catena-Poly[[tetra­aqua­[μ2-1,4-bis­(1,2,4-triazol-1-yl)butane-κ2N4:N4′]cadmium(II)] sulfate]

Song, J.-J.; Zhang, K.-L.; Ng, S.W.

doi:10.1107/S1600536810045009

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1529

https://doi.org/10.1107/S1600536810045009

Open

access

catena-Poly[[tetraaqua[μ₂-1,4-bis(1,2,4-triazol-1-yl)butane-κ²N⁴:N^4′]cadmium(II)] sulfate]

Jing-Jing Song,^a Kou-Lin Zhang ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 1 November 2010; accepted 3 November 2010; online 10 November 2010)

In the polymeric title compound, {[Cd(C₈H₁₂N₆)(H₂O)₄]SO₄}_n, the Cd^II atom is located on an inversion center and coordinated by four water molecules and two 1,4-bis(1,2,4-triazol-yl)butane ligands in a distorted CdO₄N₂ octahedral geometry. The 1,4-bis(1,2,4-triazol-yl)butane ligand is centrosymmetric, the mid-point of the central C—C bond being located on an inversion center. It links adjacent water-coordinated metal atoms into polymeric chains running along the c axis. Adjacent chains are linked by O—H⋯N hydrogen bonds. The S atom of the sulfate anion is located on a twofold rotation axis, thus the sulfate anion is equally disordered over two sites. The sulfate anion links with the polymeric chains via O—H⋯O hydrogen bonds, generating a three-dimensional supramolecular network.

Related literature

For a related structure, see: Ding et al. (2008 ).

Experimental

Crystal data

[Cd(C₈H₁₂N₆)(H₂O)₄]SO₄
M_r = 472.76
Monoclinic, C 2/c
a = 12.1858 (9) Å
b = 10.9733 (8) Å
c = 12.4916 (9) Å
β = 90.227 (1)°
V = 1670.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 295 K
0.35 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.625, T_max = 0.866
7091 measured reflections
1922 independent reflections
1703 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.075
S = 1.03
1922 reflections
145 parameters
25 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—O1	2.3308 (18)
Cd1—O2	2.2923 (19)
Cd1—N1	2.297 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H11⋯O3	0.84 (3)	1.94 (2)	2.765 (10)	169 (4)
O1—H12⋯N2ⁱ	0.84 (3)	2.04 (1)	2.855 (3)	165 (4)
O2—H21⋯O4	0.84 (3)	1.91 (1)	2.736 (4)	167 (4)
O2—H21⋯O5ⁱⁱ	0.84 (3)	1.79 (2)	2.588 (4)	158 (4)
O2—H22⋯O4ⁱⁱⁱ	0.83 (3)	1.94 (2)	2.749 (4)	162 (4)
O2—H22⋯O6^iv	0.83 (3)	1.99 (2)	2.753 (4)	152 (4)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1; (iv) $[x, -y, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810045009/xu5081sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810045009/xu5081Isup2.hkl

checkCIF report

Comment top

The flexible bis-1,4-(1,2,4-triazol-1-yl)butane ligand binds to a number of cadmium salts to render chain motifs; when the counterion is also capable of bridging, two- and three-dimensional coordination networks are formed. The cadmium atom in polymeric [Cd(H₂O)₄(C₈H₁₂N₆)^2+.SO₄^2–]_n (Scheme I, Fig. 1) lies on a center-of-inversion. The ligand links adjacent water-coordinated metal atoms into a chain; the sulfate ion is not directly involved in coordination to the metal center. Adjacent chains are linked by hydrogen bonds to the disordered sulfate ion to generate a three-dimensional hydrogen-bonded network (Table 1). The metal center shows octahedral coordination.

With cadmium bis(perchlorate) and bis(tetrafluoroborate), the cadmium atom is connected to two ligands, and the six-coordinate geometry is completed by two water molecules (Ding et al., 2008).

Related literature top

For a related structure, see: Ding et al. (2008).

Experimental top

Cadmium sulfate (0.209 g, 0.10 mmol) was dissolved in a water-DFM mixture (5 ml:3 ml), and to this was addded 1,4-bis(1,2,4-triazol-1-yl)butane (0.384 g, 0.20 mmol) dissolved in water (5 ml). The solution was set aside for the growth of colorless crystals.

Structure description top

With cadmium bis(perchlorate) and bis(tetrafluoroborate), the cadmium atom is connected to two ligands, and the six-coordinate geometry is completed by two water molecules (Ding et al., 2008).

For a related structure, see: Ding et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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

Fig. 1. [Thermal ellipsoid plot (Barbour, 2001) of a fragment of the polymeric structure of [Cd(H₂O)₄(C₈H₁₂N₆)^2+.SO₄^2–]_n at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Inversion symmetry-related atoms are not labeled.

catena-Poly[[tetraaqua[µ₂-1,4-bis(1,2,4-triazol-1-yl)butane- κ²N⁴:N^4']cadmium(II)] sulfate] top

Crystal data top

[Cd(C₈H₁₂N₆)(H₂O)₄]SO₄	F(000) = 952
M_r = 472.76	D_x = 1.880 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4284 reflections
a = 12.1858 (9) Å	θ = 2.5–27.6°
b = 10.9733 (8) Å	µ = 1.48 mm⁻¹
c = 12.4916 (9) Å	T = 295 K
β = 90.227 (1)°	Prism, colorless
V = 1670.3 (2) Å³	0.35 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1922 independent reflections
Radiation source: fine-focus sealed tube	1703 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.625, T_max = 0.866	k = −13→14
7091 measured reflections	l = −16→16

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0459P)² + 1.6989P] where P = (F_o² + 2F_c²)/3
1922 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.57 e Å⁻³
25 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

[Cd(C₈H₁₂N₆)(H₂O)₄]SO₄	V = 1670.3 (2) Å³
M_r = 472.76	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.1858 (9) Å	µ = 1.48 mm⁻¹
b = 10.9733 (8) Å	T = 295 K
c = 12.4916 (9) Å	0.35 × 0.20 × 0.10 mm
β = 90.227 (1)°

Data collection top

Bruker SMART APEX diffractometer	1922 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1703 reflections with I > 2σ(I)
T_min = 0.625, T_max = 0.866	R_int = 0.026
7091 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	25 restraints
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.57 e Å⁻³
1922 reflections	Δρ_min = −0.86 e Å⁻³
145 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cd1	0.7500	0.2500	0.5000	0.02963 (11)
S1	0.5000	0.07764 (7)	0.2500	0.02981 (18)
O1	0.60887 (16)	0.34194 (16)	0.40281 (15)	0.0409 (4)
O2	0.65422 (17)	0.07057 (19)	0.50971 (16)	0.0459 (5)
O3	0.4869 (9)	0.2093 (3)	0.2565 (9)	0.0469 (19)	0.50
O4	0.5016 (3)	0.0222 (4)	0.3542 (3)	0.0521 (10)	0.50
O5	0.4146 (3)	0.0243 (4)	0.1823 (3)	0.0525 (11)	0.50
O6	0.6087 (3)	0.0513 (4)	0.1970 (3)	0.0590 (11)	0.50
N1	0.82340 (17)	0.1877 (2)	0.34004 (15)	0.0371 (4)
N2	0.8666 (2)	0.0739 (2)	0.19781 (18)	0.0438 (5)
N3	0.87109 (16)	0.1946 (2)	0.17182 (16)	0.0347 (4)
C1	0.8375 (2)	0.0763 (3)	0.2994 (2)	0.0443 (6)
H1	0.8276	0.0059	0.3396	0.053*
C2	0.8456 (3)	0.2611 (2)	0.2566 (2)	0.0368 (6)
H2	0.8433	0.3458	0.2583	0.044*
C3	0.8972 (2)	0.2345 (2)	0.0628 (2)	0.0393 (6)
H3A	0.9610	0.1902	0.0376	0.047*
H3B	0.9154	0.3205	0.0638	0.047*
C4	0.8012 (2)	0.2132 (3)	−0.0145 (2)	0.0382 (5)
H4A	0.7828	0.1272	−0.0147	0.046*
H4B	0.8239	0.2350	−0.0864	0.046*
H11	0.579 (3)	0.296 (3)	0.358 (2)	0.064 (10)*
H12	0.619 (3)	0.4147 (14)	0.385 (3)	0.062 (10)*
H21	0.616 (3)	0.056 (4)	0.455 (2)	0.078 (12)*
H22	0.618 (3)	0.040 (4)	0.560 (2)	0.088 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03598 (16)	0.03235 (16)	0.02057 (15)	−0.00111 (8)	0.00354 (10)	−0.00067 (8)
S1	0.0366 (4)	0.0257 (4)	0.0271 (4)	0.000	−0.0052 (3)	0.000
O1	0.0520 (10)	0.0321 (10)	0.0386 (9)	−0.0044 (8)	−0.0095 (8)	0.0052 (8)
O2	0.0569 (12)	0.0455 (11)	0.0352 (10)	−0.0168 (9)	−0.0035 (9)	0.0039 (8)
O3	0.063 (5)	0.0271 (13)	0.051 (3)	0.011 (3)	−0.015 (3)	−0.009 (3)
O4	0.060 (2)	0.068 (3)	0.0287 (18)	−0.019 (2)	−0.0095 (17)	0.0215 (18)
O5	0.065 (3)	0.047 (2)	0.045 (2)	−0.019 (2)	−0.028 (2)	0.0080 (18)
O6	0.054 (2)	0.064 (3)	0.059 (3)	0.005 (2)	0.017 (2)	−0.012 (2)
N1	0.0476 (11)	0.0398 (12)	0.0240 (9)	0.0033 (9)	0.0033 (8)	−0.0036 (8)
N2	0.0611 (14)	0.0348 (11)	0.0357 (11)	0.0066 (10)	0.0042 (10)	−0.0007 (9)
N3	0.0382 (10)	0.0387 (11)	0.0273 (10)	−0.0016 (9)	0.0004 (8)	−0.0009 (9)
C1	0.0628 (16)	0.0365 (13)	0.0336 (12)	−0.0015 (12)	0.0049 (12)	0.0030 (10)
C2	0.0476 (15)	0.0340 (13)	0.0287 (13)	−0.0014 (9)	0.0025 (11)	−0.0054 (9)
C3	0.0392 (13)	0.0501 (16)	0.0287 (13)	−0.0042 (10)	0.0063 (11)	0.0036 (10)
C4	0.0464 (14)	0.0427 (13)	0.0254 (11)	−0.0018 (12)	0.0024 (10)	−0.0020 (11)

Geometric parameters (Å, º) top

Cd1—O1	2.3308 (18)	N1—C1	1.334 (3)
Cd1—O1ⁱ	2.3308 (18)	N1—C2	1.345 (4)
Cd1—O2ⁱ	2.2923 (19)	N2—C1	1.319 (3)
Cd1—O2	2.2923 (19)	N2—N3	1.365 (3)
Cd1—N1	2.297 (2)	N3—C2	1.325 (4)
Cd1—N1ⁱ	2.2967 (19)	N3—C3	1.467 (4)
S1—O4	1.437 (3)	C1—H1	0.9300
S1—O3	1.456 (3)	C2—H2	0.9300
S1—O5	1.461 (3)	C3—C4	1.533 (4)
S1—O6	1.511 (3)	C3—H3A	0.9700
O1—H11	0.84 (3)	C3—H3B	0.9700
O1—H12	0.84 (3)	C4—C4ⁱⁱ	1.530 (5)
O2—H21	0.84 (3)	C4—H4A	0.9700
O2—H22	0.83 (3)	C4—H4B	0.9700

O2ⁱ—Cd1—O2	180.0	H21—O2—H22	104 (4)
O2ⁱ—Cd1—N1	90.55 (8)	C1—N1—C2	103.1 (2)
O2—Cd1—N1	89.45 (8)	C1—N1—Cd1	130.93 (17)
O2ⁱ—Cd1—N1ⁱ	89.45 (8)	C2—N1—Cd1	125.14 (17)
O2—Cd1—N1ⁱ	90.55 (8)	C1—N2—N3	102.7 (2)
N1—Cd1—N1ⁱ	180.0	C2—N3—N2	109.6 (2)
O2ⁱ—Cd1—O1	88.59 (7)	C2—N3—C3	129.1 (2)
O2—Cd1—O1	91.41 (7)	N2—N3—C3	121.3 (2)
N1—Cd1—O1	87.98 (7)	N2—C1—N1	114.9 (2)
N1ⁱ—Cd1—O1	92.02 (7)	N2—C1—H1	122.6
O2ⁱ—Cd1—O1ⁱ	91.41 (7)	N1—C1—H1	122.6
O2—Cd1—O1ⁱ	88.59 (7)	N3—C2—N1	109.8 (2)
N1—Cd1—O1ⁱ	92.02 (7)	N3—C2—H2	125.1
N1ⁱ—Cd1—O1ⁱ	87.98 (7)	N1—C2—H2	125.1
O1—Cd1—O1ⁱ	180.0	N3—C3—C4	111.8 (2)
O4—S1—O3	111.7 (4)	N3—C3—H3A	109.3
O4—S1—O5	111.2 (2)	C4—C3—H3A	109.3
O3—S1—O5	110.6 (4)	N3—C3—H3B	109.3
O4—S1—O6	107.9 (2)	C4—C3—H3B	109.3
O3—S1—O6	108.1 (4)	H3A—C3—H3B	107.9
O5—S1—O6	107.1 (2)	C4ⁱⁱ—C4—C3	113.0 (3)
Cd1—O1—H11	114 (3)	C4ⁱⁱ—C4—H4A	109.0
Cd1—O1—H12	116 (2)	C3—C4—H4A	109.0
H11—O1—H12	118 (4)	C4ⁱⁱ—C4—H4B	109.0
Cd1—O2—H21	114 (3)	C3—C4—H4B	109.0
Cd1—O2—H22	131 (3)	H4A—C4—H4B	107.8

O2ⁱ—Cd1—N1—C1	156.6 (2)	N3—N2—C1—N1	−0.1 (3)
O2—Cd1—N1—C1	−23.4 (2)	C2—N1—C1—N2	0.0 (3)
O1—Cd1—N1—C1	−114.8 (2)	Cd1—N1—C1—N2	169.75 (18)
O1ⁱ—Cd1—N1—C1	65.2 (2)	N2—N3—C2—N1	−0.2 (3)
O2ⁱ—Cd1—N1—C2	−35.6 (2)	C3—N3—C2—N1	177.6 (2)
O2—Cd1—N1—C2	144.4 (2)	C1—N1—C2—N3	0.1 (3)
O1—Cd1—N1—C2	52.9 (2)	Cd1—N1—C2—N3	−170.44 (16)
O1ⁱ—Cd1—N1—C2	−127.1 (2)	C2—N3—C3—C4	−103.8 (3)
C1—N2—N3—C2	0.1 (3)	N2—N3—C3—C4	73.7 (3)
C1—N2—N3—C3	−177.9 (2)	N3—C3—C4—C4ⁱⁱ	63.0 (4)

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+3/2, −y+1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O3	0.84 (3)	1.94 (2)	2.765 (10)	169 (4)
O1—H12···N2ⁱⁱⁱ	0.84 (3)	2.04 (1)	2.855 (3)	165 (4)
O2—H21···O4	0.84 (3)	1.91 (1)	2.736 (4)	167 (4)
O2—H21···O5^iv	0.84 (3)	1.79 (2)	2.588 (4)	158 (4)
O2—H22···O4^v	0.83 (3)	1.94 (2)	2.749 (4)	162 (4)
O2—H22···O6^vi	0.83 (3)	1.99 (2)	2.753 (4)	152 (4)

Symmetry codes: (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1, y, −z+1/2; (v) −x+1, −y, −z+1; (vi) x, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cd(C₈H₁₂N₆)(H₂O)₄]SO₄
M_r	472.76
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	12.1858 (9), 10.9733 (8), 12.4916 (9)
β (°)	90.227 (1)
V (Å³)	1670.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.35 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.625, 0.866
No. of measured, independent and observed [I > 2σ(I)] reflections	7091, 1922, 1703
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.075, 1.03
No. of reflections	1922
No. of parameters	145
No. of restraints	25
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.86

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cd1—O1	2.3308 (18)	Cd1—N1	2.297 (2)
Cd1—O2	2.2923 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O3	0.84 (3)	1.94 (2)	2.765 (10)	169 (4)
O1—H12···N2ⁱ	0.84 (3)	2.04 (1)	2.855 (3)	165 (4)
O2—H21···O4	0.84 (3)	1.91 (1)	2.736 (4)	167 (4)
O2—H21···O5ⁱⁱ	0.84 (3)	1.79 (2)	2.588 (4)	158 (4)
O2—H22···O4ⁱⁱⁱ	0.83 (3)	1.94 (2)	2.749 (4)	162 (4)
O2—H22···O6^iv	0.83 (3)	1.99 (2)	2.753 (4)	152 (4)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1, y, −z+1/2; (iii) −x+1, −y, −z+1; (iv) x, −y, z+1/2.

Acknowledgements

We thank the Key Laboratory of Environmental Material and Environmental Engineering of Jiangsu Province, Yangzhou University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ding, J.-G., Liu, X.-G., Li, B.-L., Wang, Y.-Y. & Zhang, Y. (2008). Inorg. Chem. Commun. 11, 1079–1081. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.