Manganese(II)-azido/thiocyanato complexes of naphthylazoimidazoles: X-ray structures of Mn(β-NaiEt)2(X)2 (β-NaiEt = 1-ethyl-2-(naphthyl-β-azo)imidazole; X = N3-, NCS-)

Article abstract of DOI:10.1016/j.molstruc.2006.11.076

Manganese(II)-naphthylazoimidazole complexes using N₃^- and NCS^- as counter ions are characterized as Mn(β-NaiR)₂(X)₂(β-NaiEt = 1-alkyl-2-(naphthyl-β-azo)imidazole; X = N₃^-, NCS

Full text of DOI:10.1016/j.molstruc.2006.11.076

Journal of Molecular Structure 842 (2007) 17–23
www.elsevier.com/locate/molstruc
Manganese(II)-azido/thiocyanato complexes of
naphthylazoimidazoles: X-ray structures of Mn(b-NaiEt)2(X)2ꢀ
ꢀ
(b-NaiEt = 1-ethyl-2-(naphthyl-b-azo)imidazole; X ¼ N3 , NCS )
a
a
b
b
a,
*
D. Das , B.G. Chand , J.S. Wu , T.-H. Lu , C. Sinha
a
Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata 700 032, India
b
Department of Physics, National Tsing Hua University, Hsinchu 300, Taiwan, ROC
Received 5 May 2006; received in revised form 29 November 2006; accepted 30 November 2006
Available online 24 January 2007
Abstract
Manganese(II)-naphthylazoimidazole complexes using N3 and NCSꢀ as counter ions are characterized as Mn(b-NaiR)2(X)2(b-Nai-
Et = 1-alkyl-2-(naphthyl-b-azo)imidazole; X ¼ N3ꢀ, NCSꢀ). The ligands are unsymmetric N(imidazole), N(azo) chelating agents. The
microanalytical, spectral (FT-IR, UV–vis), magnetic (bulk moment and EPR) and electrochemical data establish the structure and com-
position of the complexes. The single crystal X-ray diffraction studies of Mn(b-NaiEt)2(N3)2 and Mn(b-NaiEt)2(NCS)2(b-NaiEt = 1-
ethyl-2-(naphthyl-b-azo)imidazole) have confirmed the three dimensional structure of the complexes. Cyclic voltammetry exhibits
high potential Mn(III)/Mn(II) couple along with azo reductions. The EPR spectra show usual pattern.
ꢀ
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Naphthylazoimidazoles; Manganese(II); Azide; Thiocyanate; X-ray structure; Electrochemistry
1. Introduction
complexes of 1-alkyl-2-(naphthyl-b-azo)imidazole, b-NaiR
(2) (Scheme 1, 2). The replacement of phenyl group by
naphthyl group has increased the steric crowding and elec-
tron density on the active function [12]. Detail structural,
magnetic and spectroscopic studies are reported hereunder
(Scheme 1).
Imidazole is ubiquitous in biology and chemistry. It is
therefore of interest to synthesize ligands containing imid-
azole and related heterocyclic system [1–3] ArAN@N+ is
attached to imidazole backbone and has synthesized 2-
(arylazo)imidazole (1) [4–9]. These ligands are endowed
with p-acidic azoimine (AN@NAC@NA) function. The
p-acidity is largely dependent on the nature of heterocycle,
ring size, number of heteroatoms and substituents in the
phenyl group [10]. In manganese(II)-azido complexes of
2. Results and discussion
2.1. Synthesis and formulation
ꢀ
1-ethyl-2-(p-tolylazo)imidazole (1), N3 acts as end-on
The reaction of b-NaiR (2), Mn(ClO4)2,6H2O and
NaN3/NH4CNS using different ligand:metal:azide/thiocya-
nate ratio (1:1:2, 2:1:2, 3:2:4) in methanol solution has
isolated complexes of identical composition of [Mn(b-
and end-to-end bridger and forms 1D chain. The complex
exhibits interesting local ferromagnetic, global antiferro-
magnetic coupling [11]. This has encouraged us to synthe-
size Mn(II) complexes with different types of ligands. In
this work we are going to report Mn(II)-azido/thiocyanato
NaiR)2(X)2] (X ¼ N (3) and NCSꢀ (4))irrespective of
ꢀ
3
the stoichiometry of the reactants. The ligand has unsym-
metric N donor centres: N(imidazole) and N(azo) refer to
N and N0, respectively. The composition of the complexes
has been determined by microanalysis (C,H,N) (vide
*
Corresponding author. Tel.: +91 9830632450; fax: +91 33 24146584.
E-mail address: c_r_sinha@yahoo.com (C. Sinha).
0022-2860/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2006.11.076

18
D. Das et al. / Journal of Molecular Structure 842 (2007) 17–23
N
N
N
R
N
N
N
N
N
Me
1
2
Scheme 1. MeaaiEt (1); b-NaiR (2). R = Me (a), Et (b), CH2Ph (c).
Section 3) and spectroscopic studies. The molar conduc-
tance measurement shows non-electrolytic nature of the
complexes in MeCN. Single crystal X-ray structure deter-
mination confirms the structure and bonding in these
complexes.
Fig. 2. Molecular structure of [Mn(b-NaiEt)2(NCS)2] (4b).
65.78(5)ꢁ (3b) and 66.62(9)ꢁ (4b)] . The effect is significantly
visible in case of MnAN(azo) bond distance (MnAN(1),
˚
˚
2.6571(16) A for 3b and MnAN(1), 2.604(4) A for 4b)
compared to MnAN(imidazole) length (MnAN(4)
2.2. Molecular structures
˚
˚
2.1776(16) A for 3b and MnAN(4), 2.179(3) A for 4b.
Although MnAN(azo) distances are very long but they
are well below the sum of van der Waals radii of Mn(II)
and N(azo) [11]. The azo distance (N(1)AN(2)),
The structures of [Mn(b-NaiEt)2(N3)2] (3b) and [Mn(b-
NaiEt)2 (NCS) ] (4b) are shown in Figs. 1 and 2. Selected
2
bond distances and angles are listed in Table 1. Each com-
plex consists of a central manganese atom surrounded bꢀy
two b-NaiEt ligands and two N donor centres from N3
or NCSꢀ. Thus MnN6 distorted octahedral coordination
environment is ensured. The two structures are essentially
isostructural, both chemically and crystallographically.
Pseudooctahedral complexes M(N,N0)2(X)2 may exist in
five different isomeric forms: two of them will carry trans-
M(X)2 and three of them have cis-M(X)2 motif [4]. The
structures in Figs. 1 and 2 reveal cis–trans–cis arrangement
in the sequence of cis-M(X)2, trans-M(N(imidazole))2 and
cis-M(N(azo))2. The structural distortion may be originat-
ed from large steric interaction between crowded naphthyl
groups and low chelate angle [N(imidazole)AMnAN(azo):
˚
˚
1.2742(19) A for 3b and 1.271(3) A for 4b) is slightly elon-
˚
gated than free ligand value (1.266(3) A [13]). The bond
parameters are compared with reported data in [Mn(Meaa-
iEt)(N3)2]n (MnAN(imidazole), 2.221(2); MnAN(azo),
˚
2.562(2); N@N, 1.267(3) A) [11]. The C(imidazole)AN(azo)
˚
˚
length (C(1)AN(2), 1.390(2) A for 3b/C(1)AN(2), 1.396(3) A
for 4b) is shorter than N(azo)AC(naphthyl) distance
˚
˚
(N(1)AC(6), 1.417(2) A for 3b and 1.430(3) A for 4b). This
is in support of the stronger interaction of azoAN with imid-
azole ring comparing with naphthyl group. The MnAN(a-
˚
zide), MnAN(5), is 2.092(2) A while MnAN(NCS)
˚
distanceꢀ(MnAN(5)) is 2.104(3) A. The distances and angles
with N3 and NCSꢀ in the complexes are comparable with
reported data [14–16] All other bond parameters lie within
the limit of estimated deviation of free ligands [13].
The CAH–p and p–p interactions present in these struc-
tures. In 3b azido-N, azo-N and imidazole/naphthyl p-rings
act as acceptor and imidazoleAC(2)AH(2), C(4)AH(4b) of
NAEt group and C(7)AH(7) of naphthyl serve as H donor
centres. Intermolecular hydrogen bonding is exhibited by
azido-N (N(7)) of one molecule with imidazole C(2)AH(2)
of neighbouring molecule [C(2)AH(2)A-N(7)*: H(2)AN(7),
0
˚
˚
2.53 A, C(2)AN(7), 3.362(1) A, \C(2)AH(2)AN(7), 149 ;
*symmetry: 1 ꢀ x, 1 ꢀ y, 1 ꢀ z]. The CAH–p and p–p inter-
actions enhance the robustness of the molecule. The
observed CAH–p interactions are C(7)AH(7)ACg(1)
˚
[H(7)ACg(1), 2.840(8) A; symmetry, 1 - x, y, 1/2 ꢀ z],
˚
C(4)AH(4b)ACg(3) [H(4b)ACg(3), 3.320(6) A; symmetry,
1 ꢀ x, y, 1/2 ꢀ z]. The p–p interaction is weak: Cg(1)ACg(2)
˚
(4.288(4) A), (where Cg(1): N(4)AC(1)AN(3)AC(2)AC(3);
Cg(2): C(6)AC(7)AC(8)AC(13)AAC(14)AC(15); symmetry,
1 ꢀ x, y, 1/2 ꢀ z) and provides interchain rigidity to the
Fig. 1. Molecular structure of [Mn(b-NaiEt)2(N3)2] (3b).

D. Das et al. / Journal of Molecular Structure 842 (2007) 17–23
19
Table 1
˚
Selected bond distances (A) and bond angles (ꢁ) for [Mn(b-NaiEt)2(N3)2] (3b) and [Mn(b-NaiEt)2(NCS)2] (4b)
˚
Bond distances (A)
Bond angles (ꢁ)
3b
4b
3b
4b
66.62(9)
MnAN(1)
MnAN(4)
MnAN(5)
N(1)AN(2)
N(5)AN(6)
N(6)AN(7)
N(5)AC(16)
C(16)AS
2.6571(16)
2.1776(16)
2.092(2)
1.2742(19)
1.138(2)
2.604(4)
2.179(3)
2.104(3)
1.271(3)
N(1)AMn(1)AN(4)
N(1)AMn(1)AN(5)
N(5)AMnAN(4)
N(5a)AMnAN(4)
N(5)AMnAN(5a)
N(4)AMnAN(4a)
N(4a)AMnAN(1)
N(5a)AMnAN(1)
N(5)AN(6)AN(7)
N(5)AC(16)AS
65.78(5)
96.56(7)
111.41(7)
90.62(7)
101.42(12)
145.47(9)
86.21(5)
154.44(7)
176.2(2)
99.18(10)
107.81(11)
92.89(11)
95.34(17)
149.33(14)
88.32(9)
1.183(3)
1.157(4)
1.614(4)
1.396(3)
1.430(3)
157.72(11)
C(1)AN(2)
C(6)AN(1)
a
1.390(2)
1.417(2)
178.1(4)
Symmetry: ꢀx, y, 3/2 ꢀ z for 3b and ꢀx, y, 1/2 ꢀ z for 4b.
solid state geometry (Fig. 3). The noncovalent interactions in
tral profile is in support of Oh–Mn(II) stereochemistry
[17].
[Mn(bANaiEt)2(NCS)2] (4b) are the CAHACg interactions
˚
(Fig. 4) [C(7)AH(7)ACg(1), 2.907(2) A; C(5)AH(5b)A
˚
Cg(3), 3.127(6) A] and weak p–p interactions [Cg(1)ACg(2),
2.4. Magnetic moment and EPR spectra
˚
˚
4.272(5) A; Cg(1)ACg(3), 4.348(1) A where Cg(1),
N(3)AC(11)AN(4)AC(13)AC(12); Cg(2), C(1)AC(2)A
C(3)AC(8)AC(9)AC(10); Cg(3), C(3)AC(4)AC(5)A
C(6)AC(7)AC(8); symmetry: 1/2 ꢀ x, 1/2 ꢀ y, 1 ꢀ z].
The magnetic moment, leff is av. 5.2–5.5 BM at 300 K
expected for an isolated S = 5/2 Mn(II) monomer [18].
The EPR spectra of a solution in MeCN at 77 K display
g ꢂ 2, ms = +1/2 to ꢀ1/2 fine structure transition split into
six hyperfine lines as expected for 55Mn(II) complex (I = 5/
2) along with superfine splitting (Fig. 5). A notable feature
of the spectra is the relatively low value of the hyperfine
coupling constant A, 80–90 G. Each hyperfine shows dou-
blet splitting at 77 K which suggests interaction of ligand–
N with Mn(II).
2.3. Spectral studies
Infrared spectra of [Mn(b-NaiR)2(N3)2] (3) show very
sharp strong stretch at 2045–2055 cmꢀ1and is assigned to
m(N3). In [Mn(bANaiR)2(NCS)2] (4) the m(NCS) appears at
2065–2080 cmꢀ1. Moderately intense stretchings at 1580–
1590 and 1400–1410 cmꢀ1 are due to m(C@N) and
m(N@N), respectively. Solution electronic spectra of the
complexes show intense transition <400 nm and are due to
ligand centered transitions. A broad band (Table 2; e ꢁ
103 dm3 molꢀ1 cmꢀ1) at P440 nm may be referred to
the combination of MLCT and d–d transitions. The spec-
2.5. Electrochemistry
Redox properties of the manganese complexes have
been studied by cyclic voltammetry (CV) using a platinum
working electrode. Voltammogram data are collected in
Fig. 3. p–p interaction incorporates supramolecularity to the molecule 3b.

20
D. Das et al. / Journal of Molecular Structure 842 (2007) 17–23
ble with free ligand values [20]. The reduction is attributed
to the electron accommodation to azo-dominated orbitals.
3. Experimental
3.1. Materials
Mn(ClO4)2Æ6H2O was prepared by adding MnCO3 to
warm HClO4 solution (1:1, v/v) and recrystallised from
water in presence of few drops of HClO4. Sodium azide
(SRL, India) were purchased from the market and used
without further purification. 1-Alkyl-2-(naphthyl-b-
azo)imidazoles (b-NaiR (2)) were prepared by a reported
procedure [13]. All other chemicals and solvents used for
preparative and spectroscopic work of reagent grade and
were used as received. Purification of MeCN [21] and prep-
aration of [n-Bu4N][ClO4] were done following the method
given in reference [20].
Caution! Azido complexes of transition metal ions con-
taining organic ligands are potentially explosive. Only a
small amount of material should be prepared, and it should
be handled with care.
3.2. Physical measurements
IR spectra (KBr discs, 4000–400 cmꢀ1) were recorded on
a RX-1 Perkin-Elmer FTIR spectrophotometer. Microa-
nalyses (C, H, and N) were done with a Perkin-Elmer
2400 CHNS/O elemental analyzer. The solution spectra
were run at room temperature on Lambda 25 Perkin-Elmer
spectrophotometer in the 200–900 nm range. Magnetic
measurements were carried out in the vibrating sample
magnetometer on polycrystalline samples working in room
temperature (298 K). The diamagnetic corrections were
evaluated from Pascal’s constants. EPR spectra were
recorded on powder samples at X-band frequency with a
BRUKER 300E automatic spectrometer at room tempera-
ture (295 K) and 77 K. Electrochemical measurements were
carried out with the use of computer controlled EG & G
PARC VersaStat model 250 Electrochemical instrument
Fig. 4. p–p interaction incorporates supramolecularity to the molecule 4b.
Table 2 and representative diagram is shown in Fig. 6. A
couple appears at 0.80–1.1 V versus SCE is referred to
Mn(III)/Mn(II) redox process [19]. The quasireversibility
of the process is examined from peak-to-peak separation,
DEp > 100 mV. One electron nature of the redox process
has been confirmed by DPV studies. Ligand reductions
are irreversible in nature and the Epc values are compara-
Table 2
UV–vis spectraa, cyclic voltammetricb and magnetic moment (l) data
Compound
UV–vis spectral data [kmax(nm)]
(10ꢀ4 e Mꢀ1 cmꢀ1
Cyclic voltammetric data (V), MnIII/ MnII ligand reduction
l (BM)
)
[Mn(b-NaiMe)2(N3)2] (3a)
[Mn(b-NaiEt)2(N3)2] (3b)
[Mn(b-NaiBz)2 (N3)2] (3c)
[Mn(b-NaiMe)2(NCS)2] (4a) 433 (0.31), 386 (0.457), 265 (0.403)
[Mn(b-NaiEt)2(NCS)2] (4b)
[Mn(b-NaiBz)2(NCS)2] (4c)
455 (0.87), 390 (0.665), 374 (0.754),
345 (0.778), 264 (1.020)
462 (1.13), 346 (0.75), 311 (0.63),
287 (1.14), 265 (1.91)
1.00 (100)
0.93 (120)
ꢀ0.45 (100)
ꢀ0.48 (110)
ꢀ1.00 (140)
ꢀ1.05 (130)
ꢀ1.35c
ꢀ1.40c
5.32
5.24
460 (1.28), 370 (1.54), 345 (1.77), 268 (1.520) 1.08 (120)
ꢀ0.40 (130)
ꢀ0.54 (100)
ꢀ0.61 (110)
ꢀ0.50 (100)
ꢀ0.95 (150)
ꢀ1.18 (140)
ꢀ1.14 (135)
ꢀ1.10 (140)
ꢀ1.35c
ꢀ1.41c
ꢀ1.45c
ꢀ1.40c
5.46
5.48
5.52
5.47
0.87 (100)
0.80 (120)
0.92 (100)
440 (0.55), 380 (0.758), 265 (0.98)
450 (0.81), 396 (0.780), 275 (1.11)
a
Solvent, MeCN.
b
Solvent, MeCN, Pt-disk working electrode; Pt-wire auxiliary and Ag/AgCl reference, [n-Bu4N][ClO4] supporting electrolyte, scan rate 50 mV sꢀ1
,
potential E1/2 = (Epa + Epc)/2 V; DEp = jEpa ꢀ Epcj mV.
c
Epc, V.

D. Das et al. / Journal of Molecular Structure 842 (2007) 17–23
21
Fig. 5. EPR spectra of [Mn(b-NaiMe)2(N3)2] in MeCN solution at 77 K.
pendent experiments were of same composition, [Mn(b-
NaiEt)2(X)2). Yield of the product is found highest in case
of 2:1:2 ligand:metal:azide/thiocyanate. This method is
described detail below.
To a methanolic solution (15 cm3) of 1-ethyl-2-(naph-
thyl-b-azo)imidazole (b-NaiEt, 0.32 g, 1.28 mmol) was
added dropwise to Mn(ClO4)2Æ6H2O (0.2 g, 0.56 mmol) in
the same solvent (20 cm3) at room temperature (298 K).
The mixture was stirred for 15 min and a small portion
of yellow mass was filtered and rejected. To this filtrate
NaN3 (0.075 g, 1.15 mmol) in MeOH was added. The mix-
ture was kept undisturbed for few days. Dark brown crys-
talline compound was filtered and washed with cold water
and methanol and dried in vacuo over silicagel indicator.
Yield: 0.2 g (60 %).
Fig. 6. Cyclic voltammogram of [Mn(b-NaiEt)2(N3)2] (3b) in MeCN.
Elemental analyses were as follows: [Mn(b-Nai-
Me)2(N3)2] (3a), C28H24N14Mn: calcd C, 55.00; H, 3.93;
N, 32.08. Found : C, 54.88; H, 3.85; N, 32.00%. [Mn(b-
NaiEt)2(N3)2] (3b), C30H28N14Mn: calcd C, 56.34; H,
using a Pt-disk working electrode and Pt-wire auxiliary
electrode. The solution was IR compensated and the results
were collected at 298 K. The reported results are referenced
to Ag/AgCl in acetonitrile and are uncorrected for junction
potential [n-Bu4N][ClO4] was used as supporting
electrolyte.
4.38; N, 30.68. Found
: C, 56.28; H, 4.32; N,
30.77%.[Mn(b-NaiBz)2 (N3)2] (3c), C40H32N14Mn: calcd
C, 62.91; H, 4.19; N, 25.69. Found: C, 63.02; H, 4.12; N,
25.75%.
[Mn(b-NaiR0)2(NCS)2] (4) were also synthesised follow-
ing similar procedure using 2 equiv of NH4CNS in the
reaction. The products were isolated in 65–70% yield. Ele-
mental analyses were as follows. Mn(b-NaiMe)2(NCS)2]
(4a), C30H24N10SMn: calcd C, 55.99; H, 3.73; N, 21.77.
Found: C, 56.11; H, 3.80; N, 21.90%. [Mn(b-Nai-
3.3. Preparation of complexes
The complexes were prepared following three different
ligand:metal:azide/thiocyanate stoichiometry, 1:1:2, 2:1:2,
3:2:4 in methanol under stirring condition using b-NaiMe
as ligand. The compound isolated from these three inde-

22
D. Das et al. / Journal of Molecular Structure 842 (2007) 17–23
Et)2(NCS)2] (4b), C32H28N10SMn: calcd C, 57.23; H, 4.17;
N, 20.87. Found: C, 57.17; H, 4.22; N, 21.00%. [Mn(b-Nai-
Bz)2(NCS)2] (4c), C42H32N10SMn: calcd C, 63.40; H, 4.03;
N, 17.61. Found: C, 63.31; H, 4.10; N, 17.72%.
respectively. The structure was solved by direct method
using SHELXS-97 [22] and successive difference
Fourier syntheses. All non-hydrogen atoms were refined
anisotropically. The hydrogen atoms were fixed geomet-
rically and refined using riding model. In the final
difference Fourier map the reꢀsi3dual maxima and minima
˚
3.4. X-ray crystal structure determination of 3b and 4b
were 0.470ꢀ3and ꢀ0.252 e A
for 3b and 0.273 and
˚
ꢀ0.247 e A for 4b. All calculations were carried out
using SHELXL-97 [23], ORTEP-32 [24], and PLA-
TON-99 [25] programs.
A crystal suitable for X-ray analysis was mounted on the
Bruker SMART CCD area detector equipped with fine-fo-
cus sealed tube graphite monochromator and MoKa radi-
˚
ation (k = 0.71073 A). Data were collected at 296(2) K for
4. Conclusion
these complexes (Table 3). Red coloured blocked crystal
size were 0.2 · 0.2 · 0.1 mm for 3b and 0.3 · 0.2 · 0.2 mm
for 4b. Unit cell parameters were determined from least-
squares refinement of setting angles with 2h range 3.8–
56.7ꢁ for 3b and 3.84–56.6ꢁ for 4b. The hkl range were
ꢀ25 6 h 6 13, ꢀ18 6 k 6 18, ꢀ16 6 l 6 17 for 3b and
ꢀ25 6 h 6 23, ꢀ15 6 k 6 18, ꢀ16 6 l 6 19 for 4b. A sum-
mary of the crystallographic data and structure refinement
parameters is given in Table 4. Of 10657 collected reflec-
tions 3781 unique reflection (I > 2r(I)) for 3b and of
10785 collected data 3914 unique data for 4b were recorded
using the x-scan technique. Data were corrected for Lor-
entz polarization effects and for linear decay. Semi-em-
pirical absorption correction based on w-scans were
applied. Data refinement and reduction were carried
out by Bruker SMART and Bruker SAINT programme,
We have synthesized Mn(II) complexes of 1-alkyl-2-
ꢀ
(naphthyl-b-azo)imidazoles with azide N3 or thiocyanate
(NCSꢀ) as counter ion. Ligand serves as bidentate unsym-
metric imidazole-N and azo-N chelator to synthesize high
spin distorted octahedral [Mn(b-NaiR0)2(X)2] (X ¼ N3
ꢀ
(3 and NCSꢀ (4); R0 = Me (a) and Et (b)). The complexes
are structurally characterized by single crystal X-ray dif-
fraction studies. The stereochemistry is also supported by
EPR spectra. Redox properties show high potential
Mn(III)/Mn(II) couple and azo reductions.
5. Supplementary data
Crystallographic data for the structural analysis are in
the Cambridge Crystallographic Data Centre, and CCDC
No. 602420 for [Mn(b-NaiEt)2(N3)2] (3b) and 601287 for
[Mn(b-NaiEt)2(NCS)2] (4b). Copies of this information
may be obtained free of charge from the Director, CCDC,
12 Union Road, Cambridge, CB2 1FZ, UK (email:depos-
it@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
Table 3
Crystallographic data of [Mn(b-NaiEt)2(N3)2] (3b) and [Mn(b-Nai-
Et)2(NCS)2] (4b)
[Mn(b-NaiEt)2(N3)2]
(3b)
[Mn(b-NaiEt)2(NCS)2]
(4b)
Acknowledgement
Empirical formula
Formula weight
Temperature (K)
Crystal system
C
639.60
296(2)
Monoclinic
C2/c
30H28N14Mn
C32H28N10S2Mn
671.70
296(2)
Monoclinic
C2/c
Financial support from Department of Science and
Technology, New Delhi is gratefully acknowledged.
Space group
Crystal size (mm)
Unit cell dimensions
a (A)
0.20 · 0.20 · 0.10
0.30 · 0.20 · 0.20
References
˚
19.2755(15)
13.9617(11)
13.4542(10)
123.2430(10)
3028.2(4)
8
0.71073
0.483
1.403
19.8815(16)
13.9714(11)
14.2612(11)
125.3960(10)
3229.2(4)
8
0.71073
0.578
1.382
˚
b (A)
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˚
c (A)
b (ꢁ)
3
˚
V (A)
Z
˚
k (A)
l (Mo-Ka) (mmꢀ1
)
Dcalcd (mg mꢀ3
)
Refine parameters
Total reflections
Observed data [I > 2r 3761
204
10657
204
10785
3914
(I)]
a
R1 [I > 2r (I)]
wR2
0.0431
0.1118
0.849
0.0556
0.1383
0.882
b
Goodness of fit
a
R = RjF0 ꢀ Fcj/RF0.
1=2
2
b
wR2 ¼ ½RwðF 20 ꢀ F c2Þ=RwF 40ꢃ
,
w = 1/[r2 (F 2oÞ þ ð0:0635PÞ ꢃ (3b);
2
w = 1/[r2 ðF o2Þ þ ð0:7000PÞ ꢃ (4b) where P ¼ ðF o2 þ 2F 2cÞ=3.
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D. Das et al. / Journal of Molecular Structure 842 (2007) 17–23
23
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