Biphenyl- and phenylnaphthalenyl-substituted 1H-imidazole-4,5- dicarbonitrile catalysts for the coupling reaction of nucleoside methyl phosphonamidites

organic compounds

Acta Crystallographica Section C

Crystal Structure

Communications

(Schell & Engels, 1997). Therefore, substituted 1H-imidazole-

4,5-dicarbonitriles were tested as activators for stereoselection

during the synthesis of dinucleoside methyl phosphonates.

Selectivities up to 84/16 (R_P/S_P) have been reported by Schell

& Engels (1998). Single crystals were obtained for three

different substituted 1H-imidazole-4,5-dicarbonitriles used for

these experiments and the crystal structures of these three

compounds, namely 2-(3⁰,5⁰-dimethylbiphenyl-2-yl)-1H-imid-

azole-4,5-dicarbonitrile, (I), 2-(2⁰,4⁰,6⁰-trimethylbiphenyl-2-yl)-

1H-imidazole-4,5-dicarbonitrile, (II), and 2-[8-(3,5-dimethyl-

phenyl)naphthalen-1-yl]-1H-imidazole-4,5-dicarbonitrile, (III),

are reported here.

ISSN 0108-2701

Biphenyl- and phenylnaphthalenyl-

substituted 1H-imidazole-4,5-dicarbo-

nitrile catalysts for the coupling reac-

tion of nucleoside methyl phosphon-

amidites

Jan W. Bats,* Peter Schell and Joachim W. Engels

Institut fur Organische Chemie und Chemische Biologie, Universitat Frankfurt, Max-

¨

von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany

Correspondence e-mail: bats@chemie.uni-frankfurt.de

Received 21 March 2013

Accepted 5 April 2013

Crystal structures are reported for three substituted 1H-

imidazole-4,5-dicarbonitrile compounds used as catalysts for

the coupling reaction of nucleoside methyl phosphonamidites,

namely 2-(3⁰,5⁰-dimethylbiphenyl-2-yl)-1H-imidazole-4,5-di-

carbonitrile, C₁₉H₁₄N₄, (I), 2-(2⁰,4⁰,6⁰-trimethylbiphenyl-2-yl)-

1H-imidazole-4,5-dicarbonitrile, C₂₀H₁₆N₄, (II), and 2-[8-(3,5-

dimethylphenyl)naphthalen-1-yl]-1H-imidazole-4,5-dicarbo-

nitrile, C₂₃H₁₆N₄, (III). The asymmetric unit of (I) contains

two independent molecules with similar conformations. There

is steric repulsion between the imidazole group and the

terminal phenyl group in all three compounds, resulting in the

nonplanarity of the molecules. The naphthalene group of (III)

shows signiﬁcant deviation from planarity. The C—N bond

lengths in the imidazole rings range from 1.325 (2) to

The crystal structure of (I) contains two crystallographically

independent molecules, A and B (Fig. 1), which have very

similar conformations. The angles between the planes of the

six-membered rings of the biphenyl group are 44.91 (6)^ꢁfor

molecule A and 42.09 (6)^ꢁfor molecule B. The angle between

the plane of the imidazole group and that of the central phenyl

group is 46.02 (7)^ꢁfor molecule A and 39.57 (7)^ꢁfor molecule

B. There is signiﬁcant steric repulsion between the dimethyl-

phenyl and imidazole groups [shortest contacts: C5ꢀ ꢀ ꢀC13 =

˚

3.115 (3) A, N5ꢀ ꢀ ꢀC20 = 3.094 (3) A, N5ꢀ ꢀ ꢀC25 = 3.144 (2) A

˚

and C20ꢀ ꢀ ꢀC32 = 3.115 (3) A]. These steric contacts are not

only responsible for the nonplanar conformation of the

biphenyl group, but also result in an out-of-plane distortion of

the dimethylphenyl and imidazole groups with respect to the

plane of the central benzene ring. Consequently, the C6—

C7—C12—C13 and C25—C26—C31—C32 torsion angles are

ꢂ6.6 (3) and ꢂ9.6 (3)^ꢁ, respectively. The amino N atoms are

planar, the sums of the three valence angles about atoms N2

and N5 being 359.4 (8) and 360.0 (9)^ꢁ, respectively. The mol-

ecules are connected by N—Hꢀ ꢀ ꢀN hydrogen bonds (Fig. 2

and Table 1) between the imidazole groups to form zigzag

chains parallel to the b-axis direction. These chains are

connected by weak intermolecular C—Hꢀ ꢀ ꢀN contacts

(Table 1) to give a three-dimensional structure.

˚

1.377 (2) A. The molecules are connected into zigzag chains

by intermolecular N—Hꢀ ꢀ ꢀN_imidazole[for (I)] or N—

Hꢀ ꢀ ꢀꢀN_cyano[for (II) and (III)] hydrogen bonds.

Comment

Methyl phosphonate oligonucleotides differ from conven-

tional oligonucleotides by the replacement of a negatively

charged O atom at the phosphonate linkage by a methyl

group. They are more stable to degradation by cellular

nucleases than are conventional oligonucleotides, and they

can be applied in the antisense concept to control gene

expression in mammalian cells (Uhlmann & Peyman, 1990).

The P atoms in methyl phosphonate oligonucleotides are

chiral, and R_P-conﬁgured molecules bind better to their target

strand than do S_P-conﬁgured ones (Lebedev & Wickstrom,

1996). The phosphoramidite approach can be used for the

The molecular structure of (II) is shown in Fig. 3. The angle

between the planes of the six-membered rings of the biphenyl

group is 71.20 (4)^ꢁ, almost 30^ꢁlarger than the corresponding

values in (I), resulting from steric repulsions between the

ortho-methyl groups and the imidazole group on one hand and

the C10—H10A bond on the other [shortest contacts:

˚

C10ꢀ ꢀ ꢀC18 = 3.261 (2) A and C1ꢀ ꢀ ꢀH20C = 2.75 A]. The angle

between the planes of the imidazole ring and the central

benzene ring is 29.39 (6)^ꢁ, slightly smaller than the corre-

sponding values observed in (I), despite the short intra-

¨

synthesis of methyl phosphonate oligonucleotides (Jager &

Engels, 1984). The reaction is activated by the use of tetrazole

but no stereocontrol occurs at the P atom. Also, the use of

tetrazoles with a chiral substituent gives only weak selectivity

˚

molecular contact distance of 2.879 (2) A between atoms N1

Acta Cryst. (2013). C69, 529–533

doi:10.1107/S0108270113009293

# 2013 International Union of Crystallography 529

organic compounds

Figure 2

The crystal packing of (I), viewed down [100]. Displacement ellipsoids are

drawn at the 50% probabilty level. C-bound H atoms have been omitted

for clarity. Intermolecular hydrogen bonds are shown as dashed lines.

3

2

1

2

1

2

3

2

1

2

1

2

[Symmetry codes: (i) ꢂx + , y + , ꢂz + ; (iii) ꢂx + , y ꢂ , ꢂz + .]

direction, the molecules are only connected by intermolecular

C—Hꢀ ꢀ ꢀꢀ_imidazolecontacts (ﬁnal three entries of Table 2).

These contacts are very weak. Consequently, the crystal habit

is a (100) plate.

The molecular structure of (III) is shown in Fig. 5. The

naphthalene group shows considerable deviation from

˚

planarity (mean deviation from best plane = 0.041 A). Ring

˚

atoms C2 and C10 deviate by 0.0567 (14) and 0.0788 (14) A,

respectively, in opposite directions from the best plane of the

naphthalene group. The out-of-plane deviation from the

naphthalene plane is even more pronounced for substituent

˚

atoms C11 and C19 [deviations of 0.221 (2) and 0.299 (2) A,

respectively] as a result of steric interactions between the di-

methylphenyl and imidazole groups. The shortest contact

Figure 1

The structures of (a) molecule A and (b) molecule B of (I), showing the

atom-labelling scheme. Displacement ellipsoids are drawn at the 50%

probability level.

and C12. The C1—C6—C11—C12 torsion angle of 2.69 (18)^ꢁ

again shows a small out-of-plane distortion of the trimethyl-

phenyl and imidazole groups from the plane of the central

benzene ring, but this distortion is smaller than the corre-

sponding distortions observed in (I). The amino N atom is

planar, the sum of the three valence angles about atom N1

being 359.6 (7)^ꢁ. The crystal packing of (II) is shown in Fig. 4.

The molecules are connected by rather weak intermolecular

hydrogen bonds between the N—H bond and a cyano N atom

of a neighbouring molecule (Table 2) to form zigzag chains

along the c-axis direction. The long Hꢀ ꢀ ꢀN distance of

ꢁ

˚

2.351 (15) A and the small N—Hꢀ ꢀ ꢀN angle of 127.7 (12)

show this hydrogen bond to be rather weak. The crystal

packing also shows two weak intermolecular C—Hꢀ ꢀ ꢀN_cyano

contacts (Table 2). One of these results in an additional

stabilization of the hydrogen-bonded chain and the other

connects the chains along the b-axis direction. Along the a axis

Figure 3

The molecular structure of (II), showing the atom-labelling scheme.

Displacement ellipsoids are drawn at the 50% probability level.

ꢃ

530 Bats et al. C₁₉H₁₄N₄, C₂₀H₁₆N₄and C₂₃H₁₆N₄

Acta Cryst. (2013). C69, 529–533

organic compounds

Figure 4

The crystal packing of (II), viewed down [010]. Displacement ellipsoids

are drawn at the 50% probabilty level. C-bound H atoms have been

omitted for clarity. Intermolecular hydrogen bonds are shown as dashed

Figure 6

The crystal packing of (III), viewed down [010]. Displacement ellipsoids

are drawn at the 50% probabilty level. C-bound H atoms have been

omitted for clarity. Intermolecular hydrogen bonds are shown as dashed

lines. [Symmetry codes: (i) ꢂx + 1, ꢂy, z + ; (ii) ꢂx + 1, ꢂy, z ꢂ .]

1

lines. [Symmetry codes: (i) x, ꢂy + , z + ; (iv) x, ꢂy + , z ꢂ .]

2

1

2

1

2

˚

distances are: C11ꢀ ꢀ ꢀN2

=

2.908 (2) A, C11ꢀ ꢀ ꢀC19

=

˚

There are no other short intermolecular contact distances. The

shortest intermolecular C—Hꢀ ꢀ ꢀN contact has an Hꢀ ꢀ ꢀN

2.988 (2) A and C12ꢀ ꢀ ꢀC19 = 2.937 (2) A. Steric repulsion

between the dimethylphenyl and imidazole groups also results

in rather large values of the C1—C2—C11, C2—C1—C10 and

C1—C10—C19 bond angles [124.59 (15), 126.37 (14) and

123.98 (14)^ꢁ, respectively]. The dihedral angle between the

naphthalene and dimethylphenyl planes is 55.20 (4)^ꢁ, between

the naphthalene and imidazole planes is 54.11 (6)^ꢁ, and

between the dimethylphenyl and imidazole planes is

22.71 (5)^ꢁ. The amino N atom is again planar, the sum of the

three valence angles about atom N2 being 359.9 (10)^ꢁ. The

crystal packing of (III) is shown in Fig. 6. The molecules are

connected by intermolecular N—Hꢀ ꢀ ꢀN_cyanohydrogen bonds

(Table 3) to form zigzag chains parallel to the c-axis direction.

˚

distance of 2.74 A.

The bond lengths and angles in the 1H-imidazole-4,5-

dicarbonitrile groups of (I), (II) and (III) are in excellent

agreement. They are also very similar to the corresponding

bond lengths and angles observed in the crystal structure of

1H-imidazole-4,5-dicarbonitrile (Barni et al., 1997). The C—N

bond lengths in the imidazole rings range from 1.325 (2) to

˚

1.377 (2) A, thus showing a considerable degree of delocali-

zation of the double bonds in the ring. The N—Hꢀ ꢀ ꢀN_imidazole

hydrogen bond in (I) is considerably shorter than the N—

Hꢀ ꢀ ꢀN_cyanohydrogen bonds in (II) and (III).

The three title compounds have been tested as activators in

the coupling reaction to produce a protected thymine di-

nucleoside methylphosphonate TpT (Schell & Engels, 1998).

The R_P/S_Pstereoselectivities were 65/35 for (I) and 77/23 for

(II), while no reaction occurred for (III). Thus, the stereo-

selectivity of these compounds depends very much on the

substituent of the imidazole group.

Experimental

The starting materials for the preparation of the title compounds

were 3⁰,5⁰-dimethylbiphenyl-2-carbonitrile for (I), 2⁰,4⁰,6⁰-trimethyl-

biphenyl-2-carbonitrile for (II) and 8-(3,5-dimethylphenyl)naphtha-

lene-1-carbonitrile for (III). The starting material (15 mmol) was

reacted for 2 h with diisobutylaluminium hydride (18 mmol) in ether

(20 ml), and then for 5 min with 2,3-diaminomaleonitrile (15 mmol)

and concentrated H₂SO₄(7.5 mmol) in tetrahydrofuran (40 ml).

Thus, the cyano group of the starting compound was replaced by a

2-amino-3-methylideneaminobut-2-enedinitrile chain (Begland et al.,

1974). The products were puriﬁed by recrystallization from di-

chloromethane–n-hexane (1:1 v/v). Subsequently, they were further

reacted with nicotinamide (18 mmol) and N-chlorosuccinimide

(15 mmol) in dimethylformamide (38 ml), resulting in the cyclization

of the 2-amino-3-methylideneaminobut-2-enedinitrile chain to form

the desired 1H-imidazole-4,5-dicarbonitrile group (Moriya et al.,

Figure 5

The molecular structure of (III), showing the atom-labelling scheme.

Displacement ellipsoids are drawn at the 50% probability level.

ꢃ

Acta Cryst. (2013). C69, 529–533

Bats et al.

C₁₉H₁₄N₄, C₂₀H₁₆N₄and C₂₃H₁₆N₄531

organic compounds

Table 1

Hydrogen-bond geometry (A, ) for (I).

Table 2

Hydrogen-bond geometry (A, ) for (II).

ꢁ

˚

D—Hꢀ ꢀ ꢀA

D—H

Hꢀ ꢀ ꢀA

Dꢀ ꢀ ꢀA

D—Hꢀ ꢀ ꢀA

D—H

Hꢀ ꢀ ꢀA

Dꢀ ꢀ ꢀA

D—Hꢀ ꢀ ꢀA

N2—H2Aꢀ ꢀ ꢀN6

0.97 (2)

0.953 (19)

0.95

0.98

2.02 (2)

1.95 (2)

2.69

2.60

2.65

2.907 (2)

2.882 (2)

3.567 (3)

3.484 (3)

3.497 (3)

150.9 (17)

164.4 (17)

154

150

145

N1—H1Aꢀ ꢀ ꢀN3ⁱ

0.901 (14)

0.95

0.98

0.95

2.351 (15)

2.62

2.66

2.96

3.07

2.9883 (16)

3.5476 (17)

3.6327 (19)

3.8507 (17)

3.8580 (18)

3.7899 (19)

127.7 (12)

166

175

158

142

N5—H5Bꢀ ꢀ ꢀN1ⁱ

C14—H14Aꢀ ꢀ ꢀN4ⁱ

C19—H19Cꢀ ꢀ ꢀN4ⁱⁱ

C16—H16Aꢀ ꢀ ꢀC3ⁱⁱⁱ

C16—H16Aꢀ ꢀ ꢀC5ⁱⁱⁱ

C19—H19Aꢀ ꢀ ꢀC2ⁱⁱⁱ

C11—H11Aꢀ ꢀ ꢀN8ⁱⁱ

C16—H16Bꢀ ꢀ ꢀN6ⁱⁱⁱ

C16—H16Cꢀ ꢀ ꢀN3^iv

0.98

2.91

150

3

1

2

3

1

Symmetry codes: (i) ꢂx þ ; y þ ; ꢂz þ ; (ii) ꢂx þ 2; ꢂy þ 1; ꢂz; (iii) ꢂx þ ; y ꢂ ,

2

1

2

1

2

1

2

1

2

1

2

1

2

3

2

ꢂz þ ; (iv) x þ ; ꢂy þ ; z þ .

Symmetry codes: (i) x; ꢂy þ ; z þ ; (ii) ꢂx þ 2; y þ ; ꢂz þ ; (iii) ꢂx þ 2; ꢂy þ 1,

2

ꢂz þ 1.

1984). The ﬁnal products were recrystallized from dichloromethane–

n-hexane (1:1 v/v), resulting in colourless crystals of (I), (II) or (III).

The yields of the three products were 74, 77 and 63%, respectively.

Compound (III)

Crystal data

3

˚

C₂₃H₁₆N₄

M_r= 348.40

Orthorhombic, Pca2₁

V = 1801.2 (3) A

Z = 4

Compound (I)

Cu Kꢂ radiation

ꢃ = 0.62 mm^ꢂ1

T = 294 K

˚

a = 16.7042 (14) A

Crystal data

˚

b = 7.1632 (7) A

˚

c = 15.0528 (11) A

3

˚

0.60 ꢄ 0.40 ꢄ 0.25 mm

C₁₉H₁₄N₄

M_r= 298.34

V = 3226.1 (8) A

Z = 8

Monoclinic, P2₁=n

Mo Kꢂ radiation

ꢃ = 0.08 mm^ꢂ1

T = 134 K

0.36 ꢄ 0.30 ꢄ 0.15 mm

Data collection

˚

a = 9.771 (2) A

˚

b = 16.807 (2) A

Enraf–Nonius CAD-4

diffractometer

Absorption correction: scan

MolEN (Fair, 1990)

1781 independent reﬂections

1753 reﬂections with I > 2ꢄ(I)

R_int= 0.019

˚

c = 19.692 (2) A

ꢁ = 93.976 (7)^ꢁ

3 standard reﬂections

every 90 min

intensity decay: 2.0%

T_min= 0.776, T_max= 0.857

3815 measured reﬂections

Data collection

Siemens SMART 1K CCD area-

detector diffractometer

Absorption correction: multi-scan

SADABS (Sheldrick, 1996)

T_min= 0.867, T_max= 0.989

47542 measured reﬂections

7317 independent reﬂections

3808 reﬂections with I > 2ꢄ(I)

R_int= 0.067

Reﬁnement

R[F²> 2ꢄ(F²)] = 0.027

wR(F²) = 0.070

S = 1.05

1781 reﬂections

251 parameters

1 restraint

H atoms treated by a mixture of

independent and constrained

reﬁnement

Reﬁnement

ꢂ3

˚

Áꢅ_max= 0.13 e A

ꢂ3

R[F²> 2ꢄ(F²)] = 0.052

wR(F²) = 0.093

S = 0.92

7317 reﬂections

428 parameters

H atoms treated by a mixture of

independent and constrained

reﬁnement

˚

Áꢅ_min= ꢂ0.12 e A

ꢂ3

˚

Áꢅ_max= 0.22 e A

ꢂ3

˚

Áꢅ_min= ꢂ0.17 e A

Friedel opposites were merged for (III) and no attempt was

made to determine the direction of the c axis for the polar space

group. C-bound H atoms were positioned geometrically and treated

˚

as riding, with planar C—H = 0.95 A for (I) and (II), and 0.93 A

˚

Compound (II)

˚

for (III), and methyl C—H = 0.98 A for (I) and (II), and 0.96 A for

(III), with U_iso(H) = 1.2U_eq(planar C) or 1.5U_eq(methyl C). N-bound

H atoms were located from difference Fourier syntheses and

their coordinates and isotropic displacement parameters were

reﬁned.

Crystal data

3

˚

V = 1691.1 (4) A

Z = 4

C₂₀H₁₆N₄

M_r= 312.37

Monoclinic, P2₁=c

Mo Kꢂ radiation

ꢃ = 0.08 mm^ꢂ1

T = 133 K

0.60 ꢄ 0.40 ꢄ 0.10 mm

˚

a = 12.373 (1) A

Data collection: SMART (Siemens, 1995) for (I) and (II);

CAD-4 Software (Enraf–Nonius, 1989) for (III). Cell reﬁnement:

SMART for (I) and (II); CAD-4 Software for (III). Data reduction:

SAINT (Siemens, 1995) for (I) and (II); MolEN (Fair, 1990) for (III).

For all three compounds, program(s) used to solve structure:

SHELXS97 (Sheldrick, 2008); program(s) used to reﬁne structure:

SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL

b = 10.303 (2) A

˚

c = 13.279 (2) A

ꢁ = 92.578 (7)^ꢁ

Data collection

Siemens SMART 1K CCD area-

detector diffractometer

Absorption correction: multi-scan

SADABS (Sheldrick, 1996)

T_min= 0.784, T_max= 0.993

25406 measured reﬂections

4381 independent reﬂections

3014 reﬂections with I > 2ꢄ(I)

R_int= 0.033

Table 3

ꢁ

˚

Hydrogen-bond geometry (A, ) for (III).

Reﬁnement

R[F²> 2ꢄ(F²)] = 0.040

wR(F²) = 0.104

S = 1.04

4381 reﬂections

225 parameters

H atoms treated by a mixture of

independent and constrained

reﬁnement

D—Hꢀ ꢀ ꢀA

N2—H2Aꢀ ꢀ ꢀN3ⁱ

Symmetry code: (i) ꢂx þ 1; ꢂy; z þ .

D—H

Hꢀ ꢀ ꢀA

Dꢀ ꢀ ꢀA

D—Hꢀ ꢀ ꢀA

0.81 (2)

2.26 (2)

3.001 (2)

152 (2)

ꢂ3

˚

Áꢅ_max= 0.23 e A

ꢂ3

˚

1

2

Áꢅ_min= ꢂ0.20 e A

ꢃ

532 Bats et al. C₁₉H₁₄N₄, C₂₀H₁₆N₄and C₂₃H₁₆N₄

Acta Cryst. (2013). C69, 529–533

organic compounds

Enraf–Nonius (1989). CAD-4 Software . Enraf–Nonius, Delft, The Nether-

lands.

Fair, C. K. (1990). MolEN . Enraf–Nonius, Delft, The Netherlands.

J a ¨g er, A. & Engels, J. (1984). Tetrahedron Lett. 25 , 1437–1440.

Lebedev, A. V . & Wickstrom, E. (1996). Perspect. Drug Discovery Des. 4 , 17–

40.

(Sheldrick, 2008); software used to prepare material for publication:

SHELXL97.

Supplementary data for this paper are available from the IUCr electronic

archives (Reference: EG3118). Services for accessing these data are

described at the back of the journal.

Moriya, O., Minamide, H.

-1058.

& Urata, Y . (1984). Synthesis , pp. 1057–

Schell, P . & E ngels, J. W. (1997). Nucleosides Nucleotides , 16 , 769–772.

Schell, P . & E ngels, J. W. (1998). Tetrahedron Lett. 39 , 8629–8632.

References

¨

Sheldrick, G. M. (1996). SADABS . University of Gottingen, Germany.

Barni, E., Bianchi, R., Gervasio, G., Peters, A. T. & Viscardi, G. (1997). J. Org.

Chem. 62 , 7037–7043.

Begland, R. W ., Hartter, D. R., Jones, F. N., Sam, D. J., Sheppard, W . A .,

Webster, O. W. & Weigert, F. J. (1974). J. Org. Chem. 39 , 2341–2350.

Sheldrick, G. M. (2008). Acta Cryst. A 64 , 112–122.

Siemens (1995). SMART and SAINT . Siemens Analytical X-ray Instruments

Inc., Madison, Wisconsin, USA.

Uhlmann, E. & Peyman, A. (1990). Chem. Rev. 90 , 543–584.

ꢃ

Acta Cryst. (2013). C69, 529–533

Bats et al.

C₁₉H₁₄N₄, C₂₀H₁₆N₄and C₂₃H₁₆N₄533

supplementary materials

Acta Cryst. (2013). C69, 529-533 [doi:10.1107/S0108270113009293]

Biphenyl- and phenylnaphthalenyl-substituted 1H-imidazole-4,5-dicarbonitrile

catalysts for the coupling reaction of nucleoside methyl phosphonamidites

Jan W. Bats, Peter Schell and Joachim W. Engels

(I) 2-(3′,5′-Dimethylbiphenyl-2-yl)-1H-imidazole-4,5-dicarbonitrile

Crystal data

C₁₉H₁₄N₄

M_r= 298.34

F(000) = 1248

D_x= 1.229 Mg m⁻³

Melting point: 425(1) K

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 244 reflections

θ = 3–23°

Monoclinic, P2₁/n

Hall symbol: -P 2yn

a = 9.771 (2) Å

b = 16.807 (2) Å

c = 19.692 (2) Å

β = 93.976 (7)°

V = 3226.1 (8) Å³

Z = 8

µ = 0.08 mm⁻¹

T = 134 K

Block, colourless

0.36 × 0.30 × 0.15 mm

Data collection

Siemens SMART 1K CCD area-detector

diffractometer

Radiation source: normal-focus sealed tube

Graphite monochromator

ω scans

47542 measured reflections

7317 independent reflections

3808 reflections with I > 2σ(I)

R_int= 0.067

θ

_max= 27.5°, θ_min= 2.1°

Absorption correction: multi-scan

SADABS (Sheldrick, 1996)

h = −12→12

k = −21→21

l = −25→25

T

_min= 0.867, T_max= 0.989

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.052

wR(F²) = 0.093

S = 0.92

7317 reflections

Hydrogen site location: inferred from

neighbouring sites

H atoms treated by a mixture of independent

and constrained refinement

w = 1/[σ²(F_o²) + (0.03P)²]

where P = (F_o²+ 2F_c²)/3

428 parameters

0 restraints

Primary atom site location: structure-invariant

direct methods

Secondary atom site location: difference Fourier

map

(Δ/σ)_max= 0.002

Δρ_max= 0.22 e Å⁻³

Δρ_min= −0.17 e Å⁻³

Extinction correction: SHELXL97 (Sheldrick,

2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4

Extinction coefficient: 0.0032 (2)

Acta Cryst. (2013). C69, 529-533

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supplementary materials

Special details

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 F²against 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)

x

y

z

U_iso*/U_eq

N1

0.65061 (16)

0.66519 (16)

0.32788 (19)

0.35949 (17)

0.83027 (16)

0.78633 (15)

1.14192 (19)

1.05867 (19)

0.8832 (2)

0.9654

0.31498 (8)

0.42836 (9)

0.22942 (10)

0.46877 (10)

0.68623 (9)

0.58594 (8)

0.77904 (11)

0.57761 (10)

0.30175 (11)

0.2729

0.18696 (7)

0.13001 (8)

0.14701 (9)

0.03112 (9)

0.21618 (8)

0.14454 (7)

0.18084 (9)

0.03535 (9)

0.36994 (10)

0.3648

0.0262 (4)

0.0240 (4)

0.0458 (5)

0.0386 (5)

0.0244 (4)

0.0246 (4)

0.0463 (5)

0.0473 (5)

0.0394 (6)

0.047*

N2

N3

N4

N5

N6

N7

N8

C1

H1A

C2

0.8079 (3)

0.6906 (3)

0.6398

0.28650 (12)

0.33087 (13)

0.3217

0.42548 (11)

0.43355 (11)

0.4722

0.0461 (6)

0.0524 (7)

0.063*

C3

H3A

C4

0.6451 (2)

0.7203 (2)

0.6886

0.38853 (12)

0.40035 (11)

0.4380

0.38642 (11)

0.33000 (10)

0.2965

0.0436 (6)

0.0331 (5)

0.040*

C5

H5A

C6

0.8407 (2)

0.9277 (2)

1.0694 (2)

1.1080

0.35880 (11)

0.37580 (10)

0.38304 (12)

0.3738

0.32105 (10)

0.26369 (10)

0.27705 (12)

0.3220

0.0306 (5)

0.0291 (5)

0.0412 (6)

0.049*

C7

C8

H8A

C9

1.1549 (2)

1.2507

0.40316 (13)

0.4080

0.22702 (13)

0.2380

0.0490 (6)

0.059*

H9A

C10

H10A

C11

H11A

C12

C13

C14

C15

C16

H16A

H16B

H16C

C17

H17A

H17B

1.1024 (2)

1.1613

0.41641 (12)

0.4311

0.16112 (12)

0.1268

0.0448 (6)

0.054*

0.9627 (2)

0.9257

0.40803 (11)

0.4163

0.14577 (11)

0.1004

0.0349 (5)

0.042*

0.87566 (19)

0.73079 (19)

0.52892 (19)

0.53520 (18)

0.8508 (3)

0.9500

0.38757 (10)

0.37624 (10)

0.32911 (10)

0.39910 (10)

0.22143 (13)

0.2245

0.19627 (10)

0.17362 (9)

0.14981 (9)

0.11427 (9)

0.47562 (11)

0.4868

0.0267 (5)

0.0239 (4)

0.0248 (4)

0.0237 (4)

0.0680 (9)

0.102*

0.8279

0.1694

0.4553

0.102*

0.8024

0.2282

0.5172

0.102*

0.5192 (3)

0.5472

0.43783 (13)

0.4893

0.39721 (12)

0.4170

0.0625 (8)

0.094*

0.4614

0.4098

0.4282

0.094*

Acta Cryst. (2013). C69, 529-533

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supplementary materials

H17C

C18

0.4674

0.4464

0.3534

0.094*

0.4169 (2)

0.4373 (2)

0.8040 (2)

0.8222

0.27400 (11)

0.43810 (11)

0.59259 (10)

0.5587

0.14893 (9)

0.06859 (10)

0.34993 (10)

0.3130

0.0301 (5)

0.0276 (5)

0.0291 (5)

0.035*

C19

C20

H20A

C21

0.8987 (2)

0.8713 (2)

0.9344

0.59682 (11)

0.64726 (12)

0.6499

0.40554 (10)

0.45888 (10)

0.4978

0.0332 (5)

0.0389 (5)

0.047*

C22

H22A

C23

0.7535 (2)

0.6598 (2)

0.5785

0.69400 (12)

0.68791 (11)

0.7191

0.45661 (10)

0.40072 (10)

0.3991

0.0390 (5)

0.0341 (5)

0.041*

C24

H24A

C25

0.6828 (2)

0.5753 (2)

0.4381 (2)

0.4155

0.63663 (11)

0.62615 (10)

0.62121 (12)

0.6290

0.34664 (9)

0.28950 (10)

0.30480 (11)

0.3505

0.0274 (5)

0.0291 (5)

0.0400 (6)

0.048*

C26

C27

H27A

C28

0.3347 (2)

0.2423

0.60536 (12)

0.6027

0.25553 (12)

0.2676

0.0466 (6)

0.056*

H28A

C29

0.3642 (2)

0.2933

0.59334 (12)

0.5807

0.18868 (12)

0.1549

0.0428 (6)

0.051*

H29A

C30

0.4988 (2)

0.5197

0.59996 (11)

0.5930

0.17173 (11)

0.1257

0.0342 (5)

0.041*

H30A

C31

0.60429 (19)

0.74044 (19)

0.93823 (19)

0.9100 (2)

1.0268 (2)

1.0887

0.61677 (10)

0.62799 (10)

0.68201 (10)

0.61976 (11)

0.54699 (12)

0.5644

0.22107 (10)

0.19571 (9)

0.17594 (9)

0.13207 (9)

0.40878 (11)

0.4472

0.0262 (4)

0.0236 (4)

0.0252 (4)

0.0260 (4)

0.0449 (6)

0.067*

C32

C33

C34

C35

H35A

H35B

H35C

C36

1.0726

0.5531

0.3664

0.067*

1.0027

0.4910

0.4149

0.067*

0.7284 (2)

0.7686

0.75154 (14)

0.8034

0.51375 (11)

0.5040

0.0598 (8)

0.090*

H36A

H36B

H36C

C37

0.7708

0.7308

0.5567

0.090*

0.6294

0.7576

0.5175

0.090*

1.0505 (2)

0.9908 (2)

0.700 (2)

0.8208 (19)

0.73625 (12)

0.59460 (11)

0.4799 (12)

0.7254 (11)

0.17970 (10)

0.07831 (10)

0.1180 (10)

0.2505 (10)

0.0325 (5)

0.0329 (5)

0.056 (7)*

0.050 (7)*

C38

H2A

H5B

Atomic displacement parameters (Å²)

U¹¹

U²²

U³³

U¹²

U¹³

U²³

N1

N2

N3

N4

N5

N6

N7

N8

C1

0.0317 (10)

0.0248 (10)

0.0473 (13)

0.0347 (11)

0.0305 (10)

0.0295 (10)

0.0491 (13)

0.0564 (14)

0.0572 (15)

0.0219 (8)

0.0200 (8)

0.0432 (12)

0.0396 (10)

0.0192 (8)

0.0209 (8)

0.0484 (12)

0.0427 (11)

0.0248 (11)

0.0251 (9)

0.0270 (9)

0.0479 (12)

0.0405 (11)

0.0234 (9)

0.0233 (9)

0.0416 (12)

0.0451 (12)

0.0334 (13)

−0.0011 (7)

−0.0018 (7)

−0.0167 (10)

−0.0026 (9)

−0.0011 (7)

−0.0021 (7)

−0.0197 (10)

−0.0145 (10)

−0.0024 (10)

0.0020 (8)

−0.0001 (7)

0.0091 (10)

−0.0049 (9)

0.0012 (7)

0.0009 (7)

0.0049 (9)

0.0186 (10)

−0.0162 (11)

0.0026 (7)

0.0029 (7)

0.0003 (9)

0.0061 (9)

−0.0035 (7)

−0.0020 (7)

−0.0053 (9)

−0.0117 (10)

−0.0026 (10)

Acta Cryst. (2013). C69, 529-533

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supplementary materials

C2

0.0819 (19)

0.095 (2)

0.0290 (12)

0.0366 (13)

0.0256 (12)

0.0218 (11)

0.0209 (10)

0.0197 (10)

0.0332 (12)

0.0482 (15)

0.0458 (14)

0.0296 (11)

0.0194 (10)

0.0219 (10)

0.0232 (10)

0.0239 (10)

0.0427 (14)

0.0422 (15)

0.0285 (11)

0.0268 (11)

0.0234 (10)

0.0283 (11)

0.0368 (12)

0.0340 (12)

0.0291 (11)

0.0235 (10)

0.0199 (10)

0.0386 (13)

0.0474 (15)

0.0420 (13)

0.0262 (11)

0.0181 (10)

0.0176 (10)

0.0231 (10)

0.0232 (10)

0.0429 (14)

0.0621 (17)

0.0319 (12)

0.0279 (11)

0.0248 (12)

0.0263 (13)

0.0405 (14)

0.0294 (12)

0.0269 (11)

0.0362 (12)

0.0479 (14)

0.0694 (18)

0.0578 (16)

0.0406 (13)

0.0331 (12)

0.0207 (10)

0.0210 (10)

0.0218 (10)

0.0311 (14)

0.0654 (18)

0.0249 (11)

0.0281 (11)

0.0272 (11)

0.0297 (12)

0.0265 (12)

0.0270 (12)

0.0340 (12)

0.0275 (11)

0.0366 (12)

0.0478 (14)

0.0673 (17)

0.0560 (16)

0.0416 (13)

0.0341 (11)

0.0235 (10)

0.0225 (10)

0.0221 (10)

0.0439 (14)

0.0377 (15)

0.0257 (12)

0.0317 (12)

−0.0129 (13)

−0.0214 (14)

−0.0087 (11)

−0.0031 (10)

−0.0022 (10)

0.0028 (9)

−0.0139 (12)

0.0097 (13)

0.0128 (12)

−0.0002 (10)

−0.0108 (10)

−0.0049 (10)

−0.0111 (11)

−0.0040 (13)

0.0097 (12)

0.0006 (10)

−0.0017 (9)

0.0021 (9)

−0.0009 (10)

−0.0066 (11)

−0.0057 (10)

0.0004 (9)

C3

C4

0.0660 (17)

0.0478 (14)

0.0422 (13)

0.0303 (12)

0.0407 (15)

0.0285 (13)

0.0316 (14)

0.0342 (13)

0.0272 (11)

0.0292 (12)

0.0307 (12)

0.0254 (11)

0.126 (3)

C5

C6

−0.0018 (9)

−0.0006 (9)

0.0016 (11)

0.0016 (13)

0.0040 (12)

0.0025 (10)

0.0011 (9)

C7

C8

0.0065 (11)

0.0048 (11)

0.0026 (11)

0.0037 (10)

0.0036 (9)

C9

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19

C20

C21

C22

C23

C24

C25

C26

C27

C28

C29

C30

C31

C32

C33

C34

C35

C36

C37

C38

0.0023 (9)

0.0003 (8)

−0.0035 (9)

−0.0009 (9)

−0.0179 (15)

−0.0048 (14)

−0.0026 (10)

−0.0073 (9)

−0.0022 (9)

−0.0018 (10)

−0.0021 (11)

0.0001 (11)

0.0039 (10)

−0.0021 (9)

0.0025 (9)

0.0050 (9)

−0.0006 (8)

0.0003 (8)

0.0009 (9)

−0.0274 (15)

0.0372 (16)

0.0049 (9)

0.0123 (11)

−0.0085 (13)

0.0022 (9)

0.084 (2)

0.0373 (13)

0.0282 (12)

0.0371 (12)

0.0414 (13)

0.0527 (15)

0.0571 (16)

0.0405 (14)

0.0322 (12)

0.0314 (12)

0.0349 (13)

0.0261 (13)

0.0291 (13)

0.0346 (13)

0.0264 (11)

0.0290 (12)

0.0299 (12)

0.0330 (12)

0.0462 (15)

0.080 (2)

0.0046 (9)

0.0023 (9)

0.0051 (9)

−0.0010 (9)

0.0026 (9)

0.0016 (10)

−0.0032 (11)

0.0099 (11)

0.0127 (10)

0.0082 (9)

0.0017 (10)

−0.0022 (10)

0.0021 (10)

0.0018 (9)

0.0065 (10)

0.0114 (11)

0.0103 (12)

−0.0056 (11)

0.0009 (10)

0.0015 (9)

−0.0009 (9)

−0.0053 (11)

−0.0083 (13)

−0.0132 (12)

−0.0069 (9)

−0.0030 (9)

0.0009 (8)

0.0038 (11)

0.0026 (11)

0.0042 (11)

0.0042 (10)

0.0023 (8)

0.0000 (8)

−0.0038 (9)

0.0017 (9)

−0.0035 (9)

−0.0003 (9)

0.0080 (11)

0.0078 (15)

−0.0049 (10)

−0.0095 (10)

−0.0009 (8)

−0.0008 (8)

−0.0007 (11)

−0.0177 (13)

−0.0042 (9)

−0.0054 (9)

0.0040 (9)

−0.0083 (11)

0.0100 (14)

0.0036 (10)

0.0072 (10)

0.0399 (13)

0.0400 (14)

Geometric parameters (Å, º)

N1—C13

N1—C14

N2—C13

N2—C15

N2—H2A

N3—C18

N4—C19

N5—C32

N5—C33

N5—H5B

1.331 (2)

C15—C19

1.426 (3)

1.373 (2)

1.356 (2)

1.377 (2)

0.97 (2)

C16—H16A

C16—H16B

C16—H16C

C17—H17A

C17—H17B

C17—H17C

C20—C21

0.9800

1.386 (3)

1.395 (3)

0.9500

1.147 (2)

1.145 (2)

1.357 (2)

1.365 (2)

C20—C25

0.953 (19)

C20—H20A

Acta Cryst. (2013). C69, 529-533

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supplementary materials

N6—C32

N6—C34

N7—C37

N8—C38

C1—C2

1.334 (2)

1.373 (2)

1.146 (2)

1.147 (2)

1.383 (3)

1.401 (2)

0.9500

C21—C22

C21—C35

C22—C23

C22—H22A

C23—C24

C23—C36

C24—C25

C24—H24A

C25—C26

C26—C27

C26—C31

C27—C28

C27—H27A

C28—C29

C28—H28A

C29—C30

C29—H29A

C30—C31

C30—H30A

C31—C32

C33—C34

C33—C37

C34—C38

C35—H35A

C35—H35B

C35—H35C

C36—H36A

C36—H36B

C36—H36C

1.390 (3)

1.504 (3)

1.392 (3)

0.9500

1.386 (3)

1.516 (3)

1.400 (2)

0.9500

C1—C6

C1—H1A

C2—C3

1.386 (3)

1.513 (3)

1.393 (3)

0.9500

C2—C16

C3—C4

1.495 (3)

1.397 (3)

1.405 (2)

1.377 (3)

0.9500

C3—H3A

C4—C5

1.388 (3)

1.510 (3)

1.390 (3)

0.9500

C4—C17

C5—C6

1.382 (3)

0.9500

C5—H5A

C6—C7

1.488 (3)

1.397 (3)

1.402 (2)

1.377 (3)

0.9500

1.383 (3)

0.9500

C7—C8

C7—C12

C8—C9

1.396 (2)

0.9500

C8—H8A

C9—C10

C9—H9A

C10—C11

C10—H10A

C11—C12

C11—H11A

C12—C13

C14—C15

C14—C18

1.465 (2)

1.372 (2)

1.424 (3)

1.428 (3)

0.9800

1.380 (3)

0.9500

1.385 (3)

0.9500

1.395 (3)

0.9500

0.9800

1.467 (2)

1.372 (2)

1.433 (3)

0.9800

C13—N1—C14

C13—N2—C15

C13—N2—H2A

C15—N2—H2A

C32—N5—C33

C32—N5—H5B

C33—N5—H5B

C32—N6—C34

C2—C1—C6

105.12 (14)

107.45 (15)

125.0 (12)

126.9 (12)

107.46 (16)

128.0 (12)

124.5 (12)

105.18 (15)

121.5 (2)

119.3

H17A—C17—H17C

H17B—C17—H17C

N3—C18—C14

109.5

178.7 (2)

179.0 (2)

121.88 (18)

119.1

N4—C19—C15

C21—C20—C25

C21—C20—H20A

C25—C20—H20A

C20—C21—C22

C20—C21—C35

C22—C21—C35

C21—C22—C23

C21—C22—H22A

C23—C22—H22A

C24—C23—C22

C24—C23—C36

C22—C23—C36

C23—C24—C25

C23—C24—H24A

C25—C24—H24A

119.1

118.4 (2)

120.88 (18)

120.73 (19)

121.5 (2)

119.3

C2—C1—H1A

C6—C1—H1A

C1—C2—C3

119.3

118.7 (2)

120.8 (2)

120.5 (2)

121.7 (2)

119.1

C1—C2—C16

C3—C2—C16

C2—C3—C4

119.3

118.90 (19)

120.3 (2)

120.8 (2)

121.2 (2)

119.4

C2—C3—H3A

C4—C3—H3A

C5—C4—C3

119.1

118.1 (2)

121.0 (2)

C5—C4—C17

119.4

Acta Cryst. (2013). C69, 529-533

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supplementary materials

C3—C4—C17

120.9 (2)

122.0 (2)

119.0

C20—C25—C24

C20—C25—C26

C24—C25—C26

C27—C26—C31

C27—C26—C25

C31—C26—C25

C28—C27—C26

C28—C27—H27A

C26—C27—H27A

C27—C28—C29

C27—C28—H28A

C29—C28—H28A

C28—C29—C30

C28—C29—H29A

C30—C29—H29A

C29—C30—C31

C29—C30—H30A

C31—C30—H30A

C30—C31—C26

C30—C31—C32

C26—C31—C32

N6—C32—N5

118.15 (19)

121.49 (17)

120.24 (18)

117.42 (19)

118.62 (18)

123.88 (18)

121.9 (2)

119.1

C4—C5—C6

C4—C5—H5A

C6—C5—H5A

C5—C6—C1

119.0

118.0 (2)

122.20 (17)

119.72 (19)

117.13 (19)

119.00 (18)

123.85 (17)

121.9 (2)

119.0

C5—C6—C7

C1—C6—C7

C8—C7—C12

C8—C7—C6

119.1

C12—C7—C6

120.5 (2)

119.7

C9—C8—C7

C9—C8—H8A

C7—C8—H8A

C8—C9—C10

119.7

119.0

118.9 (2)

120.6

120.6 (2)

119.7

C8—C9—H9A

C10—C9—H9A

C9—C10—C11

C9—C10—H10A

C11—C10—H10A

C10—C11—C12

C10—C11—H11A

C12—C11—H11A

C11—C12—C7

C11—C12—C13

C7—C12—C13

N1—C13—N2

120.6

119.7

121.1 (2)

119.4

119.0 (2)

120.5

119.4

120.5

120.14 (18)

115.67 (17)

124.10 (17)

111.24 (17)

123.37 (16)

125.13 (17)

105.98 (16)

124.07 (17)

129.88 (18)

110.14 (16)

126.50 (18)

123.28 (16)

109.5

120.6 (2)

119.7

120.69 (18)

115.99 (17)

123.27 (18)

111.46 (16)

127.54 (16)

120.83 (16)

110.63 (16)

127.52 (18)

121.81 (16)

105.33 (16)

131.59 (18)

123.06 (16)

109.5

N6—C32—C31

N5—C32—C31

N5—C33—C34

N5—C33—C37

C34—C33—C37

C33—C34—N6

C33—C34—C38

N6—C34—C38

C21—C35—H35A

C21—C35—H35B

N1—C13—C12

N2—C13—C12

C15—C14—N1

C15—C14—C18

N1—C14—C18

C14—C15—N2

C14—C15—C19

N2—C15—C19

C2—C16—H16A

C2—C16—H16B

H16A—C16—H16B

C2—C16—H16C

H16A—C16—H16C

H16B—C16—H16C

C4—C17—H17A

C4—C17—H17B

H17A—C17—H17B

C4—C17—H17C

109.5

H35A—C35—H35B

C21—C35—H35C

H35A—C35—H35C

H35B—C35—H35C

C23—C36—H36A

C23—C36—H36B

H36A—C36—H36B

C23—C36—H36C

H36A—C36—H36C

H36B—C36—H36C

N7—C37—C33

109.5

177.9 (2)

176.9 (2)

109.5

N8—C38—C34

C6—C1—C2—C3

C6—C1—C2—C16

C1—C2—C3—C4

C16—C2—C3—C4

−2.1 (3)

C25—C20—C21—C22

C25—C20—C21—C35

C20—C21—C22—C23

C35—C21—C22—C23

−0.6 (3)

176.46 (18)

1.7 (3)

178.24 (18)

−1.3 (3)

−176.88 (19)

179.77 (19)

Acta Cryst. (2013). C69, 529-533

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supplementary materials

C2—C3—C4—C5

0.5 (3)

C21—C22—C23—C24

2.1 (3)

C2—C3—C4—C17

C3—C4—C5—C6

−178.2 (2)

−2.5 (3)

C21—C22—C23—C36

C22—C23—C24—C25

C36—C23—C24—C25

C21—C20—C25—C24

C21—C20—C25—C26

C23—C24—C25—C20

C23—C24—C25—C26

C20—C25—C26—C27

C24—C25—C26—C27

C20—C25—C26—C31

C24—C25—C26—C31

C31—C26—C27—C28

C25—C26—C27—C28

C26—C27—C28—C29

C27—C28—C29—C30

C28—C29—C30—C31

C29—C30—C31—C26

C29—C30—C31—C32

C27—C26—C31—C30

C25—C26—C31—C30

C27—C26—C31—C32

C25—C26—C31—C32

C34—N6—C32—N5

C34—N6—C32—C31

C33—N5—C32—N6

C33—N5—C32—C31

C30—C31—C32—N6

C26—C31—C32—N6

C30—C31—C32—N5

C26—C31—C32—N5

C32—N5—C33—C34

C32—N5—C33—C37

N5—C33—C34—N6

C37—C33—C34—N6

N5—C33—C34—C38

C37—C33—C34—C38

C32—N6—C34—C33

C32—N6—C34—C38

−177.13 (19)

−0.9 (3)

C17—C4—C5—C6

C4—C5—C6—C1

176.30 (19)

2.1 (3)

178.36 (19)

1.8 (3)

C4—C5—C6—C7

−174.95 (18)

0.3 (3)

−174.31 (17)

−1.0 (3)

C2—C1—C6—C5

C2—C1—C6—C7

177.39 (18)

133.6 (2)

−43.3 (3)

−44.4 (3)

138.66 (19)

1.9 (3)

175.13 (18)

135.43 (19)

−40.6 (3)

−41.1 (3)

142.82 (19)

2.0 (3)

C5—C6—C7—C8

C1—C6—C7—C8

C5—C6—C7—C12

C1—C6—C7—C12

C12—C7—C8—C9

C6—C7—C8—C9

−176.26 (19)

−0.5 (3)

−174.83 (18)

0.3 (3)

C7—C8—C9—C10

C8—C9—C10—C11

C9—C10—C11—C12

C10—C11—C12—C7

C10—C11—C12—C13

C8—C7—C12—C11

C6—C7—C12—C11

C8—C7—C12—C13

C6—C7—C12—C13

C14—N1—C13—N2

C14—N1—C13—C12

C15—N2—C13—N1

C15—N2—C13—C12

C11—C12—C13—N1

C7—C12—C13—N1

C11—C12—C13—N2

C7—C12—C13—N2

C13—N1—C14—C15

C13—N1—C14—C18

N1—C14—C15—N2

C18—C14—C15—N2

N1—C14—C15—C19

C18—C14—C15—C19

C13—N2—C15—C14

C13—N2—C15—C19

−0.9 (3)

−2.0 (3)

0.9 (3)

1.4 (3)

0.6 (3)

0.9 (3)

−176.92 (18)

−1.9 (3)

−175.68 (17)

−2.5 (3)

176.11 (17)

175.41 (17)

−6.6 (3)

174.06 (17)

173.76 (17)

−9.6 (3)

0.2 (2)

−0.5 (2)

−174.96 (18)

0.0 (2)

173.90 (16)

0.6 (2)

175.52 (16)

130.2 (2)

−47.2 (3)

−44.5 (2)

138.05 (18)

−0.3 (2)

−173.62 (17)

−37.1 (3)

146.47 (18)

136.51 (18)

−39.9 (3)

−0.5 (2)

177.64 (17)

0.3 (2)

176.68 (18)

0.2 (2)

−177.49 (18)

179.01 (19)

1.2 (3)

−176.73 (19)

177.10 (18)

0.1 (3)

−0.2 (2)

0.1 (2)

−179.03 (17)

−176.85 (18)

Hydrogen-bond geometry (Å, º)

D—H···A

D—H

H···A

D···A

D—H···A

N2—H2A···N6

0.97 (2)

0.953 (19)

0.95

2.02 (2)

1.95 (2)

2.69

2.907 (2)

2.882 (2)

3.567 (3)

3.484 (3)

3.497 (3)

150.9 (17)

164.4 (17)

154

N5—H5B···N1ⁱ

C11—H11A···N8ⁱⁱ

C16—H16B···N6ⁱⁱⁱ

C16—H16C···N3^iv

0.98

2.60

150

0.98

2.65

145

Acta Cryst. (2013). C69, 529-533

sup-7

supplementary materials

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+2, −y+1, −z; (iii) −x+3/2, y−1/2, −z+1/2; (iv) x+1/2, −y+1/2, z+1/2.

(II) 2-(2′,4′,6′-Trimethylbiphenyl-2-yl)-1H-imidazole-4,5-dicarbonitrile

Crystal data

C₂₀H₁₆N₄

M_r= 312.37

F(000) = 656

D_x= 1.227 Mg m⁻³

Melting point: 486(1) K

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 247 reflections

θ = 3–23°

Monoclinic, P2₁/c

Hall symbol: -P 2ybc

a = 12.373 (1) Å

b = 10.303 (2) Å

c = 13.279 (2) Å

β = 92.578 (7)°

V = 1691.1 (4) Å³

Z = 4

µ = 0.08 mm⁻¹

T = 133 K

Plate, colourless

0.60 × 0.40 × 0.10 mm

Data collection

Siemens SMART 1K CCD area-detector

diffractometer

Radiation source: normal-focus sealed tube

Graphite monochromator

ω scans

25406 measured reflections

4381 independent reflections

3014 reflections with I > 2σ(I)

R_int= 0.033

θ

_max= 29.0°, θ_min= 2.5°

Absorption correction: multi-scan

SADABS (Sheldrick, 1996)

h = −14→16

k = −12→14

l = −18→18

T

_min= 0.784, T_max= 0.993

Refinement

Refinement on F²

Least-squares matrix: full

R[F²> 2σ(F²)] = 0.040

wR(F²) = 0.104

S = 1.04

4381 reflections

Hydrogen site location: inferred from

neighbouring sites

H atoms treated by a mixture of independent

and constrained refinement

w = 1/[σ²(F_o²) + (0.045P)²]

where P = (F_o²+ 2F_c²)/3

225 parameters

0 restraints

Primary atom site location: structure-invariant

direct methods

Secondary atom site location: difference Fourier

map

(Δ/σ)_max< 0.001

Δρ_max= 0.23 e Å⁻³

Δρ_min= −0.20 e Å⁻³

Extinction correction: SHELXL97 (Sheldrick,

2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4

Extinction coefficient: 0.0160 (17)