |
N1—C1—H1 | 119.4 | C7—C8—C7i | 117.30 (18) |
C2—C1—H1 | 119.4 | C7—C8—C9 | 121.35 (9) |
C1—C2—C3 | 119.97 (14) | C7i—C8—C9 | 121.35 (9) |
C1—C2—H2 | 120.0 | C10—C9—C10i | 118.81 (19) |
C3—C2—H2 | 120.0 | C10—C9—C8 | 120.60 (9) |
C2—C3—C4 | 118.46 (14) | C10i—C9—C8 | 120.60 (9) |
C2—C3—H3 | 120.8 | C11—C10—C9 | 120.31 (14) |
C4—C3—H3 | 120.8 | C11—C10—H10 | 119.8 |
C5—C4—C3 | 120.94 (15) | C9—C10—H10 | 119.8 |
C5—C4—H4 | 119.5 | C12—C11—C10 | 120.85 (14) |
C3—C4—H4 | 119.5 | C12—C11—H11 | 119.6 |
N1—C5—C4 | 119.57 (14) | C10—C11—H11 | 119.6 |
N1—C5—C6 | 119.43 (13) | C11i—C12—C11 | 118.85 (19) |
C4—C5—C6 | 120.98 (13) | C11i—C12—H12 | 120.6 |
N2—C6—C7 | 123.65 (13) | C11—C12—H12 | 120.6 |
O1—N1—C1—C2 | 179.18 (12) | N1—C5—C6—C7 | 54.03 (18) |
C5—N1—C1—C2 | 1.6 (2) | C4—C5—C6—C7 | −127.69 (15) |
N1—C1—C2—C3 | 0.3 (2) | N2—C6—C7—C8 | 0.43 (19) |
C1—C2—C3—C4 | −2.0 (2) | C5—C6—C7—C8 | 177.19 (10) |
C2—C3—C4—C5 | 2.0 (2) | C6—C7—C8—C7i | −0.20 (9) |
O1—N1—C5—C4 | −179.16 (12) | C6—C7—C8—C9 | 179.80 (9) |
C1—N1—C5—C4 | −1.6 (2) | C7—C8—C9—C10 | −150.68 (9) |
O1—N1—C5—C6 | −0.85 (19) | C7i—C8—C9—C10 | 29.32 (9) |
C1—N1—C5—C6 | 176.70 (12) | C7—C8—C9—C10i | 29.32 (9) |
C3—C4—C5—N1 | −0.2 (2) | C7i—C8—C9—C10i | −150.68 (9) |
C3—C4—C5—C6 | −178.46 (13) | C10i—C9—C10—C11 | −0.80 (10) |
C6i—N2—C6—C7 | −0.22 (9) | C8—C9—C10—C11 | 179.20 (10) |
C6i—N2—C6—C5 | −177.24 (12) | C9—C10—C11—C12 | 1.6 (2) |
N1—C5—C6—N2 | −128.91 (12) | C10—C11—C12—C11i | −0.81 (10) |
C4—C5—C6—N2 | 49.37 (17) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1ii | 0.95 | 2.30 | 3.1382 (18) | 147 |
C10—H10···O1iii | 0.95 | 2.35 | 3.2939 (19) | 170 |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C21H15N3O2 |
Mr | 341.36 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 120 |
a, b, c (Å) | 19.1173 (8), 10.9251 (5), 7.7581 (3) |
β (°) | 93.416 (2) |
V (Å3) | 1617.47 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.10 × 0.08 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.991, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7527, 1843, 1329 |
Rint | 0.112 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.126, 1.01 |
No. of reflections | 1843 |
No. of parameters | 121 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.28 |
Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
O1—N1 | 1.3100 (15) | N1—C5 | 1.3655 (19) |
N1—C1 | 1.3634 (19) | N2—C6 | 1.3383 (16) |
O1—N1—C1 | 119.17 (13) | C1—N1—C5 | 119.81 (13) |
O1—N1—C5 | 120.98 (12) | C6—N2—C6i | 116.95 (16) |
N1—C5—C6—N2 | −128.91 (12) | C7—C8—C9—C10 | −150.68 (9) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1ii | 0.95 | 2.30 | 3.1382 (18) | 146.5 |
C10—H10···O1iii | 0.95 | 2.35 | 3.2939 (19) | 170.1 |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, −y+1, −z. |
The title molecule lies on a crystallographic twofold axis which passes through N(2), C(8), C(9) and C(12) atoms (see Fig. 1). The compound contains weak intermolecular C—H···O hydrogen bonds which are gaining more attention in the field of crystal engineering and their significance has been reported for numerous crystal structures (Green, 1974; Taylor & Kennard, 1982; Desiraju, 1996; Steiner, 1997; McKay et al., 2004).
The aryl H atoms participate in C—H···O hydrogen bonds because of the electronic influence of the corresponding sp2 Caryl atom. The crystal structure of the compound was analysed to understand the hydrogen-bond preferences of C—H···O—N interactions. Terpyridine compounds are well represented in the Cambridge Structural Database (Allen, 2002), due to their excellent chelating and favorable hydrogen-bond-acceptor ability. Introduction of two N-oxide functionalities to the phenylterpyridine framework, provides an opportunity to explore the interdependency of two strong acceptors and molecular alignment.
The compound adopts a conformation that results from the twist about each pyridine–pyridine bond [N1—C5—C6—N2 = 128.91 (12)°]. This conformation is less skewed than that in the terpyridine trioxide [76.8 (2)°] (McKay et al., 2004), presumably due to a more sterically favorable environment of the central pyridine fragment. Other selected geometric parameters are given in Table 1.
The supramolecular motifs observed in the structure of (I) are influenced by the construction of non-bonded contacts (Table 2) as the edges of the compound (I) are constituted exclusively with O atoms and C—H groups and it is to be expected that weak C—H···O hydrogen bonds will be present in the crystal structure (Steiner, 1997; Desiraju & Steiner, 1999). In the compound, C2 and C10 form these hydrogen bonds with O1 and C—H···.O1—N1 contacts link neighboring terpyridine molecules (see Fig. 2).