In the search for ketone complexes suitable for absolute asymmetric synthesis, that is, complexes crystallizing in Sohncke space groups, we have studied complexes between copper(I) halides and acetylpyridines. The structure of polymeric [CuCl(3-acpy)]
n (3-acpy is 3-acetylpyridine, C
7H
7NO), a compound which was found to form achiral chains crystallizing in a centrosymmetric space group, is reported here. The complex forms ladder-type chains, in which the Cu
I atom is coordinated by one N atom and three Cl atoms in a tetrahedral geometry. In the crystal structure, the chains are interconnected through C—H
Cl and C—H
O intermolecular contacts.
Supporting information
CCDC reference: 277194
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.006 Å
- R factor = 0.053
- wR factor = 0.142
- Data-to-parameter ratio = 15.4
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for Cu1
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3 .. CL1 .. 2.86 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7A .. O1 .. 2.71 Ang.
0 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
1 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
Data collection: Crystal Clear (Rigaku, 2000); cell refinement: Crystal Clear; data reduction: Crystal Clear; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
catena-Poly[[(3-acetylpyridine)copper(I)]-µ
3-chloro]
top
Crystal data top
[CuCl(C7H7NO)] | F(000) = 440 |
Mr = 220.13 | Dx = 1.853 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5457 reflections |
a = 3.8230 (14) Å | θ = 3.0–26.0° |
b = 15.990 (5) Å | µ = 3.04 mm−1 |
c = 13.100 (4) Å | T = 291 K |
β = 99.768 (9)° | Needle, yellow |
V = 789.2 (5) Å3 | 0.5 × 0.2 × 0.2 mm |
Z = 4 | |
Data collection top
Rigaku R-AXIS IIC image-plate diffractometer | 1540 independent reflections |
Radiation source: rotating-anode X-ray tube, Rigaku R3h | 1081 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
Detector resolution: 105 pixels mm-1 | θmax = 26.0°, θmin = 3.0° |
φ scans | h = −4→4 |
Absorption correction: multi-scan (Crystal Clear; Rigaku, 2000) | k = −19→19 |
Tmin = 0.211, Tmax = 0.542 | l = −16→16 |
5457 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.142 | H-atom parameters constrained |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0821P)2] where P = (Fo2 + 2Fc2)/3 |
1540 reflections | (Δ/σ)max = 0.001 |
100 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
C6 | 0.6452 (11) | 0.8789 (2) | 0.4261 (3) | 0.0471 (9) | |
C7 | 0.6063 (13) | 0.9587 (3) | 0.3682 (4) | 0.0596 (11) | |
H7A | 0.7314 | 1.0021 | 0.4100 | 0.089* | |
H7B | 0.3594 | 0.9731 | 0.3513 | 0.089* | |
H7C | 0.7028 | 0.9528 | 0.3055 | 0.089* | |
O1 | 0.8126 (9) | 0.8751 (2) | 0.5127 (2) | 0.0747 (11) | |
C1 | 0.4428 (10) | 0.7335 (2) | 0.4369 (3) | 0.0443 (9) | |
H1 | 0.5328 | 0.7371 | 0.5074 | 0.053* | |
C2 | 0.4748 (9) | 0.8024 (2) | 0.3755 (3) | 0.0399 (8) | |
C3 | 0.3525 (11) | 0.7958 (3) | 0.2716 (3) | 0.0505 (10) | |
H3 | 0.3701 | 0.8408 | 0.2279 | 0.061* | |
C4 | 0.2037 (12) | 0.7221 (3) | 0.2327 (3) | 0.0580 (11) | |
H4 | 0.1235 | 0.7160 | 0.1620 | 0.070* | |
C5 | 0.1746 (11) | 0.6580 (3) | 0.2987 (3) | 0.0515 (10) | |
H5 | 0.0693 | 0.6085 | 0.2717 | 0.062* | |
N1 | 0.2904 (9) | 0.66276 (19) | 0.4005 (2) | 0.0480 (8) | |
Cl1 | 0.1669 (3) | 0.43956 (6) | 0.39548 (7) | 0.0509 (3) | |
Cu1 | 0.24840 (17) | 0.56819 (4) | 0.49662 (4) | 0.0739 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C6 | 0.048 (2) | 0.045 (2) | 0.049 (2) | 0.0003 (18) | 0.0093 (18) | −0.0038 (16) |
C7 | 0.067 (3) | 0.045 (2) | 0.067 (3) | −0.005 (2) | 0.014 (2) | 0.0005 (19) |
O1 | 0.098 (3) | 0.060 (2) | 0.055 (2) | −0.0083 (17) | −0.0198 (18) | −0.0035 (14) |
C1 | 0.047 (2) | 0.047 (2) | 0.0368 (19) | −0.0047 (17) | 0.0022 (15) | 0.0000 (15) |
C2 | 0.0364 (18) | 0.0431 (19) | 0.0395 (18) | 0.0022 (15) | 0.0043 (14) | 0.0011 (14) |
C3 | 0.057 (2) | 0.051 (2) | 0.041 (2) | −0.0022 (19) | 0.0003 (17) | 0.0077 (16) |
C4 | 0.061 (3) | 0.066 (3) | 0.042 (2) | −0.007 (2) | −0.0045 (18) | −0.0031 (18) |
C5 | 0.051 (2) | 0.049 (2) | 0.052 (2) | −0.0033 (19) | 0.0025 (18) | −0.0046 (17) |
N1 | 0.0524 (19) | 0.0440 (18) | 0.0482 (19) | −0.0018 (15) | 0.0108 (15) | 0.0018 (14) |
Cl1 | 0.0520 (6) | 0.0569 (6) | 0.0449 (5) | −0.0095 (4) | 0.0114 (4) | −0.0123 (4) |
Cu1 | 0.0955 (6) | 0.0631 (5) | 0.0653 (5) | −0.0209 (3) | 0.0202 (4) | 0.0087 (3) |
Geometric parameters (Å, º) top
C6—O1 | 1.206 (5) | C3—C4 | 1.369 (7) |
C6—C7 | 1.480 (6) | C3—H3 | 0.9300 |
C6—C2 | 1.487 (5) | C4—C5 | 1.358 (6) |
C7—H7A | 0.9600 | C4—H4 | 0.9300 |
C7—H7B | 0.9600 | C5—N1 | 1.334 (5) |
C7—H7C | 0.9600 | C5—H5 | 0.9300 |
C1—N1 | 1.325 (5) | N1—Cu1 | 1.992 (3) |
C1—C2 | 1.382 (5) | Cl1—Cu1i | 2.3013 (12) |
C1—H1 | 0.9300 | Cl1—Cu1ii | 2.4366 (14) |
C2—C3 | 1.365 (5) | Cl1—Cu1 | 2.4378 (13) |
| | | |
O1—C6—C7 | 121.1 (4) | C4—C5—H5 | 118.5 |
O1—C6—C2 | 120.1 (4) | C1—N1—C5 | 117.4 (3) |
C7—C6—C2 | 118.8 (4) | C1—N1—Cu1 | 119.9 (3) |
C6—C7—H7A | 109.5 | C5—N1—Cu1 | 122.7 (3) |
C6—C7—H7B | 109.5 | Cu1i—Cl1—Cu1ii | 107.55 (5) |
H7A—C7—H7B | 109.5 | Cu1i—Cl1—Cu1 | 75.49 (4) |
C6—C7—H7C | 109.5 | Cu1ii—Cl1—Cu1 | 73.00 (4) |
H7A—C7—H7C | 109.5 | N1—Cu1—Cl1i | 124.56 (10) |
H7B—C7—H7C | 109.5 | N1—Cu1—Cl1ii | 103.95 (10) |
N1—C1—C2 | 123.2 (3) | Cl1i—Cu1—Cl1ii | 107.55 (5) |
N1—C1—H1 | 118.4 | N1—Cu1—Cl1 | 108.27 (10) |
C2—C1—H1 | 118.4 | Cl1i—Cu1—Cl1 | 104.51 (4) |
C3—C2—C1 | 118.0 (3) | Cl1ii—Cu1—Cl1 | 107.00 (4) |
C3—C2—C6 | 123.9 (3) | N1—Cu1—Cu1ii | 117.78 (10) |
C1—C2—C6 | 118.1 (3) | Cl1i—Cu1—Cu1ii | 117.65 (4) |
C2—C3—C4 | 119.2 (4) | Cl1ii—Cu1—Cu1ii | 53.52 (3) |
C2—C3—H3 | 120.4 | Cl1—Cu1—Cu1ii | 53.48 (4) |
C4—C3—H3 | 120.4 | N1—Cu1—Cu1i | 135.47 (10) |
C5—C4—C3 | 119.1 (4) | Cl1i—Cu1—Cu1i | 54.39 (3) |
C5—C4—H4 | 120.4 | Cl1ii—Cu1—Cu1i | 118.99 (4) |
C3—C4—H4 | 120.4 | Cl1—Cu1—Cu1i | 50.13 (3) |
N1—C5—C4 | 122.9 (4) | Cu1ii—Cu1—Cu1i | 82.43 (4) |
N1—C5—H5 | 118.5 | | |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl1iii | 0.93 | 2.86 | 3.542 (4) | 131 |
C7—H7C···Cl1iv | 0.96 | 2.77 | 3.713 (5) | 168 |
C4—H4···O1v | 0.93 | 2.56 | 3.390 (5) | 148 |
C7—H7A···O1vi | 0.96 | 2.71 | 3.641 (6) | 165 |
Symmetry codes: (iii) −x, y+1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2; (v) x−1, −y+3/2, z−1/2; (vi) −x+2, −y+2, −z+1. |