Bis[(1H-1,2,3-benzotriazol-1-yl)methyl 2,2-dimethyl­propano­ato-κN3]dichlorido­copper(II)

Cao, G.; Guo, T.; Xu, S.

doi:10.1107/S1600536812015486

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m607

doi:10.1107/S1600536812015486

Open

access

Bis[(1H-1,2,3-benzotriazol-1-yl)methyl 2,2-dimethylpropanoato-κN³]dichloridocopper(II)

Gang Cao,^a Ting Guo ^a ^* and Sen Xu ^b

^aDepartment of Stomatology, Nanjing Jinling Hospital, Nanjing University School of Medicine, 305 East Zhongshan Road, 210002 Nanjing, Jiangsu Province, People's Republic of China, and ^bDepartment of Applied Chemistry, School of Material Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing, Jiangsu Province 210016, People's Republic of China
^*Correspondence e-mail: guoting69@163.com

(Received 26 March 2012; accepted 10 April 2012; online 18 April 2012)

In the title compound, [CuCl₂(C₁₂H₁₅N₃O₂)₂], the Cu^II ion is located on an inversion center and is four-coordinated in a distorted square-planar geometry by two chloride anions and two N atoms from two (1H-1,2,3-benzotriazol-1-yl)methyl 2,2-dimethylpropanoate ligands. The Cl—Cu—N angles of 90.55 (9) and 89.45 (9)° are close to ideal values. In the crystal, weak π–π stacking interactions are observed between inversion-related benzene rings [centroid–centroid distance = 4.0028 (6) Å].

Related literature

For related structures, see: Wang (2008 ); Tang et al. (2011 ). For the structure of the free benzotriazole ligand, see: Xu & Shen (2012 ).

Experimental

Crystal data

[CuCl₂(C₁₂H₁₅N₃O₂)₂]
M_r = 600.98
Monoclinic, P 2₁ /c
a = 10.1929 (19) Å
b = 14.576 (2) Å
c = 9.2565 (15) Å
β = 96.499 (14)°
V = 1366.4 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.19 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.820, T_max = 0.828
9798 measured reflections
2412 independent reflections
2025 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.101
S = 1.15
2412 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812015486/bh2425sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812015486/bh2425Isup2.hkl

checkCIF report

Comment top

We recently synthesized a new benzotriazole derivative, L, namely (1H-1,2,3-benzotriazol-1-yl)methyl 2,2-dimethylpropanoate (Xu & Shen, 2012). For continuing our work, we now synthesized the title compound, [CuCl₂(L)₂]. The asymmetric unit contains one half of a complex, with the Cu^II ion located on an inversion center (Fig. 1). The metal is four-coordinated in the common square-planar geometry by two chloride anions and two N atoms from two L ligands. Bond lengths, Cu—N = 2.018 (3) and Cu—Cl = 2.2377 (11) Å, are comparable to distances found in other reports (Wang, 2008; Tang et al., 2011). In the crystal, there are C—H···O and C—H···Cl weak hydrogen bonds interactions, and weak π–π stacking interactions between inversion-related benzene rings [centroid to centroid distance = 4.0028 (6)°].

Related literature top

For related structures, see: Wang (2008); Tang et al. (2011). For the structure of the free benzotriazole ligand, see: Xu & Shen (2012).

Experimental top

(1H-benzo[d][1,2,3]triazol-1-yl)methyl pivalate (0.25 mmol, Xu & Shen, 2012) and copper chloride (0.25 mmol) were mixed in a round bottom flask, with 10 ml of absolute ethyl alcohol, and stirred for 10 h. After reaction completed, white solids were obtained, which were dissolved in ethanol. Blue crystals suitable for X-ray analysis were obtained by slow evaporation of ethanol, at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level (Symmetry code #1: 1-x, -y, -z).

Bis[(1H-1,2,3-benzotriazol-1-yl)methyl 2,2-dimethylpropanoato-κN³]dichloridocopper(II) top

Crystal data top

[CuCl₂(C₁₂H₁₅N₃O₂)₂]	F(000) = 622
M_r = 600.98	D_x = 1.461 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3200 reflections
a = 10.1929 (19) Å	θ = 2.5–26.6°
b = 14.576 (2) Å	µ = 1.04 mm⁻¹
c = 9.2565 (15) Å	T = 296 K
β = 96.499 (14)°	Block, blue
V = 1366.4 (4) Å³	0.20 × 0.20 × 0.19 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2412 independent reflections
Radiation source: fine-focus sealed tube	2025 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.0°, θ_min = 2.0°
ϕ and ω scans	h = −11→12
Absorption correction: multi-scan (SABADS; Sheldrick, 1996)	k = −17→17
T_min = 0.820, T_max = 0.828	l = −10→11
9798 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0095P)² + 1.8659P] where P = (F_o² + 2F_c²)/3
2412 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³
0 constraints

Crystal data top

[CuCl₂(C₁₂H₁₅N₃O₂)₂]	V = 1366.4 (4) Å³
M_r = 600.98	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.1929 (19) Å	µ = 1.04 mm⁻¹
b = 14.576 (2) Å	T = 296 K
c = 9.2565 (15) Å	0.20 × 0.20 × 0.19 mm
β = 96.499 (14)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2412 independent reflections
Absorption correction: multi-scan (SABADS; Sheldrick, 1996)	2025 reflections with I > 2σ(I)
T_min = 0.820, T_max = 0.828	R_int = 0.048
9798 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.15	Δρ_max = 0.26 e Å⁻³
2412 reflections	Δρ_min = −0.39 e Å⁻³
172 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3811 (3)	−0.0246 (3)	0.2886 (4)	0.0350 (8)
C2	0.3663 (4)	−0.1197 (3)	0.2948 (4)	0.0413 (9)
H2	0.3859	−0.1575	0.2192	0.050*
C3	0.3216 (4)	−0.1545 (3)	0.4170 (4)	0.0488 (10)
H3	0.3111	−0.2176	0.4246	0.059*
C4	0.2909 (4)	−0.0983 (3)	0.5317 (4)	0.0503 (11)
H4	0.2610	−0.1253	0.6129	0.060*
C5	0.3036 (4)	−0.0055 (3)	0.5273 (4)	0.0459 (10)
H5	0.2829	0.0320	0.6028	0.055*
C6	0.3496 (3)	0.0301 (3)	0.4023 (4)	0.0350 (8)
C7	0.3690 (4)	0.2011 (3)	0.4420 (4)	0.0436 (10)
H7A	0.4024	0.1906	0.5430	0.052*
H7B	0.4236	0.2477	0.4037	0.052*
C8	0.2046 (4)	0.3077 (3)	0.3507 (4)	0.0442 (10)
C9	0.0678 (4)	0.3415 (3)	0.3700 (4)	0.0441 (10)
C10	−0.0319 (4)	0.2630 (3)	0.3583 (6)	0.0661 (14)
H10A	−0.0393	0.2379	0.2619	0.099*
H10B	−0.1165	0.2857	0.3783	0.099*
H10C	−0.0029	0.2161	0.4274	0.099*
C11	0.0769 (4)	0.3834 (3)	0.5231 (5)	0.0570 (12)
H11A	0.1074	0.3378	0.5937	0.085*
H11B	−0.0088	0.4047	0.5417	0.085*
H11C	0.1375	0.4340	0.5294	0.085*
C12	0.0271 (5)	0.4150 (3)	0.2566 (5)	0.0610 (13)
H12A	0.0880	0.4654	0.2690	0.092*
H12B	−0.0602	0.4363	0.2683	0.092*
H12C	0.0279	0.3895	0.1611	0.092*
Cl1	0.31996 (11)	−0.08447 (8)	−0.06653 (11)	0.0563 (3)
Cu1	0.5000	0.0000	0.0000	0.03856 (19)
N1	0.4260 (3)	0.0325 (2)	0.1866 (3)	0.0398 (8)
N2	0.4237 (3)	0.1178 (2)	0.2304 (3)	0.0414 (8)
N3	0.3767 (3)	0.1173 (2)	0.3608 (3)	0.0375 (7)
O1	0.2367 (3)	0.23282 (18)	0.4335 (3)	0.0461 (7)
O2	0.2812 (3)	0.3406 (2)	0.2781 (4)	0.0846 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0313 (19)	0.040 (2)	0.0332 (19)	0.0021 (16)	0.0034 (15)	−0.0014 (16)
C2	0.042 (2)	0.043 (2)	0.038 (2)	0.0008 (18)	0.0036 (17)	−0.0064 (18)
C3	0.048 (2)	0.047 (3)	0.049 (2)	−0.005 (2)	−0.0013 (19)	0.005 (2)
C4	0.052 (3)	0.060 (3)	0.040 (2)	−0.010 (2)	0.0068 (19)	0.007 (2)
C5	0.045 (2)	0.057 (3)	0.037 (2)	0.000 (2)	0.0082 (17)	−0.003 (2)
C6	0.032 (2)	0.041 (2)	0.033 (2)	0.0044 (17)	0.0076 (15)	−0.0002 (17)
C7	0.039 (2)	0.043 (2)	0.049 (2)	0.0064 (18)	0.0088 (18)	−0.0093 (19)
C8	0.053 (3)	0.041 (2)	0.040 (2)	0.001 (2)	0.0164 (19)	0.0003 (19)
C9	0.044 (2)	0.041 (2)	0.049 (2)	0.0072 (19)	0.0108 (18)	0.0018 (19)
C10	0.047 (3)	0.061 (3)	0.092 (4)	0.000 (2)	0.014 (3)	0.004 (3)
C11	0.061 (3)	0.057 (3)	0.056 (3)	0.020 (2)	0.020 (2)	0.000 (2)
C12	0.062 (3)	0.064 (3)	0.057 (3)	0.018 (2)	0.007 (2)	0.009 (2)
Cl1	0.0553 (7)	0.0696 (8)	0.0458 (6)	−0.0151 (6)	0.0141 (5)	−0.0123 (5)
Cu1	0.0461 (4)	0.0381 (4)	0.0336 (4)	0.0010 (3)	0.0136 (3)	−0.0033 (3)
N1	0.0450 (19)	0.0386 (19)	0.0374 (18)	0.0017 (15)	0.0107 (14)	−0.0057 (15)
N2	0.046 (2)	0.041 (2)	0.0382 (18)	0.0028 (15)	0.0132 (15)	−0.0009 (15)
N3	0.0396 (18)	0.0411 (19)	0.0328 (16)	0.0078 (15)	0.0087 (13)	−0.0043 (14)
O1	0.0432 (16)	0.0388 (16)	0.0592 (17)	0.0125 (13)	0.0189 (13)	0.0043 (14)
O2	0.078 (2)	0.085 (3)	0.102 (3)	0.034 (2)	0.054 (2)	0.048 (2)

Geometric parameters (Å, º) top

C1—N1	1.375 (5)	C9—C12	1.524 (5)
C1—C6	1.386 (5)	C9—C10	1.526 (6)
C1—C2	1.396 (5)	C9—C11	1.536 (5)
C2—C3	1.364 (5)	C10—H10A	0.9600
C2—H2	0.9300	C10—H10B	0.9600
C3—C4	1.404 (6)	C10—H10C	0.9600
C3—H3	0.9300	C11—H11A	0.9600
C4—C5	1.360 (6)	C11—H11B	0.9600
C4—H4	0.9300	C11—H11C	0.9600
C5—C6	1.397 (5)	C12—H12A	0.9600
C5—H5	0.9300	C12—H12B	0.9600
C6—N3	1.365 (5)	C12—H12C	0.9600
C7—O1	1.418 (4)	Cl1—Cu1	2.2377 (11)
C7—N3	1.442 (5)	Cu1—N1ⁱ	2.018 (3)
C7—H7A	0.9700	Cu1—N1	2.018 (3)
C7—H7B	0.9700	Cu1—Cl1ⁱ	2.2377 (11)
C8—O2	1.188 (5)	N1—N2	1.309 (4)
C8—O1	1.352 (5)	N2—N3	1.347 (4)
C8—C9	1.508 (5)

N1—C1—C6	107.3 (3)	C9—C10—H10A	109.5
N1—C1—C2	132.4 (3)	C9—C10—H10B	109.5
C6—C1—C2	120.3 (4)	H10A—C10—H10B	109.5
C3—C2—C1	116.8 (4)	C9—C10—H10C	109.5
C3—C2—H2	121.6	H10A—C10—H10C	109.5
C1—C2—H2	121.6	H10B—C10—H10C	109.5
C2—C3—C4	122.3 (4)	C9—C11—H11A	109.5
C2—C3—H3	118.8	C9—C11—H11B	109.5
C4—C3—H3	118.8	H11A—C11—H11B	109.5
C5—C4—C3	121.8 (4)	C9—C11—H11C	109.5
C5—C4—H4	119.1	H11A—C11—H11C	109.5
C3—C4—H4	119.1	H11B—C11—H11C	109.5
C4—C5—C6	115.9 (4)	C9—C12—H12A	109.5
C4—C5—H5	122.1	C9—C12—H12B	109.5
C6—C5—H5	122.1	H12A—C12—H12B	109.5
N3—C6—C1	104.5 (3)	C9—C12—H12C	109.5
N3—C6—C5	132.6 (4)	H12A—C12—H12C	109.5
C1—C6—C5	122.9 (4)	H12B—C12—H12C	109.5
O1—C7—N3	110.8 (3)	N1ⁱ—Cu1—N1	180.0
O1—C7—H7A	109.5	N1ⁱ—Cu1—Cl1	90.55 (9)
N3—C7—H7A	109.5	N1—Cu1—Cl1	89.45 (9)
O1—C7—H7B	109.5	N1ⁱ—Cu1—Cl1ⁱ	89.45 (9)
N3—C7—H7B	109.5	N1—Cu1—Cl1ⁱ	90.55 (9)
H7A—C7—H7B	108.1	Cl1—Cu1—Cl1ⁱ	180.0
O2—C8—O1	121.0 (4)	N2—N1—C1	110.1 (3)
O2—C8—C9	127.6 (4)	N2—N1—Cu1	120.7 (2)
O1—C8—C9	111.4 (3)	C1—N1—Cu1	129.1 (3)
C8—C9—C12	109.3 (3)	N1—N2—N3	107.0 (3)
C8—C9—C10	111.4 (3)	N2—N3—C6	111.2 (3)
C12—C9—C10	110.5 (4)	N2—N3—C7	120.5 (3)
C8—C9—C11	106.3 (3)	C6—N3—C7	128.1 (3)
C12—C9—C11	109.8 (3)	C8—O1—C7	117.5 (3)
C10—C9—C11	109.5 (4)

N1—C1—C2—C3	178.1 (4)	C6—C1—N1—Cu1	175.6 (2)
C6—C1—C2—C3	−0.8 (5)	C2—C1—N1—Cu1	−3.4 (6)
C1—C2—C3—C4	0.4 (6)	Cl1—Cu1—N1—N2	−131.5 (3)
C2—C3—C4—C5	0.2 (6)	Cl1ⁱ—Cu1—N1—N2	48.5 (3)
C3—C4—C5—C6	−0.3 (6)	Cl1—Cu1—N1—C1	53.3 (3)
N1—C1—C6—N3	0.4 (4)	Cl1ⁱ—Cu1—N1—C1	−126.7 (3)
C2—C1—C6—N3	179.5 (3)	C1—N1—N2—N3	−0.3 (4)
N1—C1—C6—C5	−178.4 (3)	Cu1—N1—N2—N3	−176.4 (2)
C2—C1—C6—C5	0.7 (6)	N1—N2—N3—C6	0.6 (4)
C4—C5—C6—N3	−178.6 (4)	N1—N2—N3—C7	176.6 (3)
C4—C5—C6—C1	−0.1 (6)	C1—C6—N3—N2	−0.6 (4)
O2—C8—C9—C12	12.0 (6)	C5—C6—N3—N2	178.0 (4)
O1—C8—C9—C12	−170.4 (3)	C1—C6—N3—C7	−176.2 (3)
O2—C8—C9—C10	134.4 (5)	C5—C6—N3—C7	2.5 (7)
O1—C8—C9—C10	−48.0 (5)	O1—C7—N3—N2	104.3 (4)
O2—C8—C9—C11	−106.5 (5)	O1—C7—N3—C6	−80.5 (5)
O1—C8—C9—C11	71.2 (4)	O2—C8—O1—C7	6.4 (6)
C6—C1—N1—N2	0.0 (4)	C9—C8—O1—C7	−171.4 (3)
C2—C1—N1—N2	−179.0 (4)	N3—C7—O1—C8	−107.4 (4)

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₂H₁₅N₃O₂)₂]
M_r	600.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.1929 (19), 14.576 (2), 9.2565 (15)
β (°)	96.499 (14)
V (Å³)	1366.4 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.20 × 0.20 × 0.19

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SABADS; Sheldrick, 1996)
T_min, T_max	0.820, 0.828
No. of measured, independent and observed [I > 2σ(I)] reflections	9798, 2412, 2025
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.101, 1.15
No. of reflections	2412
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.39

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Jinling Hospital Foundation of Nanjing Province of China (2009Q021), the Surface Project Foundation of Nanjing Military Region (11 MA099) and the Surface Project Foundation of Nanjing Military Region (10MA095).

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tang, X.-L., Dou, W., Zhou, J., Zhang, G.-L., Liu, W.-S., Yang, L.-Z. & Shao, Y.-L. (2011). CrystEngComm, 13, 2890–2898. Web of Science CSD CrossRef CAS Google Scholar
Wang, W. (2008). Acta Cryst. E64, m998. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, S. & Shen, Y. (2012). Acta Cryst. E68, o1066. CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.