Synthesis and crystal structure of chiral N-ferrocenylmethyl alkamine imine

Article abstract of DOI:10.3184/030823409X12551926920081

Two chiral ferrocenylimine alcohols have been prepared, [Fe(η⁵-(C₅H₅){η⁵-C ₅H₄CH=NCH(CH₂OH)(CH₂R)}] (R = Ph, 5a; R = Pr_i, 5b). Single crystal X-ray diffraction analysis reveals that the molecular structure of compound 5b is enantiomerically pure.

Full text of DOI:10.3184/030823409X12551926920081

JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009
NOVEMBER,ꢀ665–667ꢀ
RESEARCH PAPERꢀ 665
Synthesis and crystal structure of chiral N-ferrocenylmethyl alkamine imine
Yu-Mei Zhang*, Peng Liu and Hong-Li Zhang
College of Sciences, Hebei University of Science & Technology, Shijiazhuang 050018, P.R. China
.
5
5
Twoꢀ chiralꢀ ferrocenylimineꢀ alcoholsꢀ haveꢀ beenꢀ prepared,ꢀ [Fe(η -(C H ){η -C H CH=NCH(CH OH)(CH R)}]ꢀ (Rꢀ =ꢀ Ph,ꢀ
5
5
5
5
4
2
2
i
a;ꢀRꢀ=ꢀPr ,ꢀ5b).ꢀSingleꢀcrystalꢀX-rayꢀdiffractionꢀanalysisꢀrevealsꢀthatꢀtheꢀmolecularꢀstructureꢀofꢀcompoundꢀ5bꢀisꢀ
enantiomericallyꢀpure.
Keywords: ferrocenylimineꢀalcohols,ꢀsynthesis,ꢀcrystalꢀstructure,ꢀchirality,ꢀimine
Enantiomericallyꢀ pureꢀ ferrocenylimineꢀ alcoholꢀ compoundsꢀ
haveꢀ foundꢀ widespreadꢀ useꢀ asꢀ chiralꢀ ligandsꢀ orꢀ auxiliariesꢀ
inꢀ asymmetricꢀ reactions.ꢀ Theseꢀ compoundsꢀ areꢀ veryꢀ
effectiveꢀ catalystsꢀ forꢀ aꢀ wideꢀ rangeꢀ ofꢀ reactionsꢀ suchꢀ asꢀ
epoxidation,ꢀ epoxideꢀ ringꢀ opening,ꢀ Diels–Alderꢀ reactionsꢀ
andꢀ aldolꢀ reactions.1 ꢀ Inꢀ addition,ꢀ theꢀ stericꢀ effectꢀ ofꢀ theꢀ
specificꢀmicroenvironmentꢀcreatedꢀbyꢀtheꢀferroceneꢀskeletonꢀ
structureꢀ canꢀ modulateꢀ theꢀ catalyticꢀ behaviourꢀ ofꢀ theꢀ chiralꢀ
ferrocenylimineꢀalcohol.
Considerableꢀ effortꢀ hasꢀ focusedꢀ onꢀ theꢀ designꢀ ofꢀ
ferrocenylimineꢀalcoholꢀcompoundsꢀwithꢀpotentialꢀapplicationsꢀ
inꢀdrugꢀdeliveryꢀandꢀbiomedicalꢀengineering.ꢀInꢀthisꢀpaper,ꢀweꢀ
reportꢀtheꢀsyntheticꢀandꢀstructuralꢀinvestigationꢀofꢀtwoꢀnovelꢀ
chiralꢀferrocenylimine alcoholsꢀ5a and 5b (Schemeꢀ1).
forꢀC H ClNO :ꢀC,ꢀ55.69;ꢀH,ꢀ6.54;ꢀN,ꢀ6.49.ꢀFound:ꢀC,ꢀ55.48;ꢀH,ꢀ
10 14 2
-1 ꢀ
6
1
.39;ꢀ N,ꢀ 6.23%;ꢀ IRꢀ v/cm : 3001.85;ꢀ 2963.72;ꢀ 2625.84;ꢀ 1754.61;ꢀ
583.69;ꢀ1491.30;ꢀ1237.23.ꢀTheꢀcrystalsꢀwereꢀdissolvedꢀinꢀwaterꢀandꢀ
saturatedꢀNaHCO ꢀsolutionꢀwasꢀaddedꢀuntilꢀpHꢀ=ꢀ8.ꢀThenꢀtheꢀreactionꢀ
3
mixtureꢀwasꢀextractedꢀwithꢀmethyleneꢀchloride,ꢀtheꢀorganicꢀlayerꢀwasꢀ
washedꢀ withꢀ water,ꢀ driedꢀ overꢀ anhydrousꢀ magnesiumꢀ sulfate,ꢀ thenꢀ
evaporatedꢀ toꢀ affordꢀ L-phenylalanineꢀ methylesterꢀ (2a)ꢀ (colourlessꢀ
-4
oil).ꢀ 2aꢀ wasꢀ reducedꢀ toꢀ L-phenylalaninolꢀ (3a)ꢀ withꢀ KBH ꢀ andꢀ
4
20
CaCl ꢀasꢀtheꢀreducingꢀagent.ꢀ(Yield:ꢀ68.9%).ꢀm.p.90–91ꢀ°C,ꢀ[a]
2
D
-1
–
1
22.5ꢀ°Cꢀ (c 1.2,ꢀ C H OH);ꢀ IRꢀ v/cm :ꢀ 3380.6(OH);ꢀ 1569.8(NH );ꢀ
2 5 2
348.1(CH );ꢀ1052.3(C–O).
2
3
b: Preparedꢀ inꢀ similarꢀ mannerꢀ toꢀ 3a, startingꢀ with L-leucine.ꢀ
Theꢀ crudeꢀ materialꢀ wasꢀ recrystallisedꢀ fromꢀ ethanol–etherꢀ givingꢀ
20
whiteꢀneedleꢀcrystalsꢀofꢀ2bꢀ(9.9ꢀg,ꢀ72.1%),ꢀm.p.ꢀ150–152 ꢀ° C,ꢀ[a] ꢀ+ꢀ
D
2
6
ꢀ7
13.2ꢀ(cꢀ2.0,ꢀH O).ꢀ[lit.ꢀ[a] ꢀ+ꢀ13.4ꢀ°ꢀ(Cꢀ=ꢀ2.0,ꢀH O)]. ꢀAnal.ꢀCalcdꢀ
2
D
2
forꢀC H ClNO :ꢀC,ꢀ46.28;ꢀH,ꢀ8.88;ꢀN,ꢀ7.71,ꢀFound:ꢀC,ꢀ46.09;ꢀH,ꢀ
7
16
2
-
1
8
.25;ꢀ N,ꢀ 7.73%;ꢀ IRꢀ v/cm :ꢀ 2960.27;ꢀ 2627.68;ꢀ 1736.13;ꢀ 1583.68;ꢀ
223.37.ꢀ2bꢀwasꢀreducedꢀtoꢀL-leucinolꢀ(3b)ꢀwithꢀKBH ꢀandꢀCaCl ꢀasꢀ
1
4
2
Experimental
20
theꢀreducingꢀagent.ꢀ(Yield:ꢀ58.6%).ꢀm.p.56–58ꢀ°C,ꢀ[a] –11.2ꢀ°Cꢀ(cꢀ
D
-1
Allꢀreactionsꢀwereꢀcarriedꢀoutꢀunderꢀargonꢀandꢀmonitoredꢀbyꢀthin-
layerꢀchromatographyꢀ(TLC).ꢀDiethylꢀetherꢀwasꢀdriedꢀusingꢀNaꢀunderꢀ
reflux.ꢀ Meltingꢀ pointsꢀ (uncorrected)ꢀ wereꢀ measuredꢀ withꢀ anꢀ XT4ꢀ
1.3,ꢀC H OH);ꢀIRꢀv/cm :ꢀ3378.5(OH);ꢀ1572.8(NH );ꢀ1346.2(CH );ꢀ
2
5
2
2
1051.6(C–O).
1
meltingꢀpointꢀapparatus.ꢀ HꢀNMRꢀspectraꢀwereꢀrecordedꢀonꢀaꢀVarianꢀ
Synthesis of ferroceneimine alcohols 5
3
00ꢀspectrometer,ꢀusingꢀCDCl ꢀasꢀsolventꢀandꢀTMSꢀasꢀtheꢀinternalꢀ
Theꢀ titleꢀ compoundsꢀ wereꢀ preparedꢀ accordingꢀ toꢀ Schemeꢀ 1.ꢀ
Formylferroceneꢀ (4)ꢀ (5ꢀ mmol)ꢀ wasꢀ treatedꢀ inꢀ benzeneꢀ atꢀ 80ꢀ°ꢀ
withꢀ L-phenylalaninolꢀ (L-leucinol)ꢀ (5ꢀ mmol)ꢀ usingꢀ modificationꢀ
ofꢀ reportedꢀ procedures,ꢀ givingꢀ iminesꢀ 5aꢀ andꢀ 5bꢀ respectively.ꢀ
Afterꢀ evaporationꢀ ofꢀ theꢀ solvent,ꢀ bothꢀ iminesꢀ wereꢀ recrystallisedꢀ
fromꢀdichloromethane/petroleumꢀetherꢀgivingꢀorangeꢀcrystals.
3
standard.ꢀOpticalꢀrotationsꢀwereꢀmeasuredꢀonꢀaꢀWZZ-3ꢀpolarimeter.ꢀ
Columnꢀ chromatographyꢀ wasꢀ performedꢀ onꢀ silicaꢀ gelꢀ (200–300ꢀ
5
ꢀ
mesh).ꢀFormylferroceneꢀwasꢀpreparedꢀbyꢀaꢀliteratureꢀmethod (m.p.ꢀ
22–124ꢀ°).
1
2
0
Synthesis of chiral a-amino alcohols
a:ꢀToꢀanhydrousꢀmethanolꢀ(65ꢀmL)ꢀcontainedꢀinꢀaꢀ250ꢀmLꢀthree-
5a: 82.6%.ꢀ m.p.ꢀ 118–120ꢀ°,ꢀ [a] –123.2ꢀ (cꢀ 0.153,ꢀ CH Cl ).ꢀ
D 2 2
3
Theꢀ IRꢀ spectrumꢀ indicatedꢀ theꢀ presenceꢀ ofꢀ theꢀ unsubstitutedꢀ
-
1
-1
neckꢀflask,ꢀwithꢀstirringꢀandꢀcoolingꢀtoꢀ–10ꢀ°ꢀwithꢀanꢀice-saltꢀbath,ꢀwasꢀ
cyclopentadienylꢀringꢀ(1103.9ꢀandꢀ996.6ꢀcm ),ꢀ1022.0–1147.6ꢀcm ꢀ
-1
-1
slowlyꢀaddedꢀSOCl ꢀ(7.2ꢀmL,ꢀ0.099ꢀmol)ꢀdropꢀbyꢀdropꢀ(temperatureꢀ
(singleꢀ substitutedꢀ cyclopentadienyl),ꢀ 486.1ꢀ cm ꢀ andꢀ 509.9ꢀ cm
2
-1
1
cannotꢀexceedꢀ0°).ꢀWhenꢀtheꢀadditionꢀwasꢀfinished,ꢀtheꢀmixtureꢀwasꢀ
cooledꢀatꢀ–5–0ꢀ°ꢀforꢀaboutꢀ1ꢀh.ꢀThenꢀL-ꢀphenylalanineꢀ(8.0ꢀg,ꢀ0.076ꢀmol)ꢀ
wasꢀadded,ꢀstirringꢀwasꢀcontinuedꢀforꢀ3ꢀhꢀatꢀroomꢀtemperature,ꢀthenꢀ
theꢀ mixtureꢀ wasꢀ refluxedꢀ forꢀ 2ꢀ h.ꢀAfterꢀ cooling,ꢀ theꢀ liquidsꢀ wereꢀ
removedꢀbyꢀvacuumꢀdistillation,ꢀleavingꢀaꢀwhiteꢀcrudeꢀsolidꢀ(yieldꢀ
(n ),ꢀ 1641.1ꢀ cm (N=CH);ꢀ Hꢀ NMRꢀ (300ꢀ MHz,ꢀ CDCl ,ꢀ ppm):
F
e
-
C
3
dꢀ7.94ꢀ(s,ꢀ1H,ꢀN=CH),ꢀ7.30–7.21ꢀ(m,ꢀ5H,ꢀArH),ꢀ4.63(s,ꢀ1H,ꢀOH),ꢀ
4.45–4.31ꢀ(m,ꢀ4H,ꢀCp-H),ꢀ3.96ꢀ(s,ꢀ5H,ꢀCp-H),ꢀ3.77–3.71ꢀ(m,ꢀ2H,,ꢀ
CH –OH),ꢀ3.50–3.46ꢀ(m,ꢀ1H,ꢀN–CH),ꢀ2.92–2.86ꢀ(m,ꢀ2H,ꢀPh-CH ),
2
2
ꢀ
20
5b: 75.1%ꢀm.p.ꢀ98–100ꢀ°,ꢀ[a] –106.2ꢀ(cꢀ0.104,ꢀCH Cl ).ꢀTheꢀIRꢀ
spectrumꢀindicatedꢀtheꢀpresenceꢀofꢀtheꢀunsubstitutedꢀcyclopentadienylꢀ
ringꢀ(1100.1ꢀandꢀ996.0ꢀcm ),ꢀ1021.0–1145.6ꢀcm ꢀ(singleꢀsubstitutedꢀ
cyclopentadienyl),ꢀ 486.5ꢀ cm ꢀ andꢀ 509.7ꢀ cm (nFe-C),ꢀ 1636.2ꢀ cm
D
2
2
2
0
27
8
+
3.2%).ꢀm.p.157–159ꢀ°C,ꢀ[a] ꢀ+ꢀ37.5ꢀ°ꢀ(c 2.0,ꢀC H OH).ꢀ[lit.ꢀ[a] ꢀ
D
2
5
D
6
-1
-1
ꢀ38.1ꢀ°ꢀ(Cꢀ=ꢀ2.0,ꢀC H OH)]. ꢀTheꢀcrudeꢀmaterialꢀwasꢀrecrystallisedꢀ
2
5
-1
-1
-1
fromꢀethanol–etherꢀgivingꢀwhiteꢀneedleꢀcrystalsꢀ(11.3ꢀg).ꢀAnal.ꢀCalcdꢀ
R
R
R
SOCl
2
KBH4
CaCl2
CH OH
3
H N
COOH
H N
COOCH3
H N
CH OH
2
2
2
2
1
2
3
3a
R=
3b R=
R
R
CHO
C
N
C H OH
2
5
H
+
Fe
Fe
CH OH
2
H N
CH OH
2
2
reflux
5
3
4
5
a
5b R=
R=
Scheme 1ꢀ Preparationꢀofꢀchiralꢀferrocenylimineꢀalcohols.
ꢀCorrespondent.ꢀE-mail:ꢀzhangym.jy@gmail.com
*
PAPER:ꢀJC090707

6
66ꢀ JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009
1
(
N=CH);ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀCDCl ,ꢀppm):dꢀ8.05ꢀ(s,ꢀ1H,ꢀN=CH),ꢀ
Table 2ꢀ Selectedꢀbondꢀlengthsꢀ(Å)ꢀforꢀcompoundꢀ5b
Bondꢀlength/Åꢀ Bondꢀlength/Å
C(10)–C(11)ꢀ
3
4
3
1
3
.75(s,ꢀ1H,ꢀOH),ꢀ4.46–4.30ꢀ(m,ꢀ4H,ꢀCp-H),ꢀ4.17ꢀ(s,ꢀ5H,ꢀCp-H),ꢀ3.75–
.73ꢀ(m,ꢀ2H,,ꢀCH –OH),ꢀ2.81–2.76ꢀ(m,ꢀ1H,ꢀN–CH),ꢀ1.92–1.85,ꢀm,ꢀ
ꢀ
2
H,ꢀ(CH ) CH),ꢀ0.95–0.98ꢀ(d,ꢀ3H,ꢀJ =ꢀ7.6ꢀHz,ꢀCH ),ꢀ0.89-0.91ꢀ(d,ꢀ
3
2
3
Fe(1)–C(10)ꢀ
Fe(1)–C(9)ꢀ
Fe(1)–C(8)ꢀ
Fe(1)–C(7)ꢀ
Fe(1)–C(6)ꢀ
Fe(1)–C(5)ꢀ
Fe(1)–C(4)ꢀ
Fe(1)–C(3)ꢀ
Fe(1)–C(2)ꢀ
Fe(1)–C(1)ꢀ
O(1)–C(16)ꢀ
N(1)–C(11)ꢀ
2.025(4)ꢀ
2.056(5)ꢀ
2.058(4)ꢀ
2.047(3)ꢀ
2.041(4)ꢀ
2.050(4)ꢀ
2.043(3)ꢀ
2.035(4)ꢀ
2.040(4)ꢀ
2.041(4)ꢀ
1.430(4)ꢀ
1.269(4)ꢀ
1.454(5)
1.525(4)
1.525(4)
1.535(4)
1.530(5)
1.439(4)
1.407(7)
1.438(8)
1.409(5)
1.425(5)
1.419(6)
1.481(4)
H,ꢀJ =ꢀ7.6ꢀHz,ꢀCH3).
C(13)–C(14)ꢀ
C(12)–C(16)ꢀ
C(12)–C(13)ꢀ
C(13)–C(15)ꢀ
C(9)–C(10)ꢀ
C(2)–C(3)ꢀ
X-ray crystal-structure analysis of 5b
Crystalsꢀ suitableꢀ forꢀ X-rayꢀ structureꢀ determinationꢀ wereꢀ obtainedꢀ
fromꢀtheꢀfiltrationꢀbyꢀslowꢀevaporationꢀofꢀtheꢀsolvent.ꢀCrystal data:ꢀ
C H FeNO,ꢀ Mr =ꢀ 298.18,ꢀ Monoclinic,ꢀ C2,ꢀ a = 24.124(5)ꢀ Å,ꢀ
16
20
3
b = 8.9923(18)ꢀÅ,ꢀc = 6.6417(13)Å,ꢀV =ꢀ1433.6(5)ꢀÅ ,ꢀD =ꢀ1.381ꢀgꢀ
x
C(4)–C(5)ꢀ
-3
cm ,ꢀZ =ꢀ4,ꢀT =ꢀ113(2)K.ꢀAbsoluteꢀstructureꢀparameterꢀisꢀ–0.010(19).ꢀ
Slowꢀevaporationꢀofꢀtheꢀcompoundꢀ5bꢀinꢀpetroleumꢀetherꢀandꢀethylꢀ
acetateꢀyieldedꢀsingleꢀcrystalsꢀsuitableꢀforꢀX-rayꢀanalysis.ꢀAnꢀorangeꢀ
blockꢀcrystalꢀwithꢀapproximateꢀdimensionsꢀofꢀ0.16 × 0.12 × 0.06ꢀmmꢀ
wasꢀmountedꢀonꢀaꢀBrukerꢀSmartꢀ1000ꢀCCDꢀdiffractometerꢀequippedꢀ
withꢀ graphiteꢀ monochromatorꢀ dataꢀ collection.ꢀ Theꢀ determinationꢀ
ofꢀ unitꢀ cellꢀ parametersꢀ andꢀ dataꢀ collectionꢀ wereꢀ performedꢀ atꢀ
C(6)–C(7)ꢀ
C(7)–C(8)ꢀ
C(8)–C(9)ꢀ
N(1)–C(12)ꢀ
SingleꢀcrystalꢀX-rayꢀdiffractionꢀanalysisꢀrevealsꢀthatꢀtheꢀmolecularꢀ
structureꢀ ofꢀ 5bꢀ isꢀ essentiallyꢀ asꢀ expectedꢀ andꢀ confirmsꢀ theꢀ
formulationꢀ ofꢀ theꢀ compoundꢀ (shownꢀ inꢀ Fig.ꢀ 1).ꢀ Thisꢀ compoundꢀ
isꢀ enantiomericallyꢀ pureꢀ andꢀ crystallisesꢀ inꢀ theꢀ monoclinicꢀ C2ꢀ
spaceꢀgroup.
1
13(2)ꢀ K,ꢀ usingꢀ graphiteꢀ monochromatedꢀ MoKaꢀ (lꢀ =ꢀ 0.71073ꢀA)ꢀ
radiation.ꢀAꢀtotalꢀofꢀ29018ꢀreflectionsꢀwithꢀ3727ꢀindependentꢀonesꢀ
withꢀRintꢀ=ꢀ0.0384ꢀwereꢀmeasuredꢀinꢀtheꢀrangeꢀofꢀ2.42≤θ≤24.98ꢀ°ꢀbyꢀ
anꢀoscillationꢀmethod.ꢀAllꢀdataꢀwereꢀcorrectedꢀusingꢀtheꢀSADABSꢀ
method.ꢀ Theꢀ structureꢀ wasꢀ solvedꢀ byꢀ directꢀ methodsꢀ usingꢀ theꢀ
SHELXL-97ꢀ programꢀ andꢀ refinedꢀ byꢀ full-matrixꢀ least-squaresꢀ onꢀ
Theꢀ Fe–Cꢀ contactꢀ lengthsꢀ rangeꢀ fromꢀ 2.035ꢀ (4)ꢀ toꢀ 2.050(4)ꢀ Åꢀ
(C1–C5)ꢀandꢀfromꢀ2.041(3)ꢀtoꢀ2.058(3)ꢀÅꢀ(C6–C9)ꢀinꢀtheꢀmolecule.ꢀ
2
8
F . ꢀ Allꢀ non–hydrogenꢀ atomsꢀ wereꢀ refinedꢀ anisotropically,ꢀ andꢀ
hydrogenꢀatomsꢀwereꢀaddedꢀaccordingꢀtoꢀtheoreticalꢀmodes.ꢀTheꢀfinalꢀ
cycleꢀofꢀrefinementꢀgaveꢀRꢀ=ꢀ0.0335,ꢀwRꢀ=ꢀ0.0707ꢀ(Theꢀweightingꢀ
schemeꢀwasꢀwꢀ=ꢀ1/[s (F )ꢀ+ꢀ(0.0202P) ]ꢀwhereꢀPꢀ=ꢀ(F ꢀ+ꢀ2F )/3).ꢀ
Theꢀ finalꢀ refinementꢀ wasꢀ performedꢀ byꢀ fullꢀ matrixꢀ least-squaresꢀ
methodsꢀwithꢀanisotropicꢀthermalꢀparametersꢀforꢀnon-hydrogenꢀatomsꢀ
TheꢀFe–C10ꢀcontactꢀlengthꢀisꢀ2.025ꢀ(4)ꢀÅ.ꢀFeꢀatomsꢀareꢀalmostꢀatꢀtheꢀ
centreꢀofꢀtheꢀtwoꢀcyclopentadienylꢀrings,ꢀwithꢀtheꢀFe(1)–Cg(1)ꢀandꢀ
Fe(1)–Cg(2)ꢀdistancesꢀ1.6585ꢀÅ,ꢀ1.6405ꢀÅ,ꢀwhereꢀCg(1)andꢀCg(2)ꢀ
2
2
2
2
2
0
0
c
areꢀtheꢀcentroidsꢀofꢀtheꢀη5(C H )ꢀandꢀη5(C H )ꢀrings.ꢀTheꢀironꢀatomsꢀ
5
5
5
4
areꢀslightlyꢀcloserꢀtoꢀtheꢀplaneꢀofꢀtheꢀunsubstitutedꢀrings.ꢀTheꢀtwoꢀ
cyclopentadienylꢀringsꢀareꢀnotꢀparallel,ꢀtheꢀtwoꢀcyclopentadienylꢀringsꢀ
deviateꢀ fromꢀ anꢀ eclipsedꢀ geometryꢀ inꢀ compoundꢀ 5b,ꢀ asꢀ evidencedꢀ
2
onꢀF .ꢀMolecularꢀgraphicsꢀwereꢀdrawnꢀwithꢀtheꢀprogramꢀpackageꢀXP.ꢀ
FullꢀcrystallographicꢀdetailsꢀhaveꢀbeenꢀdepositedꢀwithꢀtheꢀCambridgeꢀ
Crystallographicꢀ Dataꢀ Centreꢀ andꢀ allocatedꢀ theꢀ depositionꢀ numberꢀ
CCDC-741091.ꢀFurtherꢀdetailsꢀofꢀtheꢀstructureꢀanalysesꢀareꢀgivenꢀinꢀ
Tableꢀ1,ꢀselectedꢀbondꢀlengthsꢀandꢀanglesꢀareꢀin Tablesꢀ2ꢀandꢀ3.
Results and discussion
Theꢀtitleꢀcompounds,ꢀferrocenylimineꢀalcohols 5a and 5b, haveꢀbeenꢀ
synthesised.ꢀ5bꢀwasꢀcharacterisedꢀbyꢀX-rayꢀdiffraction,ꢀitsꢀmolecularꢀ
structureꢀ isꢀ shownꢀ inꢀ Fig.ꢀ 1.ꢀ Theꢀ compoundsꢀ wereꢀ characterisedꢀ
1
byꢀ IRꢀ andꢀ Hꢀ NMRꢀ elementalꢀ analysis.ꢀTheꢀ spectroscopicꢀ dataꢀ ofꢀ
theꢀ complexesꢀ areꢀ foundꢀ toꢀ beꢀ identicalꢀ withꢀ expectedꢀ structures.ꢀ
1
Inꢀtheꢀ HꢀNMRꢀspectraꢀofꢀtheꢀproduct,ꢀtheꢀhydrogenꢀatomsꢀofꢀtheꢀ
unsubstitutedꢀCpꢀmoietyꢀappearꢀasꢀaꢀsharpꢀsinglet.ꢀTheꢀimineꢀfunctionꢀ
ofꢀtheꢀcompoundsꢀwasꢀregisteredꢀasꢀstrongꢀsignalsꢀatꢀaboutꢀ1636ꢀandꢀ
-
1
1
641ꢀcm ꢀinꢀtheꢀIR-spectra,ꢀasꢀwellꢀasꢀatꢀaboutꢀ7.94ꢀandꢀ8.05ꢀppmꢀinꢀ
1
theꢀ HꢀNMRꢀspectra.
Table 1ꢀ Crystallographicꢀ dataꢀ andꢀ structureꢀ refinementꢀ
summary
Fig. 1ꢀ ORTEPꢀ drawingꢀ ofꢀ theꢀ structureꢀ ofꢀ 5b.ꢀ Thermalꢀ
ellipsoidsꢀareꢀdrawnꢀatꢀ50%ꢀprobabilityꢀlevel.
CCDCꢀdepositꢀno.ꢀ
Empiricalꢀformulaꢀ
Formulaꢀweightꢀ
Temoerature(K)ꢀ
Wavelengthꢀ(MoꢀKa)ꢀ(A°)ꢀ
Crystalꢀsystemꢀ
Spaceꢀgroupꢀ
Unitꢀcellꢀdimensions
aꢀ(Å)ꢀ
741091
C16H20FeNO'ꢀ
298.18
113(2)
0.71073
Monoclinic
C2
24.124(5)
bꢀ(Å)
8.9923(18)ꢀ
6.6417(13)ꢀ
1433.6(5)ꢀ
4
c (Å)
3
Volume(Åꢀ )
Zꢀ
Crystalꢀsizeꢀꢀ
0.16 × 0.12 × 0.06ꢀ
1.381ꢀ
1.043
628
-2
CalculatedꢀdensityꢀMgꢀm ꢀ
-1
Absorptionꢀcoefficient,ꢀmm ꢀ
F(000)ꢀ
Reflectionsꢀcollected/uniqueꢀ
Completenessꢀtoꢀthetaꢀ=ꢀ24.98ꢀꢀ
Data/restraints/parametersꢀ
Limitingꢀindicesꢀꢀ
5225/2476ꢀ[R(int)ꢀ=ꢀ0.0384]
99.7%
2476/1/172
–27<ꢀ=ꢀh<ꢀ=ꢀ28,ꢀ
–
10<ꢀ=ꢀk<ꢀ=ꢀ10,ꢀ–6<ꢀ=ꢀl<ꢀ=ꢀ7
GoodnessꢀofꢀfitꢀonꢀF2ꢀ
1.159ꢀ
FinalꢀRꢀindicesꢀ[I>2ꢀsigma(I)]ꢀ
Rꢀindicesꢀ(allꢀdata)ꢀ
R1ꢀ=ꢀ0.0335,ꢀwR2ꢀ=ꢀ0.0707ꢀ
R1ꢀ=ꢀ0.0396,ꢀwR2ꢀ=ꢀ0.0721ꢀ
–0.010(19)
Absoluteꢀstructureꢀparameterꢀ
Fig. 2ꢀ Three-dimensionalꢀ molecular-packingꢀ diagramꢀ ofꢀ
compoundꢀ5b.
3
Largestꢀdiff.ꢀpeakꢀandꢀhole/e.A- ꢀ
0.428ꢀandꢀ-0.428ꢀ
PAPER:ꢀJC090707

JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009ꢀ 667
Table 3ꢀ Selectedꢀbondꢀanglesꢀandꢀtorsionꢀanglesꢀ(°)ꢀforꢀcompoundꢀ5b
ꢀ
Bondꢀangle/°ꢀ
Bondꢀangle/°
C(10)–Fe(1)–C(6)ꢀ
C(4)–Fe(1)–C(6)ꢀ
C(6)–Fe(1)–C(1)ꢀ
C(9)–C(10)–C(11)ꢀ
N(1)–C(11)–C(10)ꢀ
C(12)–N(1)–C(11)–C(10)ꢀ
C(11)–N(1)–C(12)–C(16)ꢀ
41.12(16)ꢀ
122.04(18)ꢀ
158.70(14)ꢀ
123.9(4)ꢀ
C(5)–C(1)–C(2)ꢀ
107.4(2)
107.5(3)
109.2(3)
111.6(3)
112.2(3)
ꢀ–176.5(4)
5.8(6)
N(1)–C(12)–C(16)ꢀ
N(1)–C(12)–C(13)ꢀ
C(15)–C(13)–C(12)ꢀ
O(1)–C(16)–C(12)ꢀ
C(9)–C(10)–C(11)–N(1)ꢀ
C(6)–C(10)–C(11)–N(1)ꢀ
123.3(3)ꢀ
–175.6(3)ꢀ
–141.6(3)ꢀ
5
byꢀtheꢀinterplanarꢀanglesꢀofꢀ5.1°ꢀrespectivelyꢀbetweenꢀtheꢀη (C H )ꢀ
Technologyꢀ andꢀ theꢀ Fundamentalꢀ Researchꢀ Fundꢀ ofꢀ Hebeiꢀ
UniversityꢀofꢀScienceꢀ&ꢀTechnology.
5
4
5
andꢀ η (C H )ꢀ rings.ꢀ Theꢀ C(10)–C(11)ꢀ bondꢀ lengthꢀ isꢀ 1.454(5)ꢀ Å,ꢀ
inꢀ goodꢀ agreementꢀ withꢀ valuesꢀ reportedꢀ forꢀ otherꢀ ferrocenylimineꢀ
derivatives, ꢀ whichꢀ areꢀ shorterꢀ thanꢀ theꢀ commonꢀ distanceꢀ ofꢀ theꢀ
5
5
9
Received 29 July 2009; accepted 3 October 2009
Paper 09/0707 doi: 10.3184/030823409X12551926920081
Published online: 16 November 2009
1
0
C-Cꢀsingleꢀbondꢀ1.540Å. ꢀTheꢀanglesꢀC(9)–C(10)–C(11)ꢀ=ꢀN,ꢀandꢀ
C(6)–C(10)–C(11)–N(1)ꢀareꢀ–176.5(4)ꢀandꢀ5.8(6)° respectively; thisꢀ
isꢀinꢀkeepingꢀwithꢀtheꢀsuggestionꢀthatꢀsomeꢀdelocalisationꢀofꢀelectronꢀ
densityꢀisꢀfoundꢀoverꢀtheꢀN=C–Cpꢀfragment,ꢀindicatingꢀthatꢀthereꢀisꢀ
conjugationꢀ betweenꢀ theꢀ C=Nꢀ unitꢀ andꢀ theꢀ cyclopentadienylꢀ ring.ꢀ
Theꢀ chiralꢀ centreꢀ C ꢀ substituentsꢀ areꢀ inꢀ theꢀ R-configuration.ꢀ Theꢀ
packingꢀ diagramꢀ (Fig.ꢀ 2)ꢀ showsꢀ thatꢀ thereꢀ areꢀ intermolecularꢀ
hydrogenꢀbondsꢀO1–H1…O1ꢀinꢀtheꢀunitꢀcell.
References
12
ꢀ 1ꢀ LiꢀZhengning,ꢀLiuꢀGuoshengꢀandꢀZhengꢀZhouꢀet al.,ꢀTetrahedron,ꢀ2000,ꢀ
56,ꢀ7187.
ꢀ 2ꢀ S.E.ꢀSchaus,ꢀJ.ꢀBranaltꢀandꢀE.N.ꢀJacobsen,ꢀJ.ꢀOrg.ꢀChem.ꢀ1998,ꢀ63,ꢀ403.
ꢀ
3ꢀ E.M.ꢀ Carreira,ꢀ R.A.ꢀ Singerꢀ andꢀ W.ꢀ Lee,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.ꢀ 1994,ꢀ
16,ꢀ8837.
1
CCDCꢀ 741091ꢀ containsꢀ theꢀ supplementaryꢀ crystallographicꢀ
dataꢀforꢀthisꢀpaper.ꢀTheseꢀdataꢀcanꢀbeꢀobtainedꢀfreeꢀofꢀchargeꢀ
viaꢀwww.ccdc.cam.ac.uk/data\ꢀrequest/cif,ꢀbyꢀe-mailingꢀdata\ꢀ
request@ccdc.cam.ac.uk,ꢀ orꢀ byꢀ contactingꢀ Theꢀ Cambridgeꢀ
Crystallographicꢀ Dataꢀ Centre,ꢀ 12ꢀ Unionꢀ Road,ꢀ Cambridgeꢀ
CB2ꢀ1EZ,ꢀUK;ꢀFax:ꢀ+ꢀ44ꢀ(0)ꢀ1223-336033.
ꢀ
4ꢀ W.ꢀZhang,ꢀJ.L.ꢀLoebach,.ꢀS.R.ꢀWilsonꢀandꢀE.N.ꢀJacobsen,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.ꢀ1990,ꢀ112,ꢀ801.
ꢀ 5ꢀ C.ꢀRamesh,ꢀV.ꢀAnandꢀandꢀA.ꢀMild,ꢀ1998,ꢀ28(11),ꢀ1963.
ꢀ
ꢀ
ꢀ
6ꢀ J.P.ꢀGreensteinꢀandꢀM.ꢀWinitz,ꢀChemistry of the amino acids[M],ꢀJohnꢀ
WilyꢀandꢀSons,ꢀNewꢀYork, 1961,ꢀppꢀ929-932.
7ꢀ M.ꢀSato,ꢀH.ꢀKono,ꢀM.ꢀShiga,ꢀI.ꢀMotoyamaꢀandꢀK.ꢀHata,ꢀBull. Chem. Soc.
Japan.,ꢀ1968,ꢀ41(1),ꢀ252.
8ꢀ Sheldrick,ꢀ G.M.ꢀ SHELXS-97,ꢀ Programꢀ forꢀ X-rayꢀ Crystalꢀ Structureꢀ
Solution,ꢀ Göttingenꢀ University,ꢀ Germanyꢀ 1997;ꢀ Sheldrick,ꢀ
G.M.ꢀ SHELXL-97,ꢀ Programꢀ forꢀ X-rayꢀ Crystalꢀ Structureꢀ Refinement,ꢀ
GöttingenꢀUniversity,ꢀGermany 1997.
Thisꢀ workꢀ wasꢀ financiallyꢀ supportedꢀ byꢀ theꢀ disciplineꢀ
improvementꢀ fundꢀ ofꢀ Hebeiꢀ Universityꢀ ofꢀ Scienceꢀ &ꢀ
PAPER:ꢀJC090707