Two seven-membered heterocycles with 1,2-diaza ring N atoms: 3,5,7-triphenyl-1,2-diazacyclohepta-1(7),2-diene and 3,7-bis(2-hydroxyphenyl)-5- phenyl-1,2-diazacyclohepta-1(7),2-diene

Article abstract of DOI:10.1107/S0108270113023792

The title compounds, 3,5,7-triphenyl-1,2-diazacyclohepta-1(7),2-diene, C₂₃H₂₀N2, (I), and 3,7-bis(2-hydroxyphenyl)-5-phenyl-1,2- diazacyclohepta-1(7),2-diene, C₂₃H₂₀N₂O ₂, (II), constitute the first structurally characterized examples of seven-membered heterocycles with 1,2-diaza ring N atoms. Compound (I) crystallizes in the space group P, with two independent molecules in the asymmetric unit that differ in the conformation of one of the phenyl rings, while (II) crystallizes in the space group C2/c. The C₅N₂ ring in each of (I) and (II) adopts a twist-boat conformation. Compound (I) exhibits neither C - H...π interactions nor π-π stacking interactions, whereas (II) shows both intramolecular O - H...N hydrogen bonds and a C - H...π interaction that joins the molecules into an infinite chain in the [010] direction.

Full text of DOI:10.1107/S0108270113023792

organic compounds
Acta Crystallographica Section C
Crystal Structure
presence of HOAc afford the title compounds, viz. (I) (Ar =
C6H5) and (II) (Ar = 2-HOC6H4).
Communications
ISSN 0108-2701
2. Experimental
2.1. Synthesis and crystallization
Two seven-membered heterocycles
with 1,2-diaza ring N atoms:
3,5,7-triphenyl-1,2-diazacyclohepta-
1(7),2-diene and 3,7-bis(2-hydroxy-
phenyl)-5-phenyl-1,2-diazacyclo-
hepta-1(7),2-diene
A mixture of ArCOCH2CHPhCH2COAr (4 mmol) and
80% N2H4ÁH2O (4 mmol) in the presence of HOAc (2 drops)
in EtOH (25 ml) was refluxed for 12 h. For (I), the solvent was
removed in vacuo and the resulting residue was isolated by
chromatography on silica gel. Elution with petroleum ether–
tetrahydrofuran (2:1 v/v) gave one colourless band which was
recrystallized from petroleum ether (333–363 K) and CH2Cl2
to afford a white solid of (I) (yield 0.701 g, 54%). For (II), the
resulting solid was collected, washed with EtOH, air-dried and
recrystallized from petroleum ether (333–363 K) and CH2Cl2
to give a yellow solid (yield 0.713 g, 50%).
Yao-Cheng Shi* and Hong-Yang Duan
Analysis calculated for C23H20N2, (I): C 85.15, H 6.21,
N 8.63%; found: C 85.11, H 6.34, N 8.57%; m.p. 433–435 K.
Spectroscopic analysis: IR (KBr disk, ꢁ, cmÀ1): 3029 (m),
2921 (m), 1667 (m), 1590 (m), 1547 (m), 1492 (s), 1446 (s),
1344 (m), 1254 (m), 1187 (m), 1065 (m), 1020 (m), 919 (m),
761 (vs), 697 (vs); UV ("ꢂ Â 104, in DMF): 290.00 (1.02), 375.00
College of Chemistry and Chemical Engineering, Yangzhou University, 180
SiWangTing Road, Yangzhou 225002, People’s Republic of China
Correspondence e-mail: ycshi@yzu.edu.cn
Received 10 August 2013
Accepted 23 August 2013
1
(0.86) nm; H NMR (600 MHz, CDCl3, TMS): ꢃ 6.797–7.804
The title compounds, 3,5,7-triphenyl-1,2-diazacyclohepta-
1(7),2-diene, C23H20N2, (I), and 3,7-bis(2-hydroxyphenyl)-5-
phenyl-1,2-diazacyclohepta-1(7),2-diene, C23H20N2O2, (II),
constitute the first structurally characterized examples of
seven-membered heterocycles with 1,2-diaza ring N atoms.
Compound (I) crystallizes in the space group P1, with two
independent molecules in the asymmetric unit that differ in
the conformation of one of the phenyl rings, while (II)
crystallizes in the space group C2/c. The C5N2 ring in each of
(I) and (II) adopts a twist-boat conformation. Compound (I)
exhibits neither C—HÁ Á Áꢀ interactions nor ꢀ–ꢀ stacking
interactions, whereas (II) shows both intramolecular O—
HÁ Á ÁN hydrogen bonds and a C—HÁ Á Áꢀ interaction that joins
the molecules into an infinite chain in the [010] direction.
(m, 15H, 3C6H5), 4.045–4.087 (m, 1H, CH), 3.002–3.018 (m,
4H, 2CH2).
Analysis calculated for C23H20N2O2, (II): C 77.51, H 5.66,
N 7.86%; found: C 77.75, H 5.69, N 7.67%; m.p. 510–512 K.
Spectroscopic analysis: IR (KBr disk, ꢁ, cmÀ1): 3434 (m),
3030 (m), 2921 (m), 1668 (m), 1590 (m), 1548 (m), 1493 (s),
1447 (s), 1344 (s), 1300 (m), 1255 (m), 1187 (m), 1020 (m),
919 (m), 762 (vs), 698 (vs); UV ("ꢂ Â 104, in DMF): 290.00
1
(1.16), 377.00 (0.76) nm; H NMR (600 MHz, CDCl3, TMS):
ꢃ 12.956 (s, 2H, 2OH), 6.765–7.364 (m, 14H, 2C6H5, C6H4),
4.083–4.124 (m, 1H, CH), 3.053–3.105 (m, 4H, 2CH2).
Keywords: Seven-membered ring; nitrogen-containing
heterocycle; conformational analysis; 1,5-diketone.
1. Introduction
2.2. Refinement
Nitrogen-containing heterocycles (N-heterocycles) are ubi-
quitous in natural products, pharmaceuticals and materials
science. Their synthesis represents a substantial chemical
research effort that includes the total synthesis of natural
products and medicinal chemistry (Behenna et al., 2012). To
the best of our knowledge, there are no reported examples
of 1,2-diaza heterocycles with seven-membered rings
(Pettersson, 2011). As part of an on-going project on the
syntheses of N-heterocycles (Shi et al., 2006a,b,c; Shi, Sui &
Zhu, 2006; Shi, Zhu & Ng, 2007; Shi, Sui, Cheng et al., 2007;
Shi, Cheng, Sui et al., 2007; Zhu, Shi, Shen et al., 2011), in this
article we describe the syntheses and crystal structures of two
seven-membered N-heterocycles. Reactions of 1,5-diketones
ArCOCH2CHPhCH2COAr with hydrazine hydrate in the
Crystal data, data collection and structure refinement
details are summarized in Table 1. H atoms attached to C
atoms were placed at calculated positions and treated as riding
˚
atoms, with C—H = 0.93 (CH, aromatic), 0.97 (CH2) or 0.98 A
(CH), and with Uiso(H) = 1.2Ueq(C). For (II), H atoms
attached to O atoms were located in a difference Fourier map
and refined freely with individual isotropic displacement
parameters.
3. Results and discussion
Compound (I) crystallizes in the space group P1, with two
independent molecules in the asymmetric unit, labelled (Ia)
Acta Cryst. (2013). C69, 1177–1180
doi:10.1107/S0108270113023792
# 2013 International Union of Crystallography 1177

organic compounds
Table 1
Experimental details.
(I)
(II)
Crystal data
Chemical formula
Mr
C23H20N2
324.41
C23H20N2O2
356.41
Crystal system, space group
Temperature (K)
Triclinic, P1
296
9.4245 (14), 10.6605 (16), 18.405 (3)
Monoclinic, C2/c
296
23.9715 (14), 9.5669 (16),
18.2303 (12)
90, 119.256 (3), 90
3647.5 (7)
˚
a, b, c (A)
ꢄ, ꢅ, ꢆ (ꢀ)
80.2989 (19), 85.094 (2), 78.1155 (19)
1781.1 (5)
3
˚
V (A )
Z
Radiation type
4
8
Mo Kꢄ
0.07
0.24 Â 0.20 Â 0.15
Mo Kꢄ
0.08
0.30 Â 0.28 Â 0.26
ꢇ (mmÀ1
Crystal size (mm)
)
Data collection
Diffractometer
Bruker SMART APEX CCD area-
detector diffractometer
Multi-scan (SADABS; Sheldrick,
2004)
Bruker SMART APEX CCD area-
detector diffractometer
Multi-scan (SADABS; Sheldrick,
2004)
Absorption correction
Tmin, Tmax
0.967, 0.982
15860, 8141, 5062
0.967, 0.972
12998, 3224, 1647
No. of measured, independent and
observed [I > 2ꢈ(I)] reflections
Rint
0.030
0.654
0.071
0.595
À1
˚
(sin ꢉ/ꢂ)max (A
)
Refinement
R[F2 > 2ꢈ(F2)], wR(F2), S
No. of reflections
No. of parameters
0.049, 0.149, 1.02
8141
451
H-atom parameters constrained
0.045, 0.109, 0.96
3224
253
H atoms treated by a mixture of
independent and constrained
refinement
H-atom treatment
À3
˚
Áꢊmax, Áꢊmin (e A
)
0.18, À0.21
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SIR2004 (Burla et al., 2005), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 2012) and
0.13, À0.14
publCIF (Westrip, 2010).
and (Ib) (Fig. 1 and Table 2). A quaternion fit plot of (Ia) on
inverted (Ib) (Spek, 2009) (Fig. 2) shows that molecules (Ia)
and (Ib) are conformers, differing mainly in the rotation of
one of the phenyl groups with respect to the rest of the mol-
ecule. The C1–C6 and C10–C15 planes form a dihedral angle
of 59.15 (9)ꢀ for (Ia). The corresponding angle in (Ib) for the
C24–C29 and C33–C38 planes is 51.68 (10)ꢀ. Atoms C7, C17,
C30 and C40 each adopt sp2-hybridization (Table 2). However,
the C N bonds are not conjugated with the respective phenyl
groups, the dihedral angles between the C1–C6 and N1/C7/C8
planes, and the C18–C23 and N2/C16/C17 planes, being
26.9 (2) and 28.2 (2)ꢀ, respectively, for (Ia), and the corre-
sponding dihedral angles being 33.0 (2) and 17.9 (2)ꢀ for (Ib).
Furthermore, the two C N bonds are not involved in
conjugation with each other, with C—N—N—C torsion angles
of À60.5 (2)ꢀ for (Ia) and 61.8 (2)ꢀ for (Ib). The seven-
membered ring in (Ia) displays a twist-boat conformation,
with puckering parameters (Cremer & Pople, 1975; Zotov et
˚
˚
al., 1997) q2 = 1.1007 (17) A, q3 = 0.0974 (17) A, ’2
=
ꢀ
ꢀ
˚
39.77 (9) , ’3 = 196.9 (10) and Q = 1.1049 (17) A, and this is
also indicated by the dihedral angles of 62.4 (2) and 63.0 (2)ꢀ
formed by the C8/C9/C16 plane with the N1/C7/C8 and N2/
C16/C17 planes, respectively. The seven-membered ring in
(Ib) also exhibits a similar twist-boat conformation, with
˚
˚
puckering paraꢀmeters q2 = 1.11ꢀ94 (17) A, q3 = 0.0983 (17) A,
˚
’2 = 219.87 (9) , ’3 = 18.2 (10) and Q = 1.1238 (18) A. The
C31/C32/C39 plane forms dihedral angles with the N3/C30/
Table 2
Selected geometric parameters (A, ) for (I).
ꢀ
˚
C6—C7
C7—N1
C17—N2
C17—C18
C29—C30
1.488 (2)
1.286 (2)
1.289 (2)
1.487 (2)
1.486 (2)
C30—N3
C40—N4
C40—C41
N1—N2
N3—N4
1.284 (2)
1.291 (2)
1.488 (2)
1.4056 (19)
1.4083 (19)
Table 3
Selected geometric parameters (A, ) for (II).
ꢀ
˚
C6—C7
C7—N1
C17—N2
1.471 (3)
1.297 (3)
1.300 (3)
C17—C18
N1—N2
1.468 (3)
1.394 (2)
N1—C7—C6
N1—C7—C8
C6—C7—C8
N2—C17—C18
N2—C17—C16
C18—C17—C16
117.17 (14)
121.65 (15)
121.11 (14)
117.66 (15)
122.19 (15)
120.14 (14)
N3—C30—C29
N3—C30—C31
C29—C30—C31
N4—C40—C41
N4—C40—C39
C41—C40—C39
117.17 (15)
121.53 (15)
121.22 (15)
116.91 (14)
121.36 (15)
121.68 (14)
N1—C7—C6
N1—C7—C8
C6—C7—C8
117.0 (2)
120.1 (2)
122.8 (2)
N2—C17—C18
N2—C17—C16
C18—C17—C16
116.4 (2)
119.8 (2)
123.8 (2)
C7—N1—N2—C17
À60.5 (2)
C30—N3—N4—C40
61.8 (2)
C7—N1—N2—C17
À59.8 (3)
ꢁ
1178 Shi and Duan C23H20N2 and C23H20N2O2
Acta Cryst. (2013). C69, 1177–1180

organic compounds
Figure 3
A view of (II), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 20% probability level. Dashed lines indicate
intramolecular hydrogen bonds.
Figure 1
The two independent molecules [labelled (Ia) and (Ib)] of (I), showing
the atom-numbering scheme. Displacement ellipsoids are drawn at the
20% probability level.
Figure 4
Part of the crystal structure of (II), showing the formation of the [010]
chain linked by C—HÁ Á Áꢀ interactions (dashed lines). For clarity, H atoms
not involved in the motif shown have been omitted. Atoms labelled with a
hash symbol (#) or ampersand (&) are at the symmetry positions (x, y À 1,
z) and (x, y + 1, z), respectively.
˚
of (Ia), with puckering parameters q2 = 1.087 (2) A, q3 =
Figure 2
A quaternion MOLFIT plot (PLATON; Spek, 2009) of the two
independent molecules, viz. (Ia) and inverted (Ib).
0.116 (2) A, ’2 = 36.36 (13)ꢀ, ’3 = 179.3 (12)ꢀ and Q =
1.093 (2) A. Additionally, the C1–C6 and C10–C15 planes
˚
˚
make a dihedral angle of 63.11 (13)ꢀ.
No ꢀ–ꢀ stacking interactions or C—HÁ Á Áꢀ interactions are
present in (I). The only supramolecular interaction in (II) is
C21—H21Á Á ÁCg2i (ꢀ), where Cg2 is the centroid of the C10–
C15 phenyl ring [symmetry code: (i) x, y À 1, z]. Molecules of
(II) join into an infinite chain in the b-axis direction (Table 4
and Fig. 4).
C31 and N4/C39/C40 planes of 63.0 (2) and 64.0 (2)ꢀ, respec-
tively.
Compound (II) crystallizes in the space group C2/c (Fig. 3).
Atoms C7 and C17 are both sp2-hybridized (Table 3). Although
the two C N bonds are not conjugated with each other, with
a C—N—N—C torsion angle of À59.8 (3)ꢀ, they participate in
partial conjugation with their attached phenyl rings, as shown
by the small dihedral angles of 3.6 (2)ꢀ between the C1–C6
and N1/C7/C8 planes and 4.8 (3)ꢀ between the C18–C23 and
N2/C16/C17 planes. Thus, the C6—C7 and C17—C18 bonds in
(II) are shorter than those in (I), the latter being typical single
bonds (Csp2—Csp2). The C8/C9/C16 plane forms dihedral
angles of 64.2 (3) and 60.3 (3)ꢀ with the N1/C7/C8 and N2/C16/
C17 planes, respectively. This indicates that the seven-
membered ring has a twist-boat conformation similar to that
Table 4
Hydrogen-bond geometry (A, ) for (II).
ꢀ
˚
Cg2 is the centroid of the C10–C15 benzene ring.
D—HÁ Á ÁA
D—H
HÁ Á ÁA
DÁ Á ÁA
D—HÁ Á ÁA
O1—H1OÁ Á ÁN1
O2—H2OÁ Á ÁN2
C21—H21Á Á ÁCg2i
0.95 (3)
0.97 (3)
0.93
1.71 (3)
1.65 (3)
2.74
2.539 (3)
2.532 (3)
3.495 (3)
144 (3)
150 (2)
138
Symmetry code: (i) x; y À 1; z.
ꢁ
Acta Cryst. (2013). C69, 1177–1180
Shi and Duan C23H20N2 and C23H20N2O2 1179

organic compounds
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De
Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38,
381–388.
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Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
Pettersson, B. (2011). PhD thesis, Karolinska Institutet, Stockholm, Sweden.
As in the crystalline state of (II), a low-field signal of the
OH group at 12.956 p.p.m. confirms the presence of intra-
molecular O—HÁ Á ÁN hydrogen bonds in a CDCl3 solution of
(II) (Shi, Zhang, Cheng et al., 2006; Shi & Zhang, 2007; Shi et
al., 2012).
¨
Sheldrick, G. M. (2004). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Shi, Y.-C., Cheng, H.-J., Sui, C.-X. & Zhu, B.-B. (2007). J. Chem. Crystallogr.
37, 399–405.
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633–638.
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37, 407–413.
Shi, Y.-C., Sui, C.-X. & Zhu, B.-B. (2006). Acta Cryst. E62, m2781–m2783.
Shi, Y.-C. & Zhang, S.-H. (2007). Acta Cryst. E63, o138–o140.
Shi, Y.-C., Zhang, S.-H., Cheng, H.-J. & Sun, W.-P. (2006). Acta Cryst. C62,
m407–m410.
Shi, Y.-C., Zhu, B.-B. & Ng, S. W. (2007). Acta Cryst. E63, m1385–m1387.
Shi, Y.-C., Zhu, B.-B. & Sui, C.-X. (2006a). Acta Cryst. E62, m2389–m2391.
Shi, Y.-C., Zhu, B.-B. & Sui, C.-X. (2006b). Acta Cryst. E62, m2461–m2463.
Shi, Y.-C., Zhu, B.-B. & Sui, C.-X. (2006c). Acta Cryst. C62, m577–m580.
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The authors thank the Mao Zedong Foundation of China,
Project Funded by the Priority Academic Program Develop-
ment of Jiangsu Higher Education Institutions (PAPD), the
Natural Science Foundation of China (grant No. 20572091)
and the Natural Science Foundation of Jiangsu Province
(grant No. 05KJB150151) for financial support of this work.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3507). Services for accessing these data are
described at the back of the journal.
References
Behenna, D. C., Liu, Y.-Y., Yurino, T., Kim, J., White, D. E., Virgil, S. C. &
Stoltz, B. M. (2012). Nat. Chem. 4, 130–133.
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
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37, 766–773.
ꢁ
1180 Shi and Duan C23H20N2 and C23H20N2O2
Acta Cryst. (2013). C69, 1177–1180

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 1177-1180 [doi:10.1107/S0108270113023792]
Two seven-membered heterocycles with 1,2-diaza ring N atoms: 3,5,7-tri-
phenyl-1,2-diazacyclohepta-1(7),2-diene and 3,7-bis(2-hydroxyphenyl)-5-
phenyl-1,2-diazacyclohepta-1(7),2-diene
Yao-Cheng Shi and Hong-Yang Duan
Computing details
For both compounds, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction:
SAINT (Bruker, 2009); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine
structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and WinGX (Farrugia, 2012); software
used to prepare material for publication: publCIF (Westrip, 2010).
(I) 3,5,7-triphenyl-1,2-diazacyclohepta-1(7),2-diene
Crystal data
C23H20N2
Z = 4
Mr = 324.41
Triclinic, P1
F(000) = 688
Dx = 1.210 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 5062 reflections
θ = 2.0–27.7°
a = 9.4245 (14) Å
b = 10.6605 (16) Å
c = 18.405 (3) Å
α = 80.2989 (19)°
β = 85.094 (2)°
γ = 78.1155 (19)°
V = 1781.1 (5) Å3
µ = 0.07 mm−1
T = 296 K
Block, white
0.24 × 0.20 × 0.15 mm
Data collection
Bruker SMART APEX CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
15860 measured reflections
8141 independent reflections
5062 reflections with I > 2σ(I)
Rint = 0.030
ω and φ scans
θmax = 27.7°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = −11→12
k = −13→13
l = −24→24
T
min = 0.967, Tmax = 0.982
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.049
wR(F2) = 0.149
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
S = 1.02
8141 reflections
451 parameters
Hydrogen site location: inferred from
neighbouring sites
Acta Cryst. (2013). C69, 1177-1180
sup-1

supplementary materials
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0725P)2 + 0.0625P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.18 e Å−3
Δρmin = −0.21 e Å−3
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 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)
x
y
z
Uiso*/Ueq
C1
0.45206 (19)
0.4049
0.35100 (18)
0.4128
0.06052 (10)
0.0240
0.0567 (5)
0.068*
H1
C2
0.5909 (2)
0.6366
0.2851 (2)
0.3030
0.04550 (11)
−0.0008
0.0630 (5)
0.076*
H2
C3
0.6618 (2)
0.7548
0.19324 (19)
0.1481
0.09872 (12)
0.0883
0.0650 (5)
0.078*
H3
C4
0.5946 (2)
0.6432
0.1683 (2)
0.1071
0.16752 (13)
0.2039
0.0693 (6)
0.083*
H4
C5
0.4549 (2)
0.4102
0.23370 (17)
0.2154
0.18309 (11)
0.2296
0.0589 (5)
0.071*
H5
C6
0.38163 (17)
0.23121 (17)
0.12814 (18)
0.0805
0.32626 (15)
0.39697 (16)
0.33644 (16)
0.3993
0.12960 (9)
0.14432 (9)
0.19997 (9)
0.2311
0.0459 (4)
0.0461 (4)
0.0478 (4)
0.057*
C7
C8
H8A
H8B
C9
0.1826
0.2630
0.2312
0.057*
0.01134 (17)
−0.0735
0.29026 (15)
0.2906
0.16181 (9)
0.1965
0.0442 (4)
0.053*
H9
C10
C11
H11
C12
H12
C13
H13
C14
H14
C15
H15
C16
H16A
H16B
C17
C18
0.05610 (17)
0.1572 (2)
0.2032
0.15394 (15)
0.12425 (17)
0.1885
0.14295 (9)
0.08598 (11)
0.0597
0.0444 (4)
0.0596 (5)
0.071*
0.1908 (2)
0.2587
0.00012 (19)
−0.0179
0.06769 (12)
0.0292
0.0703 (6)
0.084*
0.1246 (2)
0.1455
−0.09664 (18)
−0.1792
0.10582 (12)
0.0926
0.0658 (5)
0.079*
0.0278 (2)
−0.0157
−0.06981 (17)
−0.1352
0.16334 (11)
0.1902
0.0619 (5)
0.074*
−0.00653 (18)
−0.0723
0.05436 (17)
0.0708
0.18225 (10)
0.2218
0.0517 (4)
0.062*
−0.03654 (18)
0.0364
0.39067 (15)
0.3792
0.09335 (9)
0.0533
0.0474 (4)
0.057*
−0.1269
0.3767
0.0776
0.057*
−0.05721 (18)
−0.20589 (18)
0.52700 (15)
0.60540 (16)
0.11026 (9)
0.11874 (9)
0.0463 (4)
0.0475 (4)
Acta Cryst. (2013). C69, 1177-1180
sup-2

supplementary materials
C19
H19
C20
H20
C21
H21
C22
H22
C23
H23
C24
H24
C25
H25
C26
H26
C27
H27
C28
H28
C29
C30
C31
H31A
H31B
C32
H32
C33
C34
H34
C35
H35
C36
H36
C37
H37
C38
H38
C39
H39A
H39B
C40
C41
C42
H42
C43
H43
C44
H44
−0.32386 (19)
−0.3103
0.54717 (19)
0.4572
0.14197 (11)
0.1529
0.0592 (5)
0.071*
−0.4617 (2)
−0.5402
0.6214 (2)
0.5814
0.14902 (12)
0.1649
0.0688 (5)
0.083*
−0.4828 (2)
−0.5757
0.7542 (2)
0.8038
0.13257 (11)
0.1372
0.0690 (6)
0.083*
−0.3676 (2)
−0.3827
0.8138 (2)
0.9037
0.10936 (11)
0.0980
0.0650 (5)
0.078*
−0.2289 (2)
−0.1509
0.74058 (17)
0.7816
0.10276 (10)
0.0877
0.0553 (4)
0.066*
0.64207 (19)
0.5895
0.85674 (17)
0.8962
0.43180 (10)
0.4698
0.0542 (4)
0.065*
0.7791 (2)
0.8178
0.78340 (18)
0.7736
0.44365 (11)
0.4895
0.0612 (5)
0.073*
0.8592 (2)
0.9515
0.72444 (18)
0.6750
0.38795 (12)
0.3962
0.0638 (5)
0.077*
0.8017 (2)
0.8558
0.73931 (19)
0.7007
0.32052 (12)
0.2826
0.0664 (5)
0.080*
0.6633 (2)
0.6247
0.81159 (18)
0.8195
0.30837 (10)
0.2626
0.0594 (5)
0.071*
0.58134 (18)
0.43378 (18)
0.33390 (18)
0.3893
0.87253 (16)
0.95174 (16)
0.91588 (17)
0.8541
0.36372 (9)
0.35081 (9)
0.30130 (9)
0.2714
0.0473 (4)
0.0472 (4)
0.0492 (4)
0.059*
0.2906
0.9927
0.2684
0.059*
0.21158 (18)
0.1286
0.85520 (15)
0.8720
0.34815 (9)
0.3169
0.0455 (4)
0.055*
0.25497 (17)
0.2912 (2)
0.2901
0.70859 (15)
0.64605 (18)
0.6944
0.36832 (9)
0.43816 (11)
0.4759
0.0458 (4)
0.0702 (6)
0.084*
0.3293 (3)
0.3527
0.5110 (2)
0.4704
0.45268 (13)
0.5001
0.0803 (6)
0.096*
0.3329 (2)
0.3590
0.43795 (19)
0.3480
0.39851 (14)
0.4085
0.0700 (6)
0.084*
0.2974 (2)
0.2996
0.4986 (2)
0.4495
0.32940 (13)
0.2919
0.0720 (6)
0.086*
0.2583 (2)
0.2337
0.63236 (19)
0.6717
0.31423 (11)
0.2667
0.0625 (5)
0.075*
0.16124 (19)
0.0696
0.92650 (16)
0.9055
0.41463 (9)
0.4359
0.0510 (4)
0.061*
0.2323
0.8984
0.4521
0.061*
0.14324 (19)
−0.00265 (18)
−0.1257 (2)
−0.1177
1.07091 (16)
1.15585 (16)
1.10590 (18)
1.0166
0.39051 (9)
0.38144 (9)
0.37626 (10)
0.3806
0.0478 (4)
0.0465 (4)
0.0570 (5)
0.068*
−0.2598 (2)
−0.3410
1.1862 (2)
1.1507
0.36478 (12)
0.3617
0.0700 (6)
0.084*
−0.2728 (2)
−0.3623
1.3181 (2)
1.3724
0.35797 (12)
0.3491
0.0739 (6)
0.089*
Acta Cryst. (2013). C69, 1177-1180
sup-3

supplementary materials
C45
H45
C46
H46
N1
−0.1526 (2)
−0.1619
1.36985 (19)
1.4593
0.36436 (11)
0.3605
0.0679 (5)
0.082*
−0.0187 (2)
0.0612
1.29029 (17)
1.3263
0.37643 (10)
0.3813
0.0543 (4)
0.065*
0.19129 (15)
0.05077 (15)
0.39270 (16)
0.25420 (15)
0.50891 (14)
0.57917 (13)
1.04815 (14)
1.12582 (13)
0.10536 (8)
0.11899 (9)
0.38622 (8)
0.37384 (8)
0.0554 (4)
0.0547 (4)
0.0543 (4)
0.0514 (4)
N2
N3
N4
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C1
0.0509 (11)
0.0505 (11)
0.0481 (11)
0.0582 (12)
0.0550 (11)
0.0441 (9)
0.0454 (9)
0.0502 (10)
0.0428 (9)
0.0430 (9)
0.0628 (11)
0.0742 (13)
0.0676 (13)
0.0664 (12)
0.0498 (10)
0.0480 (9)
0.0496 (10)
0.0487 (10)
0.0520 (11)
0.0516 (11)
0.0540 (12)
0.0721 (14)
0.0574 (11)
0.0575 (11)
0.0620 (12)
0.0508 (11)
0.0614 (12)
0.0632 (12)
0.0495 (10)
0.0520 (10)
0.0558 (10)
0.0475 (9)
0.0406 (9)
0.1031 (16)
0.1083 (18)
0.0651 (13)
0.0768 (14)
0.0697 (13)
0.0633 (12)
0.0795 (14)
0.0632 (13)
0.0601 (12)
0.0534 (11)
0.0425 (9)
0.0448 (9)
0.0491 (10)
0.0434 (9)
0.0414 (9)
0.0466 (10)
0.0548 (12)
0.0435 (10)
0.0436 (10)
0.0514 (10)
0.0452 (9)
0.0416 (9)
0.0470 (10)
0.0558 (11)
0.0788 (15)
0.0847 (16)
0.0549 (11)
0.0481 (10)
0.0530 (11)
0.0569 (11)
0.0505 (11)
0.0599 (12)
0.0630 (12)
0.0440 (9)
0.0442 (9)
0.0499 (10)
0.0455 (9)
0.0437 (9)
0.0477 (11)
0.0515 (12)
0.0423 (11)
0.0593 (13)
0.0589 (12)
0.0548 (11)
−0.0083 (9)
−0.0121 (10)
−0.0011 (9)
−0.0014 (10)
−0.0087 (9)
−0.0130 (7)
−0.0134 (7)
−0.0110 (8)
−0.0112 (7)
−0.0091 (7)
−0.0158 (9)
−0.0092 (10)
−0.0076 (9)
−0.0210 (9)
−0.0135 (8)
−0.0062 (7)
−0.0092 (8)
−0.0058 (8)
−0.0107 (9)
−0.0135 (10)
0.0106 (11)
0.0058 (10)
−0.0065 (9)
−0.0146 (9)
−0.0160 (9)
−0.0095 (9)
−0.0066 (10)
−0.0114 (9)
−0.0143 (8)
−0.0146 (8)
−0.0112 (8)
−0.0116 (7)
−0.0121 (7)
−0.0147 (11)
−0.0149 (12)
−0.0113 (9)
−0.0194 (11)
−0.0102 (10)
−0.0072 (8)
−0.0010 (9)
−0.0098 (10)
−0.0164 (11)
−0.0076 (9)
−0.0082 (7)
−0.0042 (7)
−0.0026 (7)
0.0026 (7)
−0.0070 (9)
−0.0225 (10)
−0.0279 (11)
−0.0009 (10)
0.0000 (9)
C2
0.0624 (12)
0.0866 (15)
0.0836 (15)
0.0650 (12)
0.0546 (10)
0.0504 (9)
0.0445 (9)
0.0463 (9)
0.0486 (9)
0.0699 (12)
0.0814 (14)
0.0878 (15)
0.0767 (13)
0.0527 (10)
0.0494 (9)
0.0467 (9)
0.0476 (9)
0.0716 (12)
0.0807 (14)
0.0662 (13)
0.0639 (12)
0.0602 (11)
0.0543 (10)
0.0665 (12)
0.0872 (15)
0.0740 (14)
0.0515 (10)
0.0499 (10)
0.0470 (9)
0.0424 (9)
0.0455 (9)
0.0554 (10)
0.0613 (12)
0.0784 (15)
0.1010 (17)
0.0890 (16)
0.0612 (11)
C3
C4
C5
C6
−0.0090 (7)
−0.0070 (7)
−0.0069 (7)
−0.0060 (7)
−0.0033 (7)
−0.0132 (9)
−0.0226 (10)
−0.0148 (10)
0.0069 (9)
C7
C8
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
−0.0064 (7)
0.0144 (9)
0.0142 (11)
−0.0116 (11)
−0.0164 (10)
−0.0073 (8)
−0.0049 (7)
−0.0022 (7)
−0.0070 (7)
0.0001 (9)
0.0018 (8)
−0.0108 (7)
−0.0035 (7)
−0.0113 (7)
−0.0165 (9)
−0.0277 (11)
−0.0324 (11)
−0.0149 (9)
−0.0096 (8)
−0.0099 (8)
−0.0027 (9)
−0.0017 (10)
−0.0139 (10)
−0.0092 (9)
−0.0064 (7)
−0.0055 (7)
−0.0078 (7)
−0.0076 (7)
−0.0099 (8)
−0.0067 (9)
0.0026 (11)
−0.0101 (11)
−0.0340 (12)
−0.0178 (9)
0.0033 (10)
−0.0097 (10)
−0.0127 (10)
−0.0081 (9)
−0.0031 (8)
−0.0165 (10)
−0.0068 (10)
0.0123 (10)
−0.0018 (9)
−0.0007 (8)
−0.0015 (7)
−0.0014 (7)
−0.0052 (7)
−0.0008 (7)
−0.0170 (11)
−0.0161 (13)
0.0053 (12)
0.0038 (12)
−0.0049 (9)
Acta Cryst. (2013). C69, 1177-1180
sup-4

supplementary materials
C39
C40
C41
C42
C43
C44
C45
C46
N1
0.0580 (10)
0.0567 (10)
0.0530 (10)
0.0567 (11)
0.0530 (12)
0.0553 (12)
0.0683 (13)
0.0572 (11)
0.0458 (8)
0.0477 (8)
0.0531 (9)
0.0524 (9)
0.0457 (10)
0.0416 (9)
0.0446 (9)
0.0503 (10)
0.0730 (14)
0.0725 (15)
0.0482 (11)
0.0457 (10)
0.0458 (9)
0.0429 (8)
0.0462 (8)
0.0442 (8)
0.0477 (9)
0.0450 (9)
0.0423 (9)
0.0646 (12)
0.0861 (15)
0.0855 (15)
0.0821 (14)
0.0590 (11)
0.0715 (10)
0.0719 (10)
0.0660 (10)
0.0592 (9)
−0.0094 (8)
−0.0094 (8)
−0.0118 (8)
−0.0125 (9)
−0.0146 (10)
0.0038 (11)
−0.0042 (10)
−0.0097 (8)
−0.0101 (7)
−0.0101 (7)
−0.0096 (7)
−0.0085 (7)
0.0025 (8)
0.0012 (8)
0.0047 (7)
0.0048 (9)
0.0016 (10)
0.0031 (11)
0.0078 (11)
0.0054 (8)
0.0000 (7)
−0.0020 (7)
−0.0065 (7)
−0.0068 (7)
−0.0058 (7)
−0.0086 (7)
−0.0092 (7)
−0.0121 (9)
−0.0181 (11)
−0.0126 (11)
−0.0102 (10)
−0.0101 (8)
−0.0009 (7)
−0.0035 (7)
−0.0137 (7)
−0.0116 (7)
N2
N3
N4
Geometric parameters (Å, º)
C1—C2
1.381 (2)
C24—C29
1.392 (2)
C1—C6
1.393 (2)
0.9300
C24—H24
C25—C26
C25—H25
C26—C27
C26—H26
C27—C28
C27—H27
C28—C29
C28—H28
C29—C30
C30—N3
0.9300
C1—H1
1.380 (3)
0.9300
C2—C3
1.373 (3)
0.9300
C2—H2
1.368 (3)
0.9300
C3—C4
1.376 (3)
0.9300
C3—H3
1.387 (3)
0.9300
C4—C5
1.388 (3)
0.9300
C4—H4
1.392 (2)
0.9300
C5—C6
1.389 (2)
0.9300
C5—H5
1.486 (2)
1.284 (2)
1.508 (2)
1.562 (2)
0.9700
C6—C7
1.488 (2)
1.286 (2)
1.508 (2)
1.555 (2)
0.9700
C7—N1
C30—C31
C31—C32
C31—H31A
C31—H31B
C32—C33
C32—C39
C32—H32
C33—C34
C33—C38
C34—C35
C34—H34
C35—C36
C35—H35
C36—C37
C36—H36
C37—C38
C37—H37
C38—H38
C39—C40
C39—H39A
C39—H39B
C40—N4
C7—C8
C8—C9
C8—H8A
C8—H8B
C9—C10
C9—C16
C9—H9
0.9700
0.9700
1.521 (2)
1.538 (2)
0.9800
1.517 (2)
1.543 (2)
0.9800
1.380 (2)
1.382 (2)
1.395 (3)
0.9300
C10—C15
C10—C11
C11—C12
C11—H11
C12—C13
C12—H12
C13—C14
C13—H13
C14—C15
C14—H14
C15—H15
C16—C17
C16—H16A
C16—H16B
C17—N2
1.387 (2)
1.387 (2)
1.387 (3)
0.9300
1.359 (3)
0.9300
1.375 (3)
0.9300
1.362 (3)
0.9300
1.365 (3)
0.9300
1.384 (3)
0.9300
1.392 (3)
0.9300
0.9300
0.9300
1.507 (2)
0.9700
1.508 (2)
0.9700
0.9700
0.9700
1.291 (2)
1.488 (2)
1.289 (2)
C40—C41
Acta Cryst. (2013). C69, 1177-1180
sup-5

supplementary materials
C17—C18
C18—C19
C18—C23
C19—C20
C19—H19
C20—C21
C20—H20
C21—C22
C21—H21
C22—C23
C22—H22
C23—H23
C24—C25
1.487 (2)
1.385 (2)
1.396 (2)
1.384 (3)
0.9300
C41—C42
C41—C46
C42—C43
C42—H42
C43—C44
C43—H43
C44—C45
C44—H44
C45—C46
C45—H45
C46—H46
N1—N2
1.388 (2)
1.398 (2)
1.384 (3)
0.9300
1.371 (3)
0.9300
1.372 (3)
0.9300
1.380 (3)
0.9300
1.370 (3)
0.9300
1.380 (2)
0.9300
1.385 (2)
0.9300
0.9300
0.9300
1.4056 (19)
1.4083 (19)
1.379 (2)
N3—N4
C2—C1—C6
C2—C1—H1
C6—C1—H1
C3—C2—C1
C3—C2—H2
C1—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
C4—C5—C6
C4—C5—H5
C6—C5—H5
C5—C6—C1
C5—C6—C7
C1—C6—C7
N1—C7—C6
N1—C7—C8
C6—C7—C8
C7—C8—C9
C7—C8—H8A
C9—C8—H8A
C7—C8—H8B
C9—C8—H8B
H8A—C8—H8B
C10—C9—C16
C10—C9—C8
C16—C9—C8
C10—C9—H9
C16—C9—H9
C8—C9—H9
C15—C10—C11
C15—C10—C9
120.96 (17)
119.5
C29—C24—H24
C24—C25—C26
C24—C25—H25
C26—C25—H25
C27—C26—C25
C27—C26—H26
C25—C26—H26
C26—C27—C28
C26—C27—H27
C28—C27—H27
C27—C28—C29
C27—C28—H28
C29—C28—H28
C24—C29—C28
C24—C29—C30
C28—C29—C30
N3—C30—C29
N3—C30—C31
C29—C30—C31
C30—C31—C32
C30—C31—H31A
C32—C31—H31A
C30—C31—H31B
C32—C31—H31B
119.6
120.53 (18)
119.7
119.5
120.23 (18)
119.9
119.7
119.50 (18)
120.2
119.9
119.67 (18)
120.2
120.2
120.37 (19)
119.8
120.2
120.53 (18)
119.7
119.8
120.92 (18)
119.5
119.7
120.38 (18)
119.8
119.5
117.80 (16)
120.94 (15)
121.26 (16)
117.17 (15)
121.53 (15)
121.22 (15)
110.55 (13)
109.5
119.8
118.22 (16)
121.65 (15)
120.12 (15)
117.17 (14)
121.65 (15)
121.11 (14)
111.65 (13)
109.3
109.5
109.5
109.3
109.5
109.3
H31A—C31—H31B
C33—C32—C39
C33—C32—C31
C39—C32—C31
C33—C32—H32
C39—C32—H32
C31—C32—H32
C34—C33—C38
C34—C33—C32
C38—C33—C32
C33—C34—C35
108.1
109.3
114.17 (13)
112.31 (13)
109.82 (13)
106.7
108.0
111.73 (13)
114.79 (13)
109.01 (13)
107.0
106.7
106.7
107.0
117.41 (17)
123.80 (16)
118.78 (16)
120.62 (19)
107.0
117.68 (16)
120.10 (15)
Acta Cryst. (2013). C69, 1177-1180
sup-6

supplementary materials
C11—C10—C9
C12—C11—C10
C12—C11—H11
C10—C11—H11
C13—C12—C11
C13—C12—H12
C11—C12—H12
C14—C13—C12
C14—C13—H13
C12—C13—H13
C13—C14—C15
C13—C14—H14
C15—C14—H14
C10—C15—C14
C10—C15—H15
C14—C15—H15
C17—C16—C9
C17—C16—H16A
C9—C16—H16A
C17—C16—H16B
C9—C16—H16B
H16A—C16—H16B
N2—C17—C18
N2—C17—C16
C18—C17—C16
C19—C18—C23
C19—C18—C17
C23—C18—C17
C20—C19—C18
C20—C19—H19
C18—C19—H19
C21—C20—C19
C21—C20—H20
C19—C20—H20
C22—C21—C20
C22—C21—H21
C20—C21—H21
C21—C22—C23
C21—C22—H22
C23—C22—H22
C22—C23—C18
C22—C23—H23
C18—C23—H23
C25—C24—C29
C25—C24—H24
122.21 (14)
120.91 (17)
119.5
C33—C34—H34
C35—C34—H34
C36—C35—C34
C36—C35—H35
C34—C35—H35
C35—C36—C37
C35—C36—H36
C37—C36—H36
C36—C37—C38
C36—C37—H37
C38—C37—H37
C33—C38—C37
C33—C38—H38
C37—C38—H38
C40—C39—C32
C40—C39—H39A
C32—C39—H39A
C40—C39—H39B
C32—C39—H39B
119.7
119.7
121.0 (2)
119.5
119.5
120.68 (19)
119.7
119.5
118.90 (19)
120.6
119.7
119.08 (18)
120.5
120.6
120.83 (19)
119.6
120.5
120.72 (17)
119.6
119.6
121.25 (19)
119.4
119.6
120.88 (17)
119.6
119.4
109.97 (13)
109.7
119.6
110.90 (13)
109.5
109.7
109.7
109.5
109.7
109.5
H39A—C39—H39B
N4—C40—C41
N4—C40—C39
C41—C40—C39
C42—C41—C46
C42—C41—C40
C46—C41—C40
C43—C42—C41
C43—C42—H42
C41—C42—H42
C44—C43—C42
C44—C43—H43
C42—C43—H43
C43—C44—C45
C43—C44—H44
C45—C44—H44
C44—C45—C46
C44—C45—H45
C46—C45—H45
C45—C46—C41
C45—C46—H46
C41—C46—H46
C7—N1—N2
108.2
109.5
116.91 (14)
121.36 (15)
121.68 (14)
117.92 (16)
121.87 (15)
120.19 (15)
121.42 (18)
119.3
108.0
117.66 (15)
122.19 (15)
120.14 (14)
118.65 (16)
121.36 (15)
119.99 (15)
120.67 (18)
119.7
119.3
119.85 (19)
120.1
119.7
120.03 (19)
120.0
120.1
119.79 (19)
120.1
120.0
120.26 (18)
119.9
120.1
120.65 (19)
119.7
119.9
120.28 (19)
119.9
119.7
120.33 (17)
119.8
119.9
120.11 (18)
119.9
119.8
118.48 (13)
117.55 (14)
118.10 (14)
117.54 (14)
119.9
C17—N2—N1
120.87 (17)
119.6
C30—N3—N4
C40—N4—N3
C6—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
0.2 (3)
−0.8 (3)
1.0 (3)
C25—C24—C29—C30
C27—C28—C29—C24
C27—C28—C29—C30
−179.90 (16)
−1.0 (3)
179.10 (16)
Acta Cryst. (2013). C69, 1177-1180
sup-7

supplementary materials
C3—C4—C5—C6
−0.6 (3)
C24—C29—C30—N3
31.3 (2)
C4—C5—C6—C1
0.0 (3)
C28—C29—C30—N3
C24—C29—C30—C31
C28—C29—C30—C31
N3—C30—C31—C32
C29—C30—C31—C32
C30—C31—C32—C33
C30—C31—C32—C39
C39—C32—C33—C34
C31—C32—C33—C34
C39—C32—C33—C38
C31—C32—C33—C38
C38—C33—C34—C35
C32—C33—C34—C35
C33—C34—C35—C36
C34—C35—C36—C37
C35—C36—C37—C38
C34—C33—C38—C37
C32—C33—C38—C37
C36—C37—C38—C33
C33—C32—C39—C40
C31—C32—C39—C40
C32—C39—C40—N4
C32—C39—C40—C41
N4—C40—C41—C42
C39—C40—C41—C42
N4—C40—C41—C46
C39—C40—C41—C46
C46—C41—C42—C43
C40—C41—C42—C43
C41—C42—C43—C44
C42—C43—C44—C45
C43—C44—C45—C46
C44—C45—C46—C41
C42—C41—C46—C45
C40—C41—C46—C45
C6—C7—N1—N2
−148.76 (17)
−145.51 (16)
34.4 (2)
C4—C5—C6—C7
179.31 (17)
0.2 (3)
C2—C1—C6—C5
C2—C1—C6—C7
−179.12 (16)
155.10 (17)
−25.6 (2)
−27.9 (2)
151.36 (16)
71.8 (2)
−71.6 (2)
105.09 (17)
−89.81 (17)
38.37 (18)
−19.5 (2)
106.31 (19)
160.18 (16)
−73.96 (19)
0.0 (3)
C5—C6—C7—N1
C1—C6—C7—N1
C5—C6—C7—C8
C1—C6—C7—C8
N1—C7—C8—C9
C6—C7—C8—C9
−105.05 (17)
87.21 (17)
−38.97 (18)
−126.52 (16)
108.72 (17)
52.3 (2)
C7—C8—C9—C10
C7—C8—C9—C16
C16—C9—C10—C15
C8—C9—C10—C15
C16—C9—C10—C11
C8—C9—C10—C11
C15—C10—C11—C12
C9—C10—C11—C12
C10—C11—C12—C13
C11—C12—C13—C14
C12—C13—C14—C15
C11—C10—C15—C14
C9—C10—C15—C14
C13—C14—C15—C10
C10—C9—C16—C17
C8—C9—C16—C17
C9—C16—C17—N2
C9—C16—C17—C18
N2—C17—C18—C19
C16—C17—C18—C19
N2—C17—C18—C23
C16—C17—C18—C23
C23—C18—C19—C20
C17—C18—C19—C20
C18—C19—C20—C21
C19—C20—C21—C22
C20—C21—C22—C23
C21—C22—C23—C18
C19—C18—C23—C22
C17—C18—C23—C22
C29—C24—C25—C26
C24—C25—C26—C27
C25—C26—C27—C28
C26—C27—C28—C29
C25—C24—C29—C28
179.74 (18)
0.5 (3)
−0.4 (3)
−72.5 (2)
2.0 (3)
−0.1 (3)
−0.5 (3)
−176.81 (17)
−0.2 (3)
179.76 (16)
0.5 (3)
−1.6 (3)
171.24 (14)
44.09 (18)
−72.9 (2)
104.24 (17)
160.69 (16)
−16.5 (2)
−18.1 (2)
164.70 (15)
1.5 (3)
1.6 (3)
−2.1 (2)
176.75 (15)
0.3 (3)
−170.82 (13)
−42.90 (17)
72.4 (2)
−106.57 (16)
−151.71 (17)
27.3 (2)
−177.30 (17)
0.3 (3)
28.7 (2)
−1.5 (3)
−152.37 (16)
0.2 (3)
1.0 (3)
0.8 (3)
−179.48 (17)
0.3 (3)
−2.0 (3)
176.79 (16)
−178.77 (14)
4.2 (2)
−0.2 (3)
−0.4 (3)
C8—C7—N1—N2
0.9 (3)
C18—C17—N2—N1
C16—C17—N2—N1
C7—N1—N2—C17
−175.19 (14)
5.9 (2)
−0.8 (3)
178.86 (16)
0.3 (3)
−60.5 (2)
178.94 (13)
−4.2 (2)
C29—C30—N3—N4
C31—C30—N3—N4
C41—C40—N4—N3
C39—C40—N4—N3
C30—N3—N4—C40
0.1 (3)
−0.9 (3)
176.38 (14)
−6.4 (2)
1.3 (3)
0.2 (2)
61.8 (2)
Acta Cryst. (2013). C69, 1177-1180
sup-8

supplementary materials
(II) 3,7-bis(2-hydroxyphenyl)-5-phenyl-1,2-diazacyclohepta-1(7),2-diene
Crystal data
C23H20N2O2
Mr = 356.41
F(000) = 1504
Dx = 1.298 Mg m−3
Monoclinic, C2/c
a = 23.9715 (14) Å
b = 9.5669 (16) Å
c = 18.2303 (12) Å
β = 119.256 (3)°
V = 3647.5 (7) Å3
Z = 8
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 1649 reflections
θ = 2.0–25.0°
µ = 0.08 mm−1
T = 296 K
Block, yellow
0.30 × 0.28 × 0.26 mm
Data collection
Bruker SMART APEX CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
12998 measured reflections
3224 independent reflections
1647 reflections with I > 2σ(I)
Rint = 0.071
ω and φ scans
θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = −27→28
k = −11→11
l = −21→21
T
min = 0.967, Tmax = 0.972
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.045
wR(F2) = 0.109
S = 0.96
3224 reflections
Hydrogen site location: inferred from
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0426P)2]
where P = (Fo2 + 2Fc2)/3
253 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
(Δ/σ)max < 0.001
Δρmax = 0.13 e Å−3
Δρmin = −0.13 e Å−3
Extinction correction: SHELXL97 (Sheldrick,
2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.0014 (2)
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 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)
x
y
z
Uiso*/Ueq
C1
C2
H2
0.37760 (14)
0.42387 (14)
0.4647
0.7121 (3)
0.8122 (4)
0.7840
0.13321 (16)
0.14804 (18)
0.1606
0.0607 (7)
0.0827 (10)
0.099*
Acta Cryst. (2013). C69, 1177-1180
sup-9

supplementary materials
C3
0.41027 (18)
0.4421
0.9513 (4)
1.0168
0.14444 (19)
0.1552
0.0923 (11)
0.111*
H3
C4
0.34995 (17)
0.3406
0.9960 (3)
1.0909
0.12501 (17)
0.1217
0.0795 (9)
0.095*
H4
C5
0.30379 (13)
0.2631
0.8978 (3)
0.9280
0.11052 (14)
0.0973
0.0595 (7)
0.071*
H5
C6
0.31590 (12)
0.26667 (11)
0.20110 (11)
0.1692
0.7540 (3)
0.6507 (3)
0.6912 (2)
0.6360
0.11501 (14)
0.10285 (13)
0.08683 (14)
0.0408
0.0500 (6)
0.0450 (6)
0.0479 (6)
0.058*
C7
C8
H8A
H8B
C9
0.1933
0.7890
0.0709
0.058*
0.19542 (10)
0.2233
0.6666 (2)
0.7356
0.16681 (14)
0.2084
0.0420 (6)
0.050*
H9
C10
C11
H11
C12
H12
C13
H13
C14
H14
C15
H15
C16
H16A
H16B
C17
C18
C19
H19
C20
H20
C21
H21
C22
H22
C23
H1O
H2O
N1
0.12857 (11)
0.12080 (12)
0.1567
0.6920 (2)
0.7586 (2)
0.7863
0.15289 (15)
0.21469 (16)
0.2641
0.0415 (6)
0.0545 (7)
0.065*
0.06055 (14)
0.0564
0.7850 (3)
0.8293
0.20441 (19)
0.2469
0.0654 (8)
0.079*
0.00712 (14)
−0.0334
0.7458 (3)
0.7644
0.1318 (2)
0.1245
0.0647 (8)
0.078*
0.01365 (13)
−0.0226
0.6789 (3)
0.6514
0.06980 (17)
0.0207
0.0626 (7)
0.075*
0.07382 (13)
0.0776
0.6522 (2)
0.6070
0.07994 (17)
0.0374
0.0576 (7)
0.069*
0.22259 (11)
0.2685
0.5200 (2)
0.5272
0.20419 (13)
0.2400
0.0451 (6)
0.054*
0.2044
0.4902
0.2389
0.054*
0.20836 (11)
0.16451 (11)
0.12935 (11)
0.1327
0.4110 (2)
0.2931 (2)
0.2789 (2)
0.3478
0.13753 (14)
0.12071 (14)
0.16312 (15)
0.2011
0.0435 (6)
0.0425 (6)
0.0523 (7)
0.063*
0.09007 (12)
0.0677
0.1661 (3)
0.1584
0.15024 (16)
0.1798
0.0640 (7)
0.077*
0.08399 (13)
0.0576
0.0638 (3)
−0.0128
0.0752 (3)
0.0066
0.09293 (17)
0.0841
0.0646 (8)
0.077*
0.11670 (13)
0.1119
0.04939 (17)
0.0106
0.0648 (8)
0.078*
0.15679 (12)
0.3599 (15)
0.2146 (13)
0.28238 (9)
0.23654 (9)
0.39492 (9)
0.18745 (11)
0.1872 (2)
0.519 (3)
0.272 (3)
0.5199 (2)
0.41738 (19)
0.5766 (3)
0.1904 (2)
0.06208 (16)
0.1286 (18)
0.0362 (18)
0.10805 (12)
0.09215 (12)
0.13736 (12)
0.01661 (13)
0.0535 (7)
0.105 (12)*
0.098 (10)*
0.0511 (5)
0.0506 (5)
0.0776 (6)
0.0808 (6)
N2
O1
O2
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C1
C2
0.058 (2)
0.061 (2)
0.080 (2)
0.113 (3)
0.0454 (18)
0.070 (2)
−0.0123 (17)
−0.027 (2)
0.0258 (15)
0.0293 (17)
0.0017 (14)
−0.0015 (19)
Acta Cryst. (2013). C69, 1177-1180
sup-10

supplementary materials
C3
0.093 (3)
0.111 (3)
0.073 (2)
−0.057 (2)
0.040 (2)
−0.014 (2)
C4
0.106 (3)
0.077 (2)
0.064 (2)
−0.033 (2)
0.048 (2)
−0.0091 (16)
−0.0030 (13)
−0.0013 (12)
−0.0001 (12)
0.0071 (11)
−0.0032 (11)
0.0007 (11)
−0.0052 (13)
−0.0015 (16)
0.0118 (17)
−0.0028 (15)
−0.0118 (14)
0.0001 (11)
0.0044 (11)
0.0038 (11)
0.0023 (12)
0.0064 (15)
0.0076 (15)
−0.0041 (14)
−0.0023 (13)
−0.0019 (11)
−0.0040 (10)
0.0054 (12)
−0.0309 (11)
C5
0.072 (2)
0.0653 (18)
0.0622 (16)
0.0569 (16)
0.0485 (14)
0.0406 (13)
0.0380 (13)
0.0677 (16)
0.0805 (19)
0.0690 (18)
0.0701 (18)
0.0599 (16)
0.0500 (14)
0.0469 (14)
0.0420 (13)
0.0541 (15)
0.0693 (18)
0.0550 (17)
0.0436 (15)
0.0455 (15)
0.0574 (13)
0.0487 (12)
0.0947 (16)
0.0676 (13)
0.0450 (17)
0.0366 (16)
0.0330 (15)
0.0474 (16)
0.0412 (15)
0.0462 (16)
0.0495 (17)
0.070 (2)
−0.0161 (16)
−0.0098 (14)
−0.0032 (13)
−0.0001 (12)
−0.0041 (11)
−0.0021 (11)
−0.0051 (13)
−0.0008 (16)
0.0010 (15)
−0.0063 (14)
−0.0030 (14)
0.0002 (12)
0.0086 (12)
0.0028 (11)
−0.0047 (13)
−0.0088 (16)
−0.0111 (14)
−0.0040 (15)
0.0039 (13)
−0.0032 (12)
−0.0033 (11)
0.0010 (13)
−0.0172 (12)
0.0318 (15)
0.0232 (14)
0.0191 (13)
0.0229 (13)
0.0186 (12)
0.0190 (13)
0.0288 (15)
0.0474 (19)
0.042 (2)
C6
0.0528 (18)
0.0452 (17)
0.0475 (16)
0.0419 (15)
0.0382 (15)
0.0516 (18)
0.065 (2)
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
N1
0.054 (2)
0.083 (2)
0.0443 (18)
0.0498 (18)
0.0449 (15)
0.0422 (16)
0.0435 (15)
0.0556 (18)
0.067 (2)
0.065 (2)
0.0197 (16)
0.0274 (16)
0.0181 (12)
0.0195 (13)
0.0184 (13)
0.0242 (15)
0.0328 (16)
0.0231 (17)
0.0328 (17)
0.0331 (16)
0.0300 (11)
0.0339 (12)
0.0398 (12)
0.0786 (15)
0.0629 (19)
0.0377 (14)
0.0406 (15)
0.0395 (15)
0.0464 (17)
0.0589 (19)
0.064 (2)
0.064 (2)
0.078 (2)
0.069 (2)
0.0638 (18)
0.0500 (14)
0.0545 (14)
0.0528 (14)
0.1081 (17)
0.0562 (18)
0.0521 (14)
0.0572 (14)
0.0912 (16)
0.1017 (16)
N2
O1
O2
Geometric parameters (Å, º)
C1—O1
C1—C2
C1—C6
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C4—H4
C5—C6
C5—H5
C6—C7
C7—N1
C7—C8
C8—C9
C8—H8A
C8—H8B
C9—C10
C9—C16
C9—H9
C10—C11
C10—C15
1.351 (3)
C12—H12
0.9300
1.389 (4)
1.407 (3)
1.364 (4)
0.9300
C13—C14
C13—H13
C14—C15
C14—H14
C15—H15
C16—C17
C16—H16A
C16—H16B
C17—N2
1.372 (3)
0.9300
1.386 (3)
0.9300
1.378 (4)
0.9300
0.9300
1.509 (3)
0.9700
1.375 (3)
0.9300
0.9700
1.400 (3)
0.9300
1.300 (3)
1.468 (3)
1.401 (3)
1.418 (3)
1.375 (3)
0.9300
C17—C18
C18—C19
C18—C23
C19—C20
C19—H19
C20—C21
C20—H20
C21—C22
C21—H21
C22—C23
C22—H22
C23—O2
1.471 (3)
1.297 (3)
1.503 (3)
1.547 (3)
0.9700
1.386 (3)
0.9300
0.9700
1.514 (3)
1.556 (3)
0.9800
1.366 (3)
0.9300
1.381 (3)
0.9300
1.384 (3)
1.389 (3)
1.351 (3)
Acta Cryst. (2013). C69, 1177-1180
sup-11

supplementary materials
C11—C12
C11—H11
C12—C13
1.386 (3)
0.9300
N1—N2
1.394 (2)
0.95 (3)
0.97 (3)
O1—H1O
O2—H2O
1.370 (3)
O1—C1—C2
O1—C1—C6
C2—C1—C6
C3—C2—C1
C3—C2—H2
C1—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—H4
C3—C4—H4
C4—C5—C6
C4—C5—H5
C6—C5—H5
C5—C6—C1
C5—C6—C7
C1—C6—C7
N1—C7—C6
N1—C7—C8
C6—C7—C8
C7—C8—C9
C7—C8—H8A
C9—C8—H8A
C7—C8—H8B
C9—C8—H8B
H8A—C8—H8B
C10—C9—C8
C10—C9—C16
C8—C9—C16
C10—C9—H9
C8—C9—H9
C16—C9—H9
C11—C10—C15
C11—C10—C9
C15—C10—C9
C10—C11—C12
C10—C11—H11
C12—C11—H11
C13—C12—C11
C13—C12—H12
117.2 (3)
123.1 (2)
119.8 (3)
121.0 (3)
119.5
C11—C12—H12
C12—C13—C14
C12—C13—H13
C14—C13—H13
C13—C14—C15
C13—C14—H14
C15—C14—H14
C14—C15—C10
C14—C15—H15
C10—C15—H15
C17—C16—C9
C17—C16—H16A
C9—C16—H16A
C17—C16—H16B
C9—C16—H16B
120.0
119.6 (3)
120.2
120.2
120.4 (3)
119.8
119.5
120.7 (3)
119.6
119.8
120.8 (2)
119.6
119.6
118.9 (3)
120.6
119.6
112.89 (18)
109.0
120.6
122.4 (3)
118.8
109.0
109.0
118.8
109.0
117.3 (2)
121.6 (2)
121.2 (2)
117.0 (2)
120.1 (2)
122.8 (2)
110.07 (18)
109.6
H16A—C16—H16B
N2—C17—C18
N2—C17—C16
C18—C17—C16
C19—C18—C23
C19—C18—C17
C23—C18—C17
C20—C19—C18
C20—C19—H19
C18—C19—H19
C19—C20—C21
C19—C20—H20
C21—C20—H20
C22—C21—C20
C22—C21—H21
C20—C21—H21
C21—C22—C23
C21—C22—H22
C23—C22—H22
O2—C23—C22
O2—C23—C18
C22—C23—C18
C7—N1—N2
107.8
116.4 (2)
119.8 (2)
123.8 (2)
117.0 (2)
121.4 (2)
121.5 (2)
121.9 (2)
119.1
109.6
109.6
119.1
109.6
119.6 (2)
120.2
108.2
113.01 (18)
113.57 (17)
109.80 (17)
106.7
120.2
120.2 (2)
119.9
119.9
106.7
121.0 (2)
119.5
106.7
117.7 (2)
119.3 (2)
122.9 (2)
121.3 (2)
119.3
119.5
117.2 (2)
122.5 (2)
120.3 (2)
119.52 (19)
120.17 (19)
108.9 (18)
105.1 (16)
119.3
C17—N2—N1
120.1 (3)
120.0
C1—O1—H1O
C23—O2—H2O
O1—C1—C2—C3
C6—C1—C2—C3
C1—C2—C3—C4
179.5 (3)
−0.6 (4)
−0.8 (5)
C13—C14—C15—C10
C11—C10—C15—C14
C9—C10—C15—C14
0.2 (4)
0.2 (3)
−179.4 (2)
Acta Cryst. (2013). C69, 1177-1180
sup-12

supplementary materials
C2—C3—C4—C5
C3—C4—C5—C6
C4—C5—C6—C1
C4—C5—C6—C7
O1—C1—C6—C5
C2—C1—C6—C5
O1—C1—C6—C7
C2—C1—C6—C7
C5—C6—C7—N1
C1—C6—C7—N1
C5—C6—C7—C8
C1—C6—C7—C8
N1—C7—C8—C9
C6—C7—C8—C9
C7—C8—C9—C10
C7—C8—C9—C16
C8—C9—C10—C11
C16—C9—C10—C11
C8—C9—C10—C15
C16—C9—C10—C15
C15—C10—C11—C12
C9—C10—C11—C12
C10—C11—C12—C13
C11—C12—C13—C14
C12—C13—C14—C15
1.0 (4)
C10—C9—C16—C17
91.1 (2)
0.2 (4)
C8—C9—C16—C17
C9—C16—C17—N2
C9—C16—C17—C18
N2—C17—C18—C19
C16—C17—C18—C19
N2—C17—C18—C23
C16—C17—C18—C23
C23—C18—C19—C20
C17—C18—C19—C20
C18—C19—C20—C21
C19—C20—C21—C22
C20—C21—C22—C23
C21—C22—C23—O2
C21—C22—C23—C18
C19—C18—C23—O2
C17—C18—C23—O2
C19—C18—C23—C22
C17—C18—C23—C22
C6—C7—N1—N2
−36.5 (3)
69.7 (3)
−1.5 (4)
177.4 (2)
−178.4 (2)
1.7 (4)
−111.5 (2)
−177.2 (2)
4.0 (3)
2.7 (4)
4.1 (3)
−177.1 (2)
179.9 (2)
−1.3 (3)
−1.4 (3)
177.4 (2)
73.4 (3)
−105.2 (2)
−174.46 (18)
−46.5 (2)
−140.0 (2)
94.1 (2)
39.5 (3)
−86.4 (3)
0.0 (3)
−174.7 (2)
1.4 (3)
−177.4 (2)
−0.9 (4)
−0.2 (4)
0.7 (4)
179.9 (2)
−0.2 (4)
179.1 (2)
−2.1 (4)
−0.8 (3)
178.0 (2)
−176.21 (19)
5.0 (3)
C8—C7—N1—N2
179.5 (2)
−0.4 (4)
0.8 (4)
C18—C17—N2—N1
C16—C17—N2—N1
C7—N1—N2—C17
−175.34 (19)
3.5 (3)
−59.8 (3)
−0.6 (4)
Hydrogen-bond geometry (Å, º)
Cg2 is the centroid of the C10–C15 benzene ring.
D—H···A
D—H
H···A
D···A
D—H···A
O1—H1O···N1
O2—H2O···N2
C21—H21···Cg2i
0.95 (3)
0.97 (3)
0.93
1.71 (3)
1.65 (3)
2.74
2.539 (3)
2.532 (3)
3.495 (3)
144 (3)
150 (2)
138
Symmetry code: (i) x, y−1, z.
Acta Cryst. (2013). C69, 1177-1180
sup-13

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