Di-μ-aspirinato-copper(II): a redetermination

The structure of the title compound, [Cu(C₉H₇O₄)₂]_n, has been redetermined at higher resolution and including the H atoms. The structure is identical, within the s.u. values, to that described 30 years ago, but is now reported more precisely.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.030
• wR factor = 0.076
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT380_ALERT_4_C Incorrectly Oriented X(sp2)-Methyl Moiety ......         C9
PLAT764_ALERT_4_C Overcomplete CIF Bond list Detected (Rep/Expd) .       1.13 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 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
   0 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: XSCANS 2.21 (Siemens, 1996); cell refinement: XSCANS 2.21; data reduction: XSCANS 2.21; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus.

catena(copper(II) acetylsalicylate

Crystal data

[Cu(C9H7O4)2]	F(000) = 860
Mr = 421.83	Dx = 1.574 Mg m^−3
Monoclinic, P21/c	Melting point > 573 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.2118 (8) Å	Cell parameters from 69 reflections
b = 10.4158 (10) Å	θ = 4.4–12.8°
c = 21.484 (2) Å	µ = 1.27 mm^−1
β = 104.341 (8)°	T = 296 K
V = 1780.3 (3) Å^3	Needle, blue
Z = 4	0.28 × 0.24 × 0.18 mm

Data collection

Bruker P4 diffractometer	2559 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4	Rint = 0.024
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
ω scans	h = −9→4
Absorption correction: ψ scan (XSCAnS 2.21; Siemens, 1996)	k = −12→1
Tmin = 0.711, Tmax = 0.795	l = −25→25
5583 measured reflections	3 standard reflections every 97 reflections
3135 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: From a previously published refinement (Manojlović-Muir, 1973)
Least-squares matrix: full	Secondary atom site location: none
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0303P)^2 + 1.2189P] where P = (Fo^2 + 2Fc^2)/3
3135 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.34 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	0.38380 (4)	0.03515 (3)	0.028438 (13)	0.02264 (10)
O1	0.7715 (2)	0.02539 (19)	0.05100 (8)	0.0337 (4)
O2	0.5720 (2)	0.08157 (19)	0.10084 (8)	0.0327 (4)
O3	0.9843 (2)	0.23963 (18)	0.09306 (9)	0.0338 (4)
O4	1.1806 (2)	0.1073 (2)	0.07282 (9)	0.0361 (5)
O5	0.4046 (2)	0.19889 (18)	−0.01433 (9)	0.0348 (4)
O6	0.6038 (2)	0.13963 (17)	−0.06287 (9)	0.0326 (4)
O7	0.6939 (2)	0.30453 (19)	−0.14396 (9)	0.0394 (5)
O8	0.4818 (3)	0.1983 (3)	−0.21020 (11)	0.0689 (8)
C1	0.8555 (3)	0.1038 (3)	0.15665 (12)	0.0278 (6)
C2	0.9902 (3)	0.1809 (3)	0.15288 (12)	0.0290 (6)
C3	1.1165 (4)	0.2107 (3)	0.20620 (14)	0.0404 (7)
H3A	1.2048	0.2637	0.2026	0.048*
C4	1.1103 (4)	0.1609 (3)	0.26522 (14)	0.0479 (8)
H4A	1.1956	0.1793	0.3015	0.057*
C5	0.9772 (4)	0.0835 (4)	0.27031 (13)	0.0471 (8)
H5A	0.9736	0.0500	0.3101	0.057*
C6	0.8498 (4)	0.0558 (3)	0.21685 (13)	0.0391 (7)
H6A	0.7598	0.0050	0.2209	0.047*
C7	0.7220 (3)	0.0682 (2)	0.09821 (12)	0.0269 (6)
C8	1.0749 (3)	0.1874 (3)	0.05443 (13)	0.0321 (6)
C9	1.0203 (4)	0.2432 (4)	−0.01154 (15)	0.0538 (9)
H9A	1.0849	0.2056	−0.0385	0.081*
H9B	1.0377	0.3343	−0.0094	0.081*
H9C	0.9032	0.2253	−0.0291	0.081*
C10	0.4887 (3)	0.3499 (3)	−0.08178 (12)	0.0274 (6)
C11	0.5794 (3)	0.3869 (3)	−0.12565 (13)	0.0323 (6)
C12	0.5666 (4)	0.5091 (3)	−0.15086 (15)	0.0483 (8)
H12A	0.6290	0.5317	−0.1799	0.058*
C13	0.4621 (5)	0.5982 (3)	−0.13345 (15)	0.0536 (9)
H13A	0.4550	0.6810	−0.1501	0.064*
C14	0.3685 (4)	0.5635 (3)	−0.09136 (14)	0.0465 (8)
H14A	0.2960	0.6226	−0.0799	0.056*
C15	0.3815 (4)	0.4411 (3)	−0.06592 (13)	0.0357 (7)
H15A	0.3172	0.4190	−0.0375	0.043*
C16	0.5003 (3)	0.2192 (2)	−0.05114 (11)	0.0261 (6)
C17	0.6282 (4)	0.2071 (3)	−0.18552 (14)	0.0449 (8)
C18	0.7630 (5)	0.1185 (4)	−0.19384 (17)	0.0634 (10)
H18A	0.7147	0.0512	−0.2232	0.095*
H18B	0.8180	0.0819	−0.1531	0.095*
H18C	0.8434	0.1652	−0.2107	0.095*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01782 (16)	0.02529 (17)	0.02547 (16)	0.00153 (13)	0.00660 (11)	0.00045 (14)
O1	0.0237 (9)	0.0475 (11)	0.0283 (9)	0.0009 (9)	0.0036 (8)	−0.0077 (9)
O2	0.0235 (10)	0.0431 (11)	0.0315 (9)	−0.0020 (9)	0.0067 (8)	−0.0076 (9)
O3	0.0254 (10)	0.0343 (11)	0.0444 (11)	0.0045 (8)	0.0135 (8)	0.0025 (9)
O4	0.0275 (10)	0.0460 (12)	0.0377 (10)	0.0128 (10)	0.0135 (8)	0.0060 (9)
O5	0.0354 (11)	0.0310 (10)	0.0430 (10)	0.0044 (8)	0.0195 (9)	0.0072 (9)
O6	0.0323 (10)	0.0278 (10)	0.0413 (10)	0.0061 (9)	0.0158 (8)	0.0073 (9)
O7	0.0378 (11)	0.0354 (11)	0.0505 (12)	0.0055 (9)	0.0217 (9)	0.0069 (10)
O8	0.0596 (17)	0.0805 (19)	0.0556 (14)	0.0239 (14)	−0.0064 (13)	−0.0224 (14)
C1	0.0209 (13)	0.0340 (15)	0.0282 (13)	0.0045 (12)	0.0058 (10)	−0.0058 (12)
C2	0.0248 (14)	0.0300 (14)	0.0332 (13)	0.0041 (12)	0.0088 (11)	−0.0028 (12)
C3	0.0269 (15)	0.0441 (18)	0.0487 (18)	−0.0045 (13)	0.0069 (13)	−0.0114 (15)
C4	0.0344 (17)	0.068 (2)	0.0359 (16)	0.0032 (17)	−0.0015 (13)	−0.0172 (16)
C5	0.0421 (18)	0.070 (2)	0.0289 (14)	0.0054 (17)	0.0071 (13)	0.0007 (15)
C6	0.0304 (15)	0.0550 (19)	0.0329 (14)	−0.0036 (14)	0.0099 (12)	−0.0013 (14)
C7	0.0259 (14)	0.0255 (13)	0.0284 (13)	0.0006 (11)	0.0050 (11)	0.0018 (11)
C8	0.0216 (14)	0.0383 (16)	0.0377 (15)	−0.0021 (13)	0.0098 (12)	0.0019 (13)
C9	0.0342 (17)	0.077 (2)	0.0522 (19)	0.0138 (18)	0.0154 (14)	0.0226 (19)
C10	0.0266 (14)	0.0263 (14)	0.0279 (13)	0.0012 (12)	0.0040 (11)	0.0000 (11)
C11	0.0351 (15)	0.0279 (14)	0.0346 (14)	0.0044 (12)	0.0097 (12)	0.0021 (12)
C12	0.067 (2)	0.0365 (17)	0.0489 (18)	0.0037 (16)	0.0280 (17)	0.0105 (14)
C13	0.083 (3)	0.0287 (16)	0.0512 (19)	0.0094 (18)	0.0199 (18)	0.0100 (15)
C14	0.062 (2)	0.0322 (17)	0.0446 (17)	0.0179 (15)	0.0124 (16)	−0.0022 (14)
C15	0.0383 (16)	0.0333 (16)	0.0359 (15)	0.0059 (13)	0.0099 (13)	0.0001 (12)
C16	0.0214 (13)	0.0272 (14)	0.0271 (13)	−0.0008 (12)	0.0014 (11)	−0.0007 (11)
C17	0.057 (2)	0.0440 (19)	0.0370 (16)	0.0157 (17)	0.0186 (16)	0.0036 (15)
C18	0.073 (3)	0.059 (2)	0.065 (2)	0.027 (2)	0.031 (2)	0.0006 (19)

Geometric parameters (Å, º)

Cu1—O6^i	1.9581 (18)	C4—C5	1.384 (5)
Cu1—O1^i	1.9642 (17)	C4—H4A	0.9300
Cu1—O5	1.9646 (18)	C5—C6	1.379 (4)
Cu1—O2	1.9625 (17)	C5—H5A	0.9300
Cu1—O4^ii	2.2464 (18)	C6—H6A	0.9300
Cu1—Cu1^i	2.6127 (6)	C8—C9	1.494 (4)
O1—C7	1.263 (3)	C9—H9A	0.9600
O1—Cu1^i	1.9642 (17)	C9—H9B	0.9600
O2—C7	1.255 (3)	C9—H9C	0.9600
O3—C8	1.359 (3)	C10—C11	1.393 (4)
O3—C2	1.413 (3)	C10—C15	1.393 (4)
O4—C8	1.198 (3)	C10—C16	1.505 (4)
O4—Cu1^iii	2.2464 (18)	C11—C12	1.377 (4)
O5—C16	1.263 (3)	C12—C13	1.377 (5)
O6—C16	1.256 (3)	C12—H12A	0.9300
O6—Cu1^i	1.9581 (18)	C13—C14	1.372 (5)
O7—C17	1.371 (4)	C13—H13A	0.9300
O7—C11	1.399 (3)	C14—C15	1.381 (4)
O8—C17	1.191 (4)	C14—H14A	0.9300
C1—C2	1.386 (4)	C15—H15A	0.9300
C1—C6	1.398 (4)	C17—C18	1.486 (4)
C1—C7	1.494 (3)	C18—H18A	0.9600
C2—C3	1.377 (4)	C18—H18B	0.9600
C3—C4	1.383 (4)	C18—H18C	0.9600
C3—H3A	0.9300
O6^i—Cu1—O1^i	89.52 (8)	O2—C7—C1	117.3 (2)
O6^i—Cu1—O5	168.90 (7)	O1—C7—C1	116.6 (2)
O1^i—Cu1—O5	89.15 (8)	O4—C8—O3	122.6 (2)
O6^i—Cu1—O2	88.42 (8)	O4—C8—C9	127.3 (3)
O1^i—Cu1—O2	169.14 (7)	O3—C8—C9	110.0 (2)
O5—Cu1—O2	90.81 (8)	C8—C9—H9A	109.5
O6^i—Cu1—O4^ii	97.20 (7)	C8—C9—H9B	109.5
O1^i—Cu1—O4^ii	94.91 (7)	H9A—C9—H9B	109.5
O5—Cu1—O4^ii	93.89 (8)	C8—C9—H9C	109.5
O2—Cu1—O4^ii	95.92 (7)	H9A—C9—H9C	109.5
O6^i—Cu1—Cu1^i	86.58 (5)	H9B—C9—H9C	109.5
O1^i—Cu1—Cu1^i	84.02 (5)	C11—C10—C15	117.0 (2)
O5—Cu1—Cu1^i	82.32 (5)	C11—C10—C16	124.0 (2)
O2—Cu1—Cu1^i	85.22 (5)	C15—C10—C16	119.0 (2)
O4^ii—Cu1—Cu1^i	176.07 (5)	C12—C11—C10	121.3 (3)
C7—O1—Cu1^i	122.83 (16)	C12—C11—O7	116.6 (2)
C7—O2—Cu1	121.74 (16)	C10—C11—O7	122.0 (2)
C8—O3—C2	118.8 (2)	C13—C12—C11	120.5 (3)
C8—O4—Cu1^iii	130.28 (17)	C13—C12—H12A	119.7
C16—O5—Cu1	125.28 (17)	C11—C12—H12A	119.7
C16—O6—Cu1^i	120.80 (16)	C14—C13—C12	119.4 (3)
C17—O7—C11	116.9 (2)	C14—C13—H13A	120.3
C2—C1—C6	118.1 (2)	C12—C13—H13A	120.3
C2—C1—C7	121.7 (2)	C13—C14—C15	120.1 (3)
C6—C1—C7	120.2 (2)	C13—C14—H14A	119.9
C3—C2—C1	122.0 (3)	C15—C14—H14A	119.9
C3—C2—O3	120.6 (2)	C14—C15—C10	121.6 (3)
C1—C2—O3	117.1 (2)	C14—C15—H15A	119.2
C2—C3—C4	119.1 (3)	C10—C15—H15A	119.2
C2—C3—H3A	120.4	O6—C16—O5	124.9 (2)
C4—C3—H3A	120.4	O6—C16—C10	118.8 (2)
C5—C4—C3	120.0 (3)	O5—C16—C10	116.3 (2)
C5—C4—H4A	120.0	O8—C17—O7	122.6 (3)
C3—C4—H4A	120.0	O8—C17—C18	126.8 (3)
C6—C5—C4	120.5 (3)	O7—C17—C18	110.7 (3)
C6—C5—H5A	119.8	C17—C18—H18A	109.5
C4—C5—H5A	119.8	C17—C18—H18B	109.5
C5—C6—C1	120.2 (3)	H18A—C18—H18B	109.5
C5—C6—H6A	119.9	C17—C18—H18C	109.5
C1—C6—H6A	119.9	H18A—C18—H18C	109.5
O2—C7—O1	126.1 (2)	H18B—C18—H18C	109.5
O6^i—Cu1—O2—C7	87.9 (2)	C2—C1—C7—O1	49.2 (4)
O1^i—Cu1—O2—C7	8.7 (6)	C6—C1—C7—O1	−128.6 (3)
O5—Cu1—O2—C7	−81.1 (2)	Cu1^iii—O4—C8—O3	−165.43 (17)
O4^ii—Cu1—O2—C7	−175.1 (2)	Cu1^iii—O4—C8—C9	15.5 (4)
Cu1^i—Cu1—O2—C7	1.16 (19)	C2—O3—C8—O4	−12.7 (4)
O6^i—Cu1—O5—C16	1.0 (5)	C2—O3—C8—C9	166.5 (2)
O1^i—Cu1—O5—C16	−82.2 (2)	C15—C10—C11—C12	1.5 (4)
O2—Cu1—O5—C16	87.0 (2)	C16—C10—C11—C12	−178.3 (3)
O4^ii—Cu1—O5—C16	−177.1 (2)	C15—C10—C11—O7	178.4 (2)
Cu1^i—Cu1—O5—C16	1.89 (19)	C16—C10—C11—O7	−1.5 (4)
C6—C1—C2—C3	0.0 (4)	C17—O7—C11—C12	−108.0 (3)
C7—C1—C2—C3	−177.9 (3)	C17—O7—C11—C10	75.1 (3)
C6—C1—C2—O3	−173.3 (2)	C10—C11—C12—C13	−0.4 (5)
C7—C1—C2—O3	8.8 (4)	O7—C11—C12—C13	−177.4 (3)
C8—O3—C2—C3	85.4 (3)	C11—C12—C13—C14	−1.0 (5)
C8—O3—C2—C1	−101.1 (3)	C12—C13—C14—C15	1.2 (5)
C1—C2—C3—C4	0.9 (4)	C13—C14—C15—C10	0.1 (5)
O3—C2—C3—C4	174.1 (3)	C11—C10—C15—C14	−1.4 (4)
C2—C3—C4—C5	−0.9 (5)	C16—C10—C15—C14	178.5 (3)
C3—C4—C5—C6	−0.1 (5)	Cu1^i—O6—C16—O5	4.4 (3)
C4—C5—C6—C1	1.2 (5)	Cu1^i—O6—C16—C10	−176.52 (16)
C2—C1—C6—C5	−1.1 (4)	Cu1—O5—C16—O6	−4.4 (4)
C7—C1—C6—C5	176.8 (3)	Cu1—O5—C16—C10	176.55 (16)
Cu1—O2—C7—O1	0.2 (4)	C11—C10—C16—O6	3.7 (4)
Cu1—O2—C7—C1	−178.65 (17)	C15—C10—C16—O6	−176.2 (2)
Cu1^i—O1—C7—O2	−2.1 (4)	C11—C10—C16—O5	−177.2 (2)
Cu1^i—O1—C7—C1	176.70 (17)	C15—C10—C16—O5	3.0 (3)
C2—C1—C7—O2	−131.8 (3)	C11—O7—C17—O8	6.9 (4)
C6—C1—C7—O2	50.3 (4)	C11—O7—C17—C18	−172.7 (2)

Symmetry codes: (i) −x+1, −y, −z; (ii) x−1, y, z; (iii) x+1, y, z.