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

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.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in solvent or counterion
• R factor = 0.024
• wR factor = 0.075
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          1

Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          8
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          S1

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         25
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................      44.00 Perc.
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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

The water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H 0.84±0.01 Å; their temperature factors were refined.

The sulfate ion is disodered with respect to the oxygen atoms only; these were refined as half-occupancy atoms off the twofold rotation axis. The sulfur–oxygen distances were restrained to within 0.01 Å of each other as were the oxygen–oxygen distances.

Computing details

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

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]

Crystal data

[Cd(C8H12N6)(H2O)4]SO4	F(000) = 952
Mr = 472.76	Dx = 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) Å^3	0.35 × 0.20 × 0.10 mm
Z = 4

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0459P)^2 + 1.6989P] where P = (Fo^2 + 2Fc^2)/3
1922 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.57 e Å^−3
25 restraints	Δρmin = −0.86 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cd1—O1	2.3308 (18)	N1—C1	1.334 (3)
Cd1—O1^i	2.3308 (18)	N1—C2	1.345 (4)
Cd1—O2^i	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—N1^i	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—C4^ii	1.530 (5)
O2—H21	0.84 (3)	C4—H4A	0.9700
O2—H22	0.83 (3)	C4—H4B	0.9700
O2^i—Cd1—O2	180.0	H21—O2—H22	104 (4)
O2^i—Cd1—N1	90.55 (8)	C1—N1—C2	103.1 (2)
O2—Cd1—N1	89.45 (8)	C1—N1—Cd1	130.93 (17)
O2^i—Cd1—N1^i	89.45 (8)	C2—N1—Cd1	125.14 (17)
O2—Cd1—N1^i	90.55 (8)	C1—N2—N3	102.7 (2)
N1—Cd1—N1^i	180.0	C2—N3—N2	109.6 (2)
O2^i—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)
N1^i—Cd1—O1	92.02 (7)	N2—C1—H1	122.6
O2^i—Cd1—O1^i	91.41 (7)	N1—C1—H1	122.6
O2—Cd1—O1^i	88.59 (7)	N3—C2—N1	109.8 (2)
N1—Cd1—O1^i	92.02 (7)	N3—C2—H2	125.1
N1^i—Cd1—O1^i	87.98 (7)	N1—C2—H2	125.1
O1—Cd1—O1^i	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)	C4^ii—C4—C3	113.0 (3)
Cd1—O1—H11	114 (3)	C4^ii—C4—H4A	109.0
Cd1—O1—H12	116 (2)	C3—C4—H4A	109.0
H11—O1—H12	118 (4)	C4^ii—C4—H4B	109.0
Cd1—O2—H21	114 (3)	C3—C4—H4B	109.0
Cd1—O2—H22	131 (3)	H4A—C4—H4B	107.8
O2^i—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)
O1^i—Cd1—N1—C1	65.2 (2)	N2—N3—C2—N1	−0.2 (3)
O2^i—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)
O1^i—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—C4^ii	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)

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···N2^iii	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.