In the crystal structure of the title compound, [Cu(NO3)(C2H4NO)(C12H8N2)]n, the CuII atoms are linked by acetamidate ligands, forming a chain. Each CuII atom is five-coordinated by two N atoms of the 1,10-phenanthroline ligand, one nitrate O atom, and one N and one O atoms of acetamidate in a trigonal-bipyramidal geometry. In the crystal structure, the chains are linked by hydrogen bonds into a polymeric ribbon structure.
Supporting information
CCDC reference: 1176503
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.005 Å
- R factor = 0.041
- wR factor = 0.130
- Data-to-parameter ratio = 12.8
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for C13 - C14 .. 8.61 su
PLAT362_ALERT_2_B Short C(sp3)-C(sp2) Bond C13 - C14 ... 1.22 Ang.
PLAT415_ALERT_2_B Short Inter D-H..H-X H5 .. H14B .. 1.97 Ang.
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.96
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for N3 - C13 .. 5.27 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - N3 .. 7.12 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N4
0 ALERT level A = In general: serious problem
3 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
6 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
0 ALERT type 5 Informative message, check
Crystals of the title compound were synthesized using hydrothermal method in a
23 ml Teflon-lined Parr bomb, which was then sealed. Copper (II) nitrate
hexahydrate (296.3 mg, 1 mmol), phen (180.2 mg, 1 mmol), acetamide (59.1 mg, 1 mmol) and distilled water (8 g) were placed into the bomb and sealed. The bomb
was then heated under autogenous pressure up to 453 K over the course of 7 d
and allowed to cool at room temperature for 24 h. Upon opening the bomb, a
clear colorless solution was decanted from small blue crystals. These crystals
were washed with distilled water followed by ethanol, and allowed to air-dry
at room temperature.
The H atoms were positioned geometrically, with N—H = 0.86 Å (for NH), C—H
= 0.93 and 0.96 Å for aromatic and methyl H atoms, and constrained to ride
on their parent atoms, with Uiso(H) = xUeq(C,N),
where x = 1.2 for aromatic and NH H atoms and x = 1.5 for methyl
H atoms.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).
catena-Poly[[(nitrato-
κO)(1,10-phenanthroline-
κ2N,
N')copper(II)]-µ-acetamido-
κ2O:
N]
top
Crystal data top
[Cu(NO3)(C2H4NO)(C12H8N2)] | F(000) = 740 |
Mr = 363.82 | Dx = 1.820 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5781 reflections |
a = 8.680 (2) Å | θ = 2.3–27.0° |
b = 9.190 (3) Å | µ = 1.67 mm−1 |
c = 17.0137 (12) Å | T = 273 K |
β = 101.904 (2)° | Prism, blue |
V = 1328.0 (6) Å3 | 0.41 × 0.23 × 0.22 mm |
Z = 4 | |
Data collection top
Bruker APEXII area-detector diffractometer | 2679 independent reflections |
Radiation source: fine-focus sealed tube | 2285 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ϕ and ω scans | θmax = 26.7°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.624, Tmax = 0.695 | k = −11→11 |
8439 measured reflections | l = −21→21 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0915P)2 + 0.5483P] where P = (Fo2 + 2Fc2)/3 |
2679 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.80 e Å−3 |
0 restraints | Δρmin = −0.69 e Å−3 |
Crystal data top
[Cu(NO3)(C2H4NO)(C12H8N2)] | V = 1328.0 (6) Å3 |
Mr = 363.82 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.680 (2) Å | µ = 1.67 mm−1 |
b = 9.190 (3) Å | T = 273 K |
c = 17.0137 (12) Å | 0.41 × 0.23 × 0.22 mm |
β = 101.904 (2)° | |
Data collection top
Bruker APEXII area-detector diffractometer | 2679 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2285 reflections with I > 2σ(I) |
Tmin = 0.624, Tmax = 0.695 | Rint = 0.017 |
8439 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.80 e Å−3 |
2679 reflections | Δρmin = −0.69 e Å−3 |
209 parameters | |
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 | 0.66503 (4) | 0.92788 (4) | 0.803179 (19) | 0.03409 (17) | |
O1 | 0.5481 (3) | 1.0048 (3) | 0.70204 (13) | 0.0470 (6) | |
O2 | 0.3259 (4) | 0.9011 (4) | 0.72922 (19) | 0.0769 (10) | |
O3 | 0.3290 (3) | 1.0282 (4) | 0.62163 (17) | 0.0623 (7) | |
O4 | 0.6206 (3) | 0.5052 (3) | 0.74795 (15) | 0.0474 (6) | |
N1 | 0.6078 (3) | 1.0941 (3) | 0.86853 (16) | 0.0356 (5) | |
N2 | 0.7951 (3) | 0.8671 (3) | 0.90775 (14) | 0.0337 (5) | |
N3 | 0.6879 (3) | 0.7347 (2) | 0.75217 (13) | 0.0281 (5) | |
H3A | 0.7419 | 0.7239 | 0.7155 | 0.034* | |
N4 | 0.4025 (3) | 0.9775 (3) | 0.68377 (16) | 0.0403 (6) | |
C1 | 0.5201 (4) | 1.2102 (4) | 0.8464 (2) | 0.0441 (7) | |
H1 | 0.4813 | 1.2259 | 0.7919 | 0.053* | |
C2 | 0.4828 (4) | 1.3112 (4) | 0.9017 (2) | 0.0486 (8) | |
H2 | 0.4225 | 1.3930 | 0.8840 | 0.058* | |
C3 | 0.5364 (4) | 1.2873 (4) | 0.9812 (2) | 0.0474 (8) | |
H3 | 0.5094 | 1.3505 | 1.0189 | 0.057* | |
C4 | 0.6330 (4) | 1.1664 (4) | 1.00650 (19) | 0.0386 (6) | |
C5 | 0.6977 (4) | 1.1340 (4) | 1.08823 (19) | 0.0441 (7) | |
H5 | 0.6726 | 1.1923 | 1.1285 | 0.053* | |
C6 | 0.7960 (4) | 1.0188 (4) | 1.10835 (19) | 0.0443 (7) | |
H6 | 0.8381 | 1.0004 | 1.1622 | 0.053* | |
C7 | 0.8363 (4) | 0.9251 (3) | 1.04838 (18) | 0.0364 (6) | |
C8 | 0.9427 (4) | 0.8075 (4) | 1.06354 (19) | 0.0430 (7) | |
H8 | 0.9926 | 0.7856 | 1.1160 | 0.052* | |
C9 | 0.9725 (4) | 0.7261 (4) | 1.0016 (2) | 0.0450 (7) | |
H9 | 1.0438 | 0.6494 | 1.0115 | 0.054* | |
C10 | 0.8963 (4) | 0.7578 (3) | 0.92368 (19) | 0.0410 (7) | |
H10 | 0.9166 | 0.7012 | 0.8816 | 0.049* | |
C11 | 0.7675 (3) | 0.9512 (3) | 0.96854 (17) | 0.0313 (6) | |
C12 | 0.6653 (3) | 1.0726 (3) | 0.94749 (18) | 0.0319 (6) | |
C13 | 0.6164 (3) | 0.6283 (3) | 0.77790 (16) | 0.0298 (5) | |
C14 | 0.5453 (4) | 0.6522 (3) | 0.83151 (19) | 0.0384 (7) | |
H14A | 0.4521 | 0.5932 | 0.8235 | 0.058* | |
H14B | 0.5163 | 0.7531 | 0.8306 | 0.058* | |
H14C | 0.6115 | 0.6292 | 0.8825 | 0.058* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0402 (3) | 0.0328 (2) | 0.0277 (2) | 0.00245 (13) | 0.00354 (16) | 0.00106 (13) |
O1 | 0.0436 (12) | 0.0556 (15) | 0.0381 (11) | −0.0051 (11) | −0.0004 (9) | 0.0129 (11) |
O2 | 0.0571 (16) | 0.119 (3) | 0.0546 (17) | −0.0216 (17) | 0.0123 (14) | 0.0260 (18) |
O3 | 0.0540 (14) | 0.0697 (17) | 0.0541 (16) | −0.0053 (13) | −0.0104 (12) | 0.0154 (14) |
O4 | 0.0456 (12) | 0.0372 (12) | 0.0596 (14) | −0.0041 (10) | 0.0115 (11) | −0.0154 (11) |
N1 | 0.0387 (12) | 0.0327 (12) | 0.0354 (13) | 0.0003 (10) | 0.0078 (10) | 0.0046 (10) |
N2 | 0.0380 (12) | 0.0302 (12) | 0.0322 (11) | 0.0023 (10) | 0.0057 (10) | −0.0009 (10) |
N3 | 0.0357 (11) | 0.0277 (11) | 0.0226 (10) | −0.0040 (9) | 0.0097 (9) | −0.0034 (8) |
N4 | 0.0415 (13) | 0.0381 (13) | 0.0384 (13) | 0.0003 (11) | 0.0018 (11) | 0.0009 (12) |
C1 | 0.0443 (16) | 0.0401 (17) | 0.0459 (17) | 0.0061 (14) | 0.0048 (14) | 0.0030 (14) |
C2 | 0.0476 (17) | 0.0393 (17) | 0.059 (2) | 0.0113 (14) | 0.0112 (15) | 0.0014 (15) |
C3 | 0.0483 (17) | 0.0381 (17) | 0.059 (2) | 0.0077 (14) | 0.0185 (15) | −0.0056 (15) |
C4 | 0.0392 (14) | 0.0383 (15) | 0.0408 (15) | −0.0039 (12) | 0.0141 (13) | −0.0049 (13) |
C5 | 0.0510 (17) | 0.0488 (18) | 0.0362 (15) | −0.0016 (15) | 0.0177 (14) | −0.0078 (14) |
C6 | 0.0494 (17) | 0.0536 (19) | 0.0303 (14) | −0.0008 (15) | 0.0096 (13) | −0.0018 (14) |
C7 | 0.0408 (15) | 0.0374 (16) | 0.0311 (14) | −0.0032 (12) | 0.0079 (12) | 0.0029 (11) |
C8 | 0.0479 (16) | 0.0412 (16) | 0.0365 (15) | 0.0008 (14) | 0.0009 (13) | 0.0059 (13) |
C9 | 0.0485 (17) | 0.0356 (16) | 0.0464 (17) | 0.0089 (13) | −0.0007 (14) | 0.0036 (14) |
C10 | 0.0475 (16) | 0.0332 (15) | 0.0406 (16) | 0.0062 (13) | 0.0050 (13) | −0.0037 (12) |
C11 | 0.0348 (13) | 0.0288 (13) | 0.0301 (13) | −0.0028 (11) | 0.0061 (11) | 0.0005 (10) |
C12 | 0.0325 (13) | 0.0292 (14) | 0.0344 (14) | −0.0030 (10) | 0.0081 (12) | 0.0011 (11) |
C13 | 0.0297 (12) | 0.0270 (12) | 0.0308 (13) | 0.0024 (10) | 0.0019 (11) | −0.0028 (10) |
C14 | 0.0509 (16) | 0.0299 (14) | 0.0446 (15) | −0.0041 (12) | 0.0337 (14) | −0.0055 (12) |
Geometric parameters (Å, º) top
Cu1—O1 | 1.942 (2) | C3—C4 | 1.405 (5) |
Cu1—O4i | 2.322 (2) | C3—H3 | 0.9300 |
Cu1—N1 | 2.011 (3) | C4—C12 | 1.395 (4) |
Cu1—N2 | 1.981 (2) | C4—C5 | 1.420 (5) |
Cu1—N3 | 2.004 (2) | C5—C6 | 1.359 (5) |
O1—N4 | 1.263 (4) | C5—H5 | 0.9300 |
O2—N4 | 1.321 (4) | C6—C7 | 1.432 (4) |
O3—N4 | 1.210 (4) | C6—H6 | 0.9300 |
O4—C13 | 1.244 (4) | C7—C11 | 1.387 (4) |
O4—Cu1ii | 2.322 (2) | C7—C8 | 1.411 (5) |
N1—C1 | 1.320 (4) | C8—C9 | 1.360 (5) |
N1—C12 | 1.347 (4) | C8—H8 | 0.9300 |
N2—C10 | 1.325 (4) | C9—C10 | 1.385 (5) |
N2—C11 | 1.352 (4) | C9—H9 | 0.9300 |
N3—C13 | 1.283 (4) | C10—H10 | 0.9300 |
N3—H3A | 0.8600 | C11—C12 | 1.425 (4) |
C1—C2 | 1.406 (5) | C13—C14 | 1.222 (4) |
C1—H1 | 0.9300 | C14—H14A | 0.9600 |
C2—C3 | 1.355 (5) | C14—H14B | 0.9600 |
C2—H2 | 0.9300 | C14—H14C | 0.9600 |
| | | |
O1—Cu1—O4i | 82.50 (9) | C3—C4—C5 | 123.8 (3) |
O1—Cu1—N1 | 94.00 (11) | C6—C5—C4 | 120.8 (3) |
O1—Cu1—N2 | 174.61 (10) | C6—C5—H5 | 119.6 |
O1—Cu1—N3 | 91.10 (10) | C4—C5—H5 | 119.6 |
O4—Cu1—N1i | 138.52 (4) | C5—C6—C7 | 121.4 (3) |
O4—Cu1—N2i | 125.47 (5) | C5—C6—H6 | 119.3 |
O4—Cu1—N3i | 141.73 (5) | C7—C6—H6 | 119.3 |
N1—Cu1—N2 | 82.97 (10) | C11—C7—C8 | 116.4 (3) |
N1—Cu1—N3 | 165.98 (10) | C11—C7—C6 | 118.4 (3) |
N2—Cu1—N3 | 92.87 (10) | C8—C7—C6 | 125.2 (3) |
N4—O1—Cu1 | 117.34 (19) | C9—C8—C7 | 120.1 (3) |
C13—O4—Cu1ii | 121.63 (19) | C9—C8—H8 | 119.9 |
C1—N1—C12 | 118.4 (3) | C7—C8—H8 | 119.9 |
C1—N1—Cu1 | 130.6 (2) | C8—C9—C10 | 119.8 (3) |
C12—N1—Cu1 | 110.93 (19) | C8—C9—H9 | 120.1 |
C10—N2—C11 | 119.5 (3) | C10—C9—H9 | 120.1 |
C10—N2—Cu1 | 128.9 (2) | N2—C10—C9 | 121.4 (3) |
C11—N2—Cu1 | 111.59 (19) | N2—C10—H10 | 119.3 |
C13—N3—Cu1 | 115.46 (18) | C9—C10—H10 | 119.3 |
C13—N3—H3A | 122.3 | N2—C11—C7 | 122.9 (3) |
Cu1—N3—H3A | 122.3 | N2—C11—C12 | 117.1 (3) |
O3—N4—O2 | 118.6 (3) | C7—C11—C12 | 120.1 (3) |
O3—N4—O1 | 117.3 (3) | N1—C12—C4 | 122.6 (3) |
O2—N4—O1 | 124.1 (3) | N1—C12—C11 | 116.6 (3) |
N1—C1—C2 | 122.9 (3) | C4—C12—C11 | 120.7 (3) |
N1—C1—H1 | 118.6 | C14—C13—O4 | 122.1 (3) |
C2—C1—H1 | 118.6 | C14—C13—N3 | 118.1 (3) |
C3—C2—C1 | 118.8 (3) | O4—C13—N3 | 119.8 (3) |
C3—C2—H2 | 120.6 | C13—C14—H14A | 109.5 |
C1—C2—H2 | 120.6 | C13—C14—H14B | 109.5 |
C2—C3—C4 | 119.6 (3) | H14A—C14—H14B | 109.5 |
C2—C3—H3 | 120.2 | C13—C14—H14C | 109.5 |
C4—C3—H3 | 120.2 | H14A—C14—H14C | 109.5 |
C12—C4—C3 | 117.7 (3) | H14B—C14—H14C | 109.5 |
C12—C4—C5 | 118.5 (3) | | |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3iii | 0.93 | 2.50 | 3.319 (5) | 147 |
C5—H5···O2iv | 0.93 | 2.57 | 3.171 (5) | 124 |
Symmetry codes: (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x+1, −y+2, −z+2. |
Experimental details
Crystal data |
Chemical formula | [Cu(NO3)(C2H4NO)(C12H8N2)] |
Mr | 363.82 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 8.680 (2), 9.190 (3), 17.0137 (12) |
β (°) | 101.904 (2) |
V (Å3) | 1328.0 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.67 |
Crystal size (mm) | 0.41 × 0.23 × 0.22 |
|
Data collection |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.624, 0.695 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8439, 2679, 2285 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.631 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.130, 1.08 |
No. of reflections | 2679 |
No. of parameters | 209 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80, −0.69 |
Selected geometric parameters (Å, º) topCu1—O1 | 1.942 (2) | Cu1—N2 | 1.981 (2) |
Cu1—O4i | 2.322 (2) | Cu1—N3 | 2.004 (2) |
Cu1—N1 | 2.011 (3) | | |
| | | |
O1—Cu1—O4i | 82.50 (9) | O4—Cu1—N2i | 125.47 (5) |
O1—Cu1—N1 | 94.00 (11) | O4—Cu1—N3i | 141.73 (5) |
O1—Cu1—N2 | 174.61 (10) | N1—Cu1—N2 | 82.97 (10) |
O1—Cu1—N3 | 91.10 (10) | N1—Cu1—N3 | 165.98 (10) |
O4—Cu1—N1i | 138.52 (4) | N2—Cu1—N3 | 92.87 (10) |
Symmetry code: (i) −x+3/2, y+1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3ii | 0.93 | 2.50 | 3.319 (5) | 147 |
C5—H5···O2iii | 0.93 | 2.57 | 3.171 (5) | 124 |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1, −y+2, −z+2. |
The crystal structure of catena-Poly[[(nitrato-κO) (1,10-phenanthroline-κ2N,N')nickel(II)]-µ-acetamido-κ2O:N], (II), has previously been reported (Liu & Zhu, 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II). We report herein the crystal structure of (I).
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The title compound, [Cu(NO3)(C2H4NO)(C12H8N2)]n, which are linked by acetamidate ligands to form a chain. Each CuII atom is five-coordinated by two N atoms of 1,10-phenanthroline (phen) ligand, one nitrate O atom, and one N and one O atoms of acetamidate within a bipyramidal coordination geometry (Table 1). The Cu—O and Cu—N bond are in the range [1.942 (2)–2.322 (2) Å] and [1.981 (2)–2.011 (3) Å], respectively (Table 1), as in (II).
In the crystal structure, no classic C—H···O hydrogen bonds (Fig. 2 and Table 2) seem to be effective in the stabilization of the structure, resulting in the formation of a polymeric ribbon structure, as in (II).
The both compounds, (I) and (II), are isostructural.