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The title coordination polymer, poly[[tetrakis(
N,
N′-dimethylformamide)pentacopper(I,II)]-tetra-μ
2-cyano-di-μ
3-cyano], [Cu
5(CN)
6(C
3H
7NO)
4]
n, whose structure [Peng & Liaw (1986).
Inorg. Chim. Acta,
113, L11–L12] has been redetermined using CCD data, contains four crystallographically independent copper centres, including three Cu
I ions with tetrahedral or linear geometries and one Cu
II ion in an octahedral environment. These copper centres are connected by bidentate and tridentate cyanide bridges to form a unique self-penetrating network with 4
46
108 topology, which has been analyzed in detail. Three of the Cu atoms have site symmetries of
, 2 and 2.
Supporting information
CCDC reference: 251586
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (N-C) = 0.008 Å
- R factor = 0.048
- wR factor = 0.092
- Data-to-parameter ratio = 17.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.94
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.97 Ratio
PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors for O1
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors for N4
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors for N5
PLAT320_ALERT_2_C Check Hybridisation of C1 in Main Residue . ?
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.16 Ratio
Alert level G
ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be
replaced by the scaled T values. Since the ratio of scaled T's
is identical to the ratio of reported T values, the scaling
does not imply a change to the absorption corrections used in
the study.
Ratio of Tmax expected/reported 0.940
Tmax scaled 0.558 Tmin scaled 0.366
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
7 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
5 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
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Diamond (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97.
poly[[tetrakis(
N,
N'dimethylformamide)pentacopper(I,II)]-tetra-µ
2-cyano- di-µ
3-cyano]
top
Crystal data top
[Cu5(CN)6(C3H7NO)4] | F(000) = 1532 |
Mr = 766.25 | Dx = 1.752 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 718 reflections |
a = 14.054 (4) Å | θ = 2.5–23.9° |
b = 12.597 (4) Å | µ = 3.64 mm−1 |
c = 16.424 (5) Å | T = 293 K |
β = 92.008 (6)° | Prism, yellow |
V = 2905.9 (15) Å3 | 0.32 × 0.20 × 0.16 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2971 independent reflections |
Radiation source: fine-focus sealed tube | 1795 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
φ and ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −15→17 |
Tmin = 0.389, Tmax = 0.594 | k = −13→15 |
8240 measured reflections | l = −20→13 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0324P)2] where P = (Fo2 + 2Fc2)/3 |
2971 reflections | (Δ/σ)max = 0.001 |
174 parameters | Δρmax = 0.66 e Å−3 |
0 restraints | Δρmin = −0.45 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 | |
Cu1 | 0.18579 (4) | 0.67803 (5) | 0.50256 (3) | 0.03321 (19) | |
Cu2 | 0.5000 | 0.5000 | 0.5000 | 0.0300 (2) | |
Cu3 | 0.0000 | 0.63662 (9) | 0.7500 | 0.0539 (3) | |
Cu4 | 0.0000 | 0.60220 (9) | 0.2500 | 0.0533 (3) | |
N1 | 0.3879 (3) | 0.5868 (3) | 0.5134 (2) | 0.0321 (10) | |
C1 | 0.3214 (3) | 0.6380 (4) | 0.5108 (3) | 0.0326 (12) | |
N2 | 0.1143 (3) | 0.6565 (4) | 0.6034 (3) | 0.0499 (12) | |
C2 | 0.0728 (3) | 0.6443 (4) | 0.6614 (3) | 0.0372 (13) | |
N3 | 0.1197 (3) | 0.6355 (4) | 0.3983 (3) | 0.0515 (12) | |
C3 | 0.0778 (4) | 0.6158 (4) | 0.3399 (3) | 0.0395 (14) | |
O1 | 0.4221 (2) | 0.3547 (3) | 0.5534 (2) | 0.0529 (10) | |
N4 | 0.3685 (3) | 0.1884 (4) | 0.5257 (3) | 0.0459 (12) | |
C4 | 0.4191 (4) | 0.2748 (5) | 0.5117 (3) | 0.0439 (14) | |
H4 | 0.4559 | 0.2744 | 0.4657 | 0.053* | |
C5 | 0.3136 (4) | 0.1799 (6) | 0.5977 (4) | 0.0712 (19) | |
H5A | 0.3119 | 0.2475 | 0.6245 | 0.107* | |
H5B | 0.3423 | 0.1283 | 0.6339 | 0.107* | |
H5C | 0.2499 | 0.1582 | 0.5827 | 0.107* | |
C6 | 0.3707 (5) | 0.0976 (5) | 0.4721 (4) | 0.073 (2) | |
H6A | 0.3970 | 0.1181 | 0.4213 | 0.110* | |
H6B | 0.3071 | 0.0715 | 0.4624 | 0.110* | |
H6C | 0.4093 | 0.0429 | 0.4970 | 0.110* | |
O2 | 0.5506 (2) | 0.5473 (3) | 0.6152 (2) | 0.0474 (10) | |
N5 | 0.6405 (3) | 0.5192 (4) | 0.7295 (3) | 0.0526 (13) | |
C7 | 0.5967 (4) | 0.4887 (5) | 0.6624 (3) | 0.0464 (15) | |
H7 | 0.6003 | 0.4172 | 0.6489 | 0.056* | |
C8 | 0.6952 (5) | 0.4456 (7) | 0.7813 (4) | 0.097 (3) | |
H8A | 0.6909 | 0.3755 | 0.7587 | 0.145* | |
H8B | 0.6702 | 0.4455 | 0.8349 | 0.145* | |
H8C | 0.7607 | 0.4675 | 0.7844 | 0.145* | |
C9 | 0.6366 (5) | 0.6281 (5) | 0.7560 (4) | 0.0683 (19) | |
H9A | 0.6029 | 0.6697 | 0.7154 | 0.103* | |
H9B | 0.7001 | 0.6551 | 0.7638 | 0.103* | |
H9C | 0.6042 | 0.6321 | 0.8064 | 0.103* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0244 (3) | 0.0397 (4) | 0.0355 (3) | 0.0046 (3) | 0.0014 (2) | −0.0006 (3) |
Cu2 | 0.0251 (5) | 0.0290 (6) | 0.0356 (5) | 0.0110 (4) | −0.0027 (4) | −0.0045 (4) |
Cu3 | 0.0487 (6) | 0.0761 (9) | 0.0379 (6) | 0.000 | 0.0180 (5) | 0.000 |
Cu4 | 0.0588 (7) | 0.0645 (8) | 0.0353 (5) | 0.000 | −0.0179 (5) | 0.000 |
N1 | 0.027 (2) | 0.035 (3) | 0.034 (2) | 0.007 (2) | −0.0023 (19) | −0.0041 (19) |
C1 | 0.033 (3) | 0.043 (4) | 0.022 (3) | 0.006 (3) | 0.002 (2) | −0.001 (2) |
N2 | 0.045 (3) | 0.048 (3) | 0.056 (3) | 0.004 (2) | −0.004 (2) | 0.004 (3) |
C2 | 0.037 (3) | 0.052 (4) | 0.024 (3) | 0.000 (3) | 0.020 (2) | 0.005 (2) |
N3 | 0.050 (3) | 0.049 (3) | 0.055 (3) | 0.001 (2) | 0.003 (3) | 0.007 (3) |
C3 | 0.047 (3) | 0.048 (4) | 0.022 (3) | −0.002 (3) | −0.018 (2) | 0.000 (2) |
O1 | 0.045 (2) | 0.045 (3) | 0.069 (3) | 0.0029 (19) | 0.008 (2) | −0.015 (2) |
N4 | 0.041 (3) | 0.045 (3) | 0.052 (3) | 0.001 (2) | −0.001 (2) | −0.002 (2) |
C4 | 0.037 (3) | 0.049 (4) | 0.045 (3) | 0.012 (3) | 0.002 (3) | −0.003 (3) |
C5 | 0.062 (4) | 0.083 (6) | 0.069 (4) | −0.002 (4) | 0.017 (4) | 0.001 (4) |
C6 | 0.084 (5) | 0.051 (5) | 0.085 (5) | −0.010 (4) | 0.009 (4) | −0.008 (4) |
O2 | 0.045 (2) | 0.046 (3) | 0.050 (2) | 0.0142 (19) | −0.0107 (19) | −0.0045 (19) |
N5 | 0.053 (3) | 0.070 (4) | 0.034 (3) | 0.003 (3) | 0.004 (2) | 0.003 (3) |
C7 | 0.049 (3) | 0.048 (4) | 0.042 (3) | 0.008 (3) | 0.008 (3) | 0.001 (3) |
C8 | 0.105 (6) | 0.129 (8) | 0.055 (4) | 0.039 (5) | −0.006 (4) | 0.029 (5) |
C9 | 0.082 (5) | 0.070 (5) | 0.052 (4) | −0.017 (4) | 0.001 (4) | −0.008 (4) |
Geometric parameters (Å, º) top
Cu1—C1 | 1.972 (5) | N4—C4 | 1.324 (7) |
Cu1—N2 | 1.985 (5) | N4—C5 | 1.439 (6) |
Cu1—N3 | 1.993 (5) | N4—C6 | 1.444 (7) |
Cu1—C1i | 2.330 (5) | C4—H4 | 0.9300 |
Cu1—Cu1i | 2.5619 (13) | C5—H5A | 0.9600 |
Cu2—N1ii | 1.936 (4) | C5—H5B | 0.9600 |
Cu2—N1 | 1.936 (4) | C5—H5C | 0.9600 |
Cu2—O2ii | 2.084 (3) | C6—H6A | 0.9600 |
Cu2—O2 | 2.084 (3) | C6—H6B | 0.9600 |
Cu2—O1 | 2.321 (4) | C6—H6C | 0.9600 |
Cu2—O1ii | 2.321 (4) | O2—C7 | 1.237 (6) |
Cu3—C2 | 1.811 (5) | N5—C7 | 1.301 (7) |
Cu3—C2iii | 1.811 (5) | N5—C9 | 1.441 (7) |
Cu3—Cu4iv | 3.0085 (19) | N5—C8 | 1.459 (7) |
Cu4—C3 | 1.814 (5) | C7—H7 | 0.9300 |
Cu4—C3v | 1.814 (5) | C8—H8A | 0.9600 |
Cu4—Cu3iv | 3.0085 (19) | C8—H8B | 0.9600 |
N1—C1 | 1.135 (5) | C8—H8C | 0.9600 |
C1—Cu1i | 2.330 (5) | C9—H9A | 0.9600 |
N2—C2 | 1.145 (5) | C9—H9B | 0.9600 |
N3—C3 | 1.135 (6) | C9—H9C | 0.9600 |
O1—C4 | 1.217 (6) | | |
| | | |
C1—Cu1—N2 | 115.11 (18) | C4—O1—Cu2 | 116.5 (4) |
C1—Cu1—N3 | 114.22 (18) | C4—N4—C5 | 120.7 (5) |
N2—Cu1—N3 | 116.47 (18) | C4—N4—C6 | 121.5 (5) |
C1—Cu1—C1i | 107.44 (17) | C5—N4—C6 | 117.7 (5) |
N2—Cu1—C1i | 101.11 (17) | O1—C4—N4 | 126.1 (5) |
N3—Cu1—C1i | 99.75 (17) | O1—C4—H4 | 116.9 |
C1—Cu1—Cu1i | 60.19 (15) | N4—C4—H4 | 116.9 |
N2—Cu1—Cu1i | 120.12 (14) | N4—C5—H5A | 109.5 |
N3—Cu1—Cu1i | 118.02 (13) | N4—C5—H5B | 109.5 |
C1i—Cu1—Cu1i | 47.25 (12) | H5A—C5—H5B | 109.5 |
N1ii—Cu2—N1 | 180.0 (2) | N4—C5—H5C | 109.5 |
N1ii—Cu2—O2ii | 89.34 (15) | H5A—C5—H5C | 109.5 |
N1—Cu2—O2ii | 90.66 (15) | H5B—C5—H5C | 109.5 |
N1ii—Cu2—O2 | 90.66 (15) | N4—C6—H6A | 109.5 |
N1—Cu2—O2 | 89.34 (15) | N4—C6—H6B | 109.5 |
O2ii—Cu2—O2 | 180.000 (1) | H6A—C6—H6B | 109.5 |
N1ii—Cu2—O1 | 89.68 (15) | N4—C6—H6C | 109.5 |
N1—Cu2—O1 | 90.32 (15) | H6A—C6—H6C | 109.5 |
O2ii—Cu2—O1 | 88.13 (15) | H6B—C6—H6C | 109.5 |
O2—Cu2—O1 | 91.87 (15) | C7—O2—Cu2 | 123.6 (4) |
N1ii—Cu2—O1ii | 90.32 (15) | C7—N5—C9 | 121.0 (5) |
N1—Cu2—O1ii | 89.68 (15) | C7—N5—C8 | 122.1 (6) |
O2ii—Cu2—O1ii | 91.87 (15) | C9—N5—C8 | 117.0 (5) |
O2—Cu2—O1ii | 88.13 (15) | O2—C7—N5 | 125.3 (6) |
O1—Cu2—O1ii | 180.0 | O2—C7—H7 | 117.4 |
C2—Cu3—C2iii | 173.8 (3) | N5—C7—H7 | 117.4 |
C2—Cu3—Cu4iv | 93.08 (17) | N5—C8—H8A | 109.5 |
C2iii—Cu3—Cu4iv | 93.08 (17) | N5—C8—H8B | 109.5 |
C3—Cu4—C3v | 169.1 (4) | H8A—C8—H8B | 109.5 |
C3—Cu4—Cu3iv | 95.43 (17) | N5—C8—H8C | 109.5 |
C3v—Cu4—Cu3iv | 95.43 (17) | H8A—C8—H8C | 109.5 |
C1—N1—Cu2 | 171.3 (4) | H8B—C8—H8C | 109.5 |
N1—C1—Cu1 | 160.1 (5) | N5—C9—H9A | 109.5 |
N1—C1—Cu1i | 127.0 (4) | N5—C9—H9B | 109.5 |
Cu1—C1—Cu1i | 72.56 (17) | H9A—C9—H9B | 109.5 |
C2—N2—Cu1 | 179.7 (5) | N5—C9—H9C | 109.5 |
N2—C2—Cu3 | 174.2 (5) | H9A—C9—H9C | 109.5 |
C3—N3—Cu1 | 175.7 (5) | H9B—C9—H9C | 109.5 |
N3—C3—Cu4 | 171.2 (5) | | |
| | | |
N2—Cu1—C1—N1 | 77.1 (12) | Cu2—O1—C4—N4 | −170.9 (4) |
N3—Cu1—C1—N1 | −61.5 (12) | C5—N4—C4—O1 | −3.3 (9) |
C1i—Cu1—C1—N1 | −171.2 (13) | C6—N4—C4—O1 | −179.7 (5) |
Cu1i—Cu1—C1—N1 | −171.2 (13) | N1ii—Cu2—O2—C7 | −35.1 (4) |
N2—Cu1—C1—Cu1i | −111.73 (17) | N1—Cu2—O2—C7 | 144.9 (4) |
N3—Cu1—C1—Cu1i | 109.63 (17) | O1—Cu2—O2—C7 | 54.6 (4) |
C1i—Cu1—C1—Cu1i | 0.0 | O1ii—Cu2—O2—C7 | −125.4 (4) |
N1ii—Cu2—O1—C4 | −54.7 (4) | Cu2—O2—C7—N5 | 169.9 (4) |
N1—Cu2—O1—C4 | 125.3 (4) | C9—N5—C7—O2 | 1.5 (9) |
O2ii—Cu2—O1—C4 | 34.6 (4) | C8—N5—C7—O2 | −178.6 (5) |
O2—Cu2—O1—C4 | −145.4 (4) | | |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x, y, −z+3/2; (iv) −x, −y+1, −z+1; (v) −x, y, −z+1/2. |
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