Aqua­(4,5-dihydroxy­benzene-1,3-disulfonato-κO)bis­(1,10-phenanthroline-κ2N,N')cadmium(II) monohydrate

Zhang, X.; Ge, C.; Guan, L.; Sun, Z.

doi:10.1107/S1600536807067918

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m396-m397

doi:10.1107/S1600536807067918

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Aqua(4,5-dihydroxybenzene-1,3-disulfonato-κO)bis(1,10-phenanthroline-κ²N,N')cadmium(II) monohydrate

Xiangdong Zhang,^a ^* Chunhua Ge,^a Lei Guan ^a and Zhimin Sun ^a

^aCollege of Chemistry, Liaoning University, Shenyang 110036, People's Republic of China
^*Correspondence e-mail: xdzhang@lnu.edu.cn

(Received 9 December 2007; accepted 20 December 2007; online 23 January 2008)

In the title compound, [Cd(C₆H₄O₈S₂)(C₁₂H₈N₂)₂(H₂O)]·H₂O, each Cd^II ion is coordinated by four N atoms [Cd—N = 2.310 (7)–2.341 (7) Å] from two 1,10-phenanthroline ligands, one O atom [Cd—O = 2.300 (6) Å] from a 4,5-dihydroxybenzene-1,3-disulfonate ligand and one aqua O atom [Cd—O = 2.288 (7) Å] in a distorted octahedral geometry. The crystal packing exhibits intermolecular O—H⋯O and C—H⋯O hydrogen bonds and π–π interactions evidenced by relatively short distances [3.525 (5)–3.937 (6) Å] between the centroids of the six-membered rings of neighbouring molecules.

Related literature

For related literature, see: Haddad & Raymond (1986 ); Riley et al. (1983 ); Sheriff et al. (2003 ); Sun et al. (1995 ).

Experimental

Crystal data

[Cd(C₆H₄O₈S₂)(C₁₂H₈N₂)₂(H₂O)]·H₂O
M_r = 777.05
Monoclinic, P 2₁ /c
a = 16.570 (5) Å
b = 9.330 (3) Å
c = 24.585 (6) Å
β = 127.199 (16)°
V = 3027.5 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.816, T_max = 0.851
6494 measured reflections
5155 independent reflections
3318 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.223
S = 1.16
5155 reflections
426 parameters
H-atom parameters constrained
Δρ_max = 1.32 e Å⁻³
Δρ_min = −2.31 e Å⁻³

Table 1
Centroid-to-centroid distances (Å)

Cg1, Cg2, Cg3, Cg4, Cg5 and Cg6 are the centroids of N2/C6/C9–C12, N3/C13–C17, N4/C18/C21–C24, C4–C9, C16–C21 and C25–C30, respectively

Cg1⋯Cg4ⁱ	3.734 (7)
Cg1⋯Cg6ⁱⁱ	3.937 (6)
Cg2⋯Cg6ⁱⁱⁱ	3.525 (5)
Cg3⋯Cg3^iv	3.900 (7)
Cg4⋯Cg4ⁱ	3.533 (7)
Cg5⋯Cg5^v	3.606 (7)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y-1, z; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z+1; (v) -x, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3	0.82	2.15	2.790 (10)	135
O1—H1B⋯O5^vi	0.82	1.93	2.735 (10)	167
O10—H10A⋯O6^vii	0.82	2.22	2.737 (19)	121
O10—H10B⋯O7	0.82	2.18	2.876 (15)	143
O8—H8⋯O7	0.82	1.87	2.614 (11)	150
O9—H9⋯O4^viii	0.82	1.90	2.690 (9)	160
C23—H23⋯O8^ix	0.93	2.57	3.465 (15)	163
C23—H23⋯O9^ix	0.93	2.40	3.112 (17)	134
Symmetry codes: (vi) -x+1, -y+1, -z+1; (vii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (viii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ix) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067918/cv2375sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067918/cv2375Isup2.hkl

checkCIF report

Comment top

As a multi-group compound, 4,5-dihydroxybenzene-1,3-disulfonic acid (H₂dhds) is a good candidate for investigation of supramolecular assemblies (Haddad & Raymond, 1986; Riley et al., 1983; Sheriff et al., 2003; Sun et al., 1995). Herewith we present the title compound, (I), containing dhds anion as a coordinating ligand.

In (I) (Fig. 1), the dhds anion undoubtedly plays an important role in the formation and stabilization of the three dimesional supramolecular network (Fig.1). Each complex connects with six other complexes by inter-molecular O—H···O and C—H···O hydrogen bonds (Table 2). Significant π···π interactions between pairs of dhds and 1,10-phenanthroline or pairs of 1,10-phenanthrolines exist in (I) (Table 1).

Related literature top

For related literature, see: Haddad & Raymond (1986); Riley et al. (1983); Sheriff et al. (2003); Sun et al. (1995).

Experimental top

In a typical synthesis, hydrated nitrate (0.5 mmol), phen (1 mmol), 4,5-dihydroxybenzene-1,3-disulfonic acid (0.5 mmol) and NaOH (1 mmol) were mixed in ethanol:H₂O (v: v = 1:1, 20 ml) solution. The resulting mixture was stirred for 4 h and the solution was filtered. By slow evaporation of the solvent, block-shape single crystals suitable for X-ray analysis were obtained after several weeks.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a).

Figures top

Fig. 1. View of (I), showing atomic labels and displacement ellipsoids drawn at the 30% probability level. Uncoordinated water and H atoms are omitted for clarity.

Aqua(4,5-dihydroxybenzene-1,3-disulfonato-κO)bis(1,10-phenanthroline- κ²N,N')cadmium(II) monohydrate top

Crystal data top

[Cd(C₆H₄O₈S₂)(C₁₂H₈N₂)₂(H₂O)]·H₂O	F(000) = 1568
M_r = 777.05	D_x = 1.705 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 672 reflections
a = 16.570 (5) Å	θ = 2.4–22.8°
b = 9.330 (3) Å	µ = 0.93 mm⁻¹
c = 24.585 (6) Å	T = 293 K
β = 127.199 (16)°	Block, colourless
V = 3027.5 (15) Å³	0.30 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	5155 independent reflections
Radiation source: fine-focus sealed tube	3318 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −1→19
T_min = 0.816, T_max = 0.851	k = −11→1
6494 measured reflections	l = −29→24

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.223	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.084P)² + 19.1074P] where P = (F_o² + 2F_c²)/3
5155 reflections	(Δ/σ)_max < 0.001
426 parameters	Δρ_max = 1.32 e Å⁻³
0 restraints	Δρ_min = −2.31 e Å⁻³

Crystal data top

[Cd(C₆H₄O₈S₂)(C₁₂H₈N₂)₂(H₂O)]·H₂O	V = 3027.5 (15) Å³
M_r = 777.05	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.570 (5) Å	µ = 0.93 mm⁻¹
b = 9.330 (3) Å	T = 293 K
c = 24.585 (6) Å	0.30 × 0.20 × 0.18 mm
β = 127.199 (16)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5155 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3318 reflections with I > 2σ(I)
T_min = 0.816, T_max = 0.851	R_int = 0.031
6494 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.223	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.084P)² + 19.1074P] where P = (F_o² + 2F_c²)/3
5155 reflections	Δρ_max = 1.32 e Å⁻³
426 parameters	Δρ_min = −2.31 e Å⁻³

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	0.78090 (4)	0.74745 (7)	0.54487 (3)	0.0437 (2)
S1	0.87188 (16)	0.4361 (3)	0.64067 (11)	0.0466 (5)
S2	0.59688 (16)	0.4432 (3)	0.69352 (12)	0.0534 (6)
O1	0.6654 (5)	0.5671 (8)	0.4872 (4)	0.090 (3)
H1A	0.6817	0.4823	0.4953	0.135*
H1B	0.6063	0.5669	0.4528	0.135*
O2	0.8517 (5)	0.5903 (7)	0.6349 (3)	0.0574 (17)
O3	0.8155 (5)	0.3681 (8)	0.5744 (3)	0.0665 (19)
O4	0.9804 (5)	0.4051 (8)	0.6832 (4)	0.0633 (19)
O5	0.5308 (5)	0.4812 (11)	0.6236 (4)	0.084 (3)
O6	0.6305 (7)	0.5630 (14)	0.7383 (6)	0.149 (6)
O7	0.5553 (7)	0.3294 (12)	0.7104 (6)	0.123 (4)
O8	0.7292 (6)	0.1973 (10)	0.7903 (4)	0.072 (2)
H8	0.6746	0.2320	0.7770	0.108*
O9	0.8930 (5)	0.0926 (8)	0.8130 (3)	0.0590 (18)
H9	0.9284	0.0469	0.8062	0.088*
N1	0.6745 (5)	0.9283 (9)	0.4689 (4)	0.0518 (19)
N2	0.7183 (5)	0.8708 (9)	0.5940 (4)	0.0498 (18)
N3	0.9266 (5)	0.8882 (9)	0.5947 (3)	0.0489 (18)
N4	0.8570 (5)	0.6863 (9)	0.4945 (4)	0.0472 (17)
C1	0.6530 (7)	0.9512 (13)	0.4087 (5)	0.064 (3)
H1	0.6733	0.8847	0.3910	0.077*
C2	0.6005 (8)	1.0726 (15)	0.3710 (6)	0.076 (3)
H2	0.5879	1.0885	0.3292	0.092*
C3	0.5669 (8)	1.1702 (14)	0.3957 (6)	0.072 (3)
H3	0.5320	1.2520	0.3707	0.086*
C4	0.5858 (7)	1.1449 (11)	0.4582 (5)	0.057 (2)
C5	0.6410 (6)	1.0214 (10)	0.4939 (5)	0.049 (2)
C6	0.6605 (6)	0.9861 (10)	0.5582 (5)	0.048 (2)
C7	0.5465 (8)	1.2313 (11)	0.4849 (7)	0.066 (3)
H7	0.5101	1.3136	0.4614	0.079*
C8	0.5600 (7)	1.1980 (13)	0.5419 (6)	0.069 (3)
H8A	0.5327	1.2569	0.5576	0.082*
C9	0.6166 (7)	1.0715 (11)	0.5808 (5)	0.054 (2)
C10	0.6308 (8)	1.0324 (13)	0.6411 (6)	0.067 (3)
H10	0.6020	1.0862	0.6572	0.080*
C11	0.6879 (8)	0.9133 (14)	0.6760 (6)	0.066 (3)
H11	0.6971	0.8839	0.7155	0.080*
C12	0.7314 (8)	0.8380 (12)	0.6515 (5)	0.062 (3)
H12	0.7722	0.7598	0.6766	0.074*
C13	0.9588 (7)	0.9896 (11)	0.6411 (5)	0.057 (2)
H13	0.9199	1.0091	0.6559	0.069*
C14	1.0458 (8)	1.0686 (12)	0.6690 (5)	0.071 (3)
H14	1.0646	1.1392	0.7014	0.086*
C15	1.1042 (7)	1.0399 (12)	0.6476 (6)	0.071 (3)
H15	1.1638	1.0905	0.6656	0.085*
C16	1.0720 (7)	0.9326 (12)	0.5979 (5)	0.062 (3)
C17	0.9822 (6)	0.8634 (9)	0.5726 (4)	0.0409 (19)
C18	0.9451 (6)	0.7565 (9)	0.5191 (4)	0.045 (2)
C19	1.1266 (7)	0.9027 (14)	0.5705 (6)	0.072 (3)
H19	1.1869	0.9505	0.5878	0.087*
C20	1.0910 (9)	0.8066 (17)	0.5204 (7)	0.080 (4)
H20	1.1272	0.7883	0.5035	0.096*
C21	0.9986 (8)	0.7317 (11)	0.4924 (5)	0.058 (3)
C22	0.9556 (9)	0.6364 (14)	0.4378 (6)	0.074 (4)
H22	0.9876	0.6206	0.4177	0.089*
C23	0.8671 (10)	0.5656 (12)	0.4130 (6)	0.069 (3)
H23	0.8398	0.4996	0.3776	0.083*
C24	0.8199 (8)	0.5964 (11)	0.4429 (5)	0.060 (3)
H24	0.7587	0.5512	0.4257	0.072*
C25	0.7074 (5)	0.3669 (9)	0.7078 (4)	0.0366 (17)
C26	0.7595 (6)	0.2558 (9)	0.7554 (4)	0.0394 (18)
C27	0.8460 (6)	0.1997 (10)	0.7667 (4)	0.044 (2)
C28	0.8808 (6)	0.2563 (9)	0.7321 (4)	0.0389 (18)
H28	0.9399	0.2209	0.7405	0.047*
C29	0.8279 (6)	0.3649 (9)	0.6853 (4)	0.0371 (18)
C30	0.7408 (6)	0.4223 (10)	0.6727 (4)	0.0425 (19)
H30	0.7059	0.4963	0.6414	0.051*
O10	0.3768 (9)	0.3091 (18)	0.7042 (7)	0.171 (6)
H10A	0.4004	0.2821	0.7429	0.257*
H10B	0.4159	0.2782	0.6971	0.257*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0384 (4)	0.0485 (4)	0.0461 (4)	0.0018 (3)	0.0264 (3)	0.0014 (3)
S1	0.0409 (11)	0.0553 (14)	0.0491 (12)	0.0034 (10)	0.0300 (10)	0.0058 (11)
S2	0.0349 (11)	0.0722 (17)	0.0523 (13)	0.0129 (11)	0.0259 (10)	0.0076 (12)
O1	0.054 (4)	0.060 (5)	0.088 (6)	−0.013 (4)	0.007 (4)	0.008 (4)
O2	0.055 (4)	0.063 (4)	0.054 (4)	0.008 (3)	0.033 (3)	0.008 (3)
O3	0.075 (5)	0.076 (5)	0.059 (4)	0.005 (4)	0.046 (4)	−0.004 (4)
O4	0.041 (3)	0.065 (5)	0.092 (5)	0.009 (3)	0.044 (4)	0.013 (4)
O5	0.042 (4)	0.130 (8)	0.071 (5)	0.031 (4)	0.029 (4)	0.031 (5)
O6	0.056 (5)	0.181 (12)	0.154 (9)	0.017 (6)	0.034 (6)	−0.089 (9)
O7	0.078 (6)	0.142 (9)	0.194 (11)	0.045 (6)	0.107 (7)	0.087 (9)
O8	0.062 (4)	0.098 (6)	0.073 (5)	0.017 (4)	0.050 (4)	0.029 (4)
O9	0.054 (4)	0.074 (5)	0.058 (4)	0.027 (3)	0.039 (3)	0.025 (4)
N1	0.034 (4)	0.075 (6)	0.044 (4)	0.002 (4)	0.022 (3)	0.000 (4)
N2	0.041 (4)	0.063 (5)	0.049 (4)	−0.001 (4)	0.029 (3)	−0.004 (4)
N3	0.036 (4)	0.059 (5)	0.039 (4)	−0.002 (3)	0.016 (3)	−0.001 (4)
N4	0.047 (4)	0.049 (4)	0.044 (4)	−0.003 (4)	0.027 (3)	−0.002 (4)
C1	0.051 (5)	0.087 (8)	0.063 (6)	0.002 (6)	0.038 (5)	0.005 (6)
C2	0.058 (6)	0.104 (10)	0.067 (7)	0.019 (7)	0.038 (6)	0.025 (7)
C3	0.052 (6)	0.073 (8)	0.071 (7)	0.008 (6)	0.027 (5)	0.014 (6)
C4	0.043 (5)	0.054 (6)	0.069 (6)	0.002 (4)	0.031 (5)	−0.001 (5)
C5	0.032 (4)	0.050 (6)	0.060 (5)	−0.004 (4)	0.025 (4)	−0.002 (4)
C6	0.032 (4)	0.053 (6)	0.057 (5)	−0.003 (4)	0.026 (4)	−0.001 (4)
C7	0.050 (6)	0.046 (6)	0.084 (8)	0.006 (4)	0.032 (6)	−0.009 (5)
C8	0.044 (5)	0.064 (7)	0.087 (8)	−0.005 (5)	0.034 (6)	−0.026 (6)
C9	0.040 (5)	0.059 (6)	0.057 (5)	−0.017 (4)	0.026 (4)	−0.017 (5)
C10	0.054 (6)	0.084 (8)	0.073 (7)	−0.019 (6)	0.044 (6)	−0.034 (6)
C11	0.067 (6)	0.090 (9)	0.061 (6)	−0.014 (6)	0.048 (6)	−0.017 (6)
C12	0.057 (6)	0.066 (7)	0.058 (6)	0.000 (5)	0.033 (5)	0.004 (5)
C13	0.055 (5)	0.057 (6)	0.046 (5)	−0.004 (5)	0.024 (4)	−0.011 (5)
C14	0.056 (6)	0.052 (6)	0.060 (6)	−0.007 (5)	0.011 (5)	−0.007 (5)
C15	0.039 (5)	0.061 (7)	0.069 (7)	−0.009 (5)	0.010 (5)	0.005 (6)
C16	0.034 (5)	0.070 (7)	0.057 (6)	0.014 (5)	0.016 (4)	0.017 (5)
C17	0.029 (4)	0.034 (4)	0.044 (5)	0.005 (3)	0.015 (4)	0.012 (4)
C18	0.043 (4)	0.049 (5)	0.044 (4)	0.008 (4)	0.027 (4)	0.014 (4)
C19	0.042 (5)	0.087 (9)	0.090 (8)	−0.001 (5)	0.041 (6)	0.039 (7)
C20	0.054 (6)	0.110 (10)	0.092 (9)	0.017 (7)	0.052 (7)	0.023 (8)
C21	0.058 (5)	0.068 (7)	0.061 (6)	0.018 (5)	0.043 (5)	0.032 (5)
C22	0.094 (9)	0.094 (9)	0.064 (7)	0.040 (7)	0.063 (7)	0.024 (7)
C23	0.092 (8)	0.058 (7)	0.065 (7)	0.006 (6)	0.052 (7)	0.006 (5)
C24	0.065 (6)	0.057 (6)	0.054 (6)	0.003 (5)	0.034 (5)	−0.004 (5)
C25	0.028 (4)	0.042 (5)	0.035 (4)	0.005 (3)	0.016 (3)	−0.003 (4)
C26	0.037 (4)	0.051 (5)	0.034 (4)	0.001 (4)	0.023 (3)	−0.007 (4)
C27	0.033 (4)	0.054 (5)	0.037 (4)	0.008 (4)	0.017 (4)	0.004 (4)
C28	0.031 (4)	0.047 (5)	0.040 (4)	0.010 (4)	0.021 (3)	−0.006 (4)
C29	0.032 (4)	0.044 (5)	0.032 (4)	−0.003 (3)	0.018 (3)	0.000 (4)
C30	0.033 (4)	0.051 (5)	0.039 (4)	0.007 (4)	0.020 (4)	0.007 (4)
O10	0.119 (10)	0.232 (16)	0.159 (12)	0.043 (11)	0.082 (9)	0.040 (12)

Geometric parameters (Å, º) top

Cd1—O1	2.285 (7)	C7—H7	0.9300
Cd1—O2	2.299 (6)	C8—C9	1.450 (16)
Cd1—N4	2.310 (7)	C8—H8A	0.9300
Cd1—N2	2.319 (7)	C9—C10	1.400 (15)
Cd1—N1	2.337 (8)	C10—C11	1.372 (16)
Cd1—N3	2.341 (7)	C10—H10	0.9300
S1—O3	1.446 (7)	C11—C12	1.378 (14)
S1—O4	1.461 (6)	C11—H11	0.9300
S1—O2	1.464 (7)	C12—H12	0.9300
S1—C29	1.772 (8)	C13—C14	1.376 (15)
S2—O5	1.415 (7)	C13—H13	0.9300
S2—O6	1.425 (10)	C14—C15	1.380 (17)
S2—O7	1.455 (9)	C14—H14	0.9300
S2—C25	1.791 (7)	C15—C16	1.411 (16)
O1—H1A	0.8205	C15—H15	0.9300
O1—H1B	0.8202	C16—C17	1.377 (13)
O8—C26	1.343 (11)	C16—C19	1.445 (15)
O8—H8	0.8200	C17—C18	1.457 (12)
O9—C27	1.352 (11)	C18—C21	1.406 (13)
O9—H9	0.8200	C19—C20	1.337 (18)
N1—C1	1.312 (12)	C19—H19	0.9300
N1—C5	1.363 (12)	C20—C21	1.425 (16)
N2—C12	1.330 (12)	C20—H20	0.9300
N2—C6	1.353 (12)	C21—C22	1.394 (16)
N3—C13	1.320 (12)	C22—C23	1.370 (17)
N3—C17	1.343 (11)	C22—H22	0.9300
N4—C24	1.322 (12)	C23—C24	1.390 (15)
N4—C18	1.362 (11)	C23—H23	0.9300
C1—C2	1.387 (16)	C24—H24	0.9300
C1—H1	0.9300	C25—C30	1.377 (11)
C2—C3	1.385 (16)	C25—C26	1.403 (11)
C2—H2	0.9300	C26—C27	1.387 (11)
C3—C4	1.390 (15)	C27—C28	1.389 (12)
C3—H3	0.9300	C28—C29	1.378 (11)
C4—C5	1.402 (14)	C28—H28	0.9300
C4—C7	1.422 (15)	C29—C30	1.388 (11)
C5—C6	1.445 (13)	C30—H30	0.9300
C6—C9	1.402 (13)	O10—H10A	0.8197
C7—C8	1.315 (17)	O10—H10B	0.8197

Cg1···Cg4ⁱ	3.734 (7)	Cg3···Cg3^iv	3.900 (7)
Cg1···Cg6ⁱⁱ	3.937 (6)	Cg4···Cg4ⁱ	3.533 (7)
Cg2···Cg6ⁱⁱⁱ	3.525 (5)	Cg5···Cg5^v	3.606 (7)

O1—Cd1—O2	82.9 (3)	C9—C8—H8A	119.3
O1—Cd1—N4	90.6 (3)	C10—C9—C6	118.4 (10)
O2—Cd1—N4	103.4 (3)	C10—C9—C8	122.6 (10)
O1—Cd1—N2	102.6 (3)	C6—C9—C8	118.9 (9)
O2—Cd1—N2	86.8 (3)	C11—C10—C9	119.0 (10)
N4—Cd1—N2	164.4 (3)	C11—C10—H10	120.5
O1—Cd1—N1	95.3 (3)	C9—C10—H10	120.5
O2—Cd1—N1	158.3 (2)	C10—C11—C12	119.0 (10)
N4—Cd1—N1	98.2 (3)	C10—C11—H11	120.5
N2—Cd1—N1	72.5 (3)	C12—C11—H11	120.5
O1—Cd1—N3	161.8 (3)	N2—C12—C11	123.6 (11)
O2—Cd1—N3	95.1 (2)	N2—C12—H12	118.2
N4—Cd1—N3	72.2 (3)	C11—C12—H12	118.2
N2—Cd1—N3	95.4 (3)	N3—C13—C14	124.7 (10)
N1—Cd1—N3	93.1 (3)	N3—C13—H13	117.7
O3—S1—O4	113.4 (4)	C14—C13—H13	117.7
O3—S1—O2	111.6 (4)	C13—C14—C15	118.1 (10)
O4—S1—O2	112.0 (4)	C13—C14—H14	121.0
O3—S1—C29	107.9 (4)	C15—C14—H14	121.0
O4—S1—C29	105.7 (4)	C14—C15—C16	118.8 (10)
O2—S1—C29	105.9 (4)	C14—C15—H15	120.6
O5—S2—O6	113.4 (7)	C16—C15—H15	120.6
O5—S2—O7	112.1 (6)	C17—C16—C15	117.6 (10)
O6—S2—O7	112.6 (8)	C17—C16—C19	120.6 (10)
O5—S2—C25	106.7 (4)	C15—C16—C19	121.6 (11)
O6—S2—C25	106.5 (5)	N3—C17—C16	123.7 (9)
O7—S2—C25	104.9 (5)	N3—C17—C18	117.6 (7)
Cd1—O1—H1A	122.0	C16—C17—C18	118.7 (8)
Cd1—O1—H1B	132.2	N4—C18—C21	121.5 (9)
H1A—O1—H1B	105.1	N4—C18—C17	119.0 (7)
S1—O2—Cd1	132.3 (4)	C21—C18—C17	119.5 (8)
C26—O8—H8	109.5	C20—C19—C16	120.4 (10)
C27—O9—H9	109.5	C20—C19—H19	119.8
C1—N1—C5	119.9 (9)	C16—C19—H19	119.8
C1—N1—Cd1	125.3 (7)	C19—C20—C21	121.5 (11)
C5—N1—Cd1	114.5 (6)	C19—C20—H20	119.3
C12—N2—C6	118.2 (8)	C21—C20—H20	119.3
C12—N2—Cd1	127.0 (7)	C22—C21—C18	117.1 (10)
C6—N2—Cd1	114.8 (6)	C22—C21—C20	123.6 (10)
C13—N3—C17	117.1 (8)	C18—C21—C20	119.3 (11)
C13—N3—Cd1	127.2 (7)	C23—C22—C21	121.5 (10)
C17—N3—Cd1	115.7 (6)	C23—C22—H22	119.3
C24—N4—C18	118.9 (8)	C21—C22—H22	119.3
C24—N4—Cd1	125.6 (7)	C22—C23—C24	117.3 (11)
C18—N4—Cd1	115.4 (6)	C22—C23—H23	121.4
N1—C1—C2	121.3 (11)	C24—C23—H23	121.4
N1—C1—H1	119.4	N4—C24—C23	123.7 (10)
C2—C1—H1	119.4	N4—C24—H24	118.2
C3—C2—C1	120.0 (11)	C23—C24—H24	118.2
C3—C2—H2	120.0	C30—C25—C26	121.5 (7)
C1—C2—H2	120.0	C30—C25—S2	118.6 (6)
C2—C3—C4	119.5 (11)	C26—C25—S2	119.8 (6)
C2—C3—H3	120.3	O8—C26—C27	117.3 (8)
C4—C3—H3	120.3	O8—C26—C25	123.7 (7)
C3—C4—C5	117.2 (10)	C27—C26—C25	119.0 (7)
C3—C4—C7	123.7 (10)	O9—C27—C26	116.5 (8)
C5—C4—C7	119.0 (10)	O9—C27—C28	123.7 (7)
N1—C5—C4	122.0 (9)	C26—C27—C28	119.7 (8)
N1—C5—C6	117.8 (8)	C29—C28—C27	120.1 (7)
C4—C5—C6	120.1 (9)	C29—C28—H28	120.0
N2—C6—C9	121.8 (9)	C27—C28—H28	120.0
N2—C6—C5	119.7 (8)	C28—C29—C30	121.3 (7)
C9—C6—C5	118.5 (9)	C28—C29—S1	120.1 (6)
C8—C7—C4	121.8 (11)	C30—C29—S1	118.6 (6)
C8—C7—H7	119.1	C25—C30—C29	118.3 (8)
C4—C7—H7	119.1	C25—C30—H30	120.9
C7—C8—C9	121.4 (10)	C29—C30—H30	120.9
C7—C8—H8A	119.3	H10A—O10—H10B	104.8

O3—S1—O2—Cd1	−16.4 (7)	N2—C6—C9—C8	176.7 (8)
O4—S1—O2—Cd1	111.8 (5)	C5—C6—C9—C8	−4.7 (12)
C29—S1—O2—Cd1	−133.5 (5)	C7—C8—C9—C10	−179.0 (10)
O1—Cd1—O2—S1	44.5 (6)	C7—C8—C9—C6	2.2 (15)
N4—Cd1—O2—S1	−44.4 (6)	C6—C9—C10—C11	0.7 (14)
N2—Cd1—O2—S1	147.6 (5)	C8—C9—C10—C11	−178.1 (9)
N1—Cd1—O2—S1	130.8 (7)	C9—C10—C11—C12	1.5 (15)
N3—Cd1—O2—S1	−117.3 (5)	C6—N2—C12—C11	1.2 (15)
O1—Cd1—N1—C1	−76.7 (8)	Cd1—N2—C12—C11	−177.0 (8)
O2—Cd1—N1—C1	−160.6 (8)	C10—C11—C12—N2	−2.6 (16)
N4—Cd1—N1—C1	14.7 (8)	C17—N3—C13—C14	−1.5 (15)
N2—Cd1—N1—C1	−178.2 (9)	Cd1—N3—C13—C14	179.5 (8)
N3—Cd1—N1—C1	87.1 (8)	N3—C13—C14—C15	−0.3 (17)
O1—Cd1—N1—C5	108.9 (6)	C13—C14—C15—C16	0.6 (16)
O2—Cd1—N1—C5	25.0 (11)	C14—C15—C16—C17	1.0 (15)
N4—Cd1—N1—C5	−159.7 (6)	C14—C15—C16—C19	176.5 (10)
N2—Cd1—N1—C5	7.4 (6)	C13—N3—C17—C16	3.3 (13)
N3—Cd1—N1—C5	−87.3 (6)	Cd1—N3—C17—C16	−177.7 (7)
O1—Cd1—N2—C12	82.3 (8)	C13—N3—C17—C18	−177.2 (8)
O2—Cd1—N2—C12	0.3 (8)	Cd1—N3—C17—C18	1.9 (9)
N4—Cd1—N2—C12	−131.1 (10)	C15—C16—C17—N3	−3.0 (14)
N1—Cd1—N2—C12	173.9 (8)	C19—C16—C17—N3	−178.6 (8)
N3—Cd1—N2—C12	−94.5 (8)	C15—C16—C17—C18	177.4 (8)
O1—Cd1—N2—C6	−96.0 (6)	C19—C16—C17—C18	1.8 (13)
O2—Cd1—N2—C6	−178.0 (6)	C24—N4—C18—C21	−2.1 (13)
N4—Cd1—N2—C6	50.6 (12)	Cd1—N4—C18—C21	−178.9 (6)
N1—Cd1—N2—C6	−4.4 (6)	C24—N4—C18—C17	175.5 (8)
N3—Cd1—N2—C6	87.2 (6)	Cd1—N4—C18—C17	−1.2 (10)
O1—Cd1—N3—C13	−163.2 (9)	N3—C17—C18—N4	−0.5 (11)
O2—Cd1—N3—C13	−80.4 (8)	C16—C17—C18—N4	179.1 (8)
N4—Cd1—N3—C13	177.1 (8)	N3—C17—C18—C21	177.2 (8)
N2—Cd1—N3—C13	6.8 (8)	C16—C17—C18—C21	−3.2 (12)
N1—Cd1—N3—C13	79.5 (8)	C17—C16—C19—C20	−0.4 (16)
O1—Cd1—N3—C17	17.8 (12)	C15—C16—C19—C20	−175.8 (11)
O2—Cd1—N3—C17	100.6 (6)	C16—C19—C20—C21	0.3 (18)
N4—Cd1—N3—C17	−1.8 (6)	N4—C18—C21—C22	2.5 (13)
N2—Cd1—N3—C17	−172.1 (6)	C17—C18—C21—C22	−175.2 (8)
N1—Cd1—N3—C17	−99.4 (6)	N4—C18—C21—C20	−179.3 (9)
O1—Cd1—N4—C24	11.1 (8)	C17—C18—C21—C20	3.1 (13)
O2—Cd1—N4—C24	93.9 (8)	C19—C20—C21—C22	176.4 (11)
N2—Cd1—N4—C24	−136.4 (10)	C19—C20—C21—C18	−1.7 (17)
N1—Cd1—N4—C24	−84.3 (8)	C18—C21—C22—C23	−2.6 (15)
N3—Cd1—N4—C24	−174.9 (8)	C20—C21—C22—C23	179.3 (11)
O1—Cd1—N4—C18	−172.4 (6)	C21—C22—C23—C24	2.3 (16)
O2—Cd1—N4—C18	−89.6 (6)	C18—N4—C24—C23	1.8 (15)
N2—Cd1—N4—C18	40.1 (12)	Cd1—N4—C24—C23	178.2 (8)
N1—Cd1—N4—C18	92.2 (6)	C22—C23—C24—N4	−1.9 (16)
N3—Cd1—N4—C18	1.6 (6)	O5—S2—C25—C30	35.7 (8)
C5—N1—C1—C2	3.1 (15)	O6—S2—C25—C30	−85.7 (9)
Cd1—N1—C1—C2	−171.0 (8)	O7—S2—C25—C30	154.8 (8)
N1—C1—C2—C3	−2.1 (17)	O5—S2—C25—C26	−146.1 (7)
C1—C2—C3—C4	−0.3 (17)	O6—S2—C25—C26	92.5 (9)
C2—C3—C4—C5	1.5 (15)	O7—S2—C25—C26	−27.0 (9)
C2—C3—C4—C7	−173.9 (10)	C30—C25—C26—O8	−179.2 (8)
C1—N1—C5—C4	−1.8 (13)	S2—C25—C26—O8	2.6 (12)
Cd1—N1—C5—C4	172.9 (7)	C30—C25—C26—C27	−0.7 (12)
C1—N1—C5—C6	175.7 (8)	S2—C25—C26—C27	−178.9 (6)
Cd1—N1—C5—C6	−9.6 (10)	O8—C26—C27—O9	−1.2 (12)
C3—C4—C5—N1	−0.5 (14)	C25—C26—C27—O9	−179.8 (8)
C7—C4—C5—N1	175.2 (9)	O8—C26—C27—C28	−179.9 (8)
C3—C4—C5—C6	−178.0 (9)	C25—C26—C27—C28	1.5 (13)
C7—C4—C5—C6	−2.3 (13)	O9—C27—C28—C29	179.5 (8)
C12—N2—C6—C9	1.2 (13)	C26—C27—C28—C29	−1.9 (13)
Cd1—N2—C6—C9	179.7 (6)	C27—C28—C29—C30	1.5 (12)
C12—N2—C6—C5	−177.3 (8)	C27—C28—C29—S1	−179.5 (6)
Cd1—N2—C6—C5	1.1 (10)	O3—S1—C29—C28	98.1 (7)
N1—C5—C6—N2	5.9 (12)	O4—S1—C29—C28	−23.4 (8)
C4—C5—C6—N2	−176.6 (8)	O2—S1—C29—C28	−142.3 (7)
N1—C5—C6—C9	−172.7 (8)	O3—S1—C29—C30	−82.8 (8)
C4—C5—C6—C9	4.9 (13)	O4—S1—C29—C30	155.6 (7)
C3—C4—C7—C8	175.0 (11)	O2—S1—C29—C30	36.7 (8)
C5—C4—C7—C8	−0.4 (15)	C26—C25—C30—C29	0.3 (12)
C4—C7—C8—C9	0.4 (16)	S2—C25—C30—C29	178.5 (6)
N2—C6—C9—C10	−2.2 (13)	C28—C29—C30—C25	−0.7 (12)
C5—C6—C9—C10	176.4 (8)	S1—C29—C30—C25	−179.7 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3	0.82	2.15	2.790 (10)	135
O1—H1B···O5^vi	0.82	1.93	2.735 (10)	167
O10—H10A···O6^vii	0.82	2.22	2.737 (19)	121
O10—H10B···O7	0.82	2.18	2.876 (15)	143
O8—H8···O7	0.82	1.87	2.614 (11)	150
O9—H9···O4^viii	0.82	1.90	2.690 (9)	160
C23—H23···O8^ix	0.93	2.57	3.465 (15)	163
C23—H23···O9^ix	0.93	2.40	3.112 (17)	134

Symmetry codes: (vi) −x+1, −y+1, −z+1; (vii) −x+1, y−1/2, −z+3/2; (viii) −x+2, y−1/2, −z+3/2; (ix) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Cd(C₆H₄O₈S₂)(C₁₂H₈N₂)₂(H₂O)]·H₂O
M_r	777.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	16.570 (5), 9.330 (3), 24.585 (6)
β (°)	127.199 (16)
V (Å³)	3027.5 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.30 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.816, 0.851
No. of measured, independent and observed [I > 2σ(I)] reflections	6494, 5155, 3318
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.223, 1.16
No. of reflections	5155
No. of parameters	426
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.084P)² + 19.1074P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.32, −2.31

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Selected interatomic distances (Å) top

Cg1···Cg4ⁱ	3.734 (7)	Cg3···Cg3^iv	3.900 (7)
Cg1···Cg6ⁱⁱ	3.937 (6)	Cg4···Cg4ⁱ	3.533 (7)
Cg2···Cg6ⁱⁱⁱ	3.525 (5)	Cg5···Cg5^v	3.606 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3	0.82	2.15	2.790 (10)	134.9
O1—H1B···O5^vi	0.82	1.93	2.735 (10)	166.5
O10—H10A···O6^vii	0.82	2.22	2.737 (19)	121.0
O10—H10B···O7	0.82	2.18	2.876 (15)	142.5
O8—H8···O7	0.82	1.87	2.614 (11)	150.1
O9—H9···O4^viii	0.82	1.90	2.690 (9)	160.1
C23—H23···O8^ix	0.93	2.57	3.465 (15)	163
C23—H23···O9^ix	0.93	2.40	3.112 (17)	134

Symmetry codes: (vi) −x+1, −y+1, −z+1; (vii) −x+1, y−1/2, −z+3/2; (viii) −x+2, y−1/2, −z+3/2; (ix) x, −y+1/2, z−1/2.

Acknowledgements

This project was supported by the Natural Science Foundation of the Education Bureau of Liaoning Province (grant No. 05L159).

References

Bruker (2001). SMART (Version 5.624), SAINT (Version 6.04) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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