The title compound, {(C
3H
10N)
2[CdCu
2(CN)
6]}
n, has been synthesized as an alternative to the high-emitting complexes containing more expensive metals. The CN
− ligands make linkages between the Cu
I and Cd
II ions to form the coordination polymer, [CdCu
2(CN)
6]
n2−, which is a three-dimensional framework classified as pyrite net (
pyr). The net has a void space for accommodating a trimethylammonium ion located on a threefold rotation axis. The Cd
II ion lies on a special position with site symmetry -3 and is octahedrally coordinated by six N atoms. The Cu
I ion is located on a threefold rotation axis and has a trigonal-planar coordination geometry formed by three C atoms. In the three-dimensional net, two Cu
I ions are arranged closely [Cu
Cu = 3.9095 (5) Å], but the distance is not short enough to suggest a Cu
I–Cu
I interaction. The crystal studied was a merohedral twin (twin operation 2
[101]), the refined component ratio being 0.9202 (7):0.0798 (7). A powder of the title compound shows strong luminescence with an emission maximum at 509 nm and a quantum yield of 98% at room temperature.
Supporting information
CCDC reference: 1810643
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (N-C) = 0.003 Å
- R factor = 0.017
- wR factor = 0.044
- Data-to-parameter ratio = 22.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT420_ALERT_2_C D-H Without Acceptor N2 --H2 . Please Check
| Author Response: N2-H2 is a part of a trimethylammonium ion which is
trapped in void space of a negatively charged coordination
polymer. The trimethylammonium ion is a counter cation for
cancelling the negative charge, and has no definite acceptor.
|
Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension 3 Info
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 1 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please Check
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Cu1 --C1 . 5.8 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1 (II) . 1.67 Info
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed .. ! Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 12 Note
PLAT931_ALERT_5_G Found Twin Law ( 1 0 1 )[ ] Est. BASF 0.08 Check
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
8 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
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
4 ALERT type 5 Informative message, check
Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: VESTA 3 (Momma & Izumi, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).
Poly[bis[(trimethylammonium) [hexa-µ-cyanido-cadmium(II)dicopper(I)]
top
Crystal data top
(C3H10N)2[CdCu2(CN)6] | Mo Kα radiation, λ = 0.71073 Å |
Mr = 515.87 | Cell parameters from 5459 reflections |
Cubic, Pa3 | θ = 2.9–28.5° |
a = 12.3775 (9) Å | µ = 3.34 mm−1 |
V = 1896.3 (4) Å3 | T = 296 K |
Z = 4 | Block, colourless |
F(000) = 1016 | 0.32 × 0.29 × 0.22 mm |
Dx = 1.807 Mg m−3 | |
Data collection top
Bruker APEXII diffractometer | 861 independent reflections |
Radiation source: fine-focus sealed tube | 772 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 8.3333 pixels mm-1 | θmax = 28.8°, θmin = 1.7° |
phi and ω scans | h = −16→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | k = −14→16 |
Tmin = 0.627, Tmax = 0.746 | l = −15→16 |
11150 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)] = 0.017 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.044 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0208P)2 + 0.6318P] where P = (Fo2 + 2Fc2)/3 |
861 reflections | (Δ/σ)max < 0.001 |
38 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the
rounded fractional coordinates. All su's are estimated
from the variances of the (full) variance-covariance matrix.
The cell esds are taken into account in the estimation of
distances, angles and torsion angles |
Refinement. Refined as a 2-component twin. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cd1 | 0.500000 | 0.500000 | 0.000000 | 0.02365 (9) | |
Cu1 | 0.40882 (2) | 0.40882 (2) | 0.40882 (2) | 0.03148 (11) | |
N1 | 0.48328 (15) | 0.49244 (15) | 0.18799 (14) | 0.0413 (4) | |
C1 | 0.46209 (16) | 0.46692 (16) | 0.27362 (15) | 0.0335 (4) | |
N2 | 0.29859 (12) | 0.70141 (12) | 0.20141 (12) | 0.0338 (6) | |
H2 | 0.344303 | 0.655696 | 0.155697 | 0.041* | |
C2 | 0.20128 (19) | 0.6377 (2) | 0.23072 (19) | 0.0521 (6) | |
H2A | 0.222902 | 0.572912 | 0.267472 | 0.078* | |
H2B | 0.162203 | 0.619101 | 0.166360 | 0.078* | |
H2C | 0.155818 | 0.679893 | 0.277288 | 0.078* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.02365 (9) | 0.02365 (9) | 0.02365 (9) | 0.00096 (6) | 0.00096 (6) | −0.00096 (6) |
Cu1 | 0.03148 (11) | 0.03148 (11) | 0.03148 (11) | 0.00670 (10) | 0.00670 (10) | 0.00670 (10) |
N1 | 0.0470 (10) | 0.0483 (11) | 0.0286 (8) | −0.0062 (8) | 0.0020 (7) | 0.0031 (7) |
C1 | 0.0340 (9) | 0.0340 (9) | 0.0324 (9) | 0.0042 (8) | 0.0033 (8) | 0.0028 (7) |
N2 | 0.0338 (6) | 0.0338 (6) | 0.0338 (6) | 0.0038 (6) | 0.0038 (6) | −0.0038 (6) |
C2 | 0.0514 (13) | 0.0599 (14) | 0.0450 (12) | −0.0161 (11) | 0.0071 (10) | −0.0003 (11) |
Geometric parameters (Å, º) top
Cd1—N1 | 2.3379 (17) | N1—C1 | 1.137 (3) |
Cd1—N1i | 2.3379 (17) | N2—C2 | 1.485 (3) |
Cd1—N1ii | 2.3379 (17) | N2—C2i | 1.485 (3) |
Cd1—N1iii | 2.3379 (17) | N2—C2ii | 1.485 (3) |
Cd1—N1iv | 2.3379 (17) | N2—H2 | 0.9800 |
Cd1—N1v | 2.3379 (17) | C2—H2A | 0.9600 |
Cu1—C1 | 1.9371 (19) | C2—H2B | 0.9600 |
Cu1—C1vi | 1.9371 (19) | C2—H2C | 0.9600 |
Cu1—C1vii | 1.9371 (19) | | |
| | | |
N1—Cd1—N1i | 87.44 (6) | C1—Cu1—C1vii | 119.24 (8) |
N1—Cd1—N1ii | 87.44 (6) | C1vi—Cu1—C1vii | 119.24 (8) |
N1—Cd1—N1iii | 180.00 | Cd1—N1—C1 | 163.66 (17) |
N1—Cd1—N1iv | 92.56 (6) | Cu1—C1—N1 | 170.85 (18) |
N1—Cd1—N1v | 92.56 (6) | C2—N2—C2i | 111.25 (16) |
N1i—Cd1—N1ii | 87.44 (6) | C2—N2—C2ii | 111.25 (16) |
N1i—Cd1—N1iii | 92.56 (6) | C2i—N2—C2ii | 111.25 (16) |
N1i—Cd1—N1iv | 180.00 | C2—N2—H2 | 108.00 |
N1i—Cd1—N1v | 92.56 (6) | C2i—N2—H2 | 108.00 |
N1ii—Cd1—N1iii | 92.56 (6) | C2ii—N2—H2 | 108.00 |
N1ii—Cd1—N1iv | 92.56 (6) | N2—C2—H2A | 109.00 |
N1ii—Cd1—N1v | 180.00 | N2—C2—H2B | 109.00 |
N1iii—Cd1—N1iv | 87.44 (6) | N2—C2—H2C | 109.00 |
N1iii—Cd1—N1v | 87.44 (6) | H2A—C2—H2B | 109.00 |
N1iv—Cd1—N1v | 87.44 (6) | H2A—C2—H2C | 109.00 |
C1—Cu1—C1vi | 119.24 (8) | H2B—C2—H2C | 109.00 |
Symmetry codes: (i) −z+1/2, −x+1, y−1/2; (ii) −y+1, z+1/2, −x+1/2; (iii) −x+1, −y+1, −z; (iv) z+1/2, x, −y+1/2; (v) y, −z+1/2, x−1/2; (vi) z, x, y; (vii) y, z, x. |