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The title compound, C21H15N3O2, crystallizes with the mol­ecules positioned on twofold rotation axes. Two crystallographically unique inter­molecular C—H...O—N contacts produce a complex network of hydrogen bonds that assist in the stabilization of the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035398/rn2022sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035398/rn2022Isup2.hkl
Contains datablock I

CCDC reference: 657845

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](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

Comment top

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).

Related literature top

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).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I) showing 50% dispalcement ellipsoids (arbitrary spheres for the H atoms). Symmetry code: (i) -x, -y, -z.
[Figure 2] Fig. 2. The unit-cell packing of (I) viewed along the b axis. Dashed lines indicate the hydrogen bonding interactions.
4'-Phenyl-2,2':6',2''-terpyridine 1,1''-dioxide top
Crystal data top
C21H15N3O2F(000) = 712
Mr = 341.36Dx = 1.402 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1843 reflections
a = 19.1173 (8) Åθ = 2.9–27.5°
b = 10.9251 (5) ŵ = 0.09 mm1
c = 7.7581 (3) ÅT = 120 K
β = 93.416 (2)°Block, colorless
V = 1617.47 (12) Å30.10 × 0.08 × 0.05 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
1843 independent reflections
Radiation source: fine-focus sealed tube1329 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.112
ω and φ scansθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 2424
Tmin = 0.991, Tmax = 0.995k = 1413
7527 measured reflectionsl = 1010
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-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 reflectionsΔρmax = 0.26 e Å3
121 parametersΔρmin = 0.28 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0051 (11)
Crystal data top
C21H15N3O2V = 1617.47 (12) Å3
Mr = 341.36Z = 4
Monoclinic, C2/cMo Kα radiation
a = 19.1173 (8) ŵ = 0.09 mm1
b = 10.9251 (5) ÅT = 120 K
c = 7.7581 (3) Å0.10 × 0.08 × 0.05 mm
β = 93.416 (2)°
Data collection top
Nonius KappaCCD
diffractometer
1843 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
1329 reflections with I > 2σ(I)
Tmin = 0.991, Tmax = 0.995Rint = 0.112
7527 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.126H-atom parameters constrained
S = 1.01Δρmax = 0.26 e Å3
1843 reflectionsΔρmin = 0.28 e Å3
121 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.18038 (6)0.62710 (9)0.09623 (13)0.0263 (3)
N10.18001 (6)0.71228 (11)0.21502 (15)0.0208 (3)
N20.00000.71614 (14)0.25000.0185 (4)
C10.23682 (8)0.78705 (14)0.2399 (2)0.0256 (4)
H10.27600.77560.17180.031*
C20.23843 (8)0.87827 (14)0.3610 (2)0.0288 (4)
H20.27840.92970.37610.035*
C30.18193 (9)0.89553 (13)0.4611 (2)0.0285 (4)
H30.18300.95680.54810.034*
C40.12369 (8)0.82145 (13)0.43189 (19)0.0240 (4)
H40.08380.83380.49720.029*
C50.12276 (7)0.72989 (13)0.30924 (18)0.0193 (4)
C60.05943 (7)0.65209 (13)0.27456 (16)0.0185 (3)
C70.06210 (7)0.52497 (12)0.27623 (17)0.0187 (3)
H70.10570.48380.29500.022*
C80.00000.45848 (18)0.25000.0179 (4)
C90.00000.32240 (18)0.25000.0193 (5)
C100.05106 (8)0.25744 (13)0.15219 (18)0.0223 (4)
H100.08660.30030.08600.027*
C110.05025 (8)0.13022 (13)0.15108 (19)0.0259 (4)
H110.08460.08690.08160.031*
C120.00000.0657 (2)0.25000.0282 (5)
H120.00000.02130.25000.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0277 (7)0.0246 (6)0.0269 (6)0.0017 (4)0.0051 (4)0.0043 (4)
N10.0209 (7)0.0194 (7)0.0219 (6)0.0004 (5)0.0004 (5)0.0039 (5)
N20.0182 (9)0.0199 (9)0.0171 (8)0.0000.0001 (7)0.000
C10.0195 (8)0.0278 (9)0.0294 (8)0.0031 (6)0.0003 (6)0.0076 (7)
C20.0252 (9)0.0247 (8)0.0353 (9)0.0066 (6)0.0084 (7)0.0082 (7)
C30.0318 (10)0.0197 (8)0.0329 (8)0.0008 (6)0.0080 (7)0.0013 (7)
C40.0240 (8)0.0220 (8)0.0258 (8)0.0024 (6)0.0014 (6)0.0005 (6)
C50.0185 (8)0.0177 (7)0.0213 (7)0.0011 (6)0.0013 (6)0.0043 (6)
C60.0203 (8)0.0186 (7)0.0168 (7)0.0001 (6)0.0020 (5)0.0001 (6)
C70.0178 (8)0.0192 (7)0.0191 (7)0.0024 (5)0.0011 (5)0.0011 (5)
C80.0208 (11)0.0182 (10)0.0148 (9)0.0000.0023 (7)0.000
C90.0237 (11)0.0163 (10)0.0184 (9)0.0000.0055 (8)0.000
C100.0252 (9)0.0205 (8)0.0214 (8)0.0009 (6)0.0024 (6)0.0005 (6)
C110.0309 (9)0.0217 (8)0.0254 (8)0.0058 (6)0.0029 (6)0.0035 (6)
C120.0372 (14)0.0170 (10)0.0312 (11)0.0000.0097 (10)0.000
Geometric parameters (Å, º) top
O1—N11.3100 (15)C6—C71.3897 (19)
N1—C11.3634 (19)C7—C81.3963 (17)
N1—C51.3655 (19)C7—H70.9500
N2—C61.3383 (16)C8—C7i1.3963 (17)
N2—C6i1.3384 (16)C8—C91.487 (3)
C1—C21.369 (2)C9—C101.3943 (18)
C1—H10.9500C9—C10i1.3943 (18)
C2—C31.381 (2)C10—C111.390 (2)
C2—H20.9500C10—H100.9500
C3—C41.384 (2)C11—C121.3861 (19)
C3—H30.9500C11—H110.9500
C4—C51.380 (2)C12—C11i1.3861 (19)
C4—H40.9500C12—H120.9500
C5—C61.4905 (19)
O1—N1—C1119.17 (13)N2—C6—C5113.65 (12)
O1—N1—C5120.98 (12)C7—C6—C5122.63 (12)
C1—N1—C5119.81 (13)C6—C7—C8119.22 (13)
C6—N2—C6i116.95 (16)C6—C7—H7120.4
N1—C1—C2121.22 (15)C8—C7—H7120.4
N1—C1—H1119.4C7—C8—C7i117.30 (18)
C2—C1—H1119.4C7—C8—C9121.35 (9)
C1—C2—C3119.97 (14)C7i—C8—C9121.35 (9)
C1—C2—H2120.0C10—C9—C10i118.81 (19)
C3—C2—H2120.0C10—C9—C8120.60 (9)
C2—C3—C4118.46 (14)C10i—C9—C8120.60 (9)
C2—C3—H3120.8C11—C10—C9120.31 (14)
C4—C3—H3120.8C11—C10—H10119.8
C5—C4—C3120.94 (15)C9—C10—H10119.8
C5—C4—H4119.5C12—C11—C10120.85 (14)
C3—C4—H4119.5C12—C11—H11119.6
N1—C5—C4119.57 (14)C10—C11—H11119.6
N1—C5—C6119.43 (13)C11i—C12—C11118.85 (19)
C4—C5—C6120.98 (13)C11i—C12—H12120.6
N2—C6—C7123.65 (13)C11—C12—H12120.6
O1—N1—C1—C2179.18 (12)N1—C5—C6—C754.03 (18)
C5—N1—C1—C21.6 (2)C4—C5—C6—C7127.69 (15)
N1—C1—C2—C30.3 (2)N2—C6—C7—C80.43 (19)
C1—C2—C3—C42.0 (2)C5—C6—C7—C8177.19 (10)
C2—C3—C4—C52.0 (2)C6—C7—C8—C7i0.20 (9)
O1—N1—C5—C4179.16 (12)C6—C7—C8—C9179.80 (9)
C1—N1—C5—C41.6 (2)C7—C8—C9—C10150.68 (9)
O1—N1—C5—C60.85 (19)C7i—C8—C9—C1029.32 (9)
C1—N1—C5—C6176.70 (12)C7—C8—C9—C10i29.32 (9)
C3—C4—C5—N10.2 (2)C7i—C8—C9—C10i150.68 (9)
C3—C4—C5—C6178.46 (13)C10i—C9—C10—C110.80 (10)
C6i—N2—C6—C70.22 (9)C8—C9—C10—C11179.20 (10)
C6i—N2—C6—C5177.24 (12)C9—C10—C11—C121.6 (2)
N1—C5—C6—N2128.91 (12)C10—C11—C12—C11i0.81 (10)
C4—C5—C6—N249.37 (17)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1ii0.952.303.1382 (18)147
C10—H10···O1iii0.952.353.2939 (19)170
Symmetry codes: (ii) x+1/2, y+1/2, z+1/2; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC21H15N3O2
Mr341.36
Crystal system, space groupMonoclinic, C2/c
Temperature (K)120
a, b, c (Å)19.1173 (8), 10.9251 (5), 7.7581 (3)
β (°) 93.416 (2)
V3)1617.47 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.10 × 0.08 × 0.05
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.991, 0.995
No. of measured, independent and
observed [I > 2σ(I)] reflections
7527, 1843, 1329
Rint0.112
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.126, 1.01
No. of reflections1843
No. of parameters121
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
O1—N11.3100 (15)N1—C51.3655 (19)
N1—C11.3634 (19)N2—C61.3383 (16)
O1—N1—C1119.17 (13)C1—N1—C5119.81 (13)
O1—N1—C5120.98 (12)C6—N2—C6i116.95 (16)
N1—C5—C6—N2128.91 (12)C7—C8—C9—C10150.68 (9)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1ii0.952.303.1382 (18)146.5
C10—H10···O1iii0.952.353.2939 (19)170.1
Symmetry codes: (ii) x+1/2, y+1/2, z+1/2; (iii) x, y+1, z.
 

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