Dibromidobis(6-methyl-3-phenyl-s-tri­azolo[3,4-b][1,3,4]thia­diazole-κN¹)copper(II)

In the title complex, [CuBr₂(C₁₀H₈N₄S)₂], the Cu^II atom is located on an inversion centre and displays a distorted square-planar coordination geometry. The dihedral angle between the fused-ring system and its phenyl substituent is 2.1 (3)°. Inter­molecular C—H...Br hydrogen bonds and π–π contacts [with an inter­planar separation of 3.513 (3) Å] form a supra­molecular network structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.041
• wR factor = 0.106
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.92

Author Response: The nature of the crystal can be attributted to low ratio of refinement, I have synthesized the product several times in different conditions and systems, the final result is similar with this end.

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           25.19
           From the CIF: _diffrn_reflns_theta_full          25.19
           From the CIF: _reflns_number_total               1927
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         2099
           Completeness (_total/calc)             91.81%
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.101
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.10
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.92
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cu1
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       1.74

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

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

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S1. Comment

The molecular structure of 2-methyl-5-phenyl-s-triazolo(3,4 - b)-1,3,4-thiadiazole (Fornies-Marquina et al., 1974) and its substituted derivatives (Molina et al., 1989; Huang et al., 2005; Naveen et al., 2006) have been reported; however, no metal complexes of the ligand have been reported. In this paper, we report the crystal structure of the title compound, (I), a Cu complex obtained by the reaction of 2-methyl-5-phenyl-s-triazolo(3,4 - b)-1,3,4-thiadiazole with copper(II) bromide in methanol solution.

As illustrated in Fig. 1, the Cu^II atom lies on an inversion centre and has a distorted square-planar geometry with two N atoms from two 2-methyl-5-phenyl-s-triazolo(3,4 - b)-1,3,4-thiadiazole ligands and two bromine atoms (Table 1). There are intramolecular C—H···N interactions. The molecules are connected through C—H···Br hydrogen bonding and π-π stacking interactions between the phenyl ring and triazolo ring, forming a supramolecular network structure (Table 2). The centroid-centroid distance of stacked rings is 3.513 (3) Å.

Related literature

For related literature, see: Fornies-Marquina et al. (1974); Molina et al. (1989); Huang et al. (2005); Naveen et al. (2006).

S2. Experimental

The title complex was prepared by the addition of copper(II) bromide (0.0568 g, 0.25 mmol) to a hot methanol solution (10 ml) of 2-methyl-5-phenyl-s-triazolo(3,4 - b)-1,3,4-thiadiazole (0.085 g, 0.48 mmol). The resulting solution was filtered, and blue block crystals were obtained at room temperature on slow evaporation of the solvent over several days.

S3. Refinement

H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93–0.97 and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms and atoms with the suffix A are related to the labelled atoms by the symmetry operator (1 - x, 1 - y, -z).

Dibromidobis(6-methyl-3-phenyl-s-triazolo[3,4-b][1,3,4]thiadiazole-κN¹)\ copper(II)

Crystal data

[CuBr2(C10H8N4S)2]	Z = 1
Mr = 655.89	F(000) = 323
Triclinic, P1	Dx = 1.869 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8286 (10) Å	Cell parameters from 1927 reflections
b = 8.5231 (13) Å	θ = 1.9–25.2°
c = 11.3654 (16) Å	µ = 4.57 mm^−1
α = 98.442 (2)°	T = 298 K
β = 105.614 (2)°	Block, blue
γ = 108.859 (2)°	0.44 × 0.31 × 0.22 mm
V = 582.69 (15) Å^3

Data collection

Bruker APEXII area-detector diffractometer	1927 independent reflections
Radiation source: fine-focus sealed tube	1430 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.101
φ and ω scans	θmax = 25.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.196, Tmax = 0.366	k = −10→10
3511 measured reflections	l = −13→13

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 0.89	w = 1/[σ^2(Fo^2) + (0.0555P)^2] where P = (Fo^2 + 2Fc^2)/3
1927 reflections	(Δ/σ)max < 0.001
152 parameters	Δρmax = 0.74 e Å^−3
0 restraints	Δρmin = −0.82 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
Br1	0.85241 (9)	0.72698 (7)	0.06813 (5)	0.0689 (3)
Cu1	0.5000	0.5000	0.0000	0.0354 (2)
S1	0.3985 (2)	0.08848 (13)	0.13106 (10)	0.0422 (3)
N1	0.5615 (6)	0.4521 (4)	0.1695 (3)	0.0372 (9)
N2	0.6696 (6)	0.5812 (4)	0.2825 (3)	0.0373 (8)
N3	0.6000 (6)	0.3339 (4)	0.3277 (3)	0.0313 (8)
N4	0.5775 (6)	0.1935 (4)	0.3769 (3)	0.0364 (8)
C1	0.8741 (8)	0.7801 (6)	0.5408 (4)	0.0427 (11)
H1	0.8617	0.8371	0.4771	0.051*
C2	0.9722 (8)	0.8728 (6)	0.6678 (4)	0.0488 (12)
H2	1.0251	0.9920	0.6893	0.059*
C3	0.9893 (8)	0.7859 (7)	0.7602 (4)	0.0482 (12)
H3	1.0539	0.8478	0.8445	0.058*
C5	0.8168 (8)	0.5183 (6)	0.6051 (4)	0.0412 (11)
H4	0.7661	0.3992	0.5848	0.049*
C6	0.7953 (7)	0.6014 (5)	0.5107 (4)	0.0321 (9)
C4	0.9144 (9)	0.6115 (6)	0.7317 (4)	0.0498 (12)
H6	0.9280	0.5551	0.7958	0.060*
C8	0.5198 (7)	0.3057 (5)	0.2006 (4)	0.0349 (10)
C9	0.4788 (8)	0.0574 (6)	0.2846 (4)	0.0410 (11)
C10	0.4271 (9)	−0.1187 (6)	0.3017 (5)	0.0628 (15)
H17A	0.4735	−0.1134	0.3902	0.094*
H17B	0.5029	−0.1739	0.2613	0.094*
H17C	0.2715	−0.1829	0.2645	0.094*
C7	0.6928 (7)	0.5087 (5)	0.3755 (4)	0.0321 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0591 (4)	0.0724 (4)	0.0373 (3)	−0.0128 (3)	0.0003 (3)	0.0209 (3)
Cu1	0.0443 (5)	0.0328 (4)	0.0219 (4)	0.0077 (3)	0.0087 (3)	0.0071 (3)
S1	0.0511 (8)	0.0350 (6)	0.0336 (6)	0.0126 (5)	0.0102 (6)	0.0056 (5)
N1	0.045 (2)	0.0359 (19)	0.0236 (17)	0.0093 (17)	0.0078 (17)	0.0070 (15)
N2	0.045 (2)	0.0343 (19)	0.0250 (18)	0.0103 (17)	0.0083 (17)	0.0049 (15)
N3	0.038 (2)	0.0324 (19)	0.0257 (17)	0.0148 (16)	0.0108 (16)	0.0095 (15)
N4	0.041 (2)	0.039 (2)	0.0342 (19)	0.0186 (17)	0.0131 (18)	0.0151 (17)
C1	0.047 (3)	0.046 (3)	0.032 (2)	0.017 (2)	0.012 (2)	0.007 (2)
C2	0.046 (3)	0.050 (3)	0.036 (3)	0.011 (2)	0.008 (2)	−0.005 (2)
C3	0.042 (3)	0.070 (3)	0.027 (2)	0.019 (3)	0.011 (2)	0.000 (2)
C5	0.048 (3)	0.043 (2)	0.032 (2)	0.016 (2)	0.014 (2)	0.007 (2)
C6	0.034 (2)	0.040 (2)	0.025 (2)	0.016 (2)	0.013 (2)	0.0071 (18)
C4	0.057 (3)	0.066 (3)	0.028 (2)	0.023 (3)	0.016 (2)	0.015 (2)
C8	0.038 (3)	0.036 (2)	0.029 (2)	0.012 (2)	0.014 (2)	0.0072 (18)
C9	0.042 (3)	0.044 (3)	0.043 (3)	0.021 (2)	0.014 (2)	0.018 (2)
C10	0.073 (4)	0.046 (3)	0.063 (4)	0.025 (3)	0.006 (3)	0.021 (3)
C7	0.032 (2)	0.037 (2)	0.029 (2)	0.0130 (19)	0.0116 (19)	0.0100 (18)

Geometric parameters (Å, º)

Br1—Cu1	2.3834 (6)	C1—H1	0.930
Cu1—N1^i	1.990 (3)	C2—C3	1.372 (7)
Cu1—N1	1.990 (3)	C2—H2	0.930
Cu1—Br1^i	2.3834 (6)	C3—C4	1.362 (7)
S1—C8	1.722 (4)	C3—H3	0.930
S1—C9	1.770 (5)	C5—C6	1.372 (6)
N1—C8	1.311 (5)	C5—C4	1.397 (6)
N1—N2	1.398 (4)	C5—H4	0.930
N2—C7	1.300 (5)	C6—C7	1.477 (5)
N3—C8	1.353 (5)	C4—H6	0.930
N3—C7	1.372 (5)	C9—C10	1.482 (6)
N3—N4	1.376 (4)	C10—H17A	0.960
N4—C9	1.287 (6)	C10—H17B	0.960
C1—C6	1.394 (6)	C10—H17C	0.960
C1—C2	1.400 (6)
N1^i—Cu1—N1	180	C6—C5—C4	120.4 (4)
N1^i—Cu1—Br1	89.18 (10)	C6—C5—H4	119.8
N1—Cu1—Br1	90.82 (10)	C4—C5—H4	119.8
N1^i—Cu1—Br1^i	90.82 (10)	C5—C6—C1	119.9 (4)
N1—Cu1—Br1^i	89.18 (10)	C5—C6—C7	122.5 (4)
Br1—Cu1—Br1^i	180	C1—C6—C7	117.6 (4)
C8—S1—C9	87.4 (2)	C3—C4—C5	119.2 (4)
C8—N1—N2	106.6 (3)	C3—C4—H6	120.4
C8—N1—Cu1	130.2 (3)	C5—C4—H6	120.4
N2—N1—Cu1	123.2 (2)	N1—C8—N3	110.1 (4)
C7—N2—N1	108.2 (3)	N1—C8—S1	140.1 (3)
C8—N3—C7	106.1 (3)	N3—C8—S1	109.8 (3)
C8—N3—N4	117.9 (3)	N4—C9—C10	123.5 (4)
C7—N3—N4	135.9 (3)	N4—C9—S1	116.5 (3)
C9—N4—N3	108.2 (3)	C10—C9—S1	119.9 (4)
C6—C1—C2	119.4 (4)	C9—C10—H17A	109.5
C6—C1—H1	120.3	C9—C10—H17B	109.5
C2—C1—H1	120.3	H17A—C10—H17B	109.5
C3—C2—C1	119.3 (4)	C9—C10—H17C	109.5
C3—C2—H2	120.3	H17A—C10—H17C	109.5
C1—C2—H2	120.3	H17B—C10—H17C	109.5
C4—C3—C2	121.7 (4)	N2—C7—N3	109.0 (3)
C4—C3—H3	119.1	N2—C7—C6	124.9 (4)
C2—C3—H3	119.1	N3—C7—C6	126.1 (4)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H17C···Br1^ii	0.96	2.90	3.769 (5)	151
C1—H1···N2	0.93	2.56	2.871 (5)	100
C5—H4···N4	0.93	2.45	3.122 (6)	129

Symmetry code: (ii) x−1, y−1, z.