A simple hydrated salt with a complex hydrogen-bonding network: tetra­kis­(5-amino-3-carb­oxy-4H-1,2,4-triazol-1-ium) hexa­chlorido­cadmate(II) tetra­hydrate

In the title cadmium chloride salt, (C₃H₅N₄O₂)₄[CdCl₆]·4H₂O, the asymmetric unit comprises two N-protonated 5-amino-3-carb­oxy-4H-1,2,4-triazol-1-ium cations, half a [CdCl₆]⁴⁻ anion and two mol­ecules of water. The Cd²⁺ cation is located on a centre of inversion and is coordinated by six chloride anions, forming a distorted octa­hedron. In the crystal structure, alternating layers of cations and anions are arranged along the [101] direction, forming a three-dimensional supra­molecular network via a combination of hydrogen-bonding and aromatic stacking inter­actions.

Computing details

Data collection: APEX2 (Bruker, 2001); cell refinement: APEX2 (Bruker, 2001); data reduction: APEX2 (Bruker, 2001); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Tetrakis(5-amino-3-carboxy-4H-1,2,4-triazol-1-ium) hexachloridocadmate(II) tetrahydrate

Crystal data

4C3H5N4O2^+·CdCl6^4^−·4H2O	Z = 1
Mr = 913.61	F(000) = 458
Triclinic, P1	Dx = 1.890 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4373 (4) Å	Cell parameters from 6410 reflections
b = 9.5334 (4) Å	θ = 2.4–27.5°
c = 10.4848 (5) Å	µ = 1.26 mm^−1
α = 109.352 (2)°	T = 150 K
β = 110.768 (2)°	Block, pale brown
γ = 96.643 (2)°	0.52 × 0.21 × 0.11 mm
V = 802.59 (6) Å^3

Data collection

Bruker APEXII area-detector diffractometer	3565 independent reflections
Radiation source: Rotating anode	3334 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 18.4 pixels mm^-1	θmax = 27.5°, θmin = 2.5°
CCD rotation images, thin slices scans	h = −11→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	k = −12→12
Tmin = 0.665, Tmax = 0.871	l = −13→12
9881 measured reflections

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 0.4658P] where P = (Fo^2 + 2Fc^2)/3
3565 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 0.82 e Å^−3
4 restraints	Δρmin = −0.99 e Å^−3
6 constraints

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
O8	0.02998 (17)	0.48245 (17)	0.21876 (16)	0.0197 (4)
O9	0.04705 (18)	0.63653 (18)	0.44236 (17)	0.0226 (5)
N1	0.5168 (2)	0.4977 (2)	0.7572 (2)	0.0200 (5)
N3	0.38211 (19)	0.3574 (2)	0.49436 (19)	0.0163 (5)
N4	0.2601 (2)	0.3625 (2)	0.37738 (19)	0.0168 (5)
N6	0.30201 (19)	0.54971 (19)	0.59112 (19)	0.0149 (5)
C2	0.4084 (2)	0.4698 (2)	0.6243 (2)	0.0158 (6)
C5	0.2146 (2)	0.4796 (2)	0.4397 (2)	0.0146 (5)
C7	0.0855 (2)	0.5325 (2)	0.3534 (2)	0.0158 (6)
O17	0.36683 (17)	0.77460 (17)	0.40758 (16)	0.0193 (4)
O18	0.34338 (18)	0.98366 (18)	0.57315 (17)	0.0240 (4)
N10	−0.0893 (2)	0.8048 (2)	−0.0370 (2)	0.0221 (5)
N12	−0.0140 (2)	0.9749 (2)	0.21443 (19)	0.0168 (5)
N13	0.0971 (2)	1.0018 (2)	0.35292 (19)	0.0166 (5)
N15	0.11457 (19)	0.80514 (19)	0.17750 (19)	0.0147 (5)
C11	−0.0037 (2)	0.8572 (2)	0.1073 (2)	0.0154 (6)
C14	0.1725 (2)	0.8976 (2)	0.3251 (2)	0.0142 (5)
C16	0.3058 (2)	0.8787 (2)	0.4405 (2)	0.0157 (6)
Cd1	0.50000	1.00000	0.00000	0.0141 (1)
Cl1	0.39747 (6)	1.08296 (6)	0.21183 (5)	0.0175 (1)
Cl2	0.22928 (5)	0.80659 (5)	−0.18305 (5)	0.0173 (1)
Cl3	0.58603 (6)	0.77248 (6)	0.07099 (6)	0.0187 (1)
O1W	0.82954 (18)	0.75504 (19)	0.35604 (18)	0.0223 (5)
O2W	0.25195 (18)	0.60899 (19)	0.04346 (18)	0.0211 (5)
H1A	0.58030	0.44020	0.76700	0.0240*
H1B	0.52390	0.57330	0.83420	0.0240*
H3	0.43530	0.29020	0.48540	0.0190*
H6	0.29100	0.62890	0.65260	0.0180*
H9	−0.02400	0.66430	0.39310	0.0340*
H10A	−0.16120	0.84710	−0.07140	0.0270*
H10B	−0.07330	0.72810	−0.09700	0.0270*
H12	−0.08190	1.02720	0.19840	0.0200*
H15	0.14690	0.72890	0.13710	0.0180*
H18	0.41730	0.97020	0.63430	0.0360*
H1WA	0.769 (3)	0.757 (3)	0.279 (2)	0.0270*
H1WB	0.848 (3)	0.834 (2)	0.429 (2)	0.0270*
H2WB	0.329 (2)	0.656 (3)	0.040 (3)	0.0250*
H2WA	0.183 (3)	0.567 (3)	−0.044 (2)	0.0250*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O8	0.0211 (7)	0.0189 (8)	0.0154 (8)	0.0078 (6)	0.0050 (6)	0.0046 (6)
O9	0.0247 (8)	0.0253 (8)	0.0175 (8)	0.0185 (6)	0.0072 (6)	0.0062 (7)
N1	0.0222 (9)	0.0198 (9)	0.0161 (9)	0.0128 (7)	0.0062 (7)	0.0046 (8)
N3	0.0189 (8)	0.0146 (9)	0.0168 (9)	0.0108 (7)	0.0081 (7)	0.0053 (7)
N4	0.0181 (8)	0.0160 (9)	0.0152 (9)	0.0080 (7)	0.0067 (7)	0.0042 (7)
N6	0.0175 (8)	0.0126 (8)	0.0145 (8)	0.0090 (6)	0.0080 (7)	0.0022 (7)
C2	0.0175 (9)	0.0135 (10)	0.0188 (10)	0.0069 (7)	0.0098 (8)	0.0061 (8)
C5	0.0151 (9)	0.0136 (9)	0.0149 (10)	0.0051 (7)	0.0068 (8)	0.0044 (8)
C7	0.0157 (9)	0.0128 (10)	0.0194 (11)	0.0055 (7)	0.0079 (8)	0.0058 (9)
O17	0.0204 (7)	0.0194 (8)	0.0173 (7)	0.0128 (6)	0.0062 (6)	0.0056 (6)
O18	0.0281 (8)	0.0236 (8)	0.0131 (7)	0.0158 (7)	0.0022 (6)	0.0029 (7)
N10	0.0233 (9)	0.0260 (10)	0.0140 (9)	0.0157 (8)	0.0049 (7)	0.0045 (8)
N12	0.0186 (8)	0.0170 (9)	0.0149 (9)	0.0125 (7)	0.0056 (7)	0.0054 (7)
N13	0.0178 (8)	0.0164 (9)	0.0146 (8)	0.0082 (7)	0.0055 (7)	0.0054 (7)
N15	0.0169 (8)	0.0122 (8)	0.0151 (8)	0.0084 (6)	0.0070 (7)	0.0038 (7)
C11	0.0152 (9)	0.0141 (10)	0.0177 (10)	0.0072 (7)	0.0072 (8)	0.0060 (8)
C14	0.0155 (9)	0.0118 (9)	0.0156 (10)	0.0052 (7)	0.0069 (8)	0.0049 (8)
C16	0.0161 (9)	0.0159 (10)	0.0161 (10)	0.0058 (8)	0.0066 (8)	0.0074 (8)
Cd1	0.0164 (1)	0.0134 (1)	0.0116 (1)	0.0075 (1)	0.0059 (1)	0.0026 (1)
Cl1	0.0194 (2)	0.0209 (3)	0.0135 (2)	0.0112 (2)	0.0079 (2)	0.0054 (2)
Cl2	0.0170 (2)	0.0138 (2)	0.0171 (2)	0.0079 (2)	0.0056 (2)	0.0019 (2)
Cl3	0.0220 (2)	0.0172 (2)	0.0165 (2)	0.0105 (2)	0.0065 (2)	0.0062 (2)
O1W	0.0247 (8)	0.0214 (8)	0.0181 (8)	0.0150 (7)	0.0060 (7)	0.0050 (7)
O2W	0.0216 (8)	0.0251 (9)	0.0165 (8)	0.0108 (6)	0.0082 (6)	0.0066 (7)

Geometric parameters (Å, º)

Cd1—Cl1^i	2.6517 (5)	N4—C5	1.298 (3)
Cd1—Cl2^i	2.5881 (5)	N6—C5	1.374 (2)
Cd1—Cl3^i	2.6395 (6)	N6—C2	1.347 (3)
Cd1—Cl1	2.6517 (5)	N1—H1B	0.8600
Cd1—Cl2	2.5881 (5)	N1—H1A	0.8600
Cd1—Cl3	2.6395 (6)	N3—H3	0.8600
O8—C7	1.211 (2)	N6—H6	0.8600
O9—C7	1.302 (3)	N10—C11	1.315 (3)
O9—H9	0.8200	N12—N13	1.373 (3)
O17—C16	1.217 (3)	N12—C11	1.341 (3)
O18—C16	1.307 (2)	N13—C14	1.303 (3)
O18—H18	0.8200	N15—C14	1.362 (2)
O1W—H1WB	0.82 (2)	N15—C11	1.350 (3)
O1W—H1WA	0.82 (2)	N10—H10A	0.8600
O2W—H2WB	0.83 (3)	N10—H10B	0.8600
O2W—H2WA	0.835 (19)	N12—H12	0.8600
N1—C2	1.319 (3)	N15—H15	0.8600
N3—N4	1.372 (3)	C5—C7	1.490 (3)
N3—C2	1.341 (3)	C14—C16	1.482 (3)
Cl1^i—Cd1—Cl2	89.93 (2)	N13—N12—C11	111.70 (18)
Cl2—Cd1—Cl2^i	180.00	N12—N13—C14	103.32 (17)
Cl2—Cd1—Cl3^i	92.78 (2)	C11—N15—C14	106.23 (17)
Cl1^i—Cd1—Cl3	88.79 (2)	H10A—N10—H10B	120.00
Cl2^i—Cd1—Cl3	92.78 (2)	C11—N10—H10B	120.00
Cl3—Cd1—Cl3^i	180.00	C11—N10—H10A	120.00
Cl1^i—Cd1—Cl2^i	90.07 (2)	N13—N12—H12	124.00
Cl1^i—Cd1—Cl3^i	91.21 (2)	C11—N12—H12	124.00
Cl2^i—Cd1—Cl3^i	87.22 (2)	C11—N15—H15	127.00
Cl1—Cd1—Cl2	90.07 (2)	C14—N15—H15	127.00
Cl1—Cd1—Cl3	91.21 (2)	N1—C2—N3	127.3 (2)
Cl1—Cd1—Cl1^i	180.00	N1—C2—N6	126.93 (19)
Cl1—Cd1—Cl2^i	89.93 (2)	N3—C2—N6	105.78 (17)
Cl1—Cd1—Cl3^i	88.79 (2)	N6—C5—C7	124.95 (18)
Cl2—Cd1—Cl3	87.22 (2)	N4—C5—C7	122.80 (17)
C7—O9—H9	109.00	N4—C5—N6	112.23 (18)
C16—O18—H18	109.00	O9—C7—C5	110.75 (16)
H1WA—O1W—H1WB	112 (2)	O8—C7—C5	121.89 (19)
H2WB—O2W—H2WA	106 (3)	O8—C7—O9	127.4 (2)
N4—N3—C2	111.88 (18)	N12—C11—N15	105.95 (16)
N3—N4—C5	103.69 (16)	N10—C11—N15	126.93 (19)
C2—N6—C5	106.42 (17)	N10—C11—N12	127.1 (2)
C2—N1—H1B	120.00	N15—C14—C16	122.97 (18)
C2—N1—H1A	120.00	N13—C14—C16	124.24 (17)
H1A—N1—H1B	120.00	N13—C14—N15	112.78 (18)
C2—N3—H3	124.00	O17—C16—O18	127.29 (19)
N4—N3—H3	124.00	O17—C16—C14	120.89 (17)
C5—N6—H6	127.00	O18—C16—C14	111.82 (18)
C2—N6—H6	127.00
C2—N3—N4—C5	0.1 (2)	N12—N13—C14—C16	−180.0 (2)
N4—N3—C2—N1	−179.7 (2)	C14—N15—C11—N10	177.6 (2)
N4—N3—C2—N6	−0.2 (2)	C14—N15—C11—N12	−1.3 (2)
N3—N4—C5—N6	0.1 (2)	C11—N15—C14—N13	1.3 (3)
N3—N4—C5—C7	178.15 (19)	C11—N15—C14—C16	−179.45 (19)
C5—N6—C2—N1	179.7 (2)	N4—C5—C7—O8	−10.2 (3)
C5—N6—C2—N3	0.3 (2)	N6—C5—C7—O9	−11.5 (3)
C2—N6—C5—N4	−0.2 (3)	N4—C5—C7—O9	170.7 (2)
C2—N6—C5—C7	−178.24 (19)	N6—C5—C7—O8	167.7 (2)
N13—N12—C11—N15	0.9 (2)	N13—C14—C16—O17	176.8 (2)
C11—N12—N13—C14	−0.1 (3)	N13—C14—C16—O18	−2.9 (3)
N13—N12—C11—N10	−178.0 (2)	N15—C14—C16—O17	−2.3 (3)
N12—N13—C14—N15	−0.8 (2)	N15—C14—C16—O18	178.01 (19)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O1W^ii	0.82	1.71	2.491 (3)	158
O18—H18···Cl1^iii	0.82	2.16	2.977 (2)	176
O1W—H1WA···Cl3	0.82 (2)	2.32 (2)	3.128 (2)	175 (3)
O1W—H1WB···N13^iii	0.82 (2)	2.13 (2)	2.934 (2)	164 (2)
O2W—H2WA···O8^iv	0.83 (2)	2.05 (2)	2.844 (2)	158 (3)
O2W—H2WB···Cl3	0.83 (3)	2.41 (2)	3.221 (2)	167 (3)
N1—H1A···O2W^v	0.86	2.29	2.976 (3)	137
N1—H1A···O17^v	0.86	2.49	3.156 (3)	135
N1—H1B···Cl3^vi	0.86	2.39	3.237 (2)	170
N3—H3···Cl1^vii	0.86	2.76	3.301 (2)	122
N3—H3···O17^v	0.86	2.09	2.842 (3)	146
N6—H6···Cl2^vi	0.86	2.28	3.126 (2)	170
N10—H10A···Cl1^viii	0.86	2.50	3.347 (2)	168
N10—H10B···O8^iv	0.86	2.17	3.016 (3)	170
N10—H10B···N4^iv	0.86	2.60	3.071 (2)	115
N12—H12···Cl2^viii	0.86	2.23	3.088 (2)	171
N15—H15···O2W	0.86	1.86	2.695 (3)	163

Symmetry codes: (ii) x−1, y, z; (iii) −x+1, −y+2, −z+1; (iv) −x, −y+1, −z; (v) −x+1, −y+1, −z+1; (vi) x, y, z+1; (vii) x, y−1, z; (viii) −x, −y+2, −z.