catena Poly[[[bis­­(2 amino­ethane­sulfonato κ2N,O)copper(II)] μ 4,4′ bi­pyridine κ2N:N′] 4,4′ bi­pyridine monohydrate]

metal-organic papers

m72

2H6NO3S)2(C10H8N2)]C10H8N2H2O doi:10.1107/S1600536805040900 Acta Cryst.(2006). E62, m72–m73 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

catena

-Poly[[[bis(2-aminoethanesulfonato-

j

N

,

O

)-copper(II)]-

l

-4,4

-bipyridine-j

N

:

N

_{] 4,4}

_-bipyridine

monohydrate]

Jin-Hua Cai,a,bYi-Min Jiang,a* Xiu-Ju Yin,bXu-Hui Liuband Xiu-Jian Wanga

a_{College of Chemistry and Chemical}

Engineering, Guangxi Normal University, Guilin, Guangxi 541004, People’s Republic of China, andb_{Department of Chemistry and Life} Sciences, Hechi Normal College, Yizhou, Guangxi 546300, People’s Republic of China

Correspondence e-mail: cjhzse@163.com

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.004 A˚ Disorder in main residue

Rfactor = 0.047

wRfactor = 0.099

Data-to-parameter ratio = 15.3

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

The title compound, {[Cu(C2H6NO3S)2(C10H8N2)]C10H8N2 -H2O}n, was obtained by the hydrothermal reaction of Cu(CH3COO)22H2O, 4,40-bipyridne and taurine at 380 K. The 4,40_{-bipyridine ligands bridge Cu}II

ions, forming polymeric chains, in which CuII ions and the bridging ligands lie on twofold axes. Two taurine anions chelate to the CuIIion by the terminal N and O atoms, completing the distorted octahedral coordination. The uncoordinated bipyridine molecule is located on an inversion center.

Comment

Several Schiff bases derived from taurine have recently been prepared in our laboratory (Zhang & Jiang, 2002; Zenget al., 2003; Jianget al., 2004) because of the important physiological properties of taurine. As part of our ongoing investigation on taurine derivatives, we report here the synthesis and crystal structure of the title taurine–copper(II) complex, (I).

The crystal structure of (I) consists of one-dimensional complex chains, uncoordinated 4,4-bipyridine (bipy) and water molecules. The bipy ligands bridge neighboring CuII ions, forming infinite polymeric chains along the

crystal-Received 7 November 2005 Accepted 6 December 2005 Online 10 December 2005

Figure 1

A segment of the polymeric structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms) [symmetry codes: (A)x,y,1

lographicbaxis (Fig. 1). The CuIIions and bridging ligands lie on twofold axes. Two taurine anions chelate to the CuIIion by terminal N and O atoms to complete the distorted octahedral coordination. The longer Cu—O3 bond distance (Table 1) shows the typical Jahn–Teller distortion effect for the CuIIion. Within the bridging bipy ligand, the two pyridine rings are twisted with respect to each other; the dihedral angle is 53.11 (4).

The uncoordinated bipy is located on an inversion center

and displays a planar configuration. Weak C—H O

hydrogen bonding occurs between the bipy and the water molecules. Classical O—H O hydrogen bonding is also observed between the water and the complex chain (Table 2).

Experimental

A methanol solution (10 ml) of taurine (1.5 mmol) and KOH (1.5 mmol) was mixed with another methanol solution (10 ml) of Cu(CH3COO)22H2O (0.5 mmol). After stirring for 10 min, 4,40

-bipyridine (1 mmol) was added slowly to the mixture, which was then dropped into a 25 ml Teflon-stainless steel reactor and heated at 380 K for 5 d. After cooling the reactor to room temperature, single crystals of (I) were obtained (yield 65%). Analysis found (%): C 44.87, H 4.66, N 13.05, S 9.98; calculated (%): C 44.84, H 4.67, N 13.08, S 9.97. IR (KBr, cm1): 1033.3, 1168.1, 1237.4 (—SO3), 3258.4,

3304.3 (N—H).

Crystal data

[Cu(C2H6NO3S)2(C10H8N2)]

-C10H8N2H2O Mr= 642.2

Monoclinic,P2=c a= 9.8647 (11) A˚

b= 11.3846 (9) A˚

c= 12.9516 (14) A˚ = 107.446 (5)

V= 1387.6 (2) A˚3

Z= 2

Dx= 1.537 Mg m

3

MoKradiation Cell parameters from 2887

reflections = 3.3–27.5 = 0.99 mm1 T= 293 (2) K Prism, blue

0.250.200.15 mm

Data collection

Rigaku Mercury CCD diffractometer ’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.775,Tmax= 0.860

10598 measured reflections

3176 independent reflections 2681 reflections withI> 2(I)

Rint= 0.039

max= 27.5 h=11!12

k=14!14

l=16!15 Refinement

Refinement onF2 R[F2> 2(F2)] = 0.047

wR(F2_{) = 0.099} S= 1.08 3176 reflections 208 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.031P)2

+ 1.3917P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.42 e A˚

3

min=0.40 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

Cu—N1 2.166 (3)

Cu—N2 1.990 (2)

Cu—N3 2.127 (3)

Cu—O3 2.3067 (19)

N2—Cu—N2i

177.17 (13) N2—Cu—N3 91.42 (6)

Symmetry code: (i)x;y;zþ1 2.

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O1W—H1C O1 0.88 1.96 2.827 (8) 169 O1W—H1D O1ii

0.92 1.81 2.693 (7) 159 N2—H2A O2iii

0.88 2.20 2.971 (3) 145 N2—H2B N4iv

0.85 2.21 3.021 (4) 160

Symmetry codes: (ii)xþ1;y;zþ3

2; (iii)x;yþ1;z 1

2; (iv)xþ1;y;zþ 1 2.

The methylene group of aminomethylenesulfonate is disordered over two sites with 0.5 site-occupancy factors. The water molecule is located close to the twofold axis and has a 0.5 site-occupancy factor. H atoms on N and O atoms were located in a difference Fourier map and refined as riding in their as-found relative positions, with

Uiso(H) = 1.2Ueq(carrier). Other H atoms were placed in calculated

positions, with C—H = 0.93 (aromatic) or 0.97 A˚ (methylene), and refined using a riding-model approximation, with Uiso(H) =

1.2Ueq(C).

Data collection: CrystalClear (Rigaku, 2000); cell refinement:

CrustalClear; data reduction:CrystalClear; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL (Bruker, 1997); software used to prepare material for publication:SHELXTL.

This work was supported by the Natural Science Founda-tion of Guangxi Chuang Autonomous Region of China (grant No. 0339034) and the Science Research Foundation of Guangxi University.

References

Bruker (1997).SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. Jiang, Y.-M., Zeng, J.-L. & Yu, K.-B. (2004).Acta Cryst.C60, m543–m545. Rigaku (2000).CrystalClear. Rigaku Corporation, Tokyo, Japan. Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

supporting information

sup-1

supporting information

Acta Cryst. (2006). E62, m72–m73 [doi:10.1107/S1600536805040900]

catena

-Poly[[[bis(2-aminoethanesulfonato-

κ

N

,

O

)copper(II)]-

µ

-4,4

′

-bipyridine-κ

_N

_:

_N

_′

_{] 4,4}

_′

_{-bipyridine monohydrate]}

Jin-Hua Cai, Yi-Min Jiang, Xiu-Ju Yin, Xu-Hui Liu and Xiu-Jian Wang

S1. Comment

Several Schiff bases derived from taurine have recently been prepared in our laboratory (Zhang & Jiang, 2002; Zeng et

al., 2003; Jiang et al., 2004) because of the important physiological properties of taurine. As part of our ongoing

investigation on taurine derivatives, we report here the synthesis and crystal structure of the title taurine–copper(II)

complex, (I).

The crystal structure of (I) consists of one-dimensional complex chains, coordinated 4,4-bipyridine (bipy) and water

molecules. The bipy ligands bridge neighboring CuII _{ions, forming infinite polymeric chains along the crystallographic b}

axis (Fig. 1). The polymeric chain is located on a twofold axis. Two taurine anions chelate to the CuII _{ion by terminal N}

and O atoms to complete the distorted octahedral coordination. The longer Cu—O3 bond distance (Table 1) shows the

typical Jahn–Teller distortion effect for the CuII _{ion. Within the bridging bipy ligand, the two pyridine rings are twisted to}

each other with a dihedral angle of 53.11 (4)°.

The bipy is located on an inversion center and displays a planar configuration. Weak C—H···O hydrogen bonding

occurs between the bipy and the water molecules (Table 2). Classic O—H···O hydrogen bonding is also observed between

the water and the complex chain.

S2. Experimental

A methanol solution (10 ml) of taurine (1.5 mmol) and KOH (1.5 mmol) was mixed with another methanol solution (10

ml) of Cu(CH3COO)2·2H2O (0.5 mmol). After stirring for 10 min, 4,4′-bipyridne (1 mmol) was added slowly to the

mixture. It was then dropped into a 25 ml Teflon-stainless steel reactor and heated at 380 K for 5 d. After cooling the

reactor to room temperature, single crystals of (I) were obtained (yield 65%). Analysis found (%): C 44.87, H 4.66, N

13.05, S 9.98; calculated (%): C 44.84, H 4.67, N 13.08, S 9.97. IR (KBr, ν cm−1_{): 1033.3, 1168.1, 1237.4 (–SO}

3), 3258.4,

3304.3 (ν N—H).

S3. Refinement

The methylene group of aminomethylenesulfonate is disordered over two sites with 0.5 site-occupancy factors. The water

molecule is located close to the twofold axis and has a 0.5 site-occupancy factor. H atoms on N and O atoms were located

in a difference Fourier map and refined as riding in their as-found relative positions, with Uiso(H) = 1.2Ueq(carrier). Other

H atoms were placed in calculated positions, with C—H = 0.93 (aromatic) or 0.97 Å (methylene), and refined using a

Figure 1

A segment of the polymeric structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms)

[symmetry codes: (A) −x, y, 1/2 − z; (B) x, 1 + y, z; (C) 1 − x, −y, 1 − z].

catena-Poly[[[bis(2-aminoethanesulfonato-κ2_{N,O)copper(II)]-µ-4,4′- bipyridine-κ}2_{N:N′] 4,4′-bipyridine}

monohydrate]]

Crystal data

[Cu(C2H6NO3S)2(C10H8N2)]·C10H8N2·H2O

Mr = 642.2 Monoclinic, P2/c

Hall symbol: -P 2yc

a = 9.8647 (11) Å

b = 11.3846 (9) Å

c = 12.9516 (14) Å

β = 107.446 (5)°

V = 1387.6 (2) Å3

Z = 2

F(000) = 666

Dx = 1.537 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2887 reflections

θ = 3.3–27.5°

µ = 0.99 mm−1

T = 293 K Prism, blue

0.25 × 0.20 × 0.15 mm

Data collection

Rigaku Mercury CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.775, Tmax = 0.860

10598 measured reflections 3176 independent reflections 2681 reflections with I > 2σ(I)

Rint = 0.039

θmax = 27.5°, θmin = 3.3°

h = −11→12

k = −14→14

l = −16→15

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.047}

wR(F2_{) = 0.099}

3176 reflections 208 parameters 1 restraint

supporting information

sup-3

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.031P)2 + 1.3917P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001 Δρmax = 0.42 e Å−3 Δρmin = −0.40 e Å−3

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 Occ. (<1)

Cu 0.0000 0.37558 (3) 0.2500 0.02478 (14)

S 0.25875 (8) 0.39859 (6) 0.49274 (6) 0.03598 (18)

N1 0.0000 0.1853 (2) 0.2500 0.0332 (7)

N2 0.1844 (2) 0.37126 (19) 0.21701 (18) 0.0325 (5)

H2A 0.1791 0.4239 0.1658 0.039*

H2B 0.1885 0.3042 0.1896 0.039*

N3 0.0000 0.5624 (2) 0.2500 0.0280 (7)

N4 0.7300 (4) 0.1558 (3) 0.3845 (3) 0.0790 (11)

O1 0.3188 (3) 0.3010 (2) 0.5593 (2) 0.0904 (10)

O2 0.2828 (3) 0.5085 (2) 0.5489 (2) 0.0729 (8)

O3 0.1092 (2) 0.37865 (16) 0.43436 (15) 0.0370 (4)

O1W 0.5829 (8) 0.2895 (8) 0.7232 (5) 0.134 (3) 0.50

H1C 0.4958 0.2944 0.6791 0.161* 0.50

H1D 0.5936 0.2934 0.7961 0.161* 0.50

C1A 0.3188 (5) 0.3414 (5) 0.3031 (4) 0.0278 (11) 0.50

H1A1 0.3974 0.3384 0.2727 0.033* 0.50

H1A2 0.3101 0.2652 0.3340 0.033* 0.50

C2A 0.3459 (7) 0.4380 (6) 0.3919 (6) 0.0350 (15) 0.50

H2A1 0.3093 0.5126 0.3591 0.042* 0.50

H2A2 0.4472 0.4464 0.4265 0.042* 0.50

C1B 0.3085 (7) 0.4331 (8) 0.2996 (6) 0.0589 (19) 0.50

H1B1 0.3880 0.4387 0.2703 0.071* 0.50

H1B2 0.2799 0.5123 0.3113 0.071* 0.50

C2B 0.3536 (8) 0.3728 (8) 0.4012 (7) 0.053 (2) 0.50

H2B1 0.4521 0.3932 0.4364 0.063* 0.50

H2B2 0.3505 0.2891 0.3866 0.063* 0.50

C3 0.0111 (3) 0.6237 (2) 0.1647 (2) 0.0328 (6)

H3 0.0175 0.5827 0.1043 0.039*

C4 0.0134 (3) 0.7442 (2) 0.1622 (2) 0.0359 (6)

C5 0.0000 0.8084 (3) 0.2500 0.0302 (8)

C6 −0.0586 (3) 0.1244 (2) 0.1593 (2) 0.0395 (7)

H6 −0.0997 0.1655 0.0956 0.047*

C7 −0.0606 (3) 0.0027 (2) 0.1561 (3) 0.0424 (7)

H7 −0.1025 −0.0361 0.0912 0.051*

C8 0.0000 −0.0610 (3) 0.2500 0.0358 (9)

C9 0.5482 (3) 0.0322 (2) 0.4758 (3) 0.0414 (7)

C10 0.5921 (4) 0.1457 (3) 0.5069 (3) 0.0540 (9)

H10 0.5626 0.1830 0.5602 0.065*

C11 0.6802 (4) 0.2032 (3) 0.4582 (4) 0.0678 (12)

H11 0.7058 0.2802 0.4790 0.081*

C12 0.6910 (5) 0.0463 (4) 0.3565 (4) 0.0864 (15)

H12 0.7262 0.0102 0.3054 0.104*

C13 0.6007 (4) −0.0176 (3) 0.3989 (3) 0.0671 (11)

H13 0.5756 −0.0939 0.3754 0.081*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Cu 0.0296 (2) 0.0165 (2) 0.0310 (3) 0.000 0.01326 (19) 0.000

S 0.0381 (4) 0.0362 (4) 0.0315 (4) 0.0053 (3) 0.0072 (3) −0.0069 (3)

N1 0.0352 (18) 0.0186 (14) 0.046 (2) 0.000 0.0124 (15) 0.000

N2 0.0344 (12) 0.0353 (11) 0.0311 (12) 0.0008 (9) 0.0149 (10) −0.0025 (10)

N3 0.0365 (17) 0.0196 (13) 0.0311 (16) 0.000 0.0150 (14) 0.000

N4 0.086 (2) 0.0542 (19) 0.122 (3) −0.0166 (17) 0.070 (2) 0.006 (2)

O1 0.084 (2) 0.0679 (18) 0.093 (2) 0.0237 (15) −0.0139 (17) 0.0292 (16)

O2 0.0695 (17) 0.0516 (14) 0.106 (2) −0.0207 (12) 0.0397 (16) −0.0400 (14)

O3 0.0366 (11) 0.0424 (11) 0.0327 (11) 0.0007 (8) 0.0114 (9) 0.0010 (8)

O1W 0.126 (6) 0.192 (8) 0.057 (4) 0.038 (6) −0.015 (4) −0.033 (5)

C1A 0.026 (3) 0.031 (3) 0.030 (3) 0.005 (2) 0.013 (2) −0.010 (2)

C2A 0.034 (3) 0.036 (3) 0.037 (4) −0.009 (3) 0.014 (3) −0.013 (3)

C1B 0.037 (4) 0.080 (6) 0.068 (5) −0.009 (4) 0.029 (4) −0.010 (4)

C2B 0.030 (3) 0.067 (5) 0.058 (5) 0.007 (4) 0.009 (3) −0.008 (5)

C3 0.0472 (16) 0.0235 (12) 0.0312 (14) −0.0006 (11) 0.0170 (13) −0.0008 (10)

C4 0.0530 (18) 0.0242 (12) 0.0330 (15) −0.0001 (11) 0.0167 (13) 0.0047 (11)

C5 0.0309 (19) 0.0196 (16) 0.039 (2) 0.000 0.0092 (17) 0.000

C6 0.0476 (17) 0.0238 (12) 0.0429 (17) 0.0017 (12) 0.0073 (14) 0.0014 (12)

C7 0.0531 (19) 0.0247 (13) 0.0440 (17) −0.0009 (12) 0.0062 (15) −0.0031 (12)

C8 0.038 (2) 0.0234 (18) 0.047 (2) 0.000 0.0141 (19) 0.000

C9 0.0352 (15) 0.0318 (14) 0.059 (2) −0.0020 (12) 0.0173 (14) 0.0101 (14)

C10 0.053 (2) 0.0329 (16) 0.088 (3) −0.0010 (14) 0.0392 (19) 0.0029 (16)

C11 0.067 (2) 0.0331 (16) 0.119 (4) −0.0088 (16) 0.051 (3) 0.006 (2)

C12 0.109 (4) 0.069 (3) 0.112 (4) −0.022 (3) 0.080 (3) −0.012 (3)

supporting information

sup-5

Geometric parameters (Å, º)

Cu—N1 2.166 (3) C2A—H2A2 0.9700

Cu—N2 1.990 (2) C1B—C2B 1.432 (11)

Cu—N2i _{1.990 (2) C1B—H1B1 0.9700}

Cu—N3 2.127 (3) C1B—H1B2 0.9700

Cu—O3i _{2.3067 (19) C2B—H2B1 0.9700}

Cu—O3 2.3067 (19) C2B—H2B2 0.9700

S—O1 1.422 (3) C3—C4 1.373 (3)

S—O2 1.431 (2) C3—H3 0.9300

S—O3 1.460 (2) C4—C5 1.391 (3)

S—C2B 1.741 (8) C4—H4 0.9300

S—C2A 1.822 (7) C5—C4i _{1.391 (3)}

N1—C6 1.336 (3) C5—C8ii _{1.487 (5)}

N1—C6i _{1.336 (3) C6—C7 1.386 (4)}

N2—C1A 1.493 (6) C6—H6 0.9300

N2—C1B 1.534 (8) C7—C8 1.388 (3)

N2—H2A 0.8838 C7—H7 0.9300

N2—H2B 0.8482 C8—C7i _{1.388 (3)}

N3—C3i _{1.338 (3) C8—C5}iii _{1.487 (5)}

N3—C3 1.338 (3) C9—C13 1.375 (5)

N4—C11 1.313 (5) C9—C10 1.384 (4)

N4—C12 1.323 (5) C9—C9iv _{1.482 (6)}

O1W—H1C 0.8790 C10—C11 1.381 (5)

O1W—H1D 0.9192 C10—H10 0.9300

C1A—C2A 1.556 (8) C11—H11 0.9300

C1A—H1A1 0.9700 C12—C13 1.384 (5)

C1A—H1A2 0.9700 C12—H12 0.9300

C2A—H2A1 0.9700 C13—H13 0.9300

N2—Cu—N2i _{177.17 (13) S—C2A—H2A1 109.7}

N2—Cu—N3 91.42 (6) C1A—C2A—H2A2 109.7

N2i_{—Cu—N3 91.42 (6) S—C2A—H2A2 109.7}

N2—Cu—N1 88.58 (6) H2A1—C2A—H2A2 108.2

N2i_{—Cu—N1 88.58 (6) C2B—C1B—N2 112.6 (6)}

N3—Cu—N1 180.0 C2B—C1B—H1B1 109.1

N2—Cu—O3i _{87.22 (8) N2—C1B—H1B1 109.1}

N2i_—Cu—O3i _{92.83 (8) C2B—C1B—H1B2 109.1}

N3—Cu—O3i _{89.13 (5) N2—C1B—H1B2 109.1}

N1—Cu—O3i _{90.87 (5) H1B1—C1B—H1B2 107.8}

N2—Cu—O3 92.83 (8) C1B—C2B—S 117.5 (6)

N2i_{—Cu—O3 87.22 (8) C1B—C2B—H2B1 107.9}

N3—Cu—O3 89.13 (5) S—C2B—H2B1 107.9

N1—Cu—O3 90.87 (5) C1B—C2B—H2B2 107.9

O3i_{—Cu—O3 178.27 (9) S—C2B—H2B2 107.9}

O1—S—O2 113.56 (19) H2B1—C2B—H2B2 107.2

O1—S—O3 111.42 (15) N3—C3—C4 123.1 (3)

O1—S—C2B 94.0 (3) C4—C3—H3 118.4

O2—S—C2B 116.9 (3) C3—C4—C5 119.9 (3)

O3—S—C2B 106.7 (3) C3—C4—H4 120.0

O1—S—C2A 115.3 (3) C5—C4—H4 120.0

O2—S—C2A 96.1 (2) C4—C5—C4i _{116.7 (3)}

O3—S—C2A 106.7 (2) C4—C5—C8ii _{121.67 (16)}

C6—N1—C6i _{117.5 (3) C4}i_—C5—C8ii _{121.67 (16)}

C6—N1—Cu 121.25 (16) N1—C6—C7 122.9 (3)

C6i_{—N1—Cu 121.25 (16) N1—C6—H6 118.5}

C1A—N2—Cu 120.6 (2) C7—C6—H6 118.5

C1B—N2—Cu 115.4 (3) C6—C7—C8 119.8 (3)

C1A—N2—H2A 123.7 C6—C7—H7 120.1

C1B—N2—H2A 93.9 C8—C7—H7 120.1

Cu—N2—H2A 107.0 C7i_{—C8—C7 117.0 (3)}

C1A—N2—H2B 88.0 C7i_—C8—C5iii _{121.51 (17)}

C1B—N2—H2B 125.2 C7—C8—C5iii _{121.51 (17)}

Cu—N2—H2B 105.9 C13—C9—C10 116.3 (3)

H2A—N2—H2B 107.2 C13—C9—C9iv _{122.1 (3)}

C3i_{—N3—C3 117.2 (3) C10—C9—C9}iv _{121.6 (4)}

C3i_{—N3—Cu 121.42 (15) C11—C10—C9 119.6 (3)}

C3—N3—Cu 121.42 (15) C11—C10—H10 120.2

C11—N4—C12 116.4 (3) C9—C10—H10 120.2

S—O3—Cu 128.64 (12) N4—C11—C10 124.1 (3)

H1C—O1W—H1D 117.0 N4—C11—H11 118.0

N2—C1A—C2A 107.9 (4) C10—C11—H11 118.0

N2—C1A—H1A1 110.1 N4—C12—C13 123.7 (4)

C2A—C1A—H1A1 110.1 N4—C12—H12 118.2

N2—C1A—H1A2 110.1 C13—C12—H12 118.2

C2A—C1A—H1A2 110.1 C9—C13—C12 119.8 (3)

H1A1—C1A—H1A2 108.4 C9—C13—H13 120.1

C1A—C2A—S 110.0 (4) C12—C13—H13 120.1

C1A—C2A—H2A1 109.7

Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y+1, z; (iii) x, y−1, z; (iv) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1W—H1C···O1 0.88 1.96 2.827 (8) 169

O1W—H1D···O1v _{0.92 1.81 2.693 (7) 159}

N2—H2A···O2vi _{0.88 2.20 2.971 (3) 145}

N2—H2B···N4vii _{0.85 2.21 3.021 (4) 160}