Di-μ-chlorido-bis­[(2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)copper(II)] bis­(tri­fluoro­methane­sulfonate)

In the centrosymmetric title complex, [Cu₂Cl₂(C₁₅H₁₁N₃)₂](CF₃O₃S)₂, the Cu^II metal center is fivefold coordinated by two chloride ions and three nitro­gen atoms of the terpyridine ligand in a distorted square-pyramidal geometry; two tri­fluoro­methane­sulfonate ions complete the outer coordination sphere. π–π stacking inter­actions between the pyridyl rings in adjacent mol­ecules contribute to the alignment of the complexes in columns along the a-axis. This structure represents the first example of a binuclear dication of formula [Cu(terpy)₂Cl₂]²⁺ with tri­fluoro­methane­sulfonate as counter-ions.

Key indicators

• Single-crystal X-ray study
• T = 98 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.094
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.324 Check

Alert level G
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.002 Degree
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N2       .        5.0 s.u.
PLAT244_ALERT_4_G Low    'Solvent' Ueq as Compared to Neighbors of        C16 Check
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.20 Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          5 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2019); cell refinement: CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Di-µ-chlorido-bis[(2,2':6',2''-terpyridine-κ³N,N',N'')copper(II)] bis(trifluoromethanesulfonate)

Crystal data

[Cu2Cl2(C15H11N3)2](CF3O3S)2	Z = 1
Mr = 962.65	F(000) = 482
Triclinic, P1	Dx = 1.846 Mg m^−3
a = 7.2767 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8394 (2) Å	Cell parameters from 14071 reflections
c = 13.1746 (3) Å	θ = 3.1–29.5°
α = 106.667 (2)°	µ = 1.59 mm^−1
β = 91.226 (2)°	T = 98 K
γ = 105.453 (2)°	Block, clear bluish green
V = 866.08 (4) Å^3	0.47 × 0.17 × 0.1 mm

Data collection

XtaLAB AFC12 (RCD3): Kappa single diffractometer	3889 reflections with I > 2σ(I)
Radiation source: Rotating-anode X-ray tube, Rigaku (Mo) X-ray Source	Rint = 0.047
ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	h = −9→9
Tmin = 0.741, Tmax = 1.000	k = −12→12
33748 measured reflections	l = −16→17
3982 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0529P)^2 + 0.6752P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.002
3982 reflections	Δρmax = 0.55 e Å^−3
253 parameters	Δρmin = −0.41 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. H atoms were located in a difference map and refined in idealized positions using a riding model with atomic displacement parameters of U_iso(H) = 1.2U_eq(C) and with a C—H distance of 0.95 Å.

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

	x	y	z	Uiso*/Ueq
Cu1	0.49265 (4)	0.41355 (3)	0.60172 (2)	0.01772 (10)
Cl1	0.62384 (8)	0.36614 (6)	0.44902 (4)	0.02026 (13)
S1	0.50126 (8)	0.15121 (6)	0.79698 (4)	0.02142 (13)
F2	0.7785 (2)	0.02432 (18)	0.78751 (14)	0.0396 (4)
F1	0.6642 (2)	0.06787 (19)	0.93864 (12)	0.0395 (4)
F3	0.5041 (2)	−0.11260 (17)	0.80642 (16)	0.0478 (4)
O1	0.6469 (2)	0.29199 (17)	0.83604 (12)	0.0239 (3)
O3	0.3333 (2)	0.1385 (2)	0.85354 (15)	0.0336 (4)
O2	0.4661 (3)	0.0941 (2)	0.68265 (13)	0.0360 (4)
N3	0.2255 (3)	0.27262 (19)	0.55326 (14)	0.0188 (4)
N2	0.3802 (3)	0.45334 (19)	0.73563 (14)	0.0168 (3)
N1	0.7290 (3)	0.55151 (19)	0.70135 (14)	0.0184 (4)
C11	0.1030 (3)	0.2851 (2)	0.62992 (16)	0.0192 (4)
C5	0.6901 (3)	0.6111 (2)	0.80261 (16)	0.0189 (4)
C10	0.1958 (3)	0.3840 (2)	0.73629 (16)	0.0186 (4)
C6	0.4902 (3)	0.5499 (2)	0.82254 (16)	0.0179 (4)
C9	0.1110 (3)	0.4087 (2)	0.83124 (17)	0.0220 (4)
H9	−0.019262	0.358669	0.833457	0.026*
C15	0.1555 (3)	0.1851 (2)	0.45439 (17)	0.0220 (4)
H15	0.240897	0.174252	0.401071	0.026*
C14	−0.0386 (3)	0.1094 (2)	0.42706 (18)	0.0238 (5)
H14	−0.084305	0.047636	0.356325	0.029*
C12	−0.0910 (3)	0.2144 (2)	0.60811 (17)	0.0212 (4)
H12	−0.173957	0.225959	0.662670	0.025*
C13	−0.1631 (3)	0.1253 (2)	0.50390 (18)	0.0231 (4)
H13	−0.296333	0.076425	0.486484	0.028*
C7	0.4138 (3)	0.5820 (2)	0.91921 (16)	0.0208 (4)
H7	0.489630	0.651756	0.981351	0.025*
C4	0.8284 (3)	0.7197 (3)	0.87846 (17)	0.0225 (4)
H4	0.798549	0.759683	0.948670	0.027*
C8	0.2229 (3)	0.5089 (3)	0.92254 (17)	0.0237 (5)
H8	0.168203	0.527811	0.988179	0.028*
C2	1.0514 (3)	0.7057 (3)	0.74756 (18)	0.0241 (5)
H2	1.176548	0.735707	0.727006	0.029*
C16	0.6177 (3)	0.0264 (3)	0.83346 (19)	0.0266 (5)
C1	0.9066 (3)	0.5979 (2)	0.67581 (17)	0.0216 (4)
H1	0.934595	0.555208	0.605681	0.026*
C3	1.0114 (3)	0.7691 (3)	0.84983 (18)	0.0254 (5)
H3	1.107711	0.845362	0.899683	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02295 (16)	0.01815 (15)	0.01013 (14)	0.00641 (11)	0.00275 (10)	0.00076 (10)
Cl1	0.0282 (3)	0.0213 (2)	0.0128 (2)	0.0121 (2)	0.00591 (19)	0.00269 (19)
S1	0.0221 (3)	0.0223 (3)	0.0156 (3)	0.0060 (2)	−0.00080 (19)	−0.0002 (2)
F2	0.0382 (9)	0.0427 (9)	0.0461 (9)	0.0246 (7)	0.0131 (7)	0.0132 (7)
F1	0.0508 (10)	0.0437 (9)	0.0241 (7)	0.0128 (8)	−0.0061 (7)	0.0120 (7)
F3	0.0458 (10)	0.0206 (7)	0.0667 (12)	0.0001 (7)	−0.0117 (8)	0.0074 (7)
O1	0.0284 (8)	0.0199 (7)	0.0201 (8)	0.0056 (6)	0.0030 (6)	0.0021 (6)
O3	0.0230 (8)	0.0371 (10)	0.0371 (10)	0.0075 (7)	0.0075 (7)	0.0066 (8)
O2	0.0400 (10)	0.0429 (11)	0.0171 (8)	0.0111 (9)	−0.0078 (7)	−0.0016 (7)
N3	0.0262 (9)	0.0162 (8)	0.0132 (8)	0.0065 (7)	0.0020 (7)	0.0028 (7)
N2	0.0215 (9)	0.0152 (8)	0.0130 (8)	0.0063 (7)	0.0008 (6)	0.0021 (6)
N1	0.0239 (9)	0.0182 (8)	0.0133 (8)	0.0075 (7)	0.0024 (7)	0.0038 (7)
C11	0.0269 (11)	0.0159 (9)	0.0149 (9)	0.0073 (8)	0.0010 (8)	0.0037 (8)
C5	0.0248 (11)	0.0190 (10)	0.0141 (9)	0.0087 (8)	0.0032 (8)	0.0043 (8)
C10	0.0237 (10)	0.0167 (9)	0.0157 (10)	0.0073 (8)	0.0014 (8)	0.0039 (8)
C6	0.0234 (10)	0.0152 (9)	0.0144 (9)	0.0058 (8)	0.0014 (8)	0.0030 (8)
C9	0.0227 (11)	0.0225 (10)	0.0186 (10)	0.0053 (9)	0.0042 (8)	0.0039 (8)
C15	0.0332 (12)	0.0176 (10)	0.0144 (10)	0.0080 (9)	0.0016 (8)	0.0031 (8)
C14	0.0362 (12)	0.0149 (9)	0.0167 (10)	0.0056 (9)	−0.0045 (9)	0.0011 (8)
C12	0.0247 (11)	0.0182 (10)	0.0205 (10)	0.0065 (8)	0.0017 (8)	0.0054 (8)
C13	0.0259 (11)	0.0158 (10)	0.0246 (11)	0.0040 (8)	−0.0045 (9)	0.0039 (8)
C7	0.0256 (11)	0.0210 (10)	0.0122 (9)	0.0061 (9)	0.0010 (8)	0.0000 (8)
C4	0.0261 (11)	0.0241 (11)	0.0157 (10)	0.0088 (9)	0.0031 (8)	0.0020 (8)
C8	0.0282 (12)	0.0277 (11)	0.0134 (10)	0.0087 (9)	0.0055 (8)	0.0025 (8)
C2	0.0215 (11)	0.0285 (11)	0.0233 (11)	0.0074 (9)	0.0034 (8)	0.0093 (9)
C16	0.0308 (12)	0.0197 (10)	0.0240 (11)	0.0049 (9)	−0.0022 (9)	0.0010 (9)
C1	0.0266 (11)	0.0250 (11)	0.0166 (10)	0.0114 (9)	0.0055 (8)	0.0075 (8)
C3	0.0256 (11)	0.0275 (11)	0.0198 (11)	0.0063 (9)	−0.0014 (9)	0.0036 (9)

Geometric parameters (Å, º)

Cu1—Cl1	2.2265 (5)	C10—C9	1.394 (3)
Cu1—Cl1^i	2.7660 (6)	C6—C7	1.387 (3)
Cu1—N3	2.0278 (19)	C9—H9	0.9500
Cu1—N2	1.9420 (17)	C9—C8	1.390 (3)
Cu1—N1	2.0397 (18)	C15—H15	0.9500
S1—O1	1.4466 (17)	C15—C14	1.394 (3)
S1—O3	1.4409 (18)	C14—H14	0.9500
S1—O2	1.4392 (17)	C14—C13	1.376 (3)
S1—C16	1.826 (2)	C12—H12	0.9500
F2—C16	1.331 (3)	C12—C13	1.401 (3)
F1—C16	1.335 (3)	C13—H13	0.9500
F3—C16	1.337 (3)	C7—H7	0.9500
N3—C11	1.362 (3)	C7—C8	1.392 (3)
N3—C15	1.339 (3)	C4—H4	0.9500
N2—C10	1.335 (3)	C4—C3	1.391 (3)
N2—C6	1.336 (3)	C8—H8	0.9500
N1—C5	1.364 (3)	C2—H2	0.9500
N1—C1	1.336 (3)	C2—C1	1.384 (3)
C11—C10	1.481 (3)	C2—C3	1.386 (3)
C11—C12	1.380 (3)	C1—H1	0.9500
C5—C6	1.479 (3)	C3—H3	0.9500
C5—C4	1.388 (3)
Cl1—Cu1—Cl1^i	89.944 (18)	C8—C9—C10	117.9 (2)
N3—Cu1—Cl1^i	90.30 (5)	C8—C9—H9	121.0
N3—Cu1—Cl1	99.82 (5)	N3—C15—H15	118.9
N3—Cu1—N1	159.58 (7)	N3—C15—C14	122.2 (2)
N2—Cu1—Cl1^i	90.83 (5)	C14—C15—H15	118.9
N2—Cu1—Cl1	179.20 (5)	C15—C14—H14	120.4
N2—Cu1—N3	80.39 (7)	C13—C14—C15	119.1 (2)
N2—Cu1—N1	80.11 (7)	C13—C14—H14	120.4
N1—Cu1—Cl1	99.60 (5)	C11—C12—H12	120.7
N1—Cu1—Cl1^i	95.97 (5)	C11—C12—C13	118.7 (2)
Cu1—Cl1—Cu1^i	90.056 (18)	C13—C12—H12	120.7
O1—S1—C16	102.05 (10)	C14—C13—C12	119.2 (2)
O3—S1—O1	114.97 (10)	C14—C13—H13	120.4
O3—S1—C16	103.57 (11)	C12—C13—H13	120.4
O2—S1—O1	114.19 (11)	C6—C7—H7	121.0
O2—S1—O3	115.73 (12)	C6—C7—C8	118.1 (2)
O2—S1—C16	103.90 (11)	C8—C7—H7	121.0
C11—N3—Cu1	113.61 (14)	C5—C4—H4	120.6
C15—N3—Cu1	127.30 (15)	C5—C4—C3	118.8 (2)
C15—N3—C11	118.61 (19)	C3—C4—H4	120.6
C10—N2—Cu1	118.38 (14)	C9—C8—C7	121.0 (2)
C10—N2—C6	123.04 (18)	C9—C8—H8	119.5
C6—N2—Cu1	118.58 (14)	C7—C8—H8	119.5
C5—N1—Cu1	113.57 (14)	C1—C2—H2	120.5
C1—N1—Cu1	127.51 (15)	C1—C2—C3	119.1 (2)
C1—N1—C5	118.60 (19)	C3—C2—H2	120.5
N3—C11—C10	114.06 (19)	F2—C16—S1	111.78 (16)
N3—C11—C12	122.2 (2)	F2—C16—F1	107.3 (2)
C12—C11—C10	123.8 (2)	F2—C16—F3	107.8 (2)
N1—C5—C6	114.01 (18)	F1—C16—S1	110.99 (16)
N1—C5—C4	121.9 (2)	F1—C16—F3	106.5 (2)
C4—C5—C6	124.13 (19)	F3—C16—S1	112.25 (17)
N2—C10—C11	113.09 (18)	N1—C1—C2	122.5 (2)
N2—C10—C9	119.91 (19)	N1—C1—H1	118.7
C9—C10—C11	127.0 (2)	C2—C1—H1	118.7
N2—C6—C5	113.29 (18)	C4—C3—H3	120.5
N2—C6—C7	120.03 (19)	C2—C3—C4	119.1 (2)
C7—C6—C5	126.68 (19)	C2—C3—H3	120.5
C10—C9—H9	121.0
Cu1—N3—C11—C10	−7.7 (2)	N1—C5—C4—C3	0.2 (3)
Cu1—N3—C11—C12	170.55 (16)	C11—N3—C15—C14	1.5 (3)
Cu1—N3—C15—C14	−170.07 (15)	C11—C10—C9—C8	−178.6 (2)
Cu1—N2—C10—C11	−0.7 (2)	C11—C12—C13—C14	0.8 (3)
Cu1—N2—C10—C9	179.33 (15)	C5—N1—C1—C2	−1.1 (3)
Cu1—N2—C6—C5	−1.4 (2)	C5—C6—C7—C8	−177.9 (2)
Cu1—N2—C6—C7	179.33 (15)	C5—C4—C3—C2	−1.7 (3)
Cu1—N1—C5—C6	7.0 (2)	C10—N2—C6—C5	179.27 (18)
Cu1—N1—C5—C4	−172.78 (16)	C10—N2—C6—C7	0.0 (3)
Cu1—N1—C1—C2	171.97 (16)	C10—C11—C12—C13	178.98 (19)
O1—S1—C16—F2	−60.24 (18)	C10—C9—C8—C7	−0.1 (3)
O1—S1—C16—F1	59.49 (19)	C6—N2—C10—C11	178.63 (18)
O1—S1—C16—F3	178.50 (17)	C6—N2—C10—C9	−1.4 (3)
O3—S1—C16—F2	−179.95 (16)	C6—C5—C4—C3	−179.6 (2)
O3—S1—C16—F1	−60.22 (19)	C6—C7—C8—C9	−1.1 (3)
O3—S1—C16—F3	58.8 (2)	C15—N3—C11—C10	179.69 (18)
O2—S1—C16—F2	58.73 (19)	C15—N3—C11—C12	−2.1 (3)
O2—S1—C16—F1	178.47 (17)	C15—C14—C13—C12	−1.5 (3)
O2—S1—C16—F3	−62.5 (2)	C12—C11—C10—N2	−172.60 (19)
N3—C11—C10—N2	5.6 (3)	C12—C11—C10—C9	7.4 (3)
N3—C11—C10—C9	−174.4 (2)	C4—C5—C6—N2	175.9 (2)
N3—C11—C12—C13	1.0 (3)	C4—C5—C6—C7	−4.9 (3)
N3—C15—C14—C13	0.3 (3)	C1—N1—C5—C6	−178.99 (18)
N2—C10—C9—C8	1.4 (3)	C1—N1—C5—C4	1.3 (3)
N2—C6—C7—C8	1.2 (3)	C1—C2—C3—C4	1.9 (3)
N1—C5—C6—N2	−3.8 (3)	C3—C2—C1—N1	−0.4 (3)
N1—C5—C6—C7	175.3 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.