Di-μ-chlorido-bis­[2,2′-(propane-1,3-di­yl)bis­(2H-benzotriazole)-κ²N¹,N^1′]copper(I)]

Cupric chloride undergoes reduction in its reaction with 2,2′-(propane-1,3-di­yl)bis­(2H-benzotriazole) to form the centrosymmetic title compound, [Cu₂Cl₂(C₁₅H₁₄N₆)₂]. The organic ligand chelates the Cu^I atom and two adducts are linked through two chloride bridges into a dinuclear mol­ecule. The metal atom shows tetra­hedral coordination.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.104
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    -   Cl1     ..      29.99 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    -   N4      ..      10.91 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    -   Cl1_a   ..      69.69 su

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.592     0.748
            Tmin(prime) and Tmax expected:      0.681     0.734
            RR(prime) =      0.853
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.84
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   N1      ..       5.71 su

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (1)       0.94

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

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

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S1. Comment

The 2,2'-(propane-1,3-diyl)bis(2H-benzotriazole) heterocycle binds to two copper(I) atoms in the 1:1 adduct with copper(I) chloride to furnish a linear chain structure. The copper atom shows tetrahedral coordination (Table 1) as is covalently bonded to one chlorine atom and datively bonded to the adjacent one (Borsting & Steel, 2004). The present compound is a 1:1 adduct but the compound exists as a monomeric dinculear molecule as the heterocycle functions instead as a bidentate chelate (Fig. 1). However, bond dimensions involving the copper atom are not significantly difference, so that the different architectures reflect the flexible nature of the ligand, which possess three methylene linkages separating the fused-rings.

Related literature

For the isomeric chain structure, see Borsting & Steel (2004). For related literature, see: Xie et al. (2000).

S2. Experimental

A methanol solution (5 ml) of 2,2'-(propane-1,3-diyl)bis(2H-benzotriazole) (Xie et al., 2000) (55.6 mg, 0.2 mmol) was added to methanol solution (5 ml) of copper(II) dichloride dihydrate (17.1 mg, 0.1 mmol). The clear solution was set aside for a week for the growth of crystals. The yellow copper(I) chloride adduct is air stable.

S3. Refinement

The carbon-bound H atoms were placed in calculated positions [C—H = 0.93 to 0.97 Å], and were included in the refinement in the riding model approximation with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

Fig. 1. Thermal ellipsoid plot of (C15H14N6)2Cl2Cu2; displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radius. Symmetry code i: 1 – x, 1 – y, 1 – z.

Di-µ-chlorido-bis[2,2'-(propane-1,3-diyl)bis(2H-benzotriazole)-\k²N¹,N^1']copper(I)]

Crystal data

[Cu2Cl2(C15H14N6)2]	F(000) = 768
Mr = 754.62	Dx = 1.655 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3803 reflections
a = 9.886 (3) Å	θ = 2.1–27.9°
b = 10.055 (3) Å	µ = 1.63 mm^−1
c = 15.876 (4) Å	T = 295 K
β = 106.401 (4)°	Prism, yellow
V = 1514.0 (7) Å^3	0.23 × 0.20 × 0.19 mm
Z = 2

Data collection

Rigaku Saturn diffractometer	3592 independent reflections
Radiation source: fine-focus sealed tube	3425 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 27.9°, θmin = 2.8°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2006)	h = −13→12
Tmin = 0.592, Tmax = 0.748	k = −12→13
17855 measured reflections	l = −20→20

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0602P)^2 + 0.7057P] where P = (Fo^2 + 2Fc^2)/3
3592 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.81 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.37039 (3)	0.44465 (3)	0.431367 (18)	0.04155 (11)
Cl1	0.53996 (5)	0.58239 (5)	0.40490 (3)	0.03700 (13)
N1	0.16588 (17)	0.50352 (17)	0.40525 (10)	0.0339 (3)
N2	0.06485 (18)	0.42252 (17)	0.41610 (11)	0.0364 (4)
N3	−0.06712 (19)	0.4634 (2)	0.38526 (13)	0.0444 (4)
N4	0.38999 (18)	0.25130 (16)	0.39053 (11)	0.0352 (3)
N5	0.29088 (18)	0.16622 (17)	0.34729 (10)	0.0366 (3)
N6	0.3327 (2)	0.04471 (17)	0.33617 (13)	0.0431 (4)
C1	0.0923 (2)	0.6102 (2)	0.36354 (12)	0.0348 (4)
C2	0.1380 (2)	0.7295 (2)	0.33471 (13)	0.0412 (4)
H2	0.2333	0.7481	0.3440	0.049*
C3	0.0357 (3)	0.8171 (2)	0.29235 (15)	0.0504 (5)
H3	0.0623	0.8968	0.2719	0.060*
C4	−0.1112 (3)	0.7899 (3)	0.27846 (16)	0.0568 (6)
H4	−0.1773	0.8517	0.2484	0.068*
C5	−0.1564 (3)	0.6767 (3)	0.30800 (16)	0.0537 (6)
H5	−0.2518	0.6605	0.3002	0.064*
C6	−0.0523 (2)	0.5844 (2)	0.35115 (14)	0.0401 (4)
C7	0.0958 (2)	0.2884 (2)	0.45160 (13)	0.0398 (4)
H7A	0.0414	0.2703	0.4925	0.048*
H7B	0.1951	0.2816	0.4832	0.048*
C8	0.0595 (2)	0.1869 (2)	0.37756 (14)	0.0425 (4)
H8A	−0.0402	0.1937	0.3471	0.051*
H8B	0.0767	0.0984	0.4026	0.051*
C9	0.1437 (2)	0.2046 (2)	0.31134 (13)	0.0398 (4)
H9A	0.1014	0.1511	0.2598	0.048*
H9B	0.1391	0.2970	0.2931	0.048*
C10	0.4737 (2)	0.04905 (19)	0.37568 (14)	0.0390 (4)
C11	0.5774 (3)	−0.0498 (2)	0.38292 (17)	0.0509 (6)
H11	0.5546	−0.1354	0.3613	0.061*
C12	0.7128 (3)	−0.0132 (3)	0.42332 (16)	0.0509 (5)
H12	0.7843	−0.0754	0.4286	0.061*
C13	0.7485 (2)	0.1159 (2)	0.45750 (16)	0.0474 (5)
H13	0.8425	0.1354	0.4850	0.057*
C14	0.6498 (2)	0.2130 (2)	0.45152 (15)	0.0429 (4)
H14	0.6740	0.2978	0.4742	0.052*
C15	0.5096 (2)	0.17771 (19)	0.40924 (12)	0.0348 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03493 (17)	0.03753 (17)	0.04959 (18)	−0.00308 (9)	0.00770 (12)	−0.00336 (10)
Cl1	0.0374 (2)	0.0393 (2)	0.0299 (2)	−0.01079 (18)	0.00249 (17)	0.00473 (17)
N1	0.0309 (8)	0.0358 (8)	0.0344 (8)	−0.0022 (6)	0.0080 (6)	−0.0020 (6)
N2	0.0313 (8)	0.0411 (9)	0.0367 (8)	−0.0042 (7)	0.0093 (6)	−0.0022 (7)
N3	0.0321 (9)	0.0526 (11)	0.0486 (10)	−0.0010 (8)	0.0115 (8)	−0.0040 (8)
N4	0.0374 (8)	0.0316 (8)	0.0344 (8)	−0.0036 (6)	0.0064 (6)	−0.0065 (6)
N5	0.0399 (9)	0.0339 (8)	0.0335 (7)	−0.0058 (7)	0.0063 (6)	−0.0061 (6)
N6	0.0503 (11)	0.0310 (8)	0.0444 (9)	−0.0062 (7)	0.0073 (8)	−0.0058 (7)
C1	0.0350 (9)	0.0379 (10)	0.0295 (8)	0.0014 (8)	0.0060 (7)	−0.0053 (7)
C2	0.0478 (11)	0.0374 (10)	0.0380 (10)	0.0001 (9)	0.0115 (8)	−0.0031 (8)
C3	0.0694 (16)	0.0388 (11)	0.0416 (11)	0.0080 (10)	0.0134 (10)	−0.0009 (9)
C4	0.0585 (14)	0.0567 (14)	0.0488 (12)	0.0221 (12)	0.0049 (11)	−0.0015 (11)
C5	0.0389 (11)	0.0632 (15)	0.0533 (13)	0.0137 (11)	0.0038 (10)	−0.0044 (11)
C6	0.0341 (10)	0.0472 (11)	0.0374 (10)	0.0032 (8)	0.0077 (8)	−0.0065 (8)
C7	0.0425 (11)	0.0401 (10)	0.0370 (9)	−0.0067 (8)	0.0114 (8)	0.0033 (8)
C8	0.0383 (10)	0.0421 (11)	0.0445 (10)	−0.0086 (9)	0.0076 (8)	−0.0023 (9)
C9	0.0382 (10)	0.0445 (11)	0.0317 (9)	−0.0064 (8)	0.0019 (7)	−0.0062 (8)
C10	0.0486 (12)	0.0297 (9)	0.0366 (9)	−0.0023 (8)	0.0088 (8)	−0.0011 (7)
C11	0.0640 (15)	0.0319 (10)	0.0518 (13)	0.0067 (10)	0.0082 (11)	−0.0037 (9)
C12	0.0564 (14)	0.0431 (12)	0.0510 (12)	0.0149 (11)	0.0112 (11)	0.0020 (10)
C13	0.0411 (11)	0.0490 (13)	0.0496 (12)	0.0023 (10)	0.0086 (9)	−0.0012 (10)
C14	0.0416 (11)	0.0369 (10)	0.0471 (11)	−0.0024 (8)	0.0073 (9)	−0.0069 (8)
C15	0.0403 (10)	0.0323 (9)	0.0314 (8)	−0.0011 (8)	0.0093 (7)	−0.0026 (7)

Geometric parameters (Å, º)

Cu1—N1	2.034 (2)	C4—H4	0.9300
Cu1—N4	2.076 (2)	C5—C6	1.411 (3)
Cu1—Cl1	2.3028 (7)	C5—H5	0.9300
Cu1—Cl1^i	2.5131 (8)	C7—C8	1.521 (3)
Cl1—Cu1^i	2.5131 (8)	C7—H7A	0.9700
N1—N2	1.337 (2)	C7—H7B	0.9700
N1—C1	1.359 (3)	C8—C9	1.524 (3)
N2—N3	1.323 (3)	C8—H8A	0.9700
N2—C7	1.460 (3)	C8—H8B	0.9700
N3—C6	1.356 (3)	C9—H9A	0.9700
N4—N5	1.335 (2)	C9—H9B	0.9700
N4—C15	1.355 (3)	C10—C15	1.406 (3)
N5—N6	1.318 (2)	C10—C11	1.409 (3)
N5—C9	1.457 (3)	C11—C12	1.361 (4)
N6—C10	1.358 (3)	C11—H11	0.9300
C1—C2	1.404 (3)	C12—C13	1.413 (4)
C1—C6	1.411 (3)	C12—H12	0.9300
C2—C3	1.366 (3)	C13—C14	1.365 (3)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.433 (4)	C14—C15	1.405 (3)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.354 (4)
N1—Cu1—N4	112.58 (7)	C1—C6—C5	121.2 (2)
N1—Cu1—Cl1	121.38 (5)	N2—C7—C8	110.08 (17)
N1—Cu1—Cl1^i	106.40 (5)	N2—C7—H7A	109.6
N4—Cu1—Cl1	111.68 (5)	C8—C7—H7A	109.6
N4—Cu1—Cl1^i	100.66 (5)	N2—C7—H7B	109.6
Cl1—Cu1—Cl1^i	101.04 (2)	C8—C7—H7B	109.6
Cu1—Cl1—Cu1^i	78.957 (19)	H7A—C7—H7B	108.2
N2—N1—C1	103.12 (16)	C7—C8—C9	113.52 (17)
N2—N1—Cu1	122.15 (13)	C7—C8—H8A	108.9
C1—N1—Cu1	133.93 (14)	C9—C8—H8A	108.9
N3—N2—N1	117.21 (17)	C7—C8—H8B	108.9
N3—N2—C7	120.49 (17)	C9—C8—H8B	108.9
N1—N2—C7	121.96 (17)	H8A—C8—H8B	107.7
N2—N3—C6	102.74 (17)	N5—C9—C8	112.22 (17)
N5—N4—C15	103.35 (16)	N5—C9—H9A	109.2
N5—N4—Cu1	129.87 (13)	C8—C9—H9A	109.2
C15—N4—Cu1	126.57 (13)	N5—C9—H9B	109.2
N6—N5—N4	116.77 (17)	C8—C9—H9B	109.2
N6—N5—C9	120.65 (17)	H9A—C9—H9B	107.9
N4—N5—C9	122.56 (17)	N6—C10—C15	108.71 (18)
N5—N6—C10	103.20 (16)	N6—C10—C11	130.0 (2)
N1—C1—C2	131.01 (19)	C15—C10—C11	121.2 (2)
N1—C1—C6	107.76 (18)	C12—C11—C10	116.3 (2)
C2—C1—C6	121.2 (2)	C12—C11—H11	121.9
C3—C2—C1	116.7 (2)	C10—C11—H11	121.9
C3—C2—H2	121.6	C11—C12—C13	122.4 (2)
C1—C2—H2	121.6	C11—C12—H12	118.8
C2—C3—C4	122.0 (2)	C13—C12—H12	118.8
C2—C3—H3	119.0	C14—C13—C12	122.3 (2)
C4—C3—H3	119.0	C14—C13—H13	118.8
C5—C4—C3	121.8 (2)	C12—C13—H13	118.8
C5—C4—H4	119.1	C13—C14—C15	116.2 (2)
C3—C4—H4	119.1	C13—C14—H14	121.9
C4—C5—C6	117.0 (2)	C15—C14—H14	121.9
C4—C5—H5	121.5	N4—C15—C14	130.47 (19)
C6—C5—H5	121.5	N4—C15—C10	107.97 (18)
N3—C6—C1	109.17 (19)	C14—C15—C10	121.54 (19)
N3—C6—C5	129.6 (2)
N1—Cu1—Cl1—Cu1^i	117.13 (6)	C2—C3—C4—C5	1.1 (4)
N4—Cu1—Cl1—Cu1^i	−106.28 (5)	C3—C4—C5—C6	−1.7 (4)
Cl1^i—Cu1—Cl1—Cu1^i	0.0	N2—N3—C6—C1	0.2 (2)
N4—Cu1—N1—N2	40.36 (16)	N2—N3—C6—C5	179.3 (2)
Cl1—Cu1—N1—N2	176.60 (12)	N1—C1—C6—N3	0.3 (2)
Cl1^i—Cu1—N1—N2	−68.98 (14)	C2—C1—C6—N3	−179.66 (18)
N4—Cu1—N1—C1	−127.53 (17)	N1—C1—C6—C5	−178.99 (19)
Cl1—Cu1—N1—C1	8.7 (2)	C2—C1—C6—C5	1.1 (3)
Cl1^i—Cu1—N1—C1	123.13 (17)	C4—C5—C6—N3	−178.5 (2)
C1—N1—N2—N3	0.7 (2)	C4—C5—C6—C1	0.6 (3)
Cu1—N1—N2—N3	−170.33 (14)	N3—N2—C7—C8	72.4 (2)
C1—N1—N2—C7	174.18 (17)	N1—N2—C7—C8	−100.8 (2)
Cu1—N1—N2—C7	3.1 (2)	N2—C7—C8—C9	61.2 (2)
N1—N2—N3—C6	−0.6 (2)	N6—N5—C9—C8	93.2 (2)
C7—N2—N3—C6	−174.12 (18)	N4—N5—C9—C8	−88.6 (2)
N1—Cu1—N4—N5	3.63 (19)	C7—C8—C9—N5	71.6 (2)
Cl1—Cu1—N4—N5	−136.92 (15)	N5—N6—C10—C15	−0.1 (2)
Cl1^i—Cu1—N4—N5	116.54 (16)	N5—N6—C10—C11	−177.7 (2)
N1—Cu1—N4—C15	−170.15 (15)	N6—C10—C11—C12	176.9 (2)
Cl1—Cu1—N4—C15	49.30 (17)	C15—C10—C11—C12	−0.5 (3)
Cl1^i—Cu1—N4—C15	−57.23 (16)	C10—C11—C12—C13	0.9 (4)
C15—N4—N5—N6	0.4 (2)	C11—C12—C13—C14	−0.7 (4)
Cu1—N4—N5—N6	−174.49 (14)	C12—C13—C14—C15	0.0 (4)
C15—N4—N5—C9	−177.89 (17)	N5—N4—C15—C14	177.8 (2)
Cu1—N4—N5—C9	7.2 (3)	Cu1—N4—C15—C14	−7.1 (3)
N4—N5—N6—C10	−0.2 (2)	N5—N4—C15—C10	−0.4 (2)
C9—N5—N6—C10	178.15 (17)	Cu1—N4—C15—C10	174.66 (13)
N2—N1—C1—C2	179.3 (2)	C13—C14—C15—N4	−177.6 (2)
Cu1—N1—C1—C2	−11.2 (3)	C13—C14—C15—C10	0.4 (3)
N2—N1—C1—C6	−0.6 (2)	N6—C10—C15—N4	0.4 (2)
Cu1—N1—C1—C6	168.93 (14)	C11—C10—C15—N4	178.2 (2)
N1—C1—C2—C3	178.5 (2)	N6—C10—C15—C14	−178.04 (19)
C6—C1—C2—C3	−1.7 (3)	C11—C10—C15—C14	−0.2 (3)
C1—C2—C3—C4	0.6 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.