Hexaaqua­cadmium(II) bis­{[1-(4-hydroxy­phen­yl)-1H-tetra­zol-5-ylsulfan­yl]acetate}

In the title complex, [Cd(H₂O)₆](C₉H₇N₄O₃S)₂, the metal center is six-coordinate, forming an ideal centrosymmetric octa­hedral geometry. A three-dimensional supra­molecular architecture is formed through hydrogen-bonding (O—H...O) and offset π–π stacking inter­actions (distance between pairs of adjacent benzene rings = 3.532 Å and centroid-to-centroid separation = 3.672 Å).

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.025
• wR factor = 0.068
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.64
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cd1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.47
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          6

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1         (2)       2.21
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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

Beside the field of molecular chemistry based on the covalent bond, the chemistry of molecular assemblies and of intermolecular bond (Steed et al., 2000) has become a new fascinating area of interest in the last two decades (Subramanian et al., 1994). Efforts have been done to design and construct such kind of assemblies due to their potential multi-dimensional applications in the field of catalysis, non-linear optics, electrical conductivity, molecular recognition, and crystal engineering (Chen et al.,1993; Desiraju,1995). Recently, we have concentrated our attention on using H₂L (synthesized from 1-(4-hydroxyphenyl)-5-mercaptotetrazole as bridging spacer to obtain polynuclear complexes of transition-metal. Here, the synthesis and crystal structure of [Cd(H₂O)₆](HL)₂, (I), is presented.

The neutral compound consists of one [Cd(H₂O)₆]²⁺ cation and two HL^- anions, as shown in Fig. 1, in which the complex has a crystallographic center with the Zn atom situated at the center of (0. 1/2, 0). In the cations, the Cd atom is surrounded by six aqua ligands, exhibiting an ideal octahedral geometry·On the other hand, the bond lengths within the mercaptotetrazole segment exhibit the expected pattern of four long bonds [S(1)—C(7), N(1)—N(2), N(3)—N(4) and C(7)—N(1)] and two short bonds [N(2)—N(3) and C(7)—N(4)] on the whole. As shown in Fig. 2, there exist offset-panel π-π stacking interactions. The distance between the two adjacent benzene rings is 3.532 Å (centroid separation is 3.672 Å). Also intermolecular O—H···O, O—H···N hydrogen bonds are observed. Thus, all of the hydrogen bonding interactions makes the title compound extend into a three-dimensional supramolecular framework as well as the offset-panel π-π stacking interactions (Zhang et al.,2007).

Related literature

For related literature, see: Chen & Suslick (1993); Desiraju et al.(1995); Steed & Atwood (2000); Subramanian & Zaworotko (1994); Zhang et al.(2007); Zhou et al. (1998)

S2. Experimental

The synthesis of legand H₂L was prepared according to the literature (Zhou, 1998). The compound were prepared by mixing 1:2 molar ratio of cadmium chloridate and H₂L in ethanol-water(1:1,16 ml). The mixture was refluxed at 323 K for 2 h with stirring, then filtered and left to stand at the room temperature. Well shaped crystals suitable for X-ray analyses were obtained by slow evaporation of the filtrate in ca 40–50% yields within about a week.

S3. Refinement

The H atoms bonded to C atoms were positioned geometrically and refined using a riding model [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. The H atoms bonded to O atoms were located in a difference Fourier maps and their positions were refined isotropically, with O—H distances fixed by O—H = 0.85 (2) Å and H···H = 1.30 (2) Å, their displacement parameters were set to 1.5U_eq(O).

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL (Bruker, 2002).

Figures

	Fig. 1. View of the molecule of (I), showing the atom-numbering scheme. Displacement ellipsoids plotted at 30% probability level. [The atoms labelled with 'A' are related to the center of inversion].
	Fig. 2. Packing diagram for the title compound. The O—H···O hydrogen bonds and O—H···N interactions are depicted by dashed lines.

Hexaaquacadmium(II) bis{[1-(4-hydroxyphenyl)-1H-tetrazol-5-ylsulfanyl]acetate}

Crystal data

[Cd(H2O)6](C9H7N4O3S)2	Z = 1
Mr = 722.99	F(000) = 366
Triclinic, P1	Dx = 1.771 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6872 (2) Å	Cell parameters from 3100 reflections
b = 7.1478 (2) Å	θ = 2.8–26.6°
c = 15.0725 (5) Å	µ = 1.04 mm^−1
α = 98.270 (1)°	T = 296 K
β = 97.013 (1)°	Sheet, colourless
γ = 105.353 (1)°	0.49 × 0.26 × 0.03 mm
V = 677.76 (4) Å^3

Data collection

Bruker APEXII area-detector diffractometer	3099 independent reflections
Radiation source: fine-focus sealed tube	3009 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 27.6°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.650, Tmax = 0.965	k = −9→8
10159 measured reflections	l = −19→19

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0457P)^2 + 0.2797P] where P = (Fo^2 + 2Fc^2)/3
3099 reflections	(Δ/σ)max < 0.001
211 parameters	Δρmax = 0.90 e Å^−3
9 restraints	Δρmin = −0.25 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 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 (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.5000	0.0000	0.0000	0.03204 (8)
S1	0.60568 (7)	0.61474 (8)	0.29716 (3)	0.03853 (12)
O1	1.1690 (2)	0.7681 (3)	0.72338 (9)	0.0452 (4)
H1B	1.0600	0.7148	0.7407	0.068*
O1W	0.5334 (2)	−0.0704 (3)	−0.14842 (10)	0.0492 (4)
H1WA	0.629 (4)	−0.016 (5)	−0.174 (2)	0.088 (12)*
H1WB	0.427 (3)	−0.120 (4)	−0.1879 (16)	0.055 (8)*
O2	0.1602 (2)	0.4141 (2)	0.08721 (10)	0.0419 (3)
O2W	0.7407 (2)	0.3043 (2)	0.02541 (11)	0.0455 (4)
H2WA	0.862 (3)	0.319 (5)	0.049 (2)	0.084 (11)*
H2WB	0.753 (5)	0.375 (4)	−0.0139 (17)	0.064 (9)*
O3	0.1891 (2)	0.4057 (3)	0.23510 (11)	0.0554 (5)
O3W	0.2335 (3)	0.1271 (3)	−0.04036 (11)	0.0503 (4)
H3WA	0.196 (5)	0.150 (5)	−0.0907 (12)	0.072 (10)*
H3WB	0.216 (5)	0.213 (4)	−0.0029 (15)	0.068 (9)*
N1	1.0318 (2)	0.7871 (2)	0.35349 (10)	0.0315 (3)
N2	1.2008 (2)	0.8777 (3)	0.31828 (12)	0.0393 (4)
N3	1.1337 (3)	0.8776 (3)	0.23480 (12)	0.0420 (4)
N4	0.9232 (2)	0.7909 (3)	0.21196 (11)	0.0371 (4)
C1	1.1286 (3)	0.7665 (3)	0.63276 (12)	0.0333 (4)
C2	1.2963 (3)	0.8031 (4)	0.58578 (14)	0.0421 (5)
H2	1.4325	0.8273	0.6165	0.050*
C3	1.2626 (3)	0.8040 (3)	0.49351 (14)	0.0388 (4)
H3	1.3755	0.8259	0.4621	0.047*
C4	1.0596 (3)	0.7721 (3)	0.44788 (12)	0.0300 (3)
C5	0.8922 (3)	0.7356 (3)	0.49449 (13)	0.0366 (4)
H5	0.7563	0.7149	0.4641	0.044*
C6	0.9259 (3)	0.7297 (3)	0.58611 (13)	0.0364 (4)
H6	0.8121	0.7010	0.6168	0.044*
C7	0.8611 (3)	0.7346 (3)	0.28689 (12)	0.0312 (4)
C8	0.4890 (3)	0.5720 (3)	0.17878 (12)	0.0347 (4)
H8A	0.4992	0.6971	0.1591	0.042*
H8B	0.5633	0.5002	0.1418	0.042*
C9	0.2594 (3)	0.4531 (3)	0.16719 (13)	0.0334 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02480 (10)	0.03904 (13)	0.02939 (11)	0.00194 (8)	0.00382 (7)	0.01132 (7)
S1	0.0213 (2)	0.0584 (3)	0.0299 (2)	−0.00021 (19)	0.00287 (16)	0.0122 (2)
O1	0.0292 (6)	0.0662 (10)	0.0317 (7)	−0.0008 (6)	0.0009 (5)	0.0127 (7)
O1W	0.0325 (7)	0.0733 (11)	0.0293 (7)	−0.0067 (7)	0.0063 (6)	0.0097 (7)
O2	0.0285 (6)	0.0553 (9)	0.0342 (7)	0.0014 (6)	−0.0026 (5)	0.0105 (6)
O2W	0.0287 (7)	0.0483 (9)	0.0515 (9)	−0.0053 (6)	−0.0024 (6)	0.0218 (7)
O3	0.0316 (7)	0.0843 (13)	0.0388 (8)	−0.0093 (8)	0.0050 (6)	0.0239 (8)
O3W	0.0515 (9)	0.0738 (12)	0.0351 (8)	0.0314 (9)	0.0066 (7)	0.0157 (8)
N1	0.0206 (6)	0.0382 (8)	0.0318 (7)	0.0012 (6)	0.0054 (5)	0.0070 (6)
N2	0.0250 (7)	0.0517 (10)	0.0363 (8)	0.0001 (7)	0.0083 (6)	0.0107 (7)
N3	0.0282 (8)	0.0545 (11)	0.0391 (9)	0.0008 (7)	0.0091 (6)	0.0135 (8)
N4	0.0275 (7)	0.0481 (10)	0.0334 (8)	0.0037 (7)	0.0067 (6)	0.0127 (7)
C1	0.0280 (8)	0.0343 (9)	0.0316 (9)	0.0002 (7)	0.0013 (7)	0.0063 (7)
C2	0.0218 (8)	0.0582 (13)	0.0396 (10)	0.0009 (8)	−0.0002 (7)	0.0123 (9)
C3	0.0220 (8)	0.0528 (12)	0.0381 (10)	0.0021 (8)	0.0063 (7)	0.0121 (8)
C4	0.0239 (8)	0.0318 (9)	0.0302 (8)	0.0014 (7)	0.0035 (6)	0.0056 (7)
C5	0.0210 (8)	0.0506 (11)	0.0351 (9)	0.0053 (7)	0.0025 (7)	0.0093 (8)
C6	0.0238 (8)	0.0468 (11)	0.0345 (9)	0.0031 (7)	0.0056 (7)	0.0074 (8)
C7	0.0237 (8)	0.0367 (10)	0.0313 (8)	0.0044 (7)	0.0050 (6)	0.0077 (7)
C8	0.0238 (8)	0.0463 (11)	0.0292 (8)	0.0004 (7)	0.0024 (6)	0.0114 (7)
C9	0.0242 (8)	0.0394 (10)	0.0329 (9)	0.0018 (7)	0.0029 (6)	0.0106 (7)

Geometric parameters (Å, º)

Cd1—O3W^i	2.2635 (15)	N1—N2	1.355 (2)
Cd1—O3W	2.2635 (15)	N1—C4	1.435 (2)
Cd1—O1W^i	2.2727 (15)	N2—N3	1.283 (2)
Cd1—O1W	2.2727 (15)	N3—N4	1.357 (2)
Cd1—O2W	2.2857 (15)	N4—C7	1.329 (2)
Cd1—O2W^i	2.2857 (15)	C1—C2	1.385 (3)
S1—C7	1.7327 (18)	C1—C6	1.388 (2)
S1—C8	1.8064 (18)	C2—C3	1.383 (3)
O1—C1	1.358 (2)	C2—H2	0.9300
O1—H1B	0.8200	C3—C4	1.389 (2)
O1W—H1WA	0.823 (17)	C3—H3	0.9300
O1W—H1WB	0.830 (16)	C4—C5	1.380 (2)
O2—C9	1.258 (2)	C5—C6	1.380 (3)
O2W—H2WA	0.820 (17)	C5—H5	0.9300
O2W—H2WB	0.829 (17)	C6—H6	0.9300
O3—C9	1.231 (2)	C8—C9	1.520 (2)
O3W—H3WA	0.821 (17)	C8—H8A	0.9700
O3W—H3WB	0.815 (17)	C8—H8B	0.9700
N1—C7	1.355 (2)
O3W^i—Cd1—O3W	180.00 (8)	C7—N4—N3	105.59 (15)
O3W^i—Cd1—O1W^i	90.08 (6)	O1—C1—C2	118.48 (16)
O3W—Cd1—O1W^i	89.92 (6)	O1—C1—C6	122.23 (17)
O3W^i—Cd1—O1W	89.92 (6)	C2—C1—C6	119.29 (18)
O3W—Cd1—O1W	90.08 (6)	C3—C2—C1	120.47 (17)
O1W^i—Cd1—O1W	180.00 (8)	C3—C2—H2	119.8
O3W^i—Cd1—O2W	88.40 (7)	C1—C2—H2	119.8
O3W—Cd1—O2W	91.60 (7)	C2—C3—C4	119.81 (17)
O1W^i—Cd1—O2W	86.15 (6)	C2—C3—H3	120.1
O1W—Cd1—O2W	93.85 (6)	C4—C3—H3	120.1
O3W^i—Cd1—O2W^i	91.60 (7)	C5—C4—C3	119.86 (17)
O3W—Cd1—O2W^i	88.40 (7)	C5—C4—N1	121.75 (15)
O1W^i—Cd1—O2W^i	93.85 (6)	C3—C4—N1	118.33 (16)
O1W—Cd1—O2W^i	86.15 (6)	C6—C5—C4	120.16 (16)
O2W—Cd1—O2W^i	180.00 (6)	C6—C5—H5	119.9
C7—S1—C8	97.94 (9)	C4—C5—H5	119.9
C1—O1—H1B	109.5	C5—C6—C1	120.37 (17)
Cd1—O1W—H1WA	128 (2)	C5—C6—H6	119.8
Cd1—O1W—H1WB	119.9 (18)	C1—C6—H6	119.8
H1WA—O1W—H1WB	107 (2)	N4—C7—N1	108.17 (15)
Cd1—O2W—H2WA	120 (2)	N4—C7—S1	125.73 (14)
Cd1—O2W—H2WB	122 (2)	N1—C7—S1	126.10 (14)
H2WA—O2W—H2WB	104 (2)	C9—C8—S1	108.98 (12)
Cd1—O3W—H3WA	127 (2)	C9—C8—H8A	109.9
Cd1—O3W—H3WB	117 (2)	S1—C8—H8A	109.9
H3WA—O3W—H3WB	107 (2)	C9—C8—H8B	109.9
C7—N1—N2	107.85 (15)	S1—C8—H8B	109.9
C7—N1—C4	133.22 (15)	H8A—C8—H8B	108.3
N2—N1—C4	118.86 (14)	O3—C9—O2	126.70 (18)
N3—N2—N1	106.68 (15)	O3—C9—C8	118.25 (16)
N2—N3—N4	111.70 (16)	O2—C9—C8	115.05 (16)
C7—N1—N2—N3	−0.4 (2)	C4—C5—C6—C1	2.0 (3)
C4—N1—N2—N3	−177.88 (17)	O1—C1—C6—C5	177.98 (19)
N1—N2—N3—N4	0.5 (2)	C2—C1—C6—C5	−2.0 (3)
N2—N3—N4—C7	−0.4 (2)	N3—N4—C7—N1	0.1 (2)
O1—C1—C2—C3	−179.7 (2)	N3—N4—C7—S1	−179.91 (15)
C6—C1—C2—C3	0.3 (3)	N2—N1—C7—N4	0.2 (2)
C1—C2—C3—C4	1.4 (3)	C4—N1—C7—N4	177.15 (18)
C2—C3—C4—C5	−1.3 (3)	N2—N1—C7—S1	−179.80 (14)
C2—C3—C4—N1	175.88 (19)	C4—N1—C7—S1	−2.9 (3)
C7—N1—C4—C5	−15.7 (3)	C8—S1—C7—N4	7.35 (19)
N2—N1—C4—C5	160.95 (19)	C8—S1—C7—N1	−172.63 (17)
C7—N1—C4—C3	167.1 (2)	C7—S1—C8—C9	176.39 (14)
N2—N1—C4—C3	−16.2 (3)	S1—C8—C9—O3	0.1 (2)
C3—C4—C5—C6	−0.4 (3)	S1—C8—C9—O2	179.79 (15)
N1—C4—C5—C6	−177.47 (18)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O3^ii	0.82	1.77	2.586 (2)	174
O1W—H1WB···O1^iii	0.83 (2)	1.95 (2)	2.779 (2)	177 (3)
O2W—H2WA···O2^iv	0.82 (2)	1.91 (2)	2.709 (2)	164 (3)
O2W—H2WB···O2^v	0.83 (2)	2.00 (2)	2.815 (2)	167 (3)
O3W—H3WA···N4^v	0.82 (2)	2.05 (2)	2.869 (2)	174 (3)
O3W—H3WB···O2	0.82 (2)	1.97 (2)	2.788 (2)	178 (3)

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