metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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(Anilino{(Z)-2-[(E)-5-bromo-3-meth­­oxy-2-oxido­benzyl­­idene]hydrazin-1-yl­­idene-κ2O2,N2}methane­thiol­ato-κS)(4,4′-di­methyl-2,2′-bi­pyridine-κ2N,N′)zinc N,N-di­methyl­formamide monosolvate

aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: seikweng@um.edu.my

(Received 2 July 2012; accepted 12 July 2012; online 18 July 2012)

The asymmetric unit of the title compound, [Zn(C15H12BrN3O2S)(C12H12N2)]·C3H7NO, contains two independent mol­ecules with a similar structure. The doubly deprotonated Schiff base ligand O,N,S-chelates to the metal atom, and the three coordinating atoms along with one N atom of the substituted 2,2′-bipyridine ligand constitute the square plane of the distorted square pyramid surrounding the metal atom. The apical site is occupied by the second N atom of the substituted 2,2′-bipyridine. The secondary amine group of the Schiff base dianion forms a hydrogen bond to the O atom of the dimethyl­formamide solvent. In the crystal, the phenyl ring of one of the two Schiff base anions is disordered over two positions in a 1:1 ratio. The crystal studied is a racemic twin.

Related literature

For a related zinc structure, see: Seena & Kurup (2008[Seena, E. B. & Kurup, M. R. P. (2008). Spectrochim. Acta Part A, 69, 726-732.]).

[Scheme 1]

Experimental

Crystal data
  • [Zn(C15H12BrN3O2S)(C12H12N2)]·C3H7NO

  • Mr = 700.95

  • Monoclinic, P 21

  • a = 15.2674 (3) Å

  • b = 12.2422 (3) Å

  • c = 22.3402 (5) Å

  • β = 131.425 (1)°

  • V = 3130.90 (12) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.17 mm−1

  • T = 293 K

  • 0.40 × 0.30 × 0.25 mm

Data collection
  • Bruker APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.478, Tmax = 0.613

  • 52133 measured reflections

  • 14238 independent reflections

  • 9143 reflections with I > 2σ(I)

  • Rint = 0.051

Refinement
  • R[F2 > 2σ(F2)] = 0.070

  • wR(F2) = 0.211

  • S = 1.01

  • 14238 reflections

  • 676 parameters

  • 66 restraints

  • H-atom parameters constrained

  • Δρmax = 1.22 e Å−3

  • Δρmin = −1.64 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 6722 Friedel pairs

  • Flack parameter: 0.50 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3⋯O5 0.88 2.07 2.95 (1) 175
N8—H8⋯O6 0.88 2.07 2.95 (1) 172

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

A large number of first-row transition metal derivatives of Schiff bases that are synthesized by reacting salicylaldehyde-type of aldehydes with 4-phenylthiosemicarbazide has been reported. The zinc homolog has been isolated as a 2,2'-bipyridine adduct (Seena & Kurup, 2008). The metal center shows square-pyramidal coordination as one of the pyridine N atoms occupy the apical site. Substituents in the Schiff base as well as in the 2,2'-bipyridine do not perturb the square pyramidal coordination geometry in Zn(C12H12N2)(C15H12BrN3O2S).DMF (Scheme I). The compound crystallizes as a DMF solvate (Figs. 1 and 2).

The doubly-deprotonated Schiff base in O,N,S-chelates to the metal atom, and the three coordinating atoms along with the N atom of the substituted bipyridine ligand comprise the square plane of the square pyramid surrounding it. The apical site is occupied by the second N atom of the substituted 2,2'-bipyridine. In one molecule, the Zn is displaced by 0.305 (3) Å in the direction of the apical occupant (Fig. 1) whereas in the other, the displacement is 0.103 (6) Å in the opposite direction (Fig. 2). The secondary amino group of the Schiff-base dianion forms a hydrogen bond to the O atom of the DMF (Table 1).

Related literature top

For a related zinc structure, see: Seena & Kurup (2008).

Experimental top

To a stirred mixture of 2-(5-bromo-2-hydroxy-3-methoxybenzylidene)-N-phenylhydrazinecarbothioamide (0.190 g, 0.5 mmol) in a 1:1 mixture of DMF and methanol and 4,4'-dimethyl-2,2'-bipyridine (0.092 g, 0.5 mmol) in methanol, zinc(II) acetate dihydrate (0.109 g, 0.5 mmol) was added. The resulting yellow solution was heated for 3 h. Yellow crystals separated from the solution after several days.

Refinement top

Carbon- and nitrogen bound H-atoms were placed in calculated positions (C–H 0.93 to 0.96 Å, N–H 0.88 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C,N).

Omitted owing to bad disagreement was (0 1 1).

All aromatic and pyridine rings were refined as rigid hexagons of 1.39 Å sides. One of the phenyl rings of the Schiff-base anion is disordered over two positions in a 1:1 ratio. The temperature factors of the primed atoms were set to those of the unprimed ones but in the reverse order (i.e., those of C11 to those of C15), and the pair of N–Cphenyl distances were restrained to within 0.01 Å of each other.

The molecules of DMF were each restrained to lie on a plane; their. The anisotropic temperature factors were restrained to be nearly isotropic.

The final difference Fourier map had a peak at 0.91 Å from Br1 and a hole at 0.96 Å from Br2.

The base scale factor was explicitly refined.

Structure description top

A large number of first-row transition metal derivatives of Schiff bases that are synthesized by reacting salicylaldehyde-type of aldehydes with 4-phenylthiosemicarbazide has been reported. The zinc homolog has been isolated as a 2,2'-bipyridine adduct (Seena & Kurup, 2008). The metal center shows square-pyramidal coordination as one of the pyridine N atoms occupy the apical site. Substituents in the Schiff base as well as in the 2,2'-bipyridine do not perturb the square pyramidal coordination geometry in Zn(C12H12N2)(C15H12BrN3O2S).DMF (Scheme I). The compound crystallizes as a DMF solvate (Figs. 1 and 2).

The doubly-deprotonated Schiff base in O,N,S-chelates to the metal atom, and the three coordinating atoms along with the N atom of the substituted bipyridine ligand comprise the square plane of the square pyramid surrounding it. The apical site is occupied by the second N atom of the substituted 2,2'-bipyridine. In one molecule, the Zn is displaced by 0.305 (3) Å in the direction of the apical occupant (Fig. 1) whereas in the other, the displacement is 0.103 (6) Å in the opposite direction (Fig. 2). The secondary amino group of the Schiff-base dianion forms a hydrogen bond to the O atom of the DMF (Table 1).

For a related zinc structure, see: Seena & Kurup (2008).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of one Zn(C12H12N2)(C15H12BrN3O2S).DMF molecule at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in one of the phenyl rings is not shown.
[Figure 2] Fig. 2. Thermal ellipsoid plot (Barbour, 2001) of second Zn(C12H12N2)(C15H12BrN3O2S).DMF molecule at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in one of the phenyl rings is not shown
(Anilino{(Z)-2-[(E)-5-bromo-3-methoxy-2- oxidobenzylidene]hydrazin-1-ylidene-κ2O2,N2} methanethiolato-κS)(4,4'-dimethyl-2,2'-bipyridine- κ2N,N')zinc N,N-dimethylformamide monosolvate top
Crystal data top
[Zn(C15H12BrN3O2S)(C12H12N2)]·C3H7NOF(000) = 1432
Mr = 700.95Dx = 1.487 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 9863 reflections
a = 15.2674 (3) Åθ = 2.5–26.3°
b = 12.2422 (3) ŵ = 2.17 mm1
c = 22.3402 (5) ÅT = 293 K
β = 131.425 (1)°Prism, yellow
V = 3130.90 (12) Å30.40 × 0.30 × 0.25 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer
14238 independent reflections
Radiation source: fine-focus sealed tube9143 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
ω scansθmax = 27.5°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1919
Tmin = 0.478, Tmax = 0.613k = 1515
52133 measured reflectionsl = 2928
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.070H-atom parameters constrained
wR(F2) = 0.211 w = 1/[σ2(Fo2) + (0.0841P)2 + 9.813P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
14238 reflectionsΔρmax = 1.22 e Å3
676 parametersΔρmin = 1.64 e Å3
66 restraintsAbsolute structure: Flack (1983), 6722 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.50 (2)
Crystal data top
[Zn(C15H12BrN3O2S)(C12H12N2)]·C3H7NOV = 3130.90 (12) Å3
Mr = 700.95Z = 4
Monoclinic, P21Mo Kα radiation
a = 15.2674 (3) ŵ = 2.17 mm1
b = 12.2422 (3) ÅT = 293 K
c = 22.3402 (5) Å0.40 × 0.30 × 0.25 mm
β = 131.425 (1)°
Data collection top
Bruker APEXII
diffractometer
14238 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
9143 reflections with I > 2σ(I)
Tmin = 0.478, Tmax = 0.613Rint = 0.051
52133 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.070H-atom parameters constrained
wR(F2) = 0.211Δρmax = 1.22 e Å3
S = 1.01Δρmin = 1.64 e Å3
14238 reflectionsAbsolute structure: Flack (1983), 6722 Friedel pairs
676 parametersAbsolute structure parameter: 0.50 (2)
66 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br11.72718 (11)0.00210 (15)1.13837 (9)0.0914 (5)
Br21.72867 (13)0.40505 (18)0.63979 (13)0.1416 (9)
Zn11.12332 (8)0.22235 (8)0.86185 (6)0.0366 (2)
Zn21.12382 (11)0.18373 (10)0.36192 (8)0.0669 (4)
S11.02546 (19)0.3730 (2)0.85966 (14)0.0399 (5)
S21.0257 (3)0.0344 (3)0.35998 (18)0.0745 (9)
O11.3542 (6)0.0420 (9)0.8358 (4)0.074 (3)
O21.2468 (5)0.1673 (6)0.8630 (3)0.0452 (15)
O31.3522 (8)0.3694 (10)0.3332 (6)0.096 (3)
O41.2447 (8)0.2454 (9)0.3637 (6)0.098 (3)
O50.8524 (6)0.5244 (8)0.8923 (4)0.066 (2)
O60.8553 (8)0.1344 (9)0.3904 (5)0.090 (3)
N11.2588 (5)0.2765 (7)0.9809 (4)0.0347 (16)
N21.2354 (5)0.3571 (6)1.0123 (4)0.0353 (15)
N31.1036 (6)0.4821 (7)0.9878 (4)0.0450 (19)
H31.02790.49270.95710.054*0.50
H3'1.02830.49630.95550.054*0.50
N41.0594 (4)0.0801 (4)0.8728 (3)0.0368 (17)
C161.1041 (4)0.0322 (5)0.9445 (2)0.049 (2)
H161.16810.06320.99270.058*
C171.0531 (6)0.0620 (5)0.9444 (3)0.060 (3)
H171.08300.09400.99240.071*
C180.9574 (6)0.1083 (5)0.8724 (4)0.061 (3)
C190.9127 (5)0.0604 (5)0.8006 (3)0.055 (3)
H190.84860.09140.75250.066*
C200.9637 (5)0.0337 (4)0.8008 (2)0.0382 (19)
N50.9842 (4)0.1788 (5)0.7400 (2)0.0400 (17)
C220.9212 (5)0.0881 (4)0.7305 (3)0.039 (2)
C230.8202 (5)0.0574 (4)0.6547 (3)0.044 (2)
H230.77810.00330.64830.053*
C240.7822 (4)0.1174 (5)0.5884 (2)0.055 (3)
C250.8451 (5)0.2081 (5)0.5979 (3)0.066 (3)
H250.81970.24820.55350.079*
C260.9461 (5)0.2388 (4)0.6737 (3)0.047 (2)
H260.98820.29950.68010.057*
N61.2560 (10)0.1274 (9)0.4763 (7)0.080 (3)
N71.2368 (9)0.0517 (10)0.5138 (6)0.085 (3)
N81.1032 (9)0.0762 (10)0.4868 (6)0.073 (3)
H81.02760.08680.45660.088*
N91.0634 (5)0.3279 (5)0.3726 (4)0.059 (2)
C431.1100 (5)0.3757 (6)0.4448 (3)0.085 (4)
H431.17690.34670.49250.102*
C441.0566 (6)0.4668 (6)0.4458 (3)0.072 (4)
H441.08780.49880.49410.086*
C450.9566 (6)0.5102 (5)0.3745 (4)0.063 (3)
C460.9099 (5)0.4624 (5)0.3022 (3)0.051 (2)
H460.84300.49140.25450.061*
C470.9633 (5)0.3712 (5)0.3013 (3)0.049 (2)
N100.9844 (4)0.2266 (6)0.2407 (3)0.0542 (19)
C490.9190 (5)0.3154 (5)0.2305 (3)0.051 (2)
C500.8194 (6)0.3466 (5)0.1543 (4)0.067 (3)
H500.77570.40610.14750.080*
C510.7853 (5)0.2890 (6)0.0882 (3)0.069 (3)
C520.8507 (6)0.2001 (6)0.0983 (3)0.065 (3)
H520.82780.16160.05410.078*
C530.9502 (6)0.1689 (5)0.1746 (4)0.073 (3)
H530.99400.10950.18140.087*
N110.6681 (7)0.5698 (6)0.7784 (5)0.072 (3)
N120.6763 (11)0.1722 (9)0.2820 (7)0.103 (4)
C11.3953 (11)0.0425 (12)0.8147 (8)0.085 (4)
H1A1.34490.04670.75760.127*
H1B1.39500.11130.83520.127*
H1C1.47330.02570.83710.127*
C21.4122 (5)0.0630 (6)0.9134 (3)0.050 (2)
C31.5234 (5)0.0242 (5)0.9767 (4)0.062 (3)
H3A1.56130.02190.96690.074*
C41.5781 (4)0.0542 (6)1.0544 (3)0.055 (3)
C51.5216 (5)0.1230 (6)1.0690 (3)0.055 (3)
H51.55820.14311.12100.066*
C61.4103 (4)0.1619 (5)1.0057 (3)0.040 (2)
C71.3556 (4)0.1319 (5)0.9279 (3)0.051 (3)
C81.3598 (8)0.2388 (9)1.0255 (5)0.042 (2)
H8A1.40940.26291.07820.051*
C91.1356 (8)0.3981 (7)0.9630 (6)0.039 (2)
C101.1736 (15)0.5524 (14)1.0541 (8)0.043 (2)0.50
C111.1131 (11)0.622 (2)1.0646 (13)0.043 (4)0.50
H111.03220.61781.03080.051*0.50
C121.1735 (18)0.699 (2)1.1259 (17)0.083 (7)0.50
H121.13300.74571.13290.100*0.50
C131.2944 (18)0.7056 (18)1.1765 (13)0.080 (6)0.50
H131.33480.75691.21750.096*0.50
C141.3550 (10)0.6357 (15)1.1659 (9)0.060 (4)0.50
H141.43590.64021.19980.072*0.50
C151.2946 (15)0.5591 (11)1.1047 (10)0.043 (4)0.50
H151.33510.51231.09760.052*0.50
C10'1.1748 (15)0.5472 (15)1.0570 (8)0.043 (2)0.50
C11'1.1224 (10)0.635 (2)1.0620 (11)0.043 (4)0.50
H11'1.04310.64881.02070.052*0.50
C12'1.1883 (17)0.7029 (19)1.1285 (14)0.060 (4)0.50
H12'1.15320.76181.13180.072*0.50
C13'1.3067 (17)0.6826 (18)1.1902 (10)0.080 (6)0.50
H13'1.35080.72791.23470.096*0.50
C14'1.3592 (11)0.5946 (16)1.1853 (8)0.083 (7)0.50
H14'1.43840.58101.22650.100*0.50
C15'1.2933 (16)0.5269 (10)1.1187 (10)0.043 (4)0.50
H15'1.32840.46801.11540.051*0.50
C210.8951 (12)0.2053 (11)0.8731 (8)0.089 (4)
H21A0.84910.18010.88550.134*
H21B0.95190.25710.91270.134*
H21C0.84500.23950.82150.134*
C270.6743 (14)0.0869 (17)0.5059 (7)0.101 (5)
H27A0.65920.01030.50420.152*
H27B0.68500.10260.46900.152*
H27C0.60930.12820.49160.152*
C281.3964 (16)0.454 (2)0.3172 (13)0.170 (11)
H28A1.34660.46350.26050.255*
H28B1.47370.43500.33900.255*
H28C1.39920.52020.34120.255*
C291.4093 (6)0.3422 (7)0.4112 (4)0.092 (5)
C301.5205 (6)0.3817 (6)0.4740 (6)0.096 (5)
H301.55740.42820.46370.115*
C311.5764 (5)0.3518 (8)0.5520 (5)0.095 (5)
C321.5212 (7)0.2824 (8)0.5673 (4)0.094 (5)
H321.55870.26240.61950.112*
C331.4100 (7)0.2428 (7)0.5046 (5)0.080 (4)
C341.3541 (5)0.2728 (7)0.4266 (4)0.071 (3)
C351.3670 (10)0.1683 (13)0.5301 (8)0.086 (4)
H351.41520.14780.58340.103*
C361.1316 (9)0.0013 (10)0.4594 (6)0.059 (3)
C371.1745 (6)0.1450 (7)0.5566 (4)0.064 (3)
C381.1170 (5)0.2253 (8)0.5633 (5)0.081 (4)
H381.03590.22920.52580.098*
C391.1807 (9)0.2998 (7)0.6258 (6)0.091 (4)
H391.14230.35360.63020.110*
C401.3020 (9)0.2940 (7)0.6817 (5)0.095 (5)
H401.34460.34380.72360.114*
C411.3595 (5)0.2136 (8)0.6751 (4)0.086 (4)
H411.44060.20970.71250.103*
C421.2958 (6)0.1391 (7)0.6126 (5)0.075 (3)
H421.33420.08540.60810.090*
C480.8976 (13)0.6037 (14)0.3730 (8)0.086 (4)
H48A0.93710.66930.37880.130*
H48B0.89810.59850.41610.130*
H48C0.81840.60560.32310.130*
C540.6715 (11)0.3223 (13)0.0054 (6)0.077 (4)
H54A0.62600.25820.02360.116*
H54B0.68940.35930.02320.116*
H54C0.62780.37010.01130.116*
C550.7803 (10)0.5459 (7)0.8201 (7)0.068 (3)
H550.80670.54520.79260.082*
C560.6333 (15)0.5697 (15)0.8199 (11)0.143 (6)
H56A0.69470.54130.87240.214*
H56B0.56510.52480.79310.214*
H56C0.61520.64300.82380.214*
C570.5914 (11)0.5943 (11)0.6963 (6)0.086 (4)
H57A0.63560.61610.68180.129*
H57B0.54030.65270.68500.129*
H57C0.54580.53080.66620.129*
C580.7778 (10)0.1278 (9)0.3182 (8)0.080 (3)
H580.79120.09060.28860.096*
C590.6513 (12)0.2339 (13)0.3288 (9)0.112 (5)
H59A0.71380.22150.38490.168*
H59B0.64530.31060.31780.168*
H59C0.57930.20830.31310.168*
C600.5787 (17)0.1630 (16)0.1896 (12)0.161 (8)
H60A0.59660.10410.17080.241*
H60B0.50510.14920.17550.241*
H60C0.57410.23010.16540.241*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0544 (7)0.1203 (13)0.0898 (9)0.0469 (8)0.0437 (7)0.0423 (9)
Br20.0536 (8)0.1371 (17)0.1670 (18)0.0138 (9)0.0445 (11)0.0857 (15)
Zn10.0284 (4)0.0361 (5)0.0374 (5)0.0018 (5)0.0184 (4)0.0056 (5)
Zn20.0540 (7)0.0451 (7)0.0582 (8)0.0078 (6)0.0185 (6)0.0086 (7)
S10.0290 (10)0.0372 (13)0.0389 (12)0.0004 (10)0.0163 (10)0.0066 (11)
S20.0691 (19)0.0521 (18)0.0518 (17)0.0037 (16)0.0185 (15)0.0069 (15)
O10.045 (4)0.105 (7)0.063 (4)0.007 (4)0.033 (4)0.032 (5)
O20.029 (3)0.059 (4)0.028 (3)0.010 (3)0.011 (3)0.003 (3)
O30.073 (6)0.074 (6)0.112 (7)0.001 (5)0.049 (6)0.013 (6)
O40.072 (6)0.077 (7)0.112 (8)0.009 (5)0.048 (6)0.027 (6)
O50.043 (3)0.085 (5)0.054 (4)0.012 (3)0.025 (3)0.005 (4)
O60.086 (5)0.081 (5)0.052 (4)0.009 (4)0.024 (4)0.009 (4)
N10.020 (3)0.044 (4)0.026 (3)0.004 (3)0.009 (3)0.012 (3)
N20.031 (3)0.034 (4)0.033 (3)0.002 (3)0.017 (3)0.011 (3)
N30.032 (4)0.052 (5)0.044 (4)0.011 (4)0.023 (4)0.008 (4)
N40.041 (4)0.030 (4)0.030 (4)0.000 (3)0.020 (4)0.003 (3)
C160.033 (4)0.045 (6)0.047 (5)0.002 (4)0.018 (4)0.005 (5)
C170.081 (8)0.039 (6)0.053 (6)0.002 (6)0.042 (7)0.007 (5)
C180.087 (8)0.036 (6)0.079 (7)0.005 (6)0.063 (7)0.013 (6)
C190.045 (5)0.051 (6)0.059 (6)0.006 (5)0.030 (5)0.007 (5)
C200.034 (4)0.026 (4)0.050 (5)0.003 (4)0.026 (4)0.004 (4)
N50.050 (4)0.035 (4)0.040 (4)0.003 (4)0.032 (4)0.005 (4)
C220.038 (4)0.042 (5)0.040 (5)0.001 (4)0.026 (4)0.001 (4)
C230.039 (5)0.042 (5)0.048 (5)0.013 (4)0.028 (5)0.006 (5)
C240.062 (6)0.040 (5)0.041 (5)0.008 (5)0.025 (5)0.002 (5)
C250.063 (6)0.095 (10)0.027 (5)0.020 (6)0.024 (5)0.008 (6)
C260.067 (6)0.033 (5)0.048 (5)0.008 (5)0.041 (5)0.007 (5)
N60.089 (7)0.041 (6)0.079 (7)0.003 (5)0.043 (6)0.009 (5)
N70.066 (6)0.066 (8)0.077 (7)0.006 (6)0.028 (6)0.007 (6)
N80.064 (6)0.071 (7)0.055 (6)0.032 (5)0.027 (5)0.013 (5)
N90.056 (5)0.048 (6)0.048 (5)0.002 (4)0.024 (5)0.003 (5)
C430.129 (11)0.053 (8)0.046 (7)0.009 (8)0.047 (8)0.008 (6)
C440.084 (9)0.070 (9)0.052 (7)0.023 (7)0.041 (7)0.014 (7)
C450.053 (6)0.054 (7)0.059 (6)0.009 (5)0.028 (5)0.005 (6)
C460.062 (6)0.041 (6)0.042 (5)0.005 (5)0.031 (5)0.009 (5)
C470.049 (5)0.054 (6)0.034 (5)0.006 (5)0.023 (5)0.006 (5)
N100.044 (4)0.040 (4)0.050 (5)0.004 (4)0.019 (4)0.000 (5)
C490.048 (5)0.043 (6)0.047 (6)0.002 (5)0.025 (5)0.005 (5)
C500.066 (7)0.072 (8)0.035 (6)0.006 (6)0.022 (6)0.001 (6)
C510.065 (7)0.091 (10)0.045 (6)0.018 (7)0.034 (6)0.013 (7)
C520.089 (8)0.035 (6)0.054 (6)0.014 (5)0.041 (6)0.005 (5)
C530.062 (7)0.067 (8)0.063 (7)0.008 (6)0.030 (6)0.021 (7)
N110.043 (4)0.090 (6)0.050 (5)0.020 (4)0.018 (4)0.002 (4)
N120.086 (7)0.133 (8)0.073 (6)0.014 (6)0.045 (5)0.015 (6)
C10.076 (8)0.088 (9)0.102 (9)0.009 (7)0.064 (8)0.035 (8)
C20.050 (5)0.057 (7)0.053 (6)0.004 (5)0.038 (5)0.005 (5)
C30.044 (5)0.080 (8)0.067 (7)0.022 (5)0.039 (5)0.012 (6)
C40.045 (5)0.042 (5)0.075 (7)0.024 (4)0.038 (6)0.014 (5)
C50.040 (5)0.058 (7)0.049 (6)0.020 (5)0.022 (5)0.020 (5)
C60.024 (4)0.042 (5)0.048 (5)0.011 (4)0.021 (4)0.009 (4)
C70.054 (6)0.033 (5)0.077 (7)0.018 (4)0.048 (6)0.025 (5)
C80.045 (5)0.042 (6)0.034 (4)0.002 (4)0.024 (4)0.003 (4)
C90.043 (5)0.033 (5)0.053 (5)0.014 (4)0.036 (5)0.019 (4)
C100.038 (4)0.041 (5)0.048 (5)0.001 (4)0.028 (4)0.014 (4)
C110.055 (9)0.027 (6)0.060 (9)0.003 (6)0.044 (8)0.006 (6)
C120.051 (10)0.091 (14)0.089 (14)0.009 (8)0.039 (10)0.058 (11)
C130.087 (10)0.061 (12)0.072 (10)0.005 (9)0.044 (9)0.035 (10)
C140.052 (9)0.061 (10)0.058 (10)0.004 (7)0.033 (9)0.021 (8)
C150.046 (8)0.037 (8)0.050 (8)0.003 (6)0.032 (8)0.004 (7)
C10'0.038 (4)0.041 (5)0.048 (5)0.001 (4)0.028 (4)0.014 (4)
C11'0.046 (8)0.037 (8)0.050 (8)0.003 (6)0.032 (8)0.004 (7)
C12'0.052 (9)0.061 (10)0.058 (10)0.004 (7)0.033 (9)0.021 (8)
C13'0.087 (10)0.061 (12)0.072 (10)0.005 (9)0.044 (9)0.035 (10)
C14'0.051 (10)0.091 (14)0.089 (14)0.009 (8)0.039 (10)0.058 (11)
C15'0.055 (9)0.027 (6)0.060 (9)0.003 (6)0.044 (8)0.006 (6)
C210.091 (9)0.054 (7)0.096 (10)0.030 (7)0.050 (8)0.015 (7)
C270.104 (11)0.110 (14)0.048 (8)0.024 (11)0.033 (8)0.005 (9)
C280.101 (14)0.23 (3)0.19 (2)0.026 (17)0.101 (16)0.03 (2)
C290.043 (6)0.047 (7)0.148 (13)0.001 (6)0.046 (8)0.001 (9)
C300.059 (7)0.045 (7)0.132 (13)0.021 (6)0.041 (8)0.003 (8)
C310.027 (5)0.103 (12)0.098 (10)0.010 (7)0.017 (6)0.043 (9)
C320.044 (7)0.089 (11)0.090 (10)0.024 (7)0.020 (7)0.013 (9)
C330.066 (7)0.042 (7)0.081 (9)0.017 (6)0.027 (7)0.010 (6)
C340.028 (5)0.053 (7)0.066 (7)0.009 (5)0.003 (5)0.017 (6)
C350.041 (6)0.063 (8)0.071 (8)0.013 (6)0.002 (6)0.001 (7)
C360.045 (5)0.052 (7)0.047 (6)0.002 (5)0.017 (5)0.016 (5)
C370.059 (6)0.083 (9)0.038 (5)0.029 (6)0.027 (5)0.003 (6)
C380.082 (8)0.082 (10)0.071 (8)0.018 (7)0.047 (7)0.008 (7)
C390.120 (12)0.073 (10)0.095 (10)0.007 (8)0.077 (10)0.002 (8)
C400.095 (10)0.119 (14)0.054 (7)0.048 (10)0.043 (8)0.017 (8)
C410.069 (7)0.101 (11)0.074 (8)0.025 (7)0.041 (7)0.006 (7)
C420.052 (6)0.091 (9)0.061 (6)0.034 (6)0.029 (5)0.016 (7)
C480.106 (10)0.095 (11)0.080 (9)0.015 (9)0.070 (9)0.021 (8)
C540.067 (8)0.074 (10)0.040 (6)0.004 (7)0.014 (6)0.005 (6)
C550.064 (6)0.072 (6)0.057 (5)0.006 (5)0.035 (5)0.008 (5)
C560.114 (9)0.177 (11)0.142 (10)0.006 (7)0.087 (8)0.006 (8)
C570.072 (6)0.103 (7)0.050 (5)0.017 (5)0.026 (5)0.001 (5)
C580.066 (6)0.075 (7)0.064 (6)0.020 (5)0.028 (5)0.006 (5)
C590.099 (7)0.119 (8)0.105 (8)0.025 (6)0.061 (6)0.007 (6)
C600.154 (11)0.165 (12)0.130 (10)0.038 (8)0.079 (8)0.015 (8)
Geometric parameters (Å, º) top
Br1—C41.877 (4)C1—H1B0.9600
Br2—C311.908 (5)C1—H1C0.9600
Zn1—O21.987 (6)C2—C31.3900
Zn1—N42.088 (4)C2—C71.3900
Zn1—N12.124 (6)C3—C41.3900
Zn1—N52.134 (4)C3—H3A0.9300
Zn1—S12.353 (2)C4—C51.3900
Zn2—O41.970 (9)C5—C61.3900
Zn2—N62.063 (11)C5—H50.9300
Zn2—N92.077 (5)C6—C71.3900
Zn2—N102.124 (4)C6—C81.459 (10)
Zn2—S22.346 (4)C8—H8A0.9300
S1—C91.765 (10)C10—C111.3900
S2—C361.720 (11)C10—C151.3900
O1—C21.351 (8)C11—C121.3900
O1—C11.441 (12)C11—H110.9300
O2—C71.364 (7)C12—C131.3900
O3—C291.379 (12)C12—H120.9300
O3—C281.40 (2)C13—C141.3900
O4—C341.330 (11)C13—H130.9300
O5—C551.239 (13)C14—C151.3900
O6—C581.218 (14)C14—H140.9300
N1—C81.246 (11)C15—H150.9300
N1—N21.388 (9)C10'—C11'1.3900
N2—C91.251 (11)C10'—C15'1.3900
N3—C91.401 (11)C11'—C12'1.3900
N3—C10'1.409 (10)C11'—H11'0.9300
N3—C101.407 (10)C12'—C13'1.3900
N3—H30.8800C12'—H12'0.9300
N3—H3'0.8800C13'—C14'1.3900
N4—C161.3900C13'—H13'0.9300
N4—C201.3900C14'—C15'1.3900
C16—C171.3900C14'—H14'0.9300
C16—H160.9300C15'—H15'0.9300
C17—C181.3900C21—H21A0.9600
C17—H170.9300C21—H21B0.9600
C18—C191.3900C21—H21C0.9600
C18—C211.527 (11)C27—H27A0.9600
C19—C201.3900C27—H27B0.9600
C19—H190.9300C27—H27C0.9600
C20—C221.408 (5)C28—H28A0.9600
N5—C221.3900C28—H28B0.9600
N5—C261.3900C28—H28C0.9600
C22—C231.3900C29—C301.3900
C23—C241.3900C29—C341.3900
C23—H230.9300C30—C311.3900
C24—C251.3900C30—H300.9300
C24—C271.493 (14)C31—C321.3900
C25—C261.3900C32—C331.3900
C25—H250.9300C32—H320.9300
C26—H260.9300C33—C341.3900
N6—C351.368 (16)C33—C351.443 (17)
N6—N71.403 (15)C35—H350.9300
N7—C361.362 (15)C37—C381.3900
N8—C361.347 (16)C37—C421.3900
N8—C371.443 (11)C38—C391.3900
N8—H80.8800C38—H380.9300
N9—C431.3900C39—C401.3900
N9—C471.3900C39—H390.9300
C43—C441.3900C40—C411.3900
C43—H430.9300C40—H400.9300
C44—C451.3900C41—C421.3900
C44—H440.9300C41—H410.9300
C45—C461.3900C42—H420.9300
C45—C481.444 (15)C48—H48A0.9600
C46—C471.3900C48—H48B0.9600
C46—H460.9300C48—H48C0.9600
C47—C491.418 (6)C54—H54A0.9600
N10—C491.3900C54—H54B0.9600
N10—C531.3900C54—H54C0.9600
C49—C501.3900C55—H550.9300
C50—C511.3900C56—H56A0.9600
C50—H500.9300C56—H56B0.9600
C51—C521.3900C56—H56C0.9600
C51—C541.534 (12)C57—H57A0.9600
C52—C531.3900C57—H57B0.9600
C52—H520.9300C57—H57C0.9600
C53—H530.9300C58—H580.9300
N11—C551.333 (14)C59—H59A0.9600
N11—C561.339 (17)C59—H59B0.9600
N11—C571.407 (14)C59—H59C0.9600
N12—C581.301 (16)C60—H60A0.9600
N12—C591.528 (18)C60—H60B0.9600
N12—C601.56 (2)C60—H60C0.9600
C1—H1A0.9600
O2—Zn1—N4103.2 (3)O2—C7—C2116.8 (5)
O2—Zn1—N187.7 (2)C6—C7—C2120.0
N4—Zn1—N1104.9 (3)N1—C8—C6128.3 (8)
O2—Zn1—N593.9 (2)N1—C8—H8A115.9
N4—Zn1—N578.0 (2)C6—C8—H8A115.9
N1—Zn1—N5176.3 (3)N2—C9—N3119.1 (8)
O2—Zn1—S1148.2 (2)N2—C9—S1129.3 (6)
N4—Zn1—S1108.48 (15)N3—C9—S1111.4 (7)
N1—Zn1—S182.0 (2)C11—C10—C15120.0
N5—Zn1—S194.97 (17)C11—C10—N3115.3 (14)
O4—Zn2—N688.1 (4)C15—C10—N3124.6 (14)
O4—Zn2—N998.8 (4)C12—C11—C10120.0
N6—Zn2—N9106.6 (3)C12—C11—H11120.0
O4—Zn2—N1093.8 (3)C10—C11—H11120.0
N6—Zn2—N10174.8 (4)C13—C12—C11120.0
N9—Zn2—N1077.9 (2)C13—C12—H12120.0
O4—Zn2—S2151.3 (4)C11—C12—H12120.0
N6—Zn2—S281.5 (3)C12—C13—C14120.0
N9—Zn2—S2109.7 (2)C12—C13—H13120.0
N10—Zn2—S294.6 (2)C14—C13—H13120.0
C9—S1—Zn193.8 (3)C15—C14—C13120.0
C36—S2—Zn296.7 (4)C15—C14—H14120.0
C2—O1—C1120.0 (9)C13—C14—H14120.0
C7—O2—Zn1126.8 (4)C14—C15—C10120.0
C29—O3—C28119.4 (13)C14—C15—H15120.0
C34—O4—Zn2128.5 (8)C10—C15—H15120.0
C8—N1—N2117.1 (7)C11'—C10'—C15'120.0
C8—N1—Zn1123.4 (6)C11'—C10'—N3117.3 (15)
N2—N1—Zn1119.5 (5)C15'—C10'—N3122.7 (15)
C9—N2—N1114.2 (6)C12'—C11'—C10'120.0
C9—N3—C10'129.2 (11)C12'—C11'—H11'120.0
C9—N3—C10130.1 (11)C10'—C11'—H11'120.0
C10'—N3—C103.4 (16)C11'—C12'—C13'120.0
C9—N3—H3115.0C11'—C12'—H12'120.0
C10'—N3—H3115.8C13'—C12'—H12'120.0
C10—N3—H3115.0C14'—C13'—C12'120.0
C9—N3—H3'115.4C14'—C13'—H13'120.0
C10'—N3—H3'115.4C12'—C13'—H13'120.0
C10—N3—H3'114.4C15'—C14'—C13'120.0
C16—N4—C20120.0C15'—C14'—H14'120.0
C16—N4—Zn1125.1 (3)C13'—C14'—H14'120.0
C20—N4—Zn1114.9 (3)C14'—C15'—C10'120.0
C17—C16—N4120.0C14'—C15'—H15'120.0
C17—C16—H16120.0C10'—C15'—H15'120.0
N4—C16—H16120.0C18—C21—H21A109.5
C16—C17—C18120.0C18—C21—H21B109.5
C16—C17—H17120.0H21A—C21—H21B109.5
C18—C17—H17120.0C18—C21—H21C109.5
C17—C18—C19120.0H21A—C21—H21C109.5
C17—C18—C21119.4 (7)H21B—C21—H21C109.5
C19—C18—C21120.4 (7)C24—C27—H27A109.5
C20—C19—C18120.0C24—C27—H27B109.5
C20—C19—H19120.0H27A—C27—H27B109.5
C18—C19—H19120.0C24—C27—H27C109.5
C19—C20—N4120.0H27A—C27—H27C109.5
C19—C20—C22123.1 (4)H27B—C27—H27C109.5
N4—C20—C22116.9 (4)O3—C28—H28A109.5
C22—N5—C26120.0O3—C28—H28B109.5
C22—N5—Zn1113.5 (3)H28A—C28—H28B109.5
C26—N5—Zn1126.1 (3)O3—C28—H28C109.5
C23—C22—N5120.0H28A—C28—H28C109.5
C23—C22—C20123.5 (4)H28B—C28—H28C109.5
N5—C22—C20116.5 (4)O3—C29—C30121.3 (7)
C22—C23—C24120.0O3—C29—C34118.7 (7)
C22—C23—H23120.0C30—C29—C34120.0
C24—C23—H23120.0C29—C30—C31120.0
C25—C24—C23120.0C29—C30—H30120.0
C25—C24—C27118.4 (8)C31—C30—H30120.0
C23—C24—C27121.6 (8)C32—C31—C30120.0
C24—C25—C26120.0C32—C31—Br2118.7 (6)
C24—C25—H25120.0C30—C31—Br2121.3 (6)
C26—C25—H25120.0C31—C32—C33120.0
C25—C26—N5120.0C31—C32—H32120.0
C25—C26—H26120.0C33—C32—H32120.0
N5—C26—H26120.0C34—C33—C32120.0
C35—N6—N7110.1 (11)C34—C33—C35126.8 (8)
C35—N6—Zn2126.4 (10)C32—C33—C35113.2 (8)
N7—N6—Zn2122.7 (8)O4—C34—C33123.9 (7)
C36—N7—N6110.8 (10)O4—C34—C29115.9 (7)
C36—N8—C37131.6 (10)C33—C34—C29120.0
C36—N8—H8114.2N6—C35—C33120.5 (12)
C37—N8—H8114.2N6—C35—H35119.7
C43—N9—C47120.0C33—C35—H35119.7
C43—N9—Zn2124.5 (3)N8—C36—N7117.3 (11)
C47—N9—Zn2115.3 (3)N8—C36—S2116.2 (8)
C44—C43—N9120.0N7—C36—S2126.3 (10)
C44—C43—H43120.0C38—C37—C42120.0
N9—C43—H43120.0C38—C37—N8116.8 (7)
C45—C44—C43120.0C42—C37—N8123.0 (7)
C45—C44—H44120.0C39—C38—C37120.0
C43—C44—H44120.0C39—C38—H38120.0
C44—C45—C46120.0C37—C38—H38120.0
C44—C45—C48121.7 (7)C38—C39—C40120.0
C46—C45—C48118.3 (7)C38—C39—H39120.0
C47—C46—C45120.0C40—C39—H39120.0
C47—C46—H46120.0C41—C40—C39120.0
C45—C46—H46120.0C41—C40—H40120.0
C46—C47—N9120.0C39—C40—H40120.0
C46—C47—C49123.5 (5)C40—C41—C42120.0
N9—C47—C49116.5 (5)C40—C41—H41120.0
C49—N10—C53120.0C42—C41—H41120.0
C49—N10—Zn2114.0 (3)C41—C42—C37120.0
C53—N10—Zn2125.7 (3)C41—C42—H42120.0
N10—C49—C50120.0C37—C42—H42120.0
N10—C49—C47115.7 (5)C45—C48—H48A109.5
C50—C49—C47124.2 (5)C45—C48—H48B109.5
C49—C50—C51120.0H48A—C48—H48B109.5
C49—C50—H50120.0C45—C48—H48C109.5
C51—C50—H50120.0H48A—C48—H48C109.5
C50—C51—C52120.0H48B—C48—H48C109.5
C50—C51—C54118.4 (7)C51—C54—H54A109.5
C52—C51—C54121.5 (7)C51—C54—H54B109.5
C53—C52—C51120.0H54A—C54—H54B109.5
C53—C52—H52120.0C51—C54—H54C109.5
C51—C52—H52120.0H54A—C54—H54C109.5
C52—C53—N10120.0H54B—C54—H54C109.5
C52—C53—H53120.0O5—C55—N11125.5 (10)
N10—C53—H53120.0O5—C55—H55117.3
C55—N11—C56115.6 (11)N11—C55—H55117.3
C55—N11—C57122.3 (10)N11—C56—H56A109.5
C56—N11—C57122.1 (11)N11—C56—H56B109.5
C58—N12—C59121.0 (12)H56A—C56—H56B109.5
C58—N12—C60119.7 (13)N11—C56—H56C109.5
C59—N12—C60119.3 (12)H56A—C56—H56C109.5
O1—C1—H1A109.5H56B—C56—H56C109.5
O1—C1—H1B109.5N11—C57—H57A109.5
H1A—C1—H1B109.5N11—C57—H57B109.5
O1—C1—H1C109.5H57A—C57—H57B109.5
H1A—C1—H1C109.5N11—C57—H57C109.5
H1B—C1—H1C109.5H57A—C57—H57C109.5
O1—C2—C3124.2 (5)H57B—C57—H57C109.5
O1—C2—C7115.8 (5)O6—C58—N12120.6 (13)
C3—C2—C7120.0O6—C58—H58119.7
C2—C3—C4120.0N12—C58—H58119.7
C2—C3—H3A120.0N12—C59—H59A109.5
C4—C3—H3A120.0N12—C59—H59B109.5
C5—C4—C3120.0H59A—C59—H59B109.5
C5—C4—Br1121.3 (3)N12—C59—H59C109.5
C3—C4—Br1118.7 (3)H59A—C59—H59C109.5
C4—C5—C6120.0H59B—C59—H59C109.5
C4—C5—H5120.0N12—C60—H60A109.5
C6—C5—H5120.0N12—C60—H60B109.5
C5—C6—C7120.0H60A—C60—H60B109.5
C5—C6—C8116.6 (5)N12—C60—H60C109.5
C7—C6—C8123.3 (5)H60A—C60—H60C109.5
O2—C7—C6123.2 (4)H60B—C60—H60C109.5
O2—Zn1—S1—C980.2 (4)C46—C47—C49—N10179.3 (4)
N4—Zn1—S1—C995.2 (3)N9—C47—C49—N103.0 (7)
N1—Zn1—S1—C97.9 (3)C46—C47—C49—C501.7 (8)
N5—Zn1—S1—C9174.3 (3)N9—C47—C49—C50179.4 (4)
O4—Zn2—S2—C3677.1 (8)N10—C49—C50—C510.0
N6—Zn2—S2—C367.2 (5)C47—C49—C50—C51177.6 (7)
N9—Zn2—S2—C3697.5 (4)C49—C50—C51—C520.0
N10—Zn2—S2—C36176.2 (4)C49—C50—C51—C54176.8 (9)
N4—Zn1—O2—C775.8 (7)C50—C51—C52—C530.0
N1—Zn1—O2—C729.0 (7)C54—C51—C52—C53176.7 (9)
N5—Zn1—O2—C7154.4 (7)C51—C52—C53—N100.0
S1—Zn1—O2—C799.7 (7)C49—N10—C53—C520.0
N6—Zn2—O4—C3423.1 (10)Zn2—N10—C53—C52174.1 (5)
N9—Zn2—O4—C3483.4 (10)C1—O1—C2—C313.5 (13)
N10—Zn2—O4—C34161.8 (10)C1—O1—C2—C7169.2 (8)
S2—Zn2—O4—C3491.4 (12)O1—C2—C3—C4177.1 (8)
O2—Zn1—N1—C821.4 (8)C7—C2—C3—C40.0
N4—Zn1—N1—C881.7 (8)C2—C3—C4—C50.0
S1—Zn1—N1—C8171.2 (8)C2—C3—C4—Br1178.8 (5)
O2—Zn1—N1—N2159.4 (6)C3—C4—C5—C60.0
N4—Zn1—N1—N297.6 (6)Br1—C4—C5—C6178.8 (5)
S1—Zn1—N1—N29.5 (6)C4—C5—C6—C70.0
C8—N1—N2—C9174.4 (9)C4—C5—C6—C8176.4 (7)
Zn1—N1—N2—C96.2 (9)Zn1—O2—C7—C622.1 (9)
O2—Zn1—N4—C1688.1 (4)Zn1—O2—C7—C2158.2 (5)
N1—Zn1—N4—C163.1 (4)C5—C6—C7—O2179.7 (7)
N5—Zn1—N4—C16179.3 (4)C8—C6—C7—O23.5 (9)
S1—Zn1—N4—C1689.4 (3)C5—C6—C7—C20.0
O2—Zn1—N4—C2092.8 (3)C8—C6—C7—C2176.2 (7)
N1—Zn1—N4—C20176.0 (3)O1—C2—C7—O22.3 (8)
N5—Zn1—N4—C201.6 (3)C3—C2—C7—O2179.7 (7)
S1—Zn1—N4—C2089.7 (3)O1—C2—C7—C6177.4 (8)
C20—N4—C16—C170.0C3—C2—C7—C60.0
Zn1—N4—C16—C17179.1 (4)N2—N1—C8—C6173.8 (8)
N4—C16—C17—C180.0Zn1—N1—C8—C66.9 (14)
C16—C17—C18—C190.0C5—C6—C8—N1172.7 (9)
C16—C17—C18—C21174.2 (9)C7—C6—C8—N111.0 (13)
C17—C18—C19—C200.0N1—N2—C9—N3178.5 (7)
C21—C18—C19—C20174.1 (9)N1—N2—C9—S13.7 (12)
C18—C19—C20—N40.0C10'—N3—C9—N215.3 (17)
C18—C19—C20—C22178.4 (6)C10—N3—C9—N219.6 (17)
C16—N4—C20—C190.0C10'—N3—C9—S1160.3 (12)
Zn1—N4—C20—C19179.2 (4)C10—N3—C9—S1156.0 (12)
C16—N4—C20—C22178.5 (6)Zn1—S1—C9—N29.6 (9)
Zn1—N4—C20—C220.7 (5)Zn1—S1—C9—N3175.2 (6)
O2—Zn1—N5—C22106.4 (3)C9—N3—C10—C11175.4 (13)
N4—Zn1—N5—C223.7 (3)C15—C10—C11—C120.0
S1—Zn1—N5—C22104.2 (3)N3—C10—C11—C12176.7 (17)
O2—Zn1—N5—C2681.3 (4)C10—C11—C12—C130.0
N4—Zn1—N5—C26176.0 (4)C11—C12—C13—C140.0
S1—Zn1—N5—C2668.2 (3)C12—C13—C14—C150.0
C26—N5—C22—C230.0C13—C14—C15—C100.0
Zn1—N5—C22—C23172.8 (4)C11—C10—C15—C140.0
C26—N5—C22—C20178.2 (5)N3—C10—C15—C14176.3 (19)
Zn1—N5—C22—C205.3 (5)C9—N3—C10'—C11'171.4 (12)
C19—C20—C22—C234.4 (6)C15'—C10'—C11'—C12'0.0
N4—C20—C22—C23174.0 (4)N3—C10'—C11'—C12'179.5 (17)
C19—C20—C22—N5177.5 (3)C10'—C11'—C12'—C13'0.0
N4—C20—C22—N54.1 (6)C11'—C12'—C13'—C14'0.0
N5—C22—C23—C240.0C12'—C13'—C14'—C15'0.0
C20—C22—C23—C24178.0 (6)C13'—C14'—C15'—C10'0.0
C22—C23—C24—C250.0C11'—C10'—C15'—C14'0.0
C22—C23—C24—C27179.9 (10)N3—C10'—C15'—C14'179.4 (18)
C23—C24—C25—C260.0C28—O3—C29—C3012.1 (17)
C27—C24—C25—C26179.9 (10)C28—O3—C29—C34168.7 (14)
C24—C25—C26—N50.0O3—C29—C30—C31179.2 (9)
C22—N5—C26—C250.0C34—C29—C30—C310.0
Zn1—N5—C26—C25171.9 (4)C29—C30—C31—C320.0
O4—Zn2—N6—C3523.3 (12)C29—C30—C31—Br2179.6 (6)
N9—Zn2—N6—C3575.4 (11)C30—C31—C32—C330.0
S2—Zn2—N6—C35176.5 (11)Br2—C31—C32—C33179.6 (6)
O4—Zn2—N6—N7167.5 (10)C31—C32—C33—C340.0
N9—Zn2—N6—N793.9 (9)C31—C32—C33—C35177.5 (9)
S2—Zn2—N6—N714.3 (9)Zn2—O4—C34—C3312.8 (14)
C35—N6—N7—C36173.2 (11)Zn2—O4—C34—C29162.2 (7)
Zn2—N6—N7—C3616.0 (13)C32—C33—C34—O4174.8 (10)
O4—Zn2—N9—C4388.2 (5)C35—C33—C34—O48.0 (12)
N6—Zn2—N9—C432.5 (5)C32—C33—C34—C290.0
N10—Zn2—N9—C43179.8 (4)C35—C33—C34—C29177.1 (10)
S2—Zn2—N9—C4389.2 (4)O3—C29—C34—O45.5 (10)
O4—Zn2—N9—C4797.4 (5)C30—C29—C34—O4175.2 (9)
N6—Zn2—N9—C47171.9 (4)O3—C29—C34—C33179.2 (9)
N10—Zn2—N9—C475.4 (4)C30—C29—C34—C330.0
S2—Zn2—N9—C4785.2 (4)N7—N6—C35—C33176.1 (10)
C47—N9—C43—C440.0Zn2—N6—C35—C3313.5 (18)
Zn2—N9—C43—C44174.1 (5)C34—C33—C35—N66.9 (16)
N9—C43—C44—C450.0C32—C33—C35—N6175.8 (10)
C43—C44—C45—C460.0C37—N8—C36—N724.5 (17)
C43—C44—C45—C48179.1 (9)C37—N8—C36—S2160.5 (9)
C44—C45—C46—C470.0N6—N7—C36—N8178.0 (9)
C48—C45—C46—C47179.1 (8)N6—N7—C36—S27.6 (15)
C45—C46—C47—N90.0Zn2—S2—C36—N8172.4 (8)
C45—C46—C47—C49177.6 (7)Zn2—S2—C36—N72.1 (11)
C43—N9—C47—C460.0C36—N8—C37—C38173.7 (10)
Zn2—N9—C47—C46174.6 (4)C36—N8—C37—C421.4 (15)
C43—N9—C47—C49177.8 (6)C42—C37—C38—C390.0
Zn2—N9—C47—C493.2 (6)N8—C37—C38—C39175.2 (7)
O4—Zn2—N10—C49105.2 (5)C37—C38—C39—C400.0
N9—Zn2—N10—C496.9 (4)C38—C39—C40—C410.0
S2—Zn2—N10—C49102.3 (3)C39—C40—C41—C420.0
O4—Zn2—N10—C5380.4 (5)C40—C41—C42—C370.0
N9—Zn2—N10—C53178.7 (4)C38—C37—C42—C410.0
S2—Zn2—N10—C5372.2 (4)N8—C37—C42—C41174.9 (8)
C53—N10—C49—C500.0C56—N11—C55—O50.1 (4)
Zn2—N10—C49—C50174.8 (4)C57—N11—C55—O5179.4 (4)
C53—N10—C49—C47177.8 (6)C59—N12—C58—O60.0 (3)
Zn2—N10—C49—C477.5 (6)C60—N12—C58—O6179.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O50.882.072.95 (1)175
N8—H8···O60.882.072.95 (1)172

Experimental details

Crystal data
Chemical formula[Zn(C15H12BrN3O2S)(C12H12N2)]·C3H7NO
Mr700.95
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)15.2674 (3), 12.2422 (3), 22.3402 (5)
β (°) 131.425 (1)
V3)3130.90 (12)
Z4
Radiation typeMo Kα
µ (mm1)2.17
Crystal size (mm)0.40 × 0.30 × 0.25
Data collection
DiffractometerBruker APEXII
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.478, 0.613
No. of measured, independent and
observed [I > 2σ(I)] reflections
52133, 14238, 9143
Rint0.051
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.211, 1.01
No. of reflections14238
No. of parameters676
No. of restraints66
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.22, 1.64
Absolute structureFlack (1983), 6722 Friedel pairs
Absolute structure parameter0.50 (2)

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O50.882.072.95 (1)175
N8—H8···O60.882.072.95 (1)172
 

Acknowledgements

JMJ thanks the Council of Scientific and Industrial Research (India) for a Senior Research Fellowship. We thank the Sophisticated Analytical Instruments Facility, Cochin University of Science and Technology, for the diffraction measurements. We also thank the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationSeena, E. B. & Kurup, M. R. P. (2008). Spectrochim. Acta Part A, 69, 726–732.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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