Poly[[(μ2-4,4′-bipyridyl-κ2N:N′)bis­{μ2-N-[2-(2-hy­droxy­benzo­yl)carbamo­thio­yl]acetamidato-κ4O,N,O′:S}bis­(nitrato-κ2O,O′)dicadmium] di­methyl­formamide tetra­solvate]

You, M.-H.; Li, F.-J.; Yang, X.-P.; Lin, X.-X.; Ye, H.-Y.

doi:10.1107/S1600536813030055

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Pages m647-m648

doi:10.1107/S1600536813030055

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Poly[[(μ₂-4,4′-bipyridyl-κ²N:N′)bis{μ₂-N-[2-(2-hydroxybenzoyl)carbamothioyl]acetamidato-κ⁴O,N,O′:S}bis(nitrato-κ²O,O′)dicadmium] dimethylformamide tetrasolvate]

Ming-Hua You,^a ^* Fo-Jun Li,^a Xiao-Ping Yang,^a Xu-Xiang Lin ^a and Hua-Yan Ye ^a

^aZhicheng College, Fuzhou University, Fuzhou, Fujian 350108, People's Republic of China
^*Correspondence e-mail: yyomh@163.com

(Received 9 October 2013; accepted 2 November 2013; online 9 November 2013)

The asymmetric unit of the title complex, {[Cd₂(C₁₀H₁₀N₃O₃S)₂(C₁₀H₈N₂)(NO₃)₂]·4C₃H₇NO}_n, consists of one Cd^II cation, one N-[2-(2-hydroxybenzoyl)carbamothioyl]acetamidate ligand, half a 4,4′-bipyridyl ligand, one coordinating nitrate anion and two dimethylformamide solvent molecules of crystallization. The bipyridine ligand is completed by inversion symmetry. The metal cation exhibits a distorted pentagonal–bipyramidal coordination geometry provided by two O and one N atoms of the thiosemicarbazide ligand, two O atoms of the nitrate anion, one S atom of a neighbouring thiosemicarbazide ligand and one 4,4′-bipyridine N atom. The bridging role of the thiosemicarbazide ligand through the S atom leads to centrosymmetric binuclear units, which are further linked by 4,4′-bipyridine units, forming polymeric chains extending along the b-axis direction. An intramolecular N—H⋯O hydrogen bond occurs. The crystal structure also features N—H⋯O and O—H⋯O hydrogen bonds, leading to the formation of a three-dimensional network.

CCDC reference: 969916

Related literature

For background to the properties and applications of thiosemicarbazone complexes, see: Quiroga & Ranninger (2004 ); Kasuga et al. (2003 ); Floquet et al. (2009 ); Hassanien et al. (2008 ); Latheef et al. (2006 ); Babb et al. (2003 ). For related structures, see: Ke et al. (2007 ); Wang et al. (2010 ); Liu et al. (2013 ). For the synthesis of the N-(2-(2-hydroxybenzoyl)carbamothioyl)acetamide ligand, see: Wang et al. (2000 ).

Experimental

Crystal data

[Cd₂(C₁₀H₁₀N₃O₃S)₂(C₁₀H₈N₂)(NO₃)₂]·4C₃H₇NO
M_r = 1301.93
Monoclinic, P 2₁ /n
a = 13.831 (3) Å
b = 15.280 (3) Å
c = 14.363 (3) Å
β = 110.55 (3)°
V = 2842.4 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 293 K
0.30 × 0.18 × 0.08 mm

Data collection

Rigaku Saturn 724+ CCD diffractometer
Absorption correction: numerical (CrystalClear; Rigaku, 2007 ) T_min = 0.813, T_max = 0.946
18197 measured reflections
4980 independent reflections
4753 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.141
S = 1.28
4980 reflections
349 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O7ⁱ	0.86	2.01	2.871 (6)	174
N3—H3⋯O6	0.86	1.96	2.619 (6)	133
O6—H6⋯O8ⁱⁱ	0.82	1.70	2.502 (9)	164
Symmetry codes: (i) -x+2, -y, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 969916

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813030055/rz5087sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030055/rz5087Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones complexes have received considerable attentions in the past decades due to their interesting biological activities, including antibacterial, antimalarial, antiviral and antitumor activities (Quiroga & Ranninger, 2004; Kasuga et al., 2003;). In order to figure out their structure-property relationship, a great number of metal complexes based on thiosemicarbazone derivatives, particularly the 1,4-disubstituted ones have been prepared and their biological activities were investigated systematically (Floquet et al., 2009; Hassanien et al., 2008; Latheef et al., 2006; Babb et al., 2003). In this paper, we report the crystal structure of the title one-dimensional coordination polymer based on diacylthiosemicarbazone.

The asymmetric unit of the title complex consists of one cadmium(II) cation, one N-(2-(2-hydroxybenzoyl)carbamothioyl)acetamide ligand, one half of a 4,4'-bipyridine, one coordinated nitrate anion and two dimethylformamide molecules of crystallization (Fig. 1). In the structure, each Cd center adopts a distorted pentagonal bipyramidal coordination geometry with the equatorial plane formed two O atoms and one N atom from the thiosemicarbazide ligand and two O atoms from the bidentate nitrate anion. These five atoms (O1, N2, O2, O4, O3) and the metal center are almost coplanar (maximum deviation from the least-squares plane is 0.6560 (3) Å for the O3 atom). The Cd1—O3 and Cd1—O4 bond lengths involving the nitrate anion are remarkably different (2.387 (4) and 2.553 (5) Å, respectively). The axial positions are occupied by one N atom from 4,4'-bipyridine and one S atom from a neighbouring thiosemicarbazide ligand. The Cd1—N4 bond distance is 2.360 (5) Å, indicating the strong coordination between Cd and 4,4'-bipyridine, while the Cd1—S1ⁱ [symmetry code: (i) -x+2, -y, -z+1] bond length is 2.628 (5) Å, which is slightly shorter than that previously reported (2.7364 (8) Å) for a Cd complex with thiosemicarbazones (Wang et al., 2010). Due to the axial coordination of S atoms, two neighbouring cadmium(II) cations are interconnected to generate a centrosymmetric binuclear unit with a Cd···Cd separation of 5.6889 (12) Å (Fig. 2). Along the b axis, such binuclear units are further bridged by 4,4'-bipyridine linkers to form a one-dimensional zigzag coordination polymer. In the structure of the title complex, N—H···O and O—H···O hydrogen bonds (Table 1) play an important role in stabilizing the packing (Fig. 3).

Related literature top

For background to the properties and applications of thiosemicarbazone complexes, see: Quiroga & Ranninger (2004); Kasuga et al. (2003); Floquet et al. (2009); Hassanien et al. (2008); Latheef et al. (2006); Babb et al. (2003). For related structures, see: Ke et al. (2007); Wang et al. (2010); Liu et al. (2013). For the synthesis of the N-(2-(2-hydroxybenzoyl)carbamothioyl)acetamide ligand, see: Wang et al. (2000).

Experimental top

N-(2-(2-Hydroxybenzoyl)hydrazinecarbonothioyl)acetamide (H₃L) was prepared according to the literature method (Wang et al., 2000). H₃L (0.0251 g, 0.10 mmol) and cadmium nitrate tetrahydrate (0.0472 g, 0.20 mmol) were dissolved in a mixed solvent of methanol and dimethylformamide (12 ml, 5:1 v/v). 4,4'-Bipyridine (0.0102 g 0.05 mmol) was added and the solution was stirred for 4 h at room temperature. The resulting white suspension was filltered and the filtrate allowed to evaporate in air at room temperature. Colourless crystals of the title compound were separated from the filtrate after 10 days.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title complex with 30% probability displacement ellipsoids. H atoms are omitted for clarity. Symmetry code: (i) -x+2, -y, -z+1.
	Fig. 2. A view of the one-dimensional chains in the title compound. For clarity, H atoms and DMF molecules are omitted.
	Fig. 3. A packing diagram for title complex, showing intermolecular (yellow dashed lines) and intramolecular hydrogen bonds (purple dashed lines). H atoms not involved in hydrogen bonding are omitted.

Poly[[(µ₂-4,4'-bipyridyl-κ²N:N')bis{µ₂-N-[2-(2-hydroxybenzoyl)carbamothioyl]acetamidato-κ⁴O,N,O':S}bis(nitrato-κ²O,O')dicadmium] dimethylformamide tetrasolvate] top

Crystal data top

[Cd₂(C₁₀H₁₀N₃O₃S)₂(C₁₀H₈N₂)(NO₃)₂]·4C₃H₇NO	F(000) = 1324
M_r = 1301.93	D_x = 1.521 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10007 reflections
a = 13.831 (3) Å	θ = 3.0–27.5°
b = 15.280 (3) Å	µ = 0.90 mm⁻¹
c = 14.363 (3) Å	T = 293 K
β = 110.55 (3)°	Block, colourless
V = 2842.4 (12) Å³	0.30 × 0.18 × 0.08 mm
Z = 2

Data collection top

Rigaku Saturn 724+ CCD diffractometer	4980 independent reflections
Radiation source: fine-focus sealed tube	4753 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans at fixed χ = 45°	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: numerical (CrystalClear; Rigaku, 2007)	h = −16→16
T_min = 0.813, T_max = 0.946	k = −18→18
18197 measured reflections	l = −16→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.28	w = 1/[σ²(F_o²) + (0.0474P)² + 4.0842P] where P = (F_o² + 2F_c²)/3
4980 reflections	(Δ/σ)_max < 0.001
349 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

[Cd₂(C₁₀H₁₀N₃O₃S)₂(C₁₀H₈N₂)(NO₃)₂]·4C₃H₇NO	V = 2842.4 (12) Å³
M_r = 1301.93	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.831 (3) Å	µ = 0.90 mm⁻¹
b = 15.280 (3) Å	T = 293 K
c = 14.363 (3) Å	0.30 × 0.18 × 0.08 mm
β = 110.55 (3)°

Data collection top

Rigaku Saturn 724+ CCD diffractometer	4980 independent reflections
Absorption correction: numerical (CrystalClear; Rigaku, 2007)	4753 reflections with I > 2σ(I)
T_min = 0.813, T_max = 0.946	R_int = 0.043
18197 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.28	Δρ_max = 0.70 e Å⁻³
4980 reflections	Δρ_min = −0.63 e Å⁻³
349 parameters

Special details top

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 F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) 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) top

	x	y	z	U_iso*/U_eq
Cd1	0.93079 (3)	0.13619 (3)	0.35688 (3)	0.05085 (16)
N4	0.9607 (3)	0.2863 (3)	0.3953 (4)	0.0603 (11)
O2	0.8129 (3)	0.1541 (3)	0.4400 (3)	0.0618 (10)
C4	0.8420 (4)	0.1339 (3)	0.5294 (4)	0.0520 (12)
N2	1.0120 (3)	0.1051 (3)	0.5329 (3)	0.0482 (10)
C6	0.7984 (5)	0.1324 (4)	0.6899 (5)	0.0704 (17)
O4	0.7810 (3)	0.1911 (3)	0.2065 (3)	0.0824 (13)
C5	0.7705 (4)	0.1409 (4)	0.5870 (5)	0.0631 (15)
O6	0.8984 (3)	0.1126 (4)	0.7441 (3)	0.0897 (15)
H6	0.9043	0.1049	0.8024	0.108*
O5	0.8031 (4)	0.2180 (5)	0.0673 (4)	0.118 (2)
N5	0.8361 (4)	0.1955 (4)	0.1550 (4)	0.0747 (14)
O3	0.9307 (3)	0.1752 (4)	0.1959 (3)	0.0837 (13)
C7	0.7240 (6)	0.1425 (6)	0.7354 (6)	0.097 (2)
H7	0.7435	0.1375	0.8041	0.116*
C10	0.6671 (5)	0.1583 (6)	0.5319 (6)	0.094 (2)
H10	0.6465	0.1641	0.4632	0.113*
C8	0.6238 (7)	0.1596 (8)	0.6796 (8)	0.129 (4)
H8	0.5750	0.1662	0.7101	0.154*
C9	0.5949 (6)	0.1669 (8)	0.5777 (8)	0.131 (4)
H9	0.5262	0.1778	0.5395	0.157*
O1	1.1075 (3)	0.1222 (3)	0.3888 (3)	0.0616 (10)
N1	1.1819 (3)	0.0725 (3)	0.5489 (3)	0.0519 (10)
H1	1.2402	0.0541	0.5895	0.062*
N3	0.9386 (3)	0.1056 (3)	0.5792 (3)	0.0510 (10)
H3	0.9551	0.0879	0.6396	0.061*
C3	1.1007 (4)	0.0711 (3)	0.5871 (4)	0.0470 (11)
C13	0.9920 (4)	0.4559 (3)	0.4777 (4)	0.0540 (12)
C2	1.1834 (4)	0.0978 (4)	0.4592 (4)	0.0542 (13)
N6	0.5321 (4)	0.1122 (4)	0.2567 (5)	0.0908 (18)
C15	0.8837 (5)	0.3441 (4)	0.3760 (5)	0.0714 (17)
H15	0.8182	0.3272	0.3343	0.086*
C14	0.8962 (4)	0.4273 (4)	0.4146 (5)	0.0675 (16)
H14	0.8398	0.4649	0.3983	0.081*
C16	0.6130 (4)	0.0601 (5)	0.2860 (5)	0.0717 (17)
H16	0.6719	0.0790	0.2747	0.086*
C11	1.0539 (5)	0.3136 (4)	0.4533 (6)	0.089 (2)
H11	1.1093	0.2752	0.4667	0.107*
C12	1.0716 (5)	0.3966 (4)	0.4944 (6)	0.093 (2)
H12	1.1383	0.4126	0.5340	0.111*
C17	0.5353 (8)	0.1979 (6)	0.2137 (8)	0.126 (3)
H17A	0.6029	0.2080	0.2114	0.189*
H17B	0.5198	0.2422	0.2538	0.189*
H17C	0.4852	0.2002	0.1476	0.189*
C18	0.4398 (7)	0.0860 (10)	0.2729 (12)	0.218 (8)
H18A	0.4575	0.0504	0.3316	0.327*
H18B	0.3970	0.0529	0.2167	0.327*
H18C	0.4030	0.1369	0.2811	0.327*
O7	0.6180 (3)	−0.0114 (4)	0.3271 (4)	0.0868 (14)
C1	1.2880 (4)	0.0956 (5)	0.4484 (5)	0.0683 (16)
H1A	1.2857	0.0572	0.3948	0.103*
H1B	1.3385	0.0748	0.5091	0.103*
H1C	1.3062	0.1535	0.4344	0.103*
S1	1.12907 (10)	0.02354 (9)	0.70412 (10)	0.0547 (3)
N7	0.5920 (7)	0.3996 (9)	0.5419 (6)	0.167 (4)
C20	0.6425 (12)	0.4109 (13)	0.4690 (11)	0.249 (9)
H20A	0.5981	0.3896	0.4055	0.374*
H20B	0.7062	0.3788	0.4899	0.374*
H20C	0.6565	0.4719	0.4637	0.374*
C21	0.6531 (8)	0.3997 (10)	0.6491 (8)	0.169 (5)
H21A	0.6078	0.3928	0.6862	0.253*
H21B	0.6897	0.4541	0.6668	0.253*
H21C	0.7016	0.3522	0.6641	0.253*
O8	0.4333 (8)	0.3831 (12)	0.4272 (6)	0.334 (11)
C19	0.4931 (10)	0.3835 (13)	0.5125 (8)	0.235 (10)
H19	0.4658	0.3713	0.5617	0.282*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0399 (2)	0.0541 (3)	0.0550 (3)	0.00047 (16)	0.01226 (17)	−0.00090 (17)
N4	0.050 (3)	0.049 (3)	0.074 (3)	−0.001 (2)	0.012 (2)	−0.001 (2)
O2	0.044 (2)	0.076 (3)	0.063 (2)	0.0082 (18)	0.0158 (18)	0.003 (2)
C4	0.038 (3)	0.051 (3)	0.065 (3)	−0.001 (2)	0.014 (2)	−0.011 (3)
N2	0.036 (2)	0.048 (2)	0.062 (3)	−0.0030 (18)	0.0188 (19)	−0.003 (2)
C6	0.054 (3)	0.086 (4)	0.080 (4)	0.000 (3)	0.034 (3)	−0.010 (3)
O4	0.057 (2)	0.107 (4)	0.083 (3)	−0.004 (2)	0.024 (2)	0.004 (3)
C5	0.049 (3)	0.068 (4)	0.076 (4)	−0.003 (3)	0.026 (3)	−0.012 (3)
O6	0.057 (3)	0.145 (5)	0.070 (3)	0.013 (3)	0.027 (2)	0.010 (3)
O5	0.082 (3)	0.181 (6)	0.073 (3)	0.012 (4)	0.007 (3)	0.047 (4)
N5	0.064 (3)	0.086 (4)	0.064 (3)	0.000 (3)	0.011 (3)	0.010 (3)
O3	0.054 (3)	0.126 (4)	0.068 (3)	0.013 (3)	0.016 (2)	0.016 (3)
C7	0.082 (5)	0.138 (7)	0.089 (5)	0.008 (5)	0.052 (4)	−0.006 (5)
C10	0.047 (4)	0.147 (7)	0.091 (5)	0.008 (4)	0.026 (3)	−0.016 (5)
C8	0.074 (6)	0.217 (12)	0.118 (7)	0.014 (6)	0.062 (5)	−0.008 (7)
C9	0.049 (4)	0.228 (12)	0.120 (7)	0.025 (6)	0.034 (4)	−0.019 (8)
O1	0.043 (2)	0.081 (3)	0.059 (2)	0.0057 (18)	0.0148 (18)	0.0052 (19)
N1	0.033 (2)	0.056 (3)	0.064 (3)	0.0051 (18)	0.0145 (19)	0.001 (2)
N3	0.042 (2)	0.058 (3)	0.054 (2)	0.0056 (19)	0.0178 (19)	−0.002 (2)
C3	0.038 (2)	0.041 (3)	0.058 (3)	−0.001 (2)	0.013 (2)	−0.009 (2)
C13	0.042 (3)	0.051 (3)	0.063 (3)	−0.001 (2)	0.011 (2)	0.002 (2)
C2	0.041 (3)	0.052 (3)	0.068 (3)	−0.005 (2)	0.017 (3)	−0.007 (3)
N6	0.056 (3)	0.108 (5)	0.110 (5)	0.027 (3)	0.032 (3)	0.027 (4)
C15	0.049 (3)	0.061 (4)	0.086 (4)	0.003 (3)	0.002 (3)	−0.010 (3)
C14	0.048 (3)	0.055 (3)	0.086 (4)	0.006 (3)	0.007 (3)	−0.004 (3)
C16	0.039 (3)	0.102 (5)	0.069 (4)	0.004 (3)	0.012 (3)	−0.005 (4)
C11	0.051 (4)	0.060 (4)	0.133 (6)	0.007 (3)	0.003 (4)	−0.024 (4)
C12	0.042 (3)	0.064 (4)	0.144 (7)	−0.002 (3)	−0.002 (4)	−0.031 (4)
C17	0.126 (8)	0.112 (7)	0.150 (9)	0.042 (6)	0.061 (7)	0.028 (7)
C18	0.066 (6)	0.262 (16)	0.35 (2)	0.055 (8)	0.103 (9)	0.148 (15)
O7	0.056 (3)	0.102 (4)	0.096 (3)	0.014 (2)	0.019 (2)	0.022 (3)
C1	0.042 (3)	0.087 (4)	0.081 (4)	0.000 (3)	0.028 (3)	0.000 (3)
S1	0.0464 (7)	0.0602 (8)	0.0516 (7)	0.0013 (6)	0.0098 (6)	−0.0056 (6)
N7	0.105 (6)	0.306 (14)	0.098 (6)	−0.052 (8)	0.043 (5)	0.008 (7)
C20	0.192 (15)	0.40 (3)	0.210 (15)	−0.070 (17)	0.140 (13)	0.001 (17)
C21	0.094 (7)	0.279 (16)	0.115 (8)	−0.040 (9)	0.012 (6)	−0.018 (9)
O8	0.182 (9)	0.72 (3)	0.071 (5)	−0.177 (13)	0.015 (5)	0.056 (9)
C19	0.119 (9)	0.51 (3)	0.070 (6)	−0.087 (13)	0.028 (6)	0.031 (11)

Geometric parameters (Å, º) top

Cd1—O1	2.332 (4)	C13—C14	1.388 (7)
Cd1—O2	2.350 (4)	C13—C13ⁱⁱ	1.476 (10)
Cd1—N4	2.362 (5)	C2—C1	1.509 (7)
Cd1—O3	2.387 (4)	N6—C16	1.317 (8)
Cd1—N2	2.426 (4)	N6—C18	1.433 (10)
Cd1—O4	2.553 (5)	N6—C17	1.456 (10)
Cd1—S1ⁱ	2.6270 (15)	C15—C14	1.373 (8)
N4—C11	1.332 (7)	C15—H15	0.9300
N4—C15	1.336 (7)	C14—H14	0.9300
O2—C4	1.242 (7)	C16—O7	1.232 (8)
C4—N3	1.346 (6)	C16—H16	0.9300
C4—C5	1.499 (8)	C11—C12	1.384 (9)
N2—C3	1.307 (6)	C11—H11	0.9300
N2—N3	1.396 (5)	C12—H12	0.9300
C6—O6	1.361 (8)	C17—H17A	0.9600
C6—C5	1.397 (9)	C17—H17B	0.9600
C6—C7	1.408 (9)	C17—H17C	0.9600
O4—N5	1.237 (6)	C18—H18A	0.9600
C5—C10	1.395 (9)	C18—H18B	0.9600
O6—H6	0.8200	C18—H18C	0.9600
O5—N5	1.229 (7)	C1—H1A	0.9600
N5—O3	1.270 (6)	C1—H1B	0.9600
C7—C8	1.361 (12)	C1—H1C	0.9600
C7—H7	0.9300	S1—Cd1ⁱ	2.6270 (15)
C10—C9	1.382 (10)	N7—C19	1.305 (14)
C10—H10	0.9300	N7—C20	1.458 (13)
C8—C9	1.380 (12)	N7—C21	1.474 (12)
C8—H8	0.9300	C20—H20A	0.9600
C9—H9	0.9300	C20—H20B	0.9600
O1—C2	1.232 (6)	C20—H20C	0.9600
N1—C2	1.352 (7)	C21—H21A	0.9600
N1—C3	1.412 (6)	C21—H21B	0.9600
N1—H1	0.8600	C21—H21C	0.9600
N3—H3	0.8600	O8—C19	1.214 (13)
C3—S1	1.745 (5)	C19—H19	0.9300
C13—C12	1.381 (8)

O1—Cd1—O2	140.93 (13)	N2—C3—S1	125.9 (4)
O1—Cd1—N4	87.55 (15)	N1—C3—S1	116.1 (3)
O2—Cd1—N4	82.21 (15)	C12—C13—C14	115.3 (5)
O1—Cd1—O3	81.83 (14)	C12—C13—C13ⁱⁱ	122.4 (6)
O2—Cd1—O3	134.28 (14)	C14—C13—C13ⁱⁱ	122.3 (6)
N4—Cd1—O3	85.65 (18)	O1—C2—N1	125.1 (5)
O1—Cd1—N2	72.96 (13)	O1—C2—C1	119.6 (5)
O2—Cd1—N2	69.13 (13)	N1—C2—C1	115.3 (5)
N4—Cd1—N2	88.16 (15)	C16—N6—C18	119.0 (8)
O3—Cd1—N2	154.27 (14)	C16—N6—C17	122.1 (7)
O1—Cd1—O4	132.81 (14)	C18—N6—C17	118.8 (7)
O2—Cd1—O4	83.67 (14)	N4—C15—C14	123.3 (5)
N4—Cd1—O4	84.38 (16)	N4—C15—H15	118.3
O3—Cd1—O4	51.27 (14)	C14—C15—H15	118.3
N2—Cd1—O4	152.53 (14)	C15—C14—C13	120.8 (5)
O1—Cd1—S1ⁱ	99.58 (10)	C15—C14—H14	119.6
O2—Cd1—S1ⁱ	94.80 (10)	C13—C14—H14	119.6
N4—Cd1—S1ⁱ	171.58 (11)	O7—C16—N6	126.0 (6)
O3—Cd1—S1ⁱ	90.91 (14)	O7—C16—H16	117.0
N2—Cd1—S1ⁱ	98.16 (10)	N6—C16—H16	117.0
O4—Cd1—S1ⁱ	87.47 (12)	N4—C11—C12	122.8 (6)
C11—N4—C15	116.7 (5)	N4—C11—H11	118.6
C11—N4—Cd1	120.1 (4)	C12—C11—H11	118.6
C15—N4—Cd1	122.1 (4)	C13—C12—C11	121.1 (5)
C4—O2—Cd1	117.7 (3)	C13—C12—H12	119.5
O2—C4—N3	122.0 (5)	C11—C12—H12	119.5
O2—C4—C5	121.0 (5)	N6—C17—H17A	109.5
N3—C4—C5	117.0 (5)	N6—C17—H17B	109.5
C3—N2—N3	114.0 (4)	H17A—C17—H17B	109.5
C3—N2—Cd1	133.8 (3)	N6—C17—H17C	109.5
N3—N2—Cd1	110.3 (3)	H17A—C17—H17C	109.5
O6—C6—C5	118.2 (5)	H17B—C17—H17C	109.5
O6—C6—C7	121.3 (7)	N6—C18—H18A	109.5
C5—C6—C7	120.4 (6)	N6—C18—H18B	109.5
N5—O4—Cd1	92.1 (3)	H18A—C18—H18B	109.5
C10—C5—C6	117.7 (6)	N6—C18—H18C	109.5
C10—C5—C4	116.4 (6)	H18A—C18—H18C	109.5
C6—C5—C4	125.9 (5)	H18B—C18—H18C	109.5
C6—O6—H6	109.5	C2—C1—H1A	109.5
O5—N5—O4	123.0 (6)	C2—C1—H1B	109.5
O5—N5—O3	119.6 (6)	H1A—C1—H1B	109.5
O4—N5—O3	117.4 (5)	C2—C1—H1C	109.5
N5—O3—Cd1	99.2 (3)	H1A—C1—H1C	109.5
C8—C7—C6	120.5 (8)	H1B—C1—H1C	109.5
C8—C7—H7	119.8	C3—S1—Cd1ⁱ	97.32 (16)
C6—C7—H7	119.8	C19—N7—C20	120.1 (10)
C9—C10—C5	121.1 (8)	C19—N7—C21	119.3 (9)
C9—C10—H10	119.4	C20—N7—C21	120.4 (10)
C5—C10—H10	119.4	N7—C20—H20A	109.5
C7—C8—C9	119.8 (7)	N7—C20—H20B	109.5
C7—C8—H8	120.1	H20A—C20—H20B	109.5
C9—C8—H8	120.1	N7—C20—H20C	109.5
C8—C9—C10	120.6 (8)	H20A—C20—H20C	109.5
C8—C9—H9	119.7	H20B—C20—H20C	109.5
C10—C9—H9	119.7	N7—C21—H21A	109.5
C2—O1—Cd1	136.2 (4)	N7—C21—H21B	109.5
C2—N1—C3	130.9 (4)	H21A—C21—H21B	109.5
C2—N1—H1	114.6	N7—C21—H21C	109.5
C3—N1—H1	114.6	H21A—C21—H21C	109.5
C4—N3—N2	120.1 (4)	H21B—C21—H21C	109.5
C4—N3—H3	119.9	O8—C19—N7	126.4 (11)
N2—N3—H3	119.9	O8—C19—H19	116.8
N2—C3—N1	118.1 (5)	N7—C19—H19	116.8

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O7ⁱ	0.86	2.01	2.871 (6)	174
N3—H3···O6	0.86	1.96	2.619 (6)	133
N3—H3···S1	0.86	2.46	2.901 (4)	113
O6—H6···O8ⁱⁱⁱ	0.82	1.70	2.502 (9)	164

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O7ⁱ	0.86	2.01	2.871 (6)	174.1
N3—H3···O6	0.86	1.96	2.619 (6)	132.6
O6—H6···O8ⁱⁱ	0.82	1.70	2.502 (9)	163.8

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

Acknowledgements

This work was supported by the National Training Programs of Innovation and Entrepreneurship for Undergraduates (grant No. 201313470010).

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