trans-Bis(3-amino-1,2,4-triazolium-κN¹)­di­chloro­copper(II) tetra­chloro­cuprate(II) dihydrate

The title compound, trans-[CuCl₂(tzH)₂][CuCl₄]·2H₂O (thz is 3-amino-1,2,4-triazolium, C₂H₅N₄), was obtained by the decomposition of a 1,2,4-triazolo-[1,5-a]­pyrimidine derivative in concentrated hydro­chloric acid in the presence of Cu^II. The two Cu^II ions occupy crystallographic inversion centres and display square-planar (or tetragonally very elongated) geometries. The complex cation of this salt is an example of a positively charged species (protonated 3-amino-1,2,4-triazole) coordinated to a metal atom.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](N-C) = 0.002 Å
• R factor = 0.018
• wR factor = 0.046
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

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Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio

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

   3 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
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: Bruker SMART (Bruker, 1999); cell refinement: Bruker SMART; data reduction: Bruker SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal_GX (Hall & du Boulay, 1997) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

trans-Bis(3-amino-1,2,4-triazolium-κN¹)dichlorocopper(II) tetrachlorocuprate(II) dihydrate

Crystal data

[CuCl2(C2H5N4)2][CuCl4]·2H2O	Z = 1
Mr = 546.01	F(000) = 270
Triclinic, P1	Dx = 2.177 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1505 (6) Å	Cell parameters from 3558 reflections
b = 7.6367 (8) Å	θ = 3.6–28.0°
c = 9.7197 (10) Å	µ = 3.53 mm^−1
α = 95.0132 (15)°	T = 100 K
β = 99.9045 (15)°	Prismatic, green
γ = 110.2812 (14)°	0.26 × 0.25 × 0.22 mm
V = 416.47 (7) Å^3

Data collection

Bruker SMART APEX CCD diffractometer	1867 independent reflections
Radiation source: fine-focus sealed tube	1800 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
Detector resolution: 66.06 pixels mm^-1	θmax = 28.3°, θmin = 2.2°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 1999)	k = −10→10
Tmin = 0.380, Tmax = 0.460	l = −12→12
4759 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.046	w = 1/[σ^2(Fo^2) + (0.02P)^2 + 0.2P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1867 reflections	Δρmax = 0.30 e Å^−3
110 parameters	Δρmin = −0.33 e Å^−3
2 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: heavy-atom method	Extinction coefficient: 0.079 (2)

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
Cu1	0.5000	0.5000	0.0000	0.02586 (9)
Cl1	0.70181 (7)	0.54832 (5)	0.23901 (4)	0.02737 (11)
Cl2	0.77967 (7)	0.76437 (6)	−0.03392 (4)	0.02997 (11)
Cu2	0.5000	0.5000	0.5000	0.02415 (9)
Cl3	0.31753 (7)	0.70168 (5)	0.43559 (4)	0.02755 (11)
N1	0.2106 (2)	0.27671 (18)	0.39413 (14)	0.0228 (3)
N2	0.0043 (2)	0.29145 (18)	0.32524 (14)	0.0233 (3)
H2	−0.0185	0.3961	0.3220	0.028*
C3	−0.1552 (3)	0.1224 (2)	0.26424 (16)	0.0234 (3)
N3	−0.3714 (3)	0.0830 (2)	0.19151 (17)	0.0338 (3)
H31	−0.4240	0.1724	0.1791	0.041*
H32	−0.4607	−0.0321	0.1563	0.041*
N4	−0.0499 (2)	−0.00194 (19)	0.29491 (15)	0.0274 (3)
H4	−0.1124	−0.1226	0.2697	0.033*
C5	0.1719 (3)	0.0977 (2)	0.37260 (18)	0.0268 (3)
H5	0.2821	0.0447	0.4059	0.032*
O1W	0.2751 (2)	0.7072 (2)	0.09221 (15)	0.0383 (3)
H1W	0.258 (4)	0.672 (3)	0.169 (2)	0.046*
H2W	0.148 (3)	0.708 (3)	0.056 (2)	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02404 (15)	0.02084 (15)	0.02380 (15)	0.00095 (11)	−0.00190 (11)	0.00270 (11)
Cl1	0.0289 (2)	0.02138 (19)	0.0266 (2)	0.00780 (15)	−0.00315 (15)	0.00148 (14)
Cl2	0.0254 (2)	0.0263 (2)	0.0300 (2)	0.00069 (15)	0.00337 (15)	0.00453 (15)
Cu2	0.02161 (15)	0.01495 (14)	0.03194 (16)	0.00688 (11)	−0.00269 (11)	−0.00035 (10)
Cl3	0.0283 (2)	0.02016 (19)	0.0324 (2)	0.01148 (15)	−0.00179 (15)	0.00104 (15)
N1	0.0226 (6)	0.0191 (6)	0.0250 (7)	0.0080 (5)	0.0015 (5)	0.0012 (5)
N2	0.0220 (6)	0.0174 (6)	0.0293 (7)	0.0080 (5)	0.0016 (5)	0.0012 (5)
C3	0.0255 (7)	0.0201 (7)	0.0228 (7)	0.0075 (6)	0.0040 (6)	0.0009 (6)
N3	0.0262 (7)	0.0235 (7)	0.0437 (9)	0.0073 (6)	−0.0054 (6)	−0.0016 (6)
N4	0.0291 (7)	0.0150 (6)	0.0322 (7)	0.0058 (5)	−0.0013 (6)	−0.0016 (5)
C5	0.0285 (8)	0.0197 (8)	0.0295 (8)	0.0095 (6)	−0.0012 (6)	0.0013 (6)
O1W	0.0312 (7)	0.0436 (8)	0.0376 (7)	0.0109 (6)	0.0056 (6)	0.0091 (6)

Geometric parameters (Å, º)

Cu1—Cl2	2.2467 (4)	N2—H2	0.8600
Cu1—Cl2^i	2.2467 (4)	C3—N3	1.312 (2)
Cu1—Cl1	2.3695 (4)	C3—N4	1.349 (2)
Cu1—Cl1^i	2.3695 (4)	N3—H31	0.8600
Cu2—N1^ii	2.0233 (13)	N3—H32	0.8600
Cu2—N1	2.0233 (13)	N4—C5	1.355 (2)
Cu2—Cl3	2.2691 (4)	N4—H4	0.8600
Cu2—Cl3^ii	2.2691 (4)	C5—H5	0.9300
N1—C5	1.295 (2)	O1W—H1W	0.828 (16)
N1—N2	1.3749 (18)	O1W—H2W	0.806 (16)
N2—C3	1.330 (2)
Cl2—Cu1—Cl2^i	180.0	C3—N2—H2	124.5
Cl2—Cu1—Cl1	89.901 (15)	N1—N2—H2	124.5
Cl2^i—Cu1—Cl1	90.099 (15)	N3—C3—N2	127.60 (15)
Cl2—Cu1—Cl1^i	90.099 (15)	N3—C3—N4	126.81 (15)
Cl2^i—Cu1—Cl1^i	89.900 (15)	N2—C3—N4	105.58 (13)
Cl1—Cu1—Cl1^i	180.0	C3—N3—H31	119.9
N1^ii—Cu2—N1	180.0	C3—N3—H32	120.1
N1^ii—Cu2—Cl3	89.47 (4)	H31—N3—H32	120.0
N1—Cu2—Cl3	90.53 (4)	C3—N4—C5	107.61 (13)
N1^ii—Cu2—Cl3^ii	90.53 (4)	C3—N4—H4	126.1
N1—Cu2—Cl3^ii	89.47 (4)	C5—N4—H4	126.2
Cl3—Cu2—Cl3^ii	180.0	N1—C5—N4	111.03 (14)
C5—N1—N2	104.80 (13)	N1—C5—H5	124.4
C5—N1—Cu2	131.20 (11)	N4—C5—H5	124.6
N2—N1—Cu2	124.00 (10)	H1W—O1W—H2W	105 (2)
C3—N2—N1	110.98 (13)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1^iii	0.86	2.46	3.2084 (14)	146
N3—H32···O1W^iv	0.86	2.05	2.892 (2)	168
N4—H4···Cl1^iv	0.86	2.34	3.1899 (14)	170
O1W—H1W···Cl3	0.83 (2)	2.53 (2)	3.3078 (15)	157 (2)
O1W—H2W···Cl2^iii	0.81 (2)	2.48 (2)	3.2728 (15)	171 (2)

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