Di-μ-salicyl­ato-κ⁴O:O′-bis[(2,2′-bi­pyridine-κ²N,N′)copper(II)] bis­(salicylic acid)

The title complex, [Cu₂(C₇H₄O₃)₂(C₁₀H₈N₂)₂]·2C₇H₆O₃, crystallizes as a centrosymmetric dimer containing two Cu^II atoms bridged by two phenolato O atoms from salicyl­ate ligands. Each Cu^II atom lies in an approximate square planar environment and is bonded to two N atoms of a 2,2′-bi­pyridine ligand, the phenolato O and the carboxyl­ato O atoms of a salicyl­ate ligand. The coordination of Cu^II is completed by bonding to a phenolato O atom in the axial direction, giving square pyramidal geometry. The dimer is stabilized by a strong intermolecular π–π interaction involving pairs of bi­pyridine ligands and a salicyl­ate ring. The crystal structure is stabilized by π–π interactions and hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.044
• wR factor = 0.131
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.35
PLAT128_ALERT_4_C Non-standard setting of Space group P21/c   ....    P21/a
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O3_a    ..       5.96 su

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

   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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CrystalStructure (Rigaku & Rigaku/MSC, 2000-2004); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SIR97 (Altomare et al., 1999) and DIRDIF (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Scheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure.

(I)

Crystal data

[Cu2(C7H4O3)2(C10H8N2)2]·2C7H6O3	F(000) = 1012.00
Mr = 987.91	Dx = 1.550 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -p_2yab	Cell parameters from 13777 reflections
a = 10.46 (1) Å	θ = 3.1–27.4°
b = 17.79 (2) Å	µ = 1.08 mm^−1
c = 12.04 (1) Å	T = 296 K
β = 109.25 (4)°	Lath, blue
V = 2115 (4) Å^3	0.50 × 0.10 × 0.05 mm
Z = 2

Data collection

Rigaku RAXIS-RAPID diffractometer	2392 reflections with F^2 > 2σ(F^2)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.034
ω scans	θmax = 27.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
Tmin = 0.534, Tmax = 0.948	k = −23→22
20430 measured reflections	l = −15→15
4824 independent reflections

Refinement

Refinement on F^2	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.044	w = 1/[σ^2(Fo^2) + (0.0917P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.131	(Δ/σ)max < 0.001
S = 0.85	Δρmax = 1.08 e Å^−3
4824 reflections	Δρmin = −0.46 e Å^−3
304 parameters

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Cu1	0.84570 (4)	0.03137 (2)	0.95208 (3)	0.0443 (1)
O1	0.7985 (2)	0.0186 (1)	1.0908 (2)	0.0530 (5)
O2	0.8037 (2)	0.0326 (1)	1.2739 (2)	0.0581 (6)
O3	1.0062 (2)	0.0837 (1)	1.0318 (1)	0.0468 (5)
O4	0.3529 (3)	0.1023 (1)	0.6149 (2)	0.0768 (7)
O5	0.3791 (3)	0.0649 (1)	0.7980 (2)	0.0614 (6)
O6	0.5186 (3)	0.1988 (1)	0.5793 (2)	0.0898 (9)
N1	0.6862 (3)	−0.0283 (1)	0.8569 (2)	0.0442 (5)
N2	0.8560 (3)	0.0546 (1)	0.7926 (2)	0.0453 (6)
C1	0.6662 (3)	−0.0284 (1)	0.7395 (2)	0.0440 (6)
C2	0.5631 (4)	−0.0694 (2)	0.6623 (3)	0.0596 (9)
C3	0.4809 (4)	−0.1116 (2)	0.7059 (3)	0.068 (1)
C4	0.5032 (4)	−0.1135 (2)	0.8258 (3)	0.068 (1)
C5	0.6062 (3)	−0.0703 (2)	0.8985 (3)	0.0534 (8)
C6	0.7632 (3)	0.0173 (1)	0.7043 (2)	0.0460 (7)
C7	0.7656 (4)	0.0202 (2)	0.5901 (3)	0.067 (1)
C8	0.8617 (5)	0.0631 (2)	0.5671 (3)	0.086 (1)
C9	0.9582 (5)	0.1033 (2)	0.6572 (3)	0.079 (1)
C10	0.9503 (4)	0.0972 (2)	0.7694 (3)	0.0571 (8)
C11	0.9591 (3)	0.1046 (1)	1.2145 (2)	0.0435 (6)
C12	1.0291 (3)	0.1193 (1)	1.1338 (2)	0.0413 (6)
C13	1.1345 (3)	0.1734 (1)	1.1634 (3)	0.0504 (7)
C14	1.1732 (4)	0.2096 (2)	1.2739 (3)	0.0607 (9)
C15	1.1048 (4)	0.1943 (2)	1.3514 (3)	0.068 (1)
C16	0.9997 (4)	0.1434 (2)	1.3220 (3)	0.0574 (8)
C17	0.8485 (3)	0.0491 (2)	1.1916 (2)	0.0447 (7)
C18	0.5345 (3)	0.1519 (1)	0.7711 (3)	0.0477 (7)
C19	0.5812 (4)	0.1970 (2)	0.6965 (3)	0.0637 (9)
C20	0.6964 (4)	0.2411 (2)	0.7420 (4)	0.078 (1)
C21	0.7639 (4)	0.2422 (2)	0.8640 (4)	0.078 (1)
C22	0.7190 (4)	0.1976 (2)	0.9403 (3)	0.0644 (9)
C23	0.6064 (3)	0.1538 (2)	0.8932 (3)	0.0531 (8)
C24	0.4139 (3)	0.1039 (2)	0.7216 (3)	0.0525 (7)
H1	0.5495	−0.0686	0.5820	0.072*
H2	0.4099	−0.1389	0.6550	0.082*
H3	0.4499	−0.1432	0.8566	0.082*
H4	0.6206	−0.0704	0.9789	0.064*
H5	0.7028	−0.0065	0.5303	0.081*
H6	0.8638	0.0659	0.4906	0.103*
H7	1.0241	0.1326	0.6420	0.095*
H8	1.0121	0.1234	0.8306	0.068*
H9	1.1783	0.1851	1.1098	0.060*
H10	1.2447	0.2437	1.2942	0.073*
H11	1.1297	0.2185	1.4239	0.082*
H12	0.9542	0.1344	1.3752	0.069*
H13	0.7286	0.2696	0.6921	0.094*
H14	0.8394	0.2728	0.8948	0.093*
H15	0.7647	0.1979	1.0209	0.077*
H16	0.5762	0.1242	0.9433	0.064*
H17	0.4524	0.1731	0.5650	0.078*
H18	0.309	0.038	0.777	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0457 (2)	0.0549 (2)	0.0323 (2)	−0.0062 (2)	0.0129 (1)	−0.0049 (1)
O1	0.054 (1)	0.071 (1)	0.036 (1)	−0.017 (1)	0.0174 (9)	−0.0098 (9)
O2	0.059 (1)	0.083 (2)	0.037 (1)	−0.018 (1)	0.022 (1)	−0.008 (1)
O3	0.049 (1)	0.058 (1)	0.0353 (9)	−0.010 (1)	0.0160 (9)	−0.0081 (9)
O4	0.095 (2)	0.081 (2)	0.045 (1)	−0.018 (1)	0.011 (1)	−0.004 (1)
O5	0.059 (2)	0.076 (2)	0.052 (1)	−0.019 (1)	0.023 (1)	−0.003 (1)
O6	0.123 (3)	0.089 (2)	0.059 (2)	−0.023 (2)	0.032 (2)	0.016 (1)
N1	0.045 (1)	0.048 (1)	0.037 (1)	0.001 (1)	0.010 (1)	−0.003 (1)
N2	0.055 (2)	0.046 (1)	0.034 (1)	−0.002 (1)	0.014 (1)	−0.004 (1)
C1	0.045 (2)	0.044 (1)	0.039 (1)	0.005 (1)	0.008 (1)	−0.004 (1)
C2	0.068 (2)	0.063 (2)	0.039 (2)	−0.005 (2)	0.005 (1)	−0.008 (1)
C3	0.062 (2)	0.072 (2)	0.062 (2)	−0.022 (2)	0.008 (2)	−0.018 (2)
C4	0.059 (2)	0.075 (2)	0.072 (2)	−0.022 (2)	0.021 (2)	−0.012 (2)
C5	0.053 (2)	0.060 (2)	0.050 (2)	−0.008 (2)	0.020 (1)	−0.010 (1)
C6	0.052 (2)	0.049 (2)	0.033 (1)	0.005 (1)	0.009 (1)	−0.002 (1)
C7	0.086 (3)	0.076 (2)	0.036 (1)	−0.011 (2)	0.015 (2)	−0.005 (2)
C8	0.118 (4)	0.105 (3)	0.042 (2)	−0.024 (3)	0.036 (2)	0.000 (2)
C9	0.107 (3)	0.084 (3)	0.052 (2)	−0.022 (2)	0.034 (2)	−0.001 (2)
C10	0.069 (2)	0.058 (2)	0.051 (2)	−0.007 (2)	0.029 (2)	0.004 (1)
C11	0.051 (2)	0.045 (1)	0.035 (1)	−0.000 (1)	0.014 (1)	−0.003 (1)
C12	0.042 (2)	0.042 (1)	0.039 (1)	0.001 (1)	0.012 (1)	−0.002 (1)
C13	0.051 (2)	0.045 (1)	0.055 (2)	−0.003 (1)	0.017 (1)	−0.006 (1)
C14	0.067 (2)	0.049 (2)	0.063 (2)	−0.010 (2)	0.017 (2)	−0.014 (2)
C15	0.095 (3)	0.062 (2)	0.047 (2)	−0.015 (2)	0.022 (2)	−0.022 (2)
C16	0.079 (2)	0.057 (2)	0.040 (2)	−0.007 (2)	0.026 (2)	−0.010 (1)
C17	0.044 (2)	0.055 (2)	0.037 (1)	−0.000 (1)	0.016 (1)	−0.000 (1)
C18	0.053 (2)	0.045 (1)	0.051 (2)	0.004 (1)	0.026 (1)	0.000 (1)
C19	0.083 (3)	0.055 (2)	0.058 (2)	0.003 (2)	0.030 (2)	0.005 (2)
C20	0.081 (3)	0.059 (2)	0.101 (3)	−0.008 (2)	0.039 (2)	0.009 (2)
C21	0.066 (3)	0.065 (2)	0.102 (3)	−0.007 (2)	0.026 (2)	−0.003 (2)
C22	0.052 (2)	0.060 (2)	0.080 (2)	0.004 (2)	0.020 (2)	−0.010 (2)
C23	0.058 (2)	0.056 (2)	0.052 (2)	0.006 (2)	0.026 (2)	0.001 (1)
C24	0.060 (2)	0.050 (2)	0.049 (2)	0.004 (1)	0.022 (2)	−0.003 (1)

Geometric parameters (Å, º)

Cu1—O1	1.906 (2)	C8—H6	0.93
Cu1—O3	1.882 (2)	C9—C10	1.385 (5)
Cu1—N1	1.991 (2)	C9—H7	0.93
Cu1—N2	2.002 (3)	C10—H8	0.93
Cu1—O3^i	2.536 (3)	C11—C12	1.421 (5)
O1—C17	1.275 (3)	C11—C16	1.404 (4)
O2—C17	1.263 (4)	C11—C17	1.476 (4)
O3—C12	1.332 (3)	C12—C13	1.417 (4)
O4—C24	1.232 (3)	C13—C14	1.413 (4)
O5—C24	1.298 (4)	C13—H9	0.93
O5—H18	0.84	C14—C15	1.378 (6)
O6—C19	1.347 (4)	C14—H10	0.93
O6—H17	0.80	C15—C16	1.378 (5)
N1—C1	1.359 (4)	C15—H11	0.93
N1—C5	1.336 (4)	C16—C11	1.404 (4)
N2—C6	1.354 (3)	C16—C15	1.378 (5)
N2—C10	1.345 (5)	C16—H12	0.93
C1—C2	1.379 (4)	C18—C19	1.406 (5)
C1—C6	1.467 (5)	C18—C23	1.415 (4)
C2—C3	1.369 (6)	C18—C24	1.477 (4)
C2—H1	0.93	C19—C20	1.390 (5)
C3—C4	1.385 (5)	C20—C21	1.405 (6)
C3—H2	0.93	C20—H13	0.93
C4—C5	1.377 (4)	C21—C22	1.406 (6)
C4—H3	0.93	C21—H14	0.93
C5—H4	0.93	C22—C23	1.370 (5)
C6—C7	1.386 (5)	C22—H15	0.93
C7—C8	1.361 (7)	C23—H16	0.93
C7—H5	0.93	H12—C16	0.93
C8—C9	1.409 (5)
O1—Cu1—O3	93.27 (9)	C10—C9—C8	117.0 (4)
O1—Cu1—N1	91.8 (1)	C10—C9—H7	121.5
O1—Cu1—N2	167.8 (1)	H7—C9—C8	121.5
O3—Cu1—N1	174.0 (1)	H8—C10—N2	119.0
O3—Cu1—N2	93.83 (9)	H8—C10—C9	119.0
N1—Cu1—N2	81.8 (1)	C12—C11—C17	123.0 (2)
C17—O1—Cu1	129.8 (2)	C12—C11—C16	118.2 (3)
C12—O3—Cu1	124.4 (2)	C16—C11—C17	118.8 (3)
C24—O5—H18	120.8	C13—C12—O3	116.3 (3)
C19—O6—H17	107.4	C13—C12—C11	119.1 (3)
C1—N1—Cu1	114.3 (2)	C14—C13—C12	120.3 (3)
C1—N1—C5	119.3 (2)	C14—C13—H9	119.9
C5—N1—Cu1	126.3 (2)	H9—C13—C12	119.8
C6—N2—Cu1	113.6 (2)	C15—C14—C13	119.7 (3)
C6—N2—C10	119.9 (3)	C15—C14—H10	120.1
C10—N2—Cu1	126.2 (2)	H10—C14—C13	120.1
C2—C1—N1	121.3 (3)	C16—C15—C14	120.3 (3)
C2—C1—C6	124.1 (3)	C16—C15—H11	119.8
C6—C1—N1	114.6 (2)	H11—C15—C14	119.8
C3—C2—C1	118.8 (3)	C11—C16—H12	118.9
C3—C2—H1	120.6	C11—C16—C15	122.2 (3)
H1—C2—C1	120.6	C15—C16—H12	118.9
C4—C3—C2	120.1 (3)	C19—C18—C23	118.3 (3)
C4—C3—H2	119.9	C19—C18—C24	120.2 (3)
H2—C3—C2	119.9	C23—C18—C24	121.6 (3)
C5—C4—C3	118.5 (4)	C20—C19—O6	117.3 (4)
C5—C4—H3	120.8	C20—C19—C18	120.6 (3)
H3—C4—C3	120.8	C21—C20—C19	119.5 (4)
H4—C5—N1	119.0	C21—C20—H13	120.3
H4—C5—C4	119.0	H13—C20—C19	120.3
C7—C6—N2	121.2 (3)	C22—C21—C20	120.9 (3)
C7—C6—C1	123.3 (3)	C22—C21—H14	119.5
C8—C7—C6	118.7 (3)	H14—C21—C20	119.5
C8—C7—H5	120.6	C23—C22—H15	120.7
H5—C7—C6	120.7	C23—C22—C21	118.5 (3)
C9—C8—C7	121.2 (4)	H15—C22—C21	120.7
C9—C8—H6	119.4	H16—C23—C22	118.9
H6—C8—C7	119.4	H16—C23—C18	118.9
O3—Cu1—O1—C17	11.9 (2)	C7—C8—C9—C10	−0.1 (5)
O1—Cu1—O3—C12	−22.0 (2)	C8—C9—C10—N2	0.5 (5)
O1—Cu1—N1—C1	172.8 (2)	C16—C11—C12—O3	176.2 (2)
O1—Cu1—N2—C6	−63.0 (4)	C12—C11—C16—C15	−0.4 (4)
Cu1—O1—C17—O2	−179.3 (2)	C12—C11—C17—O1	−9.2 (4)
Cu1—O1—C17—C11	0.9 (4)	C12—C11—C17—O2	171.0 (3)
Cu1—O3—C12—C11	20.7 (3)	O3—C12—C13—C14	−174.9 (3)
Cu1—N1—C1—C2	177.5 (2)	C12—C13—C14—C15	−2.4 (4)
Cu1—N1—C5—C4	−175.8 (3)	C13—C14—C15—C16	0.6 (5)
Cu1—N2—C6—C1	4.4 (3)	C14—C15—C16—C11	0.9 (5)
Cu1—N2—C10—C9	172.6 (3)	C23—C18—C19—O6	−179.8 (3)
N1—C1—C2—C3	−0.9 (5)	C19—C18—C23—C22	−0.2 (4)
N1—C1—C6—N2	−1.8 (4)	C19—C18—C24—O4	0.3 (5)
C1—C2—C3—C4	−1.0 (5)	C19—C18—C24—O5	−179.7 (3)
C2—C3—C4—C5	2.2 (5)	O6—C19—C20—C21	178.8 (4)
C3—C4—C5—N1	−1.5 (5)	C19—C20—C21—C22	1.9 (6)
N2—C6—C7—C8	−1.6 (5)	C20—C21—C22—C23	−1.0 (6)
C6—C7—C8—C9	0.6 (6)	C21—C22—C23—C18	0.1 (4)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H17···O4	0.80	1.86	2.574 (4)	149
O5—H18···O2^ii	0.84	1.69	2.514 (3)	165

Symmetry code: (ii) −x+1, −y, −z+2.