A trinuclear copper complex, [Cu₃L₂](ClO₄)₂, where H₂L is 1,3-bis(2-hydroxy­benzoyl­imino)­propane

The crystal structure determination of the title complex, bis­[μ-1,3-bis(2-oxy­benzoyl­imino)­propane]­tricopper(II) ­diper­­chlor­­ate, [Cu₃(C₁₇N₂H₁₆O₂)₂](ClO₄)₂, shows that a Cu^II atom, located on a crystallographic inversion centre, is coordinated by four bridging O atoms of two L ligands [H₂L is 1,3-bis(2-hydroxy­benzoyl­imino)­propane] and two perchlorate O atoms, in elongated octahedral geometry. The other two Cu^II atoms are in a distorted square-pyramidal geometry, ligated by N and O atoms of the L ligand and an O atom of a perchlorate ion. In the complex, the Cu—N bond length is 1.948 (4) Å and the Cu—O bond lengths are in the range 1.930 (3)–1.984 (3) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.053
• wR factor = 0.110
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT220_ALERT_2_A Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       5.35 Ratio

Author Response: For all oxygen atoms, O4 and O6 atoms have high Ueq. Because the data is collected at 25^o^C. O4 and O6 atoms are disorder.

PLAT242_ALERT_2_A Check Low    U(eq) as Compared to Neighbors ....        Cl1

Author Response: Because the data is collected at 25^o^C.

Alert level C
PLAT213_ALERT_2_C Atom O6      has ADP max/min Ratio .............       3.30 prolat
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....         O3
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7

   2 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 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
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998) and SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97.

bis[µ-1,3-bis(2-hydroxylbenzoylimino)propane]tricopper(II) bis(perchlorate)

Crystal data

[Cu3(C17N2H16O2)2](ClO4)2	F(000) = 962
Mr = 950.19	Dx = 1.791 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4098 reflections
a = 8.8249 (10) Å	θ = 2–28.3°
b = 11.9200 (13) Å	µ = 2.02 mm^−1
c = 17.2030 (19) Å	T = 293 K
β = 103.161 (2)°	Needle, blue
V = 1762.1 (3) Å^3	0.15 × 0.10 × 0.05 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	4099 independent reflections
Radiation source: fine-focus sealed tube	2716 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→11
Tmin = 0.788, Tmax = 0.899	k = −12→15
10495 measured reflections	l = −22→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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0367P)^2] where P = (Fo^2 + 2Fc^2)/3
4099 reflections	(Δ/σ)max < 0.001
250 parameters	Δρmax = 0.62 e Å^−3
10 restraints	Δρmin = −0.39 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.82135 (6)	0.17767 (4)	0.05775 (3)	0.03302 (17)
Cu2	1.0000	0.0000	0.0000	0.0316 (2)
O1	0.9814 (3)	0.0683 (2)	0.09910 (17)	0.0350 (7)
O2	0.7888 (3)	0.0671 (2)	−0.02754 (17)	0.0344 (7)
N1	0.9020 (4)	0.2777 (3)	0.1471 (2)	0.0387 (9)
N2	0.6279 (4)	0.2554 (3)	0.0110 (2)	0.0385 (10)
C1	1.0477 (5)	0.0503 (4)	0.1760 (3)	0.0321 (10)
C2	1.1039 (5)	−0.0558 (4)	0.2023 (3)	0.0380 (11)
H2A	1.0908	−0.1178	0.1658	0.080*
C3	1.1779 (6)	−0.0717 (4)	0.2805 (3)	0.0472 (13)
H3A	1.2124	−0.1456	0.2985	0.080*
C4	1.2049 (6)	0.0168 (5)	0.3348 (3)	0.0573 (15)
H4B	1.2620	0.0056	0.3888	0.080*
C5	1.1470 (6)	0.1201 (4)	0.3091 (3)	0.0508 (13)
H5A	1.1651	0.1819	0.3458	0.080*
C6	1.0634 (5)	0.1384 (4)	0.2310 (3)	0.0356 (11)
C7	0.9965 (5)	0.2483 (4)	0.2110 (3)	0.0402 (12)
H7A	1.0274	0.3058	0.2505	0.080*
C8	0.8517 (6)	0.3961 (4)	0.1390 (3)	0.0509 (14)
H8A	0.8914	0.4312	0.0975	0.080*
H8B	0.8930	0.4354	0.1880	0.080*
C9	0.6777 (6)	0.4039 (4)	0.1191 (3)	0.0548 (15)
H9A	0.6486	0.4793	0.1288	0.080*
H9B	0.6379	0.3553	0.1542	0.080*
C10	0.6032 (6)	0.3733 (4)	0.0338 (3)	0.0521 (14)
H10A	0.4932	0.3862	0.0252	0.080*
H10B	0.6423	0.4227	−0.0011	0.080*
C11	0.5184 (5)	0.2096 (4)	−0.0404 (3)	0.0409 (12)
H11A	0.4244	0.2525	−0.0561	0.080*
C12	0.5185 (5)	0.1003 (4)	−0.0786 (3)	0.0346 (11)
C13	0.3785 (6)	0.0644 (4)	−0.1268 (3)	0.0469 (13)
H13A	0.2875	0.1104	−0.1316	0.080*
C14	0.3665 (6)	−0.0356 (4)	−0.1678 (3)	0.0482 (13)
H14A	0.2689	−0.0589	−0.2009	0.080*
C15	0.4994 (6)	−0.1018 (4)	−0.1603 (3)	0.0451 (12)
H15A	0.4934	−0.1716	−0.1887	0.080*
C16	0.6386 (5)	−0.0678 (4)	−0.1124 (3)	0.0383 (11)
H16A	0.7280	−0.1154	−0.1073	0.080*
C17	0.6534 (5)	0.0329 (4)	−0.0713 (2)	0.0308 (10)
Cl1	0.91122 (16)	−0.29566 (10)	0.04110 (9)	0.0531 (4)
O3	0.8836 (4)	−0.1766 (3)	0.0370 (2)	0.0667 (11)
O4	0.8927 (7)	−0.3300 (4)	0.1151 (4)	0.147 (3)
O5	1.0623 (5)	−0.3150 (3)	0.0307 (3)	0.0833 (14)
O6	0.8018 (6)	−0.3447 (5)	−0.0178 (5)	0.184 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0366 (3)	0.0287 (3)	0.0333 (3)	0.0106 (2)	0.0071 (3)	−0.0026 (2)
Cu2	0.0296 (4)	0.0347 (4)	0.0285 (4)	0.0104 (3)	0.0026 (3)	−0.0078 (3)
O1	0.0428 (19)	0.0316 (17)	0.0281 (18)	0.0144 (14)	0.0027 (15)	−0.0049 (13)
O2	0.0274 (17)	0.0394 (18)	0.0348 (19)	0.0070 (14)	0.0040 (14)	−0.0050 (14)
N1	0.046 (3)	0.030 (2)	0.041 (3)	0.0061 (18)	0.011 (2)	−0.0047 (17)
N2	0.038 (2)	0.033 (2)	0.047 (3)	0.0104 (18)	0.015 (2)	0.0039 (18)
C1	0.027 (2)	0.037 (3)	0.033 (3)	−0.0011 (19)	0.007 (2)	−0.002 (2)
C2	0.035 (3)	0.041 (3)	0.037 (3)	0.005 (2)	0.007 (2)	0.003 (2)
C3	0.042 (3)	0.052 (3)	0.050 (4)	0.007 (2)	0.014 (3)	0.014 (3)
C4	0.063 (4)	0.074 (4)	0.032 (3)	0.014 (3)	0.006 (3)	0.003 (3)
C5	0.059 (4)	0.057 (3)	0.033 (3)	0.006 (3)	0.003 (3)	−0.009 (2)
C6	0.031 (3)	0.044 (3)	0.031 (3)	0.003 (2)	0.006 (2)	−0.006 (2)
C7	0.045 (3)	0.038 (3)	0.041 (3)	−0.004 (2)	0.017 (3)	−0.011 (2)
C8	0.061 (4)	0.030 (3)	0.063 (4)	0.013 (2)	0.017 (3)	−0.009 (2)
C9	0.076 (4)	0.025 (3)	0.072 (4)	0.015 (3)	0.034 (3)	−0.006 (2)
C10	0.053 (3)	0.034 (3)	0.071 (4)	0.017 (2)	0.017 (3)	0.000 (3)
C11	0.032 (3)	0.045 (3)	0.047 (3)	0.012 (2)	0.012 (2)	0.016 (2)
C12	0.030 (3)	0.042 (3)	0.033 (3)	0.008 (2)	0.010 (2)	0.009 (2)
C13	0.029 (3)	0.066 (4)	0.046 (3)	0.000 (2)	0.008 (2)	0.011 (3)
C14	0.035 (3)	0.066 (4)	0.043 (3)	−0.012 (3)	0.007 (2)	0.002 (3)
C15	0.041 (3)	0.051 (3)	0.043 (3)	−0.010 (2)	0.009 (3)	0.000 (2)
C16	0.033 (3)	0.041 (3)	0.040 (3)	−0.002 (2)	0.007 (2)	−0.004 (2)
C17	0.026 (2)	0.039 (3)	0.028 (3)	−0.0015 (19)	0.006 (2)	0.0039 (19)
Cl1	0.0484 (8)	0.0382 (7)	0.0777 (11)	−0.0033 (6)	0.0249 (8)	−0.0071 (6)
O3	0.071 (3)	0.044 (2)	0.086 (3)	−0.0028 (19)	0.020 (2)	0.0118 (19)
O4	0.214 (6)	0.095 (4)	0.184 (6)	0.057 (4)	0.150 (6)	0.080 (4)
O5	0.060 (3)	0.100 (3)	0.098 (4)	0.023 (2)	0.033 (3)	0.015 (3)
O6	0.089 (4)	0.154 (5)	0.290 (9)	−0.020 (4)	0.003 (5)	−0.163 (6)

Geometric parameters (Å, º)

Cu1—O1	1.935 (3)	C6—C7	1.446 (6)
Cu1—O2	1.944 (3)	C7—H7A	0.96
Cu1—N2	1.948 (4)	C8—C9	1.498 (7)
Cu1—N1	1.948 (4)	C8—H8A	0.96
Cu1—Cu2	2.9446 (5)	C8—H8B	0.96
Cu2—O1^i	1.930 (3)	C9—C10	1.510 (7)
Cu2—O1	1.930 (3)	C9—H9A	0.96
Cu2—O2	1.984 (3)	C9—H9B	0.96
Cu2—O2^i	1.984 (3)	C10—H10A	0.96
Cu2—Cu1^i	2.9446 (5)	C10—H10B	0.96
O1—C1	1.336 (5)	C11—C12	1.459 (6)
O2—C17	1.323 (5)	C11—H11A	0.96
N1—C7	1.268 (6)	C12—C13	1.390 (6)
N1—C8	1.476 (5)	C12—C17	1.418 (6)
N2—C11	1.275 (6)	C13—C14	1.377 (7)
N2—C10	1.488 (5)	C13—H13A	0.96
C1—C2	1.396 (6)	C14—C15	1.395 (6)
C1—C6	1.398 (6)	C14—H14A	0.96
C2—C3	1.367 (6)	C15—C16	1.375 (6)
C2—H2A	0.96	C15—H15A	0.96
C3—C4	1.394 (7)	C16—C17	1.384 (6)
C3—H3A	0.96	C16—H16A	0.96
C4—C5	1.367 (7)	Cl1—O6	1.362 (5)
C4—H4B	0.96	Cl1—O4	1.381 (5)
C5—C6	1.395 (6)	Cl1—O5	1.404 (4)
C5—H5A	0.96	Cl1—O3	1.439 (3)
O1—Cu1—O2	77.93 (12)	C5—C6—C1	118.9 (4)
O1—Cu1—N2	165.97 (14)	C5—C6—C7	117.9 (4)
O2—Cu1—N2	92.62 (14)	C1—C6—C7	123.2 (4)
O1—Cu1—N1	90.98 (14)	N1—C7—C6	127.5 (4)
O2—Cu1—N1	167.22 (14)	N1—C7—H7A	116.2
N2—Cu1—N1	99.40 (16)	C6—C7—H7A	116.3
O1—Cu1—Cu2	40.30 (8)	N1—C8—C9	110.6 (4)
O2—Cu1—Cu2	41.96 (8)	N1—C8—H8A	109.5
N2—Cu1—Cu2	133.54 (12)	C9—C8—H8A	109.3
N1—Cu1—Cu2	125.38 (11)	N1—C8—H8B	109.8
O1^i—Cu2—O1	180.0	C9—C8—H8B	109.6
O1^i—Cu2—O2	102.91 (12)	H8A—C8—H8B	108.0
O1—Cu2—O2	77.09 (12)	C8—C9—C10	113.9 (4)
O1^i—Cu2—O2^i	77.09 (12)	C8—C9—H9A	108.6
O1—Cu2—O2^i	102.91 (12)	C10—C9—H9A	108.8
O2—Cu2—O2^i	180.0	C8—C9—H9B	108.7
O1^i—Cu2—Cu1^i	40.42 (8)	C10—C9—H9B	109.0
O1—Cu2—Cu1^i	139.58 (8)	H9A—C9—H9B	107.7
O2—Cu2—Cu1^i	139.07 (8)	N2—C10—C9	115.3 (4)
O2^i—Cu2—Cu1^i	40.93 (8)	N2—C10—H10A	108.3
O1^i—Cu2—Cu1	139.58 (8)	C9—C10—H10A	108.2
O1—Cu2—Cu1	40.42 (8)	N2—C10—H10B	108.6
O2—Cu2—Cu1	40.93 (8)	C9—C10—H10B	108.7
O2^i—Cu2—Cu1	139.07 (8)	H10A—C10—H10B	107.5
Cu1^i—Cu2—Cu1	180.0	N2—C11—C12	128.1 (4)
C1—O1—Cu2	134.5 (3)	N2—C11—H11A	115.9
C1—O1—Cu1	126.2 (2)	C12—C11—H11A	116.0
Cu2—O1—Cu1	99.28 (13)	C13—C12—C17	119.5 (4)
C17—O2—Cu1	126.7 (3)	C13—C12—C11	116.9 (4)
C17—O2—Cu2	133.6 (3)	C17—C12—C11	123.5 (4)
Cu1—O2—Cu2	97.11 (13)	C14—C13—C12	121.7 (5)
C7—N1—C8	118.1 (4)	C14—C13—H13A	119.1
C7—N1—Cu1	124.4 (3)	C12—C13—H13A	119.2
C8—N1—Cu1	117.6 (3)	C13—C14—C15	118.6 (5)
C11—N2—C10	117.0 (4)	C13—C14—H14A	120.6
C11—N2—Cu1	122.5 (3)	C15—C14—H14A	120.9
C10—N2—Cu1	120.5 (3)	C16—C15—C14	120.4 (5)
O1—C1—C2	120.6 (4)	C16—C15—H15A	119.9
O1—C1—C6	120.2 (4)	C14—C15—H15A	119.7
C2—C1—C6	119.2 (4)	C15—C16—C17	122.0 (4)
C3—C2—C1	120.0 (4)	C15—C16—H16A	118.9
C3—C2—H2A	119.7	C17—C16—H16A	119.1
C1—C2—H2A	120.3	O2—C17—C16	121.7 (4)
C2—C3—C4	121.6 (5)	O2—C17—C12	120.5 (4)
C2—C3—H3A	119.4	C16—C17—C12	117.8 (4)
C4—C3—H3A	119.0	O6—Cl1—O4	110.2 (4)
C5—C4—C3	118.1 (5)	O6—Cl1—O5	111.6 (3)
C5—C4—H4B	120.9	O4—Cl1—O5	112.6 (3)
C3—C4—H4B	121.0	O6—Cl1—O3	107.7 (3)
C4—C5—C6	121.9 (5)	O4—Cl1—O3	106.4 (3)
C4—C5—H5A	118.9	O5—Cl1—O3	108.1 (2)
C6—C5—H5A	119.1
O1—Cu1—Cu2—O1^i	180.0	N1—Cu1—N2—C11	−165.4 (4)
O2—Cu1—Cu2—O1^i	34.11 (18)	Cu2—Cu1—N2—C11	29.4 (4)
N2—Cu1—Cu2—O1^i	18.4 (2)	O1—Cu1—N2—C10	152.6 (5)
N1—Cu1—Cu2—O1^i	−143.60 (19)	O2—Cu1—N2—C10	−160.3 (3)
O2—Cu1—Cu2—O1	−145.89 (18)	N1—Cu1—N2—C10	15.3 (3)
N2—Cu1—Cu2—O1	−161.6 (2)	Cu2—Cu1—N2—C10	−149.9 (3)
N1—Cu1—Cu2—O1	36.40 (19)	Cu2—O1—C1—C2	−26.7 (6)
O1—Cu1—Cu2—O2	145.89 (18)	Cu1—O1—C1—C2	150.6 (3)
N2—Cu1—Cu2—O2	−15.68 (19)	Cu2—O1—C1—C6	152.4 (3)
N1—Cu1—Cu2—O2	−177.71 (19)	Cu1—O1—C1—C6	−30.4 (5)
O1—Cu1—Cu2—O2^i	−34.11 (18)	O1—C1—C2—C3	176.9 (4)
O2—Cu1—Cu2—O2^i	180.0	C6—C1—C2—C3	−2.1 (6)
N2—Cu1—Cu2—O2^i	164.32 (19)	C1—C2—C3—C4	−2.6 (7)
N1—Cu1—Cu2—O2^i	2.29 (19)	C2—C3—C4—C5	3.8 (8)
O2—Cu2—O1—C1	155.6 (4)	C3—C4—C5—C6	−0.2 (8)
O2^i—Cu2—O1—C1	−24.4 (4)	C4—C5—C6—C1	−4.5 (7)
Cu1^i—Cu2—O1—C1	−2.3 (5)	C4—C5—C6—C7	175.3 (5)
Cu1—Cu2—O1—C1	177.7 (5)	O1—C1—C6—C5	−173.5 (4)
O2—Cu2—O1—Cu1	−22.14 (12)	C2—C1—C6—C5	5.6 (6)
O2^i—Cu2—O1—Cu1	157.86 (12)	O1—C1—C6—C7	6.7 (7)
Cu1^i—Cu2—O1—Cu1	180.0	C2—C1—C6—C7	−174.2 (4)
O2—Cu1—O1—C1	−155.5 (3)	C8—N1—C7—C6	−178.6 (4)
N2—Cu1—O1—C1	−107.0 (6)	Cu1—N1—C7—C6	0.2 (7)
N1—Cu1—O1—C1	30.9 (3)	C5—C6—C7—N1	−170.8 (5)
Cu2—Cu1—O1—C1	−178.0 (4)	C1—C6—C7—N1	9.0 (7)
O2—Cu1—O1—Cu2	22.54 (12)	C7—N1—C8—C9	−126.2 (5)
N2—Cu1—O1—Cu2	71.0 (6)	Cu1—N1—C8—C9	54.9 (5)
N1—Cu1—O1—Cu2	−151.06 (15)	N1—C8—C9—C10	−74.6 (5)
O1—Cu1—O2—C17	141.7 (3)	C11—N2—C10—C9	147.3 (5)
N2—Cu1—O2—C17	−27.8 (3)	Cu1—N2—C10—C9	−33.4 (5)
N1—Cu1—O2—C17	172.0 (6)	C8—C9—C10—N2	63.0 (6)
Cu2—Cu1—O2—C17	163.5 (4)	C10—N2—C11—C12	173.5 (4)
O1—Cu1—O2—Cu2	−21.77 (12)	Cu1—N2—C11—C12	−5.8 (7)
N2—Cu1—O2—Cu2	168.69 (14)	N2—C11—C12—C13	173.6 (5)
N1—Cu1—O2—Cu2	8.5 (7)	N2—C11—C12—C17	−8.9 (7)
O1^i—Cu2—O2—C17	40.2 (4)	C17—C12—C13—C14	0.2 (7)
Cu1^i—Cu2—O2—C17	18.3 (4)	C11—C12—C13—C14	177.9 (4)
Cu1—Cu2—O2—C17	−161.7 (4)	C12—C13—C14—C15	−0.1 (7)
O1^i—Cu2—O2—Cu1	−158.10 (12)	C13—C14—C15—C16	0.5 (7)
O1—Cu2—O2—Cu1	21.90 (12)	C14—C15—C16—C17	−1.2 (7)
Cu1^i—Cu2—O2—Cu1	180.0	Cu1—O2—C17—C16	−159.6 (3)
O1—Cu1—N1—C7	−15.4 (4)	Cu2—O2—C17—C16	−2.5 (6)
O2—Cu1—N1—C7	−44.9 (9)	Cu1—O2—C17—C12	21.5 (5)
N2—Cu1—N1—C7	155.1 (4)	Cu2—O2—C17—C12	178.6 (3)
Cu2—Cu1—N1—C7	−38.0 (4)	C15—C16—C17—O2	−177.6 (4)
O1—Cu1—N1—C8	163.4 (3)	C15—C16—C17—C12	1.3 (7)
O2—Cu1—N1—C8	133.9 (6)	C13—C12—C17—O2	178.1 (4)
N2—Cu1—N1—C8	−26.1 (3)	C11—C12—C17—O2	0.6 (6)
Cu2—Cu1—N1—C8	140.8 (3)	C13—C12—C17—C16	−0.8 (6)
O1—Cu1—N2—C11	−28.1 (8)	C11—C12—C17—C16	−178.3 (4)
O2—Cu1—N2—C11	19.0 (4)

Symmetry code: (i) −x+2, −y, −z.