Dichlorido[3-meth­oxy­methyl-4-phenyl-5-(2-pyrid­yl)-4H-1,2,4-triazole-κ2N1,N5]copper(II)

Cao, S.; Wang, Z.; Jin, X.

doi:10.1107/S160053681103296X

metal-organic compounds

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Volume 67| Part 9| September 2011| Page m1273

doi:10.1107/S160053681103296X

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Dichlorido[3-methoxymethyl-4-phenyl-5-(2-pyridyl)-4H-1,2,4-triazole-κ²N¹,N⁵]copper(II)

Shouping Cao,^a Zuoxiang Wang ^a ^* and Xiaofei Jin ^a

^aSchool of Chemistry and Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: wangzx0908@yahoo.com.cn

(Received 17 July 2011; accepted 14 August 2011; online 27 August 2011)

In the title complex, [CuCl₂(C₁₅H₁₄N₄O)], the Cu^II atom possesses a highly distorted square-planar geometry with N—Cu—N and Cl—Cu—Cl angles of 79.86 (8) and 98.65 (3)°, respectively, while the Cl—Cu—N angles fall into two distinct groups with values of 95.26 (6), 98.75 (6), 150.56 (6) and 152.04 (6)°. The pyridyl ring is twisted by 9.4 (2)° with respect to the triazole ring, which is oriented at approximately right angles [84.66 (8)°] with respect to the phenyl ring.

Related literature

For general background on the coordination chemistry of 1,2,4-triazoles, see: Klingele & Brooker (2003 ); Rubio et al. (2011 ). For the biological activity of triazoles, see: Isloor et al. (2009 ). For a related structure, see: Ren et al. (2006 ).

Experimental

Crystal data

[CuCl₂(C₁₅H₁₄N₄O)]
M_r = 400.74
Orthorhombic, P b c a
a = 16.6512 (11) Å
b = 11.2056 (7) Å
c = 17.9966 (11) Å
V = 3357.9 (4) Å³
Z = 8
Mo Kα radiation
μ = 1.63 mm⁻¹
T = 296 K
0.15 × 0.13 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.792, T_max = 0.829
22829 measured reflections
3043 independent reflections
2288 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.068
S = 1.00
3043 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681103296X/pv2432sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681103296X/pv2432Isup2.hkl

checkCIF report

Comment top

The coordination chemistry of 1,2,4-triazoles as ligands has been widely studied (Klingele & Brooker 2003; Rubio et al., 2011). Some 1,2,4-triazole compounds show biological activities (Isloor et al., 2009). We report here the crystal structure analysis of the title compound.

In the title complex (Fig. 1), copper(II) atom is coordinated by two N atoms of a 3-(methoxymethyl)-4-phenyl-5-(2-pyridyl)-4H-1,2,4-triazole and two chloride anion atoms, and exhibits a highly distorted square-planar geometry (Ren et al., 2006) with N1–Cu1–N4 and Cl1–Cu1–Cl2 angles 79.86 (8) and 98.65 (3)°, respectively, while the Cl–Cu–N angles fall in two distinct categories with values 95.26 (6), 98.75 (6), 150.56 (6) and 152.04 (6)°. The pyridyl ring (N4/C3–C7) is twisted by 9.4 (2)° with respect to the triazole ring. The phenyl ring is oriented at approximately right angles (84.66 (8)°) with respect to the triazole ring.

Related literature top

For general background on the coordination chemistry of 1,2,4-triazoles, see: Klingele & Brooker (2003); Rubio et al. (2011). For the biological activity of triazoles, see: Isloor et al. (2009). For a related structure, see: Ren et al. (2006).

Experimental top

To a warm solution of 3-methoxymethyl-4-phenyl-5-(2-pyridyl)-4H-1,2,4-triazole (0.532 g, 2 mmol) in ethanol (20 ml), CuCl₂.2H₂O (0.340 g, 2 mmol) was added. The filtrate was left to stand at room temperature for several days. The title compound crystallized as a green product which was collected and a single crystal suitable for X-ray diffraction was selected.

Computing details top

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atomic labels; displacement ellipsoids are shown at 30% probability level.

Dichlorido[3-methoxymethyl-4-phenyl-5-(2-pyridyl)-4H-1,2,4- triazole-κ²N¹,N⁵]copper(II) top

Crystal data top

[CuCl₂(C₁₅H₁₄N₄O)]	F(000) = 1624
M_r = 400.74	D_x = 1.585 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9999 reflections
a = 16.6512 (11) Å	θ = 2.5–23.3°
b = 11.2056 (7) Å	µ = 1.63 mm⁻¹
c = 17.9966 (11) Å	T = 296 K
V = 3357.9 (4) Å³	Plate, green
Z = 8	0.15 × 0.13 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	3043 independent reflections
Radiation source: fine-focus sealed tube	2288 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω scans	θ_max = 25.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −19→19
T_min = 0.792, T_max = 0.829	k = −13→13
22829 measured reflections	l = −21→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0297P)² + 1.3987P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.003
3043 reflections	Δρ_max = 0.27 e Å⁻³
210 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00051 (11)

Crystal data top

[CuCl₂(C₁₅H₁₄N₄O)]	V = 3357.9 (4) Å³
M_r = 400.74	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 16.6512 (11) Å	µ = 1.63 mm⁻¹
b = 11.2056 (7) Å	T = 296 K
c = 17.9966 (11) Å	0.15 × 0.13 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	3043 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2288 reflections with I > 2σ(I)
T_min = 0.792, T_max = 0.829	R_int = 0.052
22829 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.00	Δρ_max = 0.27 e Å⁻³
3043 reflections	Δρ_min = −0.30 e Å⁻³
210 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.050004 (18)	0.14725 (3)	0.291744 (16)	0.03113 (11)
Cl1	−0.00195 (5)	0.07124 (6)	0.39349 (4)	0.0465 (2)
Cl2	0.04038 (5)	0.33855 (6)	0.32076 (4)	0.0497 (2)
N1	0.11465 (12)	0.00815 (17)	0.25962 (11)	0.0307 (5)
N2	0.15782 (13)	−0.08048 (19)	0.29457 (12)	0.0363 (5)
N3	0.17649 (12)	−0.09025 (18)	0.17273 (11)	0.0320 (5)
N4	0.05062 (13)	0.17404 (17)	0.17923 (12)	0.0315 (5)
C1	0.19497 (15)	−0.1381 (2)	0.24098 (15)	0.0360 (6)
O1	0.22057 (13)	−0.34971 (18)	0.22443 (12)	0.0537 (6)
C2	0.12619 (14)	0.0011 (2)	0.18771 (13)	0.0288 (6)
C3	0.08684 (14)	0.0871 (2)	0.13891 (14)	0.0298 (6)
C4	0.08315 (17)	0.0841 (2)	0.06246 (14)	0.0409 (7)
H4	0.1081	0.0233	0.0359	0.049*
C5	0.04137 (18)	0.1740 (3)	0.02592 (16)	0.0471 (8)
H5	0.0372	0.1734	−0.0256	0.057*
C6	0.00641 (18)	0.2635 (3)	0.06654 (16)	0.0433 (7)
H6	−0.0209	0.3251	0.0429	0.052*
C7	0.01245 (16)	0.2607 (2)	0.14301 (15)	0.0390 (7)
H7	−0.0111	0.3218	0.1703	0.047*
C8	0.21233 (15)	−0.1229 (2)	0.10221 (14)	0.0336 (6)
C9	0.27888 (17)	−0.0607 (3)	0.07879 (16)	0.0484 (8)
H9	0.2997	0.0011	0.1074	0.058*
C10	0.31432 (19)	−0.0914 (3)	0.01219 (18)	0.0623 (9)
H10	0.3596	−0.0506	−0.0043	0.075*
C11	0.2831 (2)	−0.1813 (4)	−0.02921 (19)	0.0651 (10)
H11	0.3071	−0.2013	−0.0742	0.078*
C12	0.2167 (2)	−0.2431 (3)	−0.00585 (18)	0.0623 (10)
H12	0.1961	−0.3045	−0.0350	0.075*
C13	0.17992 (18)	−0.2144 (3)	0.06103 (16)	0.0473 (7)
H13	0.1349	−0.2558	0.0775	0.057*
C14	0.25175 (18)	−0.2404 (3)	0.25097 (17)	0.0472 (7)
H14A	0.3014	−0.2228	0.2250	0.057*
H14B	0.2643	−0.2486	0.3034	0.057*
C15	0.1611 (2)	−0.3976 (3)	0.2710 (2)	0.0763 (11)
H15A	0.1833	−0.4112	0.3195	0.114*
H15B	0.1424	−0.4718	0.2507	0.114*
H15C	0.1171	−0.3426	0.2746	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03540 (19)	0.03221 (18)	0.02578 (18)	0.00298 (15)	0.00322 (14)	−0.00052 (13)
Cl1	0.0637 (5)	0.0446 (4)	0.0313 (4)	−0.0037 (4)	0.0134 (3)	0.0013 (3)
Cl2	0.0754 (5)	0.0342 (4)	0.0396 (4)	0.0099 (4)	0.0052 (4)	−0.0038 (3)
N1	0.0329 (12)	0.0315 (12)	0.0276 (12)	0.0032 (10)	0.0021 (9)	0.0020 (9)
N2	0.0372 (12)	0.0378 (13)	0.0340 (12)	0.0046 (10)	−0.0014 (10)	0.0035 (10)
N3	0.0321 (12)	0.0328 (12)	0.0309 (12)	0.0015 (10)	0.0033 (10)	0.0003 (10)
N4	0.0355 (12)	0.0314 (12)	0.0275 (11)	0.0026 (10)	0.0021 (10)	0.0027 (9)
C1	0.0340 (14)	0.0364 (15)	0.0377 (16)	0.0016 (13)	0.0009 (12)	0.0006 (13)
O1	0.0589 (13)	0.0432 (12)	0.0591 (14)	0.0147 (11)	0.0039 (11)	−0.0017 (11)
C2	0.0276 (14)	0.0302 (14)	0.0286 (14)	−0.0020 (11)	0.0017 (11)	−0.0014 (11)
C3	0.0305 (14)	0.0300 (14)	0.0290 (14)	−0.0034 (11)	0.0018 (11)	−0.0002 (11)
C4	0.0520 (17)	0.0395 (16)	0.0310 (16)	0.0062 (14)	0.0013 (13)	−0.0033 (13)
C5	0.063 (2)	0.0525 (19)	0.0256 (15)	0.0009 (16)	−0.0030 (14)	0.0052 (13)
C6	0.0492 (18)	0.0427 (17)	0.0381 (17)	0.0049 (14)	−0.0037 (14)	0.0105 (13)
C7	0.0412 (16)	0.0374 (16)	0.0382 (16)	0.0048 (13)	0.0040 (13)	0.0040 (13)
C8	0.0330 (14)	0.0370 (15)	0.0309 (15)	0.0083 (12)	0.0041 (12)	−0.0035 (12)
C9	0.0444 (17)	0.0537 (19)	0.0469 (18)	−0.0072 (15)	0.0098 (14)	−0.0069 (15)
C10	0.049 (2)	0.089 (3)	0.049 (2)	−0.0019 (19)	0.0160 (16)	−0.0052 (19)
C11	0.061 (2)	0.094 (3)	0.040 (2)	0.017 (2)	0.0122 (17)	−0.0105 (19)
C12	0.076 (3)	0.067 (2)	0.044 (2)	0.005 (2)	−0.0070 (18)	−0.0258 (17)
C13	0.0486 (18)	0.0480 (18)	0.0452 (19)	−0.0026 (15)	0.0009 (14)	−0.0070 (15)
C14	0.0394 (17)	0.0500 (19)	0.0521 (19)	0.0116 (15)	−0.0024 (14)	0.0048 (15)
C15	0.065 (2)	0.062 (2)	0.102 (3)	0.000 (2)	0.017 (2)	0.007 (2)

Geometric parameters (Å, º) top

Cu1—N1	1.981 (2)	C5—H5	0.9300
Cu1—N4	2.047 (2)	C6—C7	1.380 (4)
Cu1—Cl1	2.1969 (7)	C6—H6	0.9300
Cu1—Cl2	2.2121 (7)	C7—H7	0.9300
N1—C2	1.311 (3)	C8—C9	1.375 (4)
N1—N2	1.378 (3)	C8—C13	1.376 (4)
N2—C1	1.315 (3)	C9—C10	1.380 (4)
N3—C2	1.350 (3)	C9—H9	0.9300
N3—C1	1.375 (3)	C10—C11	1.356 (5)
N3—C8	1.449 (3)	C10—H10	0.9300
N4—C7	1.331 (3)	C11—C12	1.371 (5)
N4—C3	1.356 (3)	C11—H11	0.9300
C1—C14	1.496 (4)	C12—C13	1.388 (4)
O1—C15	1.403 (4)	C12—H12	0.9300
O1—C14	1.414 (3)	C13—H13	0.9300
C2—C3	1.459 (3)	C14—H14A	0.9700
C3—C4	1.377 (3)	C14—H14B	0.9700
C4—C5	1.390 (4)	C15—H15A	0.9600
C4—H4	0.9300	C15—H15B	0.9600
C5—C6	1.371 (4)	C15—H15C	0.9600

N1—Cu1—N4	79.86 (8)	C7—C6—H6	120.5
N1—Cu1—Cl1	98.75 (6)	N4—C7—C6	122.7 (3)
N4—Cu1—Cl1	152.04 (6)	N4—C7—H7	118.7
N1—Cu1—Cl2	150.56 (6)	C6—C7—H7	118.7
N4—Cu1—Cl2	95.26 (6)	C9—C8—C13	121.9 (3)
Cl1—Cu1—Cl2	98.65 (3)	C9—C8—N3	118.2 (2)
C2—N1—N2	109.3 (2)	C13—C8—N3	119.9 (2)
C2—N1—Cu1	114.52 (16)	C8—C9—C10	119.0 (3)
N2—N1—Cu1	135.85 (16)	C8—C9—H9	120.5
C1—N2—N1	105.3 (2)	C10—C9—H9	120.5
C2—N3—C1	104.8 (2)	C11—C10—C9	119.9 (3)
C2—N3—C8	128.4 (2)	C11—C10—H10	120.0
C1—N3—C8	126.3 (2)	C9—C10—H10	120.0
C7—N4—C3	118.3 (2)	C10—C11—C12	121.1 (3)
C7—N4—Cu1	126.09 (18)	C10—C11—H11	119.5
C3—N4—Cu1	115.22 (16)	C12—C11—H11	119.5
N2—C1—N3	111.0 (2)	C11—C12—C13	120.3 (3)
N2—C1—C14	125.8 (2)	C11—C12—H12	119.9
N3—C1—C14	123.2 (2)	C13—C12—H12	119.9
C15—O1—C14	112.8 (3)	C8—C13—C12	117.8 (3)
N1—C2—N3	109.5 (2)	C8—C13—H13	121.1
N1—C2—C3	119.3 (2)	C12—C13—H13	121.1
N3—C2—C3	131.2 (2)	O1—C14—C1	113.0 (2)
N4—C3—C4	122.1 (2)	O1—C14—H14A	109.0
N4—C3—C2	110.6 (2)	C1—C14—H14A	109.0
C4—C3—C2	127.2 (2)	O1—C14—H14B	109.0
C3—C4—C5	118.5 (3)	C1—C14—H14B	109.0
C3—C4—H4	120.7	H14A—C14—H14B	107.8
C5—C4—H4	120.7	O1—C15—H15A	109.5
C6—C5—C4	119.4 (3)	O1—C15—H15B	109.5
C6—C5—H5	120.3	H15A—C15—H15B	109.5
C4—C5—H5	120.3	O1—C15—H15C	109.5
C5—C6—C7	118.9 (3)	H15A—C15—H15C	109.5
C5—C6—H6	120.5	H15B—C15—H15C	109.5

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₅H₁₄N₄O)]
M_r	400.74
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	16.6512 (11), 11.2056 (7), 17.9966 (11)
V (Å³)	3357.9 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.63
Crystal size (mm)	0.15 × 0.13 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.792, 0.829
No. of measured, independent and observed [I > 2σ(I)] reflections	22829, 3043, 2288
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.068, 1.00
No. of reflections	3043
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.30

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We are grateful to Jingye Pharmochemical Pilot Plant for financial assistance though project 8507040052.

References

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