Synthesis of 2-(2-hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles

Article abstract of DOI:10.1007/s10593-013-1208-2

The reaction of 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles and 6-chloro-2-(2-hetarylidene)-3-oxohexanenitriles with amines was studied. It was shown that the reaction of primary aliphatic amines with 6-chloro-2-(2- hetarylidene)-3-oxohexanenitriles takes place through a stage involving the formation of 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles followed by opening of the furanylidene fragment of the latter and the formation of 2-(2-hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles.

Full text of DOI:10.1007/s10593-013-1208-2

Chemistry of Heterocyclic Compounds, Vol. 48, No. 12, March, 2013 (Russian Original Vol. 48, No. 12, December, 2012)
SYNTHESIS OF 2-(2-HETARYL)-6-HYDROXY-
3-(R-AMINO)-2-HEXENENITRILES
O. V. Khilya1*, T. A. Volovnenko1, A. V. Turov1, R. I. Zubatyuk2,
O. V. Shishkin2, and Yu. M. Volovenko1
The reaction of 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles and 6-chloro-2-(2-hetarylidene)-
3-oxohexanenitriles with amines was studied. It was shown that the reaction of primary aliphatic
amines with 6-chloro-2-(2-hetarylidene)-3-oxohexanenitriles takes place through a stage involving the
formation of 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles followed by opening of the
furanylidene fragment of the latter and the formation of 2-(2-hetaryl)-6-hydroxy-3-(R-amino)-
2-hexenenitriles.
Keywords: hetarylacetonitriles, 2-(2-hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles, 2-hetaryl-2-(tetra-
hydrofuran-2-ylidene)acetonitriles, primary amines, amination.
Earlier [1-3] we developed a method for the synthesis of 2-hetaryl-2-(tetrahydrofuran-2-ylidene)-
acetonitriles from the corresponding 6-chloro-2-(2-hetarylidene)-3-oxohexane(heptane)nitriles.
R
CN
HetH
CN
Het
Cl
R
O
O
R = H, Me
The starting nitriles contain a γ-chlorobutyric acid fragment, which motivated our interest in the further
research of these substances as substrates for amination. In view of the fact that γ-aminobutyric acid is a
mediator in the central nervous system, replacement of the chlorine atom in these compounds by an amino
group could lead to the appearance of useful biological properties.
The amination of α-bromoacetylphenylacetonitrile, resulting in the formation of 4-dialkylamino-
3-hydroxy-2-phenyl-2-butenenitriles, has been well studied [4]. Their further intramolecular cyclization by
interaction of the nitrile and amino groups, leading to the formation of 1-R-2-amino-3-phenyl-4(5H)-
oxopyrroles, is possible. If secondary aliphatic and aliphatic-aromatic amines are used, then the last stage is
accompanied by dealkylation of the amino group [4].
_______
*To whom correspondence should be addressed, e-mail: olgakhilya@mail.ru.
1Kyiv Taras Shevchenko National University, 64 Volodymirska St., Kyiv 01601, Ukraine.
2Scientific-Technological Complex "Institute of Monocrystals", National Academy of Sciences of Ukraine, 60
Lenina Ave., Kharkiv 61001, Ukraine; e-mail: shishkin@xray.isc.kharkov.com.
________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1891-1902, December, 2012.
Original article submitted July 4, 2012.
1770
0009-3122/13/4812-1770©2013 Springer Science+Business Media New York

Replacement of the aryl fragment by azahetaryl leads to an increase in the number of possible reaction
products. Thus, the reaction of 2-(2-azahetarylidene)-4-chloro-3-ketobutanenitriles with primary aliphatic
amines can take place in two directions [5]: alkylation of the amine followed by addition of a secondary amino
group to the nitrile group, leading to 1-alkyl-2-amino-3-(2-azahetaryl)-4(5H)-oxopyrroles [5, 6] or
intramolecular alkylation with the formation of pyrrolo[1,2-a]azaheterocycles [7]. Reaction with primary
aromatic amines also leads to cyclization to 1-alkyl-2-amino-3-(2-azahetaryl)-4(5H)-oxopyrroles [5, 8].
RNH2
CN
CN
NHR
N
H
N
H
Cl
O
O
R1R2NH
NH2
N
CN
O
CN
N
N
N
R
H
.
.
.
2N
R1R
O
O
The reaction of 2-(2-azahetarylidene)-4-chloro-3-ketobutanenitriles with highly basic secondary amines
also takes place in various ways: in addition to the products from substitution of the halogen atom by an amino
group, products from intramolecular alkylation (pyrrolo[1,2-a]azaheterocycles) are also formed [5]. Reaction
with N,N-disubstituted hydrazine also results in amination [6]. Alkylation of the amino group is favored by
decrease in the basicity of the amine nitrogen atom of the heterocycle and by its steric screening [5].
It is also known [9, 10] that during amination of methyl 6-chloro-3-oxohexanoate, which contains a
γ-chlorobutyryl fragment, by primary amines, the chlorine atom is substituted by an amine residue, and
cyclization to 2-methylidenepyrrolidine derivatives occurs. In addition, the basicity of the amine facilitates the
formation of 2-methylidenetetrahydrofuran as a side product.
OMe
CO2Me
RNH2
CO2Me
Cl
+
N
R
O
O
O
In the present work, the reaction of 6-chloro-2-(2-hetarylidene)-3-oxohexanenitriles 1a-i with primary
aliphatic amines was studied. In view of the results from the above-mentioned investigations, we expected to
obtain 6-amino-2-(2-hetarylidene)-3-oxohexanenitriles A, 2-hetaryl-2-(tetrahydro-1H-2-pyrrolylidene)aceto-
nitriles A', or 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles 2a-i upon heating the compounds 1a-i with a
twofold excess of an amine in dioxane.
1
According to the H NMR spectral data, all the reaction products only contain small amounts of the
intramolecular cyclization products 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles 2a-i [3]. Performing the
reaction with an equimolar amount of the amine increases the yield of the cyclic compounds 2a-i to 40-60%
(Table 1). By using 1.1 equiv. of the amine after pretreatment of the nitriles 1a-i with 1 equiv. of Et3N it was
possible to obtain the main reaction product in a pure form (without compounds 2a-i as impurities). However,
according to the spectral characteristics this does not correspond to the expected structure A or A'; in addition to
1
the signals required for these structures, the H NMR spectra contain an additional triplet in the region of
4.5-4.8 ppm that exchanges with D2O, which is typical of hydroxyl group protons.
1771

O
HetH
Cl
CN
R3
1a–i
R3
R4NH2
CN
Het
O
HetH
NHR4
O
R3
N
R4
Het
CN
R3
A
A'
CN
2a–i
R3
Het
4HN
CN
R3
R4NH2
H
OH
O
Het
R
H
Het
R3
NC
N
R4
N
R4
H
CN
OH
3a–w
C
B
O
R1
H
N
H
N
Me
NH
1 a–e HetH =
; f–h HetH =
; i HetH =
X
S
N
H
R2
O
R1
Me
N
X
N
S
NH
2a–e, 3a–n Het =
; 2f–h, 3o–v Het =
; 2i, 3w Het =
N
R2
1, 2 f, 3o-r X = NH; 1, 2 g, 3s X = NMe; 1, 2 h, 3t–v X = S; 1, 2 а,e, 3a-g R1 = R2 = H;
1, 2 b, 3h-k R1 = Me, R2 = H; 1, 2 c, 3m,n R1 = R2 = Me; 1, 2 d, 3l R1 = Br, R2 = H;
1, 2 a-d,f-h, 3a-e,g-w R3 = H; 1, 2 e, 3f R3 = Me; 3 a,o R4 = H; b,r R4 = Me;
c,f,h,l,p R4 = (CH2)2OMe; d,k,n,s,t R4 = Bn; e,u R4 = (CH2)2Ph; g,q,w R4 = 3-CH2Py;
i R4 = CH(Me)Ph; j R4 = c-C6H11; m R4 = (CH2)3OMe; v R4 = (CH2)3NMe2
It should be noted that reaction of the compounds 2a-i with an equimolar amount of the corresponding
amine leads to the same compounds. The identity of the products obtained from compounds 1a-i and 2a-i upon
the action of amines is supported by the spectral characteristics, the chromatographic data, and the absence of a
melting point depression in a mixed melting test with authentic samples.
In the course of further investigations it was established that the action of amines both on compounds
1a-i and on the furan derivatives 2a-i leads to the formation of (Z)-2-(2-hetaryl)-6-hydroxy-3-(R-amino)-
2-hexenenitriles 3a-w. Thus, when the acyl derivatives 1a-i are used as starting compounds, the amine at the
first stage acts as a base leading to cyclization to the products 2a-i, which further react with a second equivalent
of the amine as a nucleophile to form the amino derivatives 3a-w.
A similar transformation is realized for 2-(acylmethylene)tetrahydrofuran derivatives during their
reaction with primary aliphatic amines [11, 12].
R1
R1NH2
O
HN
COR
OH
O
R
R = Alk, Ar
1772

TABLE 1. The Physicochemical Characteristics of the Synthesized
Compounds 3a-w
Found, %
Calculated, %
——————
Com-
pound
Empirical
formula
Mp*, °С
Yield, %
С
Н
N
Br
—
—
—
—
—
—
—
—
—
—
—
C14H14N4O2
C15H16N4O2
C17H20N4O3
C21H20N4O2
C22H22N4O2
C18H22N4O3
C20H19N5O2
C18H22N4O3
C23H24N4O2
C21H26N4O2
C22H22N4O2
C17H19BrN4O3
C20H26N4O3
C23H24N4O2
C13H14N4O
C16H20N4O2
C19H19N5O
C14H16N4O
C21H22N4O
C20H19N3OS*4
C21H21N3OS*5
C18H24N4OS
C16H18N4OS
62.28
62.21
63.30
63.37
62.27
62.18
69.91
69.98
70.69
70.57
63.21
63.14
66.60
66.47
63.10
63.14
71.23
71.11
68.91
68.83
70.74
70.57
50.27
50.14
64.96
64.84
71.22
71.11
64.40
64.45
63.90
63.98
68.50
68.45
65.54
65.61
72.89
72.81
68.82
68.74
69.58
69.39
62.59
62.76
61.25
61.12
5.36
5.22
5.86
5.67
6.19
6.14
5.77
5.59
5.86
5.92
6.62
6.48
5.43
5.30
6.59
6.48
6.44
6.23
7.25
7.15
6.07
5.92
4.89
4.70
7.21
7.07
6.17
6.23
5.96
5.82
6.88
6.71
5.69
5.74
6.44
6.29
6.52
6.40
5.39
5.48
5.93
5.82
7.16
7.02
5.98
5.77
20.81
20.73
19.85
19.71
17.31
17.06
15.78
15.55
15.23
14.96
16.57
16.36
19.44
19.38
16.60
16.36
14.65
14.42
15.41
15.29
15.23
14.96
13.90
13.76
15.33
15.13
14.71
14.42
23.27
23.13
18.88
18.65
21.15
21.01
21.77
21.86
16.31
16.17
12.30
12.02
11.73
11.56
16.22
16.26
17.89
17.82
211-212
216-217
182-183
179-181
177-178
153-154
189-190
164-165
169-170
196-197
186-187
175-176
187-188
237-239
170-171
151-152
180-181
162-163
137-139
129-130
160-161
103-104
74-75
88
3a
3b
3c
3d
3e
3f
73
91
81*2, 36*3
83*2
96
76
3g
3h
3i
94
82
81
3j
91
3k
3l
19.85
19.62
74*2
88
—
—
—
—
—
—
—
—
—
—
—
3m
3n
3o
3p
3q
3r
3s
78*2
78
85
84
83
76, 41*3
78
3t
80
3u
3v
3w
85
81
_______
*Compounds 3a,g,o-w were recrystallized from EtOH, compounds 3b,c,f,m
from n-BuOH, compounds 3d,e,h-l,n from 2-PrOH.
*2Synthesis by method B.
*3Synthesis with dibenzylamine.
*4Found: S 9.44%. Calculated: S 9.18%.
*5Found: S 9.08%. Calculated: S 8.82%.
1
In the H NMR spectra of compounds 3a-w, the aromatic proton signals are observed in the region of
6.79-8.07 ppm, and there are three protons which exchange with the D2O (the protons of the hydroxyl group and
the two amino groups). In particular, the proton of the heterocycle NH group resonates at 9.93-11.96 ppm, while
1773

the hydroxyl group triplet is observed in the region of 4.6-4.8 ppm. The signals of the methylene protons appear
1
at 1.45-3.60 ppm (Table 2). An unambiguous assignment of the signals was made on the basis of the H NMR
correlation spectra (COSY). The COSY spectrum of compound 3f showed the existence of interaction between
the downfield signal of the NH group (12.32 ppm) and the signal of the methylene group at 3.68 ppm and also
revealed coupling between the aliphatic protons. This allowed an unambiguous assignment of the NH signals.
1
A feature of the H NMR spectra of compounds 3f,i is the magnetic nonequivalence of the methylene
protons (4,5-CH2 for compound 3f and 5-CH2 for compound 3i), resulting from the presence of chiral centers in
the molecules of these compounds.
The reaction of the cyclic nitriles 2a-i evidently begins with nucleophilic attack on the C-2 atom of the
tetrahydrofuran ring contained in the acrylonitrile fragment, which leads to a Michael adduct (structure B). The
tetrahydrofuran ring is then opened with the formation of the intermediate C, which changes into (Z)-2-(2-het-
aryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles 3a-w as a result of prototropy.
It should be noted that in the reaction of compounds 2a,b,g with dibenzylamine, the formation of
compounds identical with the products 3d,k,s, in which there is only one benzyl substituent, was observed
instead of the expected products containing a dibenzylamine group. The yields of the (Z)-3-benzylamino-
6-hydroxy-2-hetaryl-2-hexenenitriles 3d,k,s in this reaction are small. The identity of these compounds was
confirmed by the spectral characteristics, the absence of a melting point depression in a mixed melting test with
an authentic sample, and the data from X-ray structural analysis. The literature contains examples of the
elimination of benzyl [4, 13] and ethyl [13] cations during the cyclization of ω-dialkylaminonitriles. The
elimination of the benzyl group may occur as a result of steric strain arising during placement of the bulky
substituents in the Z-configuration, or at the stage of intermediate C formation.
In the 1H NMR spectra of compounds 3d,k, the signal for the quinazoline H-8 proton is located upfield
relative to other aromatic protons, resulting from screening by the ring currents of the phenyl ring. The steric
proximity of the H-8 proton of quinazolinone to the benzylamine fragment is confirmed by the NOE data. Thus,
additional irradiation at the frequency of the benzylamino NH proton leads to an increased intensity of the
signals for the protons of the phenyl ring and the H-8 proton of the quinazolinone fragment.
Fig. 1. The structure of compound 3d according to X-ray structural analysis.
1774

The structure of compounds 3a-w was finally confirmed by X-ray crystallographic investigation of
3-benzylamino-6-hydroxy-2-(4-oxo-3,4-dihydro-2-quinazolinyl)-2-hexenenitrile 3d (Fig. 1).
In the molecule of compound 3d in addition to the quinazoline and benzene rings, it is possible to
identify several more planar fragments: the С(7), С(9), С(11), N(4), С(12), С(13), and С(19) atoms together
with the nitrile group and also the non-hydrogen atoms of the propanol substituent. Their angles of rotation in
relation to the plane of the quinazoline ring system amount to 8.3° and 76.5°, respectively. The benzene ring is
rotated by 46.4° in relation to the quinazoline fragment. The propanol substituent has the trans-trans
configuration (torsion angles С(11)–С(19)–С(20)–С(21) -179.9(2)° and С(19)–С(20)–С(21)–O(2) -176.9(2)°).
The nearly planar orientation of the quinazoline and aminobutene fragments is further stabilized by the
formation of an intramolecular resonance stabilized hydrogen bond N(4)–H···N(l) (H···N 1.96 Å, N–H···N
138°).
Strong conjugation in the fragment between the proton donor and acceptor leads to shortening of the
N(4)–C(11) bond to 1.327(2) Å (average value 1.34 Å [14]) and С(7)–С(9) bond to 1.448(3) Å (1.46 Å) and the
lengthening of the С(9)–С(11) bond to 1.394(3) Å (1.33 Å), and N(l)–C(7) bond to 1.304(2) Å (1.28 Å). Thus,
on the basis of the bond lengths it is possible to assume that the zwitterionic structure makes a substantial
contribution to the structure of compound 3d (Fig. 2).
The molecules 3d form centrosymmetric dimers in the crystalline state, as a result of intermolecular
hydrogen bonds O(2)–Н···O(1) [1-x, 2-y, 1-z] (Н···О 2.00 Å, О–Н···О 168°), which increases the O(1)–C(8)
bond length to 1.233(2) Å (average value 1.210 Å).
Fig. 2. Electron density polarization in the crystal of compound 3d according to X-ray structural analysis.
Thus, 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles, formed from the corresponding 6-chloro-2-(2-
het-arylidene)-3-oxohexanenitriles, are capable of undergoing selective amination and are potential
polyfunctional reagents for the preparation of (Z)-2-(2-hetaryl)-6-hydroxy-(R-amino)-2-hexenenitriles.
EXPERIMENTAL
1
The IR spectra were recorded in KBr pellets on a Pye-Unicam SP 3-300 instrument. The H NMR
spectra were recorded on a Varian Mercury 400 instrument (400 MHz) in DMSO-d6 with TMS as internal
standard. Elemental analysis was performed on a Vario MICRO Cube instrument. The melting points were
determined on small-scale Boetius hot stage apparatus with a VEB Analytik PHMK viewing device. The
reactions and the purity of the synthesized compounds were monitored by TLC on Silufol UV-254 plates in a
9:1 CHCl3–MeOH system.
Synthesis of (Z)-2-(2-Hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles 3a-w from 2-Hetaryl-
2-(tetrahydrofuran-2-ylidene)acetonitriles 2a-i.
1775

1776

1777

1778

(Z)-3-Amino-2-hetaryl-6-hydroxy-2-hexenenitriles 3a,o (General Method). A solution of the
2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitrile 2a-f (3 mmol) in ammonia-saturated MeOH (20-25 ml), was
refluxed for 3-4 h, while the degree of reaction completion was monitored by chromatography. The reaction
mixture was cooled, and the precipitated product was filtered off, washed with water and cooled EtOH, and
dried. A further quantity of the product can also be isolated after evaporation of the filtrate under vacuum.
Water (5-10 ml) was added to the dry residue, and the residue was filtered off.
(Z)-6-Hydroxy-3-methylamino-2-(4-oxo-3,4-dihydroquinazolin-2-yl)-2-hexenenitrile (3b). This
compound was obtained similarly by adding a 3.5-fold excess of a 40% aqueous methylamine to the alcohol
solution of the corresponding acetonitrile, instead of using the methanol solution of ammonia.
(Z)-2-(2-Hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles 3c,e,f,h-j,l,m,p,r,u,v (General Method).
The corresponding amine (8.4 mmol) was added to a suspension of 2-hetaryl-2-(tetrahydrofuran-2-yl-
idene)acetonitrile 2a-h (8.0 mmol) in dioxane (20 ml), and the mixture was refluxed for 30-60 min until the
starting compound had disappeared. As a rule, the crystallization of product began 10-20 min after the
beginning of the reaction. The reaction mixture was cooled, and the precipitate was filtered off and washed with
cooled EtOH. The filtrate was evaporated under vacuum, and 2-PrOH or EtOH (1-2 ml) was added to the dry
residue, the mixture was rubbed, and the precipitate was filtered off and washed with cooled EtOH, thus
isolating an additional crop of the product. The targeted nitriles are obtained in a sufficiently pure form but can
be recrystallized from a suitable solvent (Table 1) if required.
(Z)-3-Benzylamino-2-hetaryl-6-hydroxy-2-hexenenitriles 3d,k,n,s,t (General Method). Benzyl-
amine (0.26 ml, 2.4 mmol) was added to a suspension of 2-hetaryl-2-(tetrahydrofuran-2-yli-dene)acetonitrile
2a-c,g,h (2.0 mmol) in dioxane (7-10 ml). The mixture was refluxed for 2-3 h, while the degree of reaction
completion was monitored by chromatography. The reaction mixture was cooled, and the precipitated product
was filtered off and washed with cooled EtOH. (In the case of compound 3s, PhMe (1-1.5 ml) was added to the
reaction mixture in order to initiate crystallization of the product.) The filtrate was evaporated under vacuum.
EtOH (1-2 ml) was added to the dry residue, the mixture was rubbed, and an additional quantity of the product
was filtered off and washed with cooled EtOH.
(Z)-2-Hetaryl-6-hydroxy-3-(3-pyridylmethyl)amino-2-hexenenitriles 3g,q,w (General Method).
3-Pyridinylmethylamine (2.8 mmol) was added to a solution of 2-hetaryl-2-(tetrahydrofuran-2-ylidene)-
acetonitrile 2a,f,i (2.0 mmol) in dioxane (20 ml). The reaction mixture was refluxed for 10-15 h, while the
degree of reaction completion was monitored by chromatography. A small amount of water was added to the
cooled solution, and the precipitate that formed was filtered off, washed with H2O and EtOH, and dried.
Synthesis of (Z)-3-Benzylamino-2-hetaryl-6-hydroxy-2-hexenenitriles 3d,k,s from 2-Hetaryl-
2-(tetrahydrofuran-2-ylidene)acetonitriles 2a,b,g and Dibenzylamine. During the preparation of compounds
3d,k,s from 2-hetaryl-2-(tetrahydrofuran-2-ylidene)acetonitriles 2a,b,g and dibenzylamine, a threefold excess of
the latter was used, and the reaction mixture was refluxed for 24-30 h. The reaction mixture was evaporated
under vacuum. 2-PrOH (3-5 ml) was added to the residue, the mixture was rubbed, and the precipitated
compounds 3d,k,s were filtered off.
Synthesis of (Z)-2-(2-Hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles 3a-w from 6-Chloro-2-(2-het-
arylidene)-3-oxohexanenitriles 1a-i. Et3N (5.0 mmol) was added to a suspension of 6-chloro-2-(2-hetarylidene)-
3-oxohexanenitrile 1a-i (5.0 mmol), and the mixture was refluxed for 1-2 h until the starting compound had
disappeared (according to TLC). The corresponding amine (5.5 mmol) (6.0 mmol in the case of benzylamine)
was added to the reaction mixture. The mixture was refluxed for 0.5-3 h, while the degree of reaction
completion was monitored by chromatography. The precipitate was filtered from the neutral solution, washed
with EtOH and H2O, and dried. The filtrate was evaporated to dryness under vacuum, and 2-PrOH or EtOH
(5-10 ml) was added. The precipitate was rubbed, filtered off, and washed with cold EtOH, giving an additional
crop of the product.
1779

X-ray Crystallographic Investigation of Compound 3d. The crystals of compound 3d (C21H40N4O2)
are triclinic, at 20°C: a 8.586(2), b 10.867(2), c 11.016(3) Å; α 90.03(2), β 108.82(2), γ 109.73(2)°; V 908.8(4)
Å3; M 360.41; Z 2; space group – , d
1.317 g/cm3; μ(MoKα) 0.087 mm-1; F(000) 380. The unit cell
P1
calc
parameters and the intensities of 3439 reflections (3208 independent, Rint 0.035) were recorded on an automatic
four-circle Siemens P3/PC diffractometer (MoKα, graphite monochromator, 2θ/θ scan, 2θmax 50°). The structure
was interpreted by the direct method using SHELXTL software package [15]. The positions of the hydrogen
atoms were revealed from an electron density difference synthesis and were refined by the “rider” model with
Uiso = nUeq (n = 1.5 for the hydrogen atoms of the hydroxy group and n = 1.2 for the remaining hydrogen
atoms). The structure was refined by F2 full-matrix least-squares treatment in anisotropic approximation for the
non-hydrogen atoms to wR2 0.109 in 3200 reflections (R1 0.041 in 1605 reflections with F > 4σ(F), S 0.914).
The crystallographic data were deposited at the Cambridge Crystallographic Data Center (deposit CCDC
887982).
REFERENCES
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