(2,2′ Di­amino 4,4′ bi 1,3 thia­zole κ2N,N′)bis­­(glycinato κ2N,O)zinc(II) dihydrate

metal-organic papers

Acta Cryst.(2006). E62, m67–m68 doi:10.1107/S1600536805040857 Liuet al. _[Zn(C

2H4NO2)2(C6H6N4S2)]2H2O

m67

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

(2,2

_-Diamino-4,4

_{-bi-1,3-thiazole-j}

_N

_,

_N

)-bis(glycinato-j

N

,

O

)zinc(II) dihydrate

Bing-Xin Liu,aJian-Yong Yuaand Duan-Jun Xub*

a

Department of Chemistry, Shanghai University, People’s Republic of China, andbDepartment of Chemistry, Zhejiang University, People’s Republic of China

Correspondence e-mail: xudj@mail.hz.zj.cn

Key indicators

Single-crystal X-ray study

T= 295 K

Mean(C–C) = 0.002 A˚

Rfactor = 0.021

wRfactor = 0.054

Data-to-parameter ratio = 16.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2006 International Union of Crystallography Printed in Great Britain – all rights reserved

In the title ZnIIcomplex, [Zn(C2H4NO2)2(C6H6N4S2)]2H2O, the ZnII ion is coordinated by two glycinate anions and a diaminobithiazole (DABT) molecule in a distorted octahedral geometry. Two thiazole rings of the same DABT are twisted with respect to each other with a dihedral angle of 10.56 (6)_. The glycinate chelates to the ZnIIion by the amino N and carboxylate O atoms; the chelating five-membered ring displays an envelope configuration. A twofold rotation axis passes through the Zn atom and the mid-point of the C—C bond linking the two thiazole rings.

Comment

We are interested in metal complexes with diaminobithiazole (DABT) because of their potential magnetic properties (Sun et al., 1997). As part of an ongoing investigation of DABT complexes (Liu et al., 2001), we present here the crystal structure of the title ZnIIcomplex, (I).

The molecular structure of (I) is shown in Fig. 1. A twofold rotation axis passes through the Zn atom and the mid-point of the C—C bond linking the two thiazole rings. Two glycinate anions and one DABT molecule chelate to the ZnIIion in a distorted octahedral geometry (Table 1). Thiazole rings of the same DABT are twisted with respect to the each other with a dihedral angle of 10.56 (6)_{, comparable to the Co}II _analog [9.68 (6)_{; Yuet al., 2005]. The chelating five-membered ring of} the glycinate anion displays an envelope conformation, atom N3 being displaced 0.390 (2) A˚ from the mean plane formed by the other four atoms.

The classical O—H O and N—H O hydrogen-bonding network stabilizes the crystal structure (Table 2).

Experimental

An aqueous solution (20 ml) containing DABT (1 mmol) and ZnCl2

(1 mmol) was mixed with another aqueous solution (10 ml) of glycine (2 mmol) and NaOH (1 mmol). The mixture was refluxed for 4 h. The

solution was filtered after cooling to room temperature. Single crys-tals of (I) were obtained from the filtrate after one week.

Crystal data

[Zn(C2H4NO2)2(C6H6N4S2)]2H2O Mr= 447.79

Monoclinic,C2=c a= 13.121 (2) A˚

b= 9.0063 (16) A˚

c= 14.124 (2) A˚

= 92.365 (6)

V= 1667.7 (5) A˚3

Z= 4

Dx= 1.783 Mg m

3

MoKradiation Cell parameters from 5886

reflections

= 2.8–25.0

= 1.77 mm1

T= 295 (2) K Prism, colorless 0.250.200.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

!scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995)

Tmin= 0.628,Tmax= 0.750

7912 measured reflections

1918 independent reflections 1808 reflections withI> 2(I)

Rint= 0.018

max= 27.5

h=16!16

k=10!11

l=18!18

Refinement

Refinement onF2 R[F2> 2(F2)] = 0.021

wR(F2_{) = 0.054} S= 1.08 1918 reflections 115 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0209P)2

+ 2.0364P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001 max= 0.30 e A˚

3

min=0.22 e A˚

3

Extinction correction:SHELXL97

Extinction coefficient: 0.0134 (5)

Table 1

Selected bond lengths (A˚ ).

Zn—O1 2.1714 (11)

Zn—N1 2.1823 (13)

Zn—N3 2.1185 (13)

S1—C2 1.7219 (19)

S1—C3 1.7417 (17)

N1—C1 1.3901 (19)

N1—C3 1.3212 (19)

N2—C3 1.333 (2)

C1—C2 1.344 (2)

C1—C1i

1.469 (3)

Symmetry code: (i)xþ1;y;zþ1 2.

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O1W—H1A O1ii

0.88 2.18 2.976 (2) 151

O1W—H1B O2 0.90 2.00 2.878 (2) 167

N2—H2A O1i

0.87 2.37 3.098 (2) 141

N2—H2B O2iii

0.86 2.09 2.9059 (19) 159

N3—H3A O2iv

0.88 2.47 3.3209 (19) 165

N3—H3B O1Wv

0.90 2.22 3.051 (2) 154

Symmetry codes: (i) xþ1;y;zþ1

2; (ii) xþ1;yþ2;zþ1; (iii)

x1 2;yþ

3 2;z

1 2; (iv)xþ

3 2;y

1 2;zþ

1

2; (v)x;yþ2;z 1 2.

H atoms bonded to C atoms were placed in calculated positions, with C—H = 0.93 A˚ (aromatic) or 0.97 A˚ (methylene), and included in the final cycles of refinement as riding,withUiso(H) = 1.2Ueq(C).

Other H atoms were located in a difference Fourier map and refined as riding in their as-found relative positions with Uiso(H) =

1.5Ueq(carrier).

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refine-ment:PROCESS-AUTO; data reduction:CrystalStructure(Rigaku/ MSC, 2002); program(s) used to solve structure:SIR92(Altomareet al., 1993); program(s) used to refine structure: SHELXL97 (Shel-drick, 1997); molecular graphics: ORTEP3 for Windows(Farrugia, 1997); software used to prepare material for publication: WinGX

(Farrugia, 1999).

The project was supported by the Educational Develop-ment Foundation of Shanghai Educational Committee, China (No. AB0448).

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993).J. Appl. Cryst.26, 343–350.

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.

Higashi, T. (1995).ABSCOR. Rigaku Corporation, Tokyo, Japan.

Liu, J.-G., Nie, J.-J., Xu, D.-J., Xu, Y.-Z., Wu, J.-Y. & Chiang, M. Y. (2001).Acta Cryst.C57, 354–355.

Rigaku (1998).PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Rigaku/MSC (2002).CrystalStructure. Version 3.00. Rigaku/MSC, 900 New

Trails Drive, The Woodlands, TX 77381-5209, USA.

Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Sun, W., Gao, X. & Lu, F.-J. (1997).Appl. Polym. Sci.64, 2309–2315. Yu, J.-R., Liu, B.-X. & Xu, D.-J. (2005).Acta Cryst.E61, m2232–m2233.

Figure 1

The molecular structure of (I), with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). Dashed lines indicate hydrogen bonds [symmetry code: (i)x+ 1,y,z+1

supporting information

sup-1

Acta Cryst. (2006). E62, m67–m68

supporting information

Acta Cryst. (2006). E62, m67–m68 [doi:10.1107/S1600536805040857]

(2,2

′

-Diamino-4,4

′

-bi-1,3-thiazole-

κ

N

,

N

′

)bis(glycinato-

κ

N

,

O

)zinc(II)

dihydrate

Bing-Xin Liu, Jian-Yong Yu and Duan-Jun Xu

S1. Comment

We are interested in metal complexes with diaminobithiazole (DABT) because of their potential magnetic properties (Sun

et al., 1997). As part of an ongoing investigation of DABT complexes (Liu et al., 2001), we present here the X-ray

structure of the title ZnII _{complex, (I).}

The molecular structure of (I) is shown in Fig. 1. The ZnII _{complex has twofold symmetry. Two glycinate anions and}

one DABT molecule chelate to the ZnII _{ion in a distorted octahedral geometry (Table 1). Thiazole rings of the same}

DABT are twisted with respect to the each other with a dihedral angle of 10.56 (6)°, comparable to the CoII _analogue

[9.68 (6)°; Yu et al., 2005]. The chelating five-membered ring of the glycinate anion displays an envelope configuration,

the N3 atom being displaced 0.390 (2) Å from the mean plane formed by other four atoms.

The classic O—H···O and N—H···O hydrogen-bonding network stabilizes the crystal structure (Table 2).

S2. Experimental

An aqueous solution (20 ml) containing DABT (1 mmol) and ZnCl2 (1 mmol) was mixed with another aqueous solution

(10 ml) of glycine (2 mmol) and NaOH (1 mmol). The mixture was refluxed for 4 h. The solution was filtered after

cooling to room temperature. Single crystals of (I) were obtained from the filtrate after one week.

S3. Refinement

H atoms bonded to C atoms were placed in calculated positions, with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene),

and included in the final cycles of refinement as riding,with Uiso(H) = 1.2Ueq(C). Other H atoms were located in a

Figure 1

The molecular structure of (I), with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). Dashed lines

indicate hydrogen bonds [symmetry code: (i) −x + 1,y,-z + 1/2].

(2,2′-Diamino-4,4′-bi-1,3-thiazole-κ2_{N,N′)bis(glycinato-κ}2_{N,O)zinc(II) dihydrate}

Crystal data

[Zn(C2H4NO2)2(C6H6N4S2)]·2H2O Mr = 447.79

Monoclinic, C2/c Hall symbol: -C 2yc a = 13.121 (2) Å b = 9.0063 (16) Å c = 14.124 (2) Å β = 92.365 (6)°

V = 1667.7 (5) Å3 Z = 4

F(000) = 920 Dx = 1.783 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 5886 reflections θ = 2.8–25.0°

supporting information

sup-3

Acta Cryst. (2006). E62, m67–m68

T = 295 K Prism, colorless

0.25 × 0.20 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 10 pixels mm-1 ω scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.628, Tmax = 0.750

7912 measured reflections 1918 independent reflections 1808 reflections with I > 2σ(I) Rint = 0.018

θmax = 27.5°, θmin = 2.7° h = −16→16

k = −10→11 l = −18→18

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.021} wR(F2_{) = 0.054} S = 1.08 1918 reflections 115 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0209P)2 + 2.0364P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.30 e Å−3

Δρmin = −0.22 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.0134 (5)

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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

Zn 0.5000 0.71733 (3) 0.2500 0.02228 (10)

S1 0.37183 (3) 0.32835 (5) 0.05293 (3) 0.03481 (12) N1 0.45516 (10) 0.52922 (14) 0.16024 (9) 0.0238 (3) N2 0.37698 (11) 0.62134 (18) 0.01891 (10) 0.0373 (3)

H2A 0.3961 0.7127 0.0285 0.056*

H2B 0.3357 0.6014 −0.0281 0.056*

N3 0.64785 (10) 0.74766 (16) 0.19830 (9) 0.0271 (3)

H3A 0.6760 0.6673 0.1761 0.041*

H3B 0.6445 0.8100 0.1486 0.041*

H1A 0.5571 0.9931 0.5852 0.090*

H1B 0.6401 0.9832 0.5208 0.090*

C1 0.47278 (11) 0.39244 (17) 0.20349 (10) 0.0244 (3) C2 0.43515 (13) 0.27356 (18) 0.15629 (12) 0.0318 (3)

H2 0.4423 0.1757 0.1766 0.038*

C3 0.40309 (12) 0.51226 (18) 0.07889 (11) 0.0265 (3) C4 0.71545 (13) 0.8164 (2) 0.27111 (13) 0.0360 (4)

H4A 0.7625 0.8824 0.2407 0.043*

H4B 0.7552 0.7394 0.3034 0.043*

C5 0.65800 (11) 0.90340 (17) 0.34356 (10) 0.0250 (3)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Zn 0.02056 (14) 0.02147 (15) 0.02446 (14) 0.000 −0.00306 (9) 0.000

S1 0.0346 (2) 0.0353 (2) 0.0343 (2) −0.00850 (17) −0.00265 (16) −0.01341 (17) N1 0.0244 (6) 0.0231 (6) 0.0234 (6) −0.0012 (5) −0.0036 (5) −0.0025 (5) N2 0.0414 (8) 0.0401 (8) 0.0292 (7) −0.0059 (7) −0.0133 (6) 0.0006 (6) N3 0.0275 (7) 0.0290 (7) 0.0248 (6) −0.0001 (5) 0.0011 (5) −0.0038 (5) O1 0.0235 (5) 0.0321 (6) 0.0344 (6) −0.0006 (5) 0.0007 (4) −0.0096 (5) O2 0.0332 (6) 0.0327 (6) 0.0357 (6) −0.0029 (5) −0.0096 (5) −0.0071 (5) O1W 0.0585 (10) 0.0659 (11) 0.0558 (9) 0.0021 (8) 0.0156 (8) −0.0077 (8) C1 0.0207 (7) 0.0235 (7) 0.0292 (8) −0.0002 (6) 0.0023 (6) −0.0023 (6) C2 0.0314 (8) 0.0254 (8) 0.0388 (9) −0.0030 (6) 0.0023 (7) −0.0046 (7) C3 0.0226 (7) 0.0307 (8) 0.0261 (7) −0.0033 (6) 0.0000 (6) −0.0064 (6) C4 0.0223 (7) 0.0468 (10) 0.0388 (9) −0.0021 (7) 0.0008 (6) −0.0136 (8) C5 0.0262 (7) 0.0224 (7) 0.0259 (7) 0.0011 (6) −0.0046 (6) 0.0014 (5)

Geometric parameters (Å, º)

Zn—O1 2.1714 (11) N3—C4 1.467 (2)

Zn—O1i _{2.1714 (11) N3—H3A 0.8765}

Zn—N1 2.1823 (13) N3—H3B 0.8990

Zn—N1i _{2.1823 (13) O1—C5 1.2629 (19)}

Zn—N3i _{2.1185 (13) O2—C5 1.2516 (19)}

Zn—N3 2.1185 (13) O1W—H1A 0.8763

S1—C2 1.7219 (19) O1W—H1B 0.8952

S1—C3 1.7417 (17) C1—C2 1.344 (2)

N1—C1 1.3901 (19) C1—C1i _{1.469 (3)}

N1—C3 1.3212 (19) C2—H2 0.9300

N2—C3 1.333 (2) C4—C5 1.514 (2)

N2—H2A 0.8692 C4—H4A 0.9700

N2—H2B 0.8585 C4—H4B 0.9700

N3i_{—Zn—N3 165.18 (8) Zn—N3—H3A 115.0}

N3i_{—Zn—O1 91.32 (5) C4—N3—H3B 107.0}

N3—Zn—O1 78.46 (5) Zn—N3—H3B 109.5

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Acta Cryst. (2006). E62, m67–m68

N3—Zn—O1i _{91.32 (5) C5—O1—Zn 114.99 (10)}

O1—Zn—O1i _{93.25 (7) H1A—O1W—H1B 109.9}

N3i_{—Zn—N1 94.11 (5) C2—C1—N1 115.90 (14)}

N3—Zn—N1 97.39 (5) C2—C1—C1i _{126.76 (10)}

O1—Zn—N1 171.33 (5) N1—C1—C1i _{117.31 (8)}

O1i_{—Zn—N1 94.46 (5) C1—C2—S1 110.28 (13)}

N3i_—Zn—N1i _{97.39 (5) C1—C2—H2 124.9}

N3—Zn—N1i _{94.11 (5) S1—C2—H2 124.9}

O1—Zn—N1i _{94.46 (5) N1—C3—N2 125.29 (15)}

O1i_—Zn—N1i _{171.33 (5) N1—C3—S1 113.69 (12)}

N1—Zn—N1i _{78.15 (7) N2—C3—S1 121.00 (12)}

C2—S1—C3 89.59 (8) N3—C4—C5 112.87 (13)

C3—N1—C1 110.51 (13) N3—C4—H4A 109.0

C3—N1—Zn 135.43 (11) C5—C4—H4A 109.0

C1—N1—Zn 113.37 (9) N3—C4—H4B 109.0

C3—N2—H2A 122.3 C5—C4—H4B 109.0

C3—N2—H2B 118.4 H4A—C4—H4B 107.8

H2A—N2—H2B 119.2 O2—C5—O1 124.57 (15)

C4—N3—Zn 110.40 (10) O2—C5—C4 117.07 (14)

C4—N3—H3A 110.4 O1—C5—C4 118.32 (14)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1W—H1A···O1ii _{0.88 2.18 2.976 (2) 151}

O1W—H1B···O2 0.90 2.00 2.878 (2) 167

N2—H2A···O1i _{0.87 2.37 3.098 (2) 141}

N2—H2B···O2iii _{0.86 2.09 2.9059 (19) 159}

N3—H3A···O2iv _{0.88 2.47 3.3209 (19) 165}

N3—H3B···O1Wv _{0.90 2.22 3.051 (2) 154}