Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011710/wn6032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011710/wn6032Isup2.hkl |
CCDC reference: 170871
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.008 Å
- R factor = 0.053
- wR factor = 0.133
- Data-to-parameter ratio = 12.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
CHEMW_01 Alert A The ratio of given/expected molecular weight as calculated from the _chemical_formula_sum lies outside the range 0.90 <> 1.10 Calculated formula weight = 331.7862 Formula weight given = 165.9000 DENSD_01 Alert A The ratio of the submitted crystal density and that calculated from the formula is outside the range 0.90 <> 1.10 Crystal density given = 1.657 Calculated crystal density = 0.829
Alert Level C:
CHEMW_01 Alert C The difference between the given and expected weight for compound is greater 1 mass unit. Check that all hydrogen atoms have been taken into account. PLAT_420 Alert C D-H Without Acceptor N(5) - H(5A) ? General Notes
ABSTM_02 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 1.353 Tmax scaled 0.743 Tmin scaled 0.679 CHEMW_03 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_weight 165.90 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 10.00 120.11 H 1.01 8.00 8.06 N 14.01 10.00 140.07 Cu 63.55 1.00 63.55 Calculated formula weight 331.79 ALERT: The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.90 <> 1.10
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
To an aqueous solution (20 ml) of Cu2Cl2·2H2O (0.085 g, 0.5 mm mol), sodium dicyanamide (0.09 g, 1 mmol) was added. After stirring the mixture for about 30 min, a DMF solution (10 ml) of imidazole (0.07 g, 0.5 mmol) was added. This mixture was stirred and heated for 1 h, then filtered while hot. Well shaped crystals were obtained from the mother liquor by slow evaporation at room temperature over a period of several days.
H-atom positions were generated geometrically and the H atoms were allowed to ride on their respective parent C atoms.
Data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.
Fig. 1. The structure of the title molecule with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
[Cu(C2N3)2(C3H4N2)2] | F(000) = 334 |
Mr = 165.90 | Dx = 1.657 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2024 (11) Å | Cell parameters from 97 reflections |
b = 7.5897 (9) Å | θ = 2.3–25.1° |
c = 9.7251 (11) Å | µ = 1.65 mm−1 |
β = 101.790 (2)° | T = 293 K |
V = 664.90 (13) Å3 | Plate, blue |
Z = 2 | 0.28 × 0.21 × 0.18 mm |
Siemens SMART CCD diffractometer | 1173 independent reflections |
Radiation source: fine-focus sealed tube | 817 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ω scans | θmax = 25.1°, θmin = 2.3° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −10→9 |
Tmin = 0.502, Tmax = 0.549 | k = −9→7 |
3295 measured reflections | l = −10→11 |
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) = 0.133 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0553P)2 + 1.568P] where P = (Fo2 + 2Fc2)/3 |
1173 reflections | (Δ/σ)max < 0.001 |
97 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
[Cu(C2N3)2(C3H4N2)2] | V = 664.90 (13) Å3 |
Mr = 165.90 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2024 (11) Å | µ = 1.65 mm−1 |
b = 7.5897 (9) Å | T = 293 K |
c = 9.7251 (11) Å | 0.28 × 0.21 × 0.18 mm |
β = 101.790 (2)° |
Siemens SMART CCD diffractometer | 1173 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 817 reflections with I > 2σ(I) |
Tmin = 0.502, Tmax = 0.549 | Rint = 0.053 |
3295 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.53 e Å−3 |
1173 reflections | Δρmin = −0.50 e Å−3 |
97 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu | 0.0000 | 0.0000 | 0.0000 | 0.0319 (3) | |
C1 | −0.2054 (6) | 0.1436 (8) | 0.4526 (5) | 0.0332 (13) | |
C2 | −0.0605 (6) | 0.1148 (8) | 0.2922 (6) | 0.0343 (13) | |
C3 | 0.3058 (6) | 0.0457 (8) | 0.1766 (6) | 0.0428 (16) | |
H3B | 0.2848 | −0.0159 | 0.2529 | 0.051* | |
H4A | 0.4941 | 0.2631 | 0.0093 | 0.051* | |
H5B | 0.2473 | 0.2088 | −0.1135 | 0.051* | |
H5A | 0.5176 | 0.1209 | 0.2341 | 0.051* | |
C4 | 0.4225 (5) | 0.2003 (7) | 0.0427 (6) | 0.0298 (12) | |
C5 | 0.2863 (6) | 0.1694 (8) | −0.0232 (6) | 0.0415 (15) | |
N1 | −0.3095 (5) | 0.1204 (7) | 0.4989 (5) | 0.0475 (13) | |
N2 | −0.0856 (5) | 0.1844 (7) | 0.4082 (5) | 0.0416 (12) | |
N3 | −0.0271 (5) | 0.0608 (7) | 0.1920 (5) | 0.0427 (13) | |
N4 | 0.2104 (5) | 0.0759 (6) | 0.0518 (4) | 0.0311 (10) | |
N5 | 0.4376 (6) | 0.1227 (10) | 0.1686 (7) | 0.082 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0308 (5) | 0.0402 (6) | 0.0271 (5) | −0.0043 (5) | 0.0114 (3) | −0.0047 (5) |
C1 | 0.034 (3) | 0.036 (3) | 0.030 (3) | 0.003 (3) | 0.007 (2) | −0.004 (2) |
C2 | 0.030 (3) | 0.033 (3) | 0.039 (3) | −0.005 (2) | 0.005 (2) | 0.001 (3) |
C3 | 0.039 (3) | 0.056 (5) | 0.033 (3) | −0.006 (3) | 0.005 (2) | −0.001 (3) |
C4 | 0.023 (3) | 0.037 (3) | 0.032 (3) | −0.009 (2) | 0.010 (2) | 0.002 (2) |
C5 | 0.044 (3) | 0.046 (4) | 0.036 (3) | 0.004 (3) | 0.012 (3) | 0.005 (3) |
N1 | 0.043 (3) | 0.055 (4) | 0.049 (3) | 0.007 (3) | 0.019 (2) | 0.003 (3) |
N2 | 0.041 (3) | 0.053 (3) | 0.036 (3) | −0.009 (2) | 0.020 (2) | −0.016 (2) |
N3 | 0.038 (3) | 0.061 (4) | 0.032 (3) | −0.005 (2) | 0.013 (2) | −0.010 (2) |
N4 | 0.031 (2) | 0.036 (3) | 0.030 (2) | −0.004 (2) | 0.014 (2) | 0.001 (2) |
N5 | 0.043 (3) | 0.095 (6) | 0.102 (5) | −0.005 (4) | 0.000 (3) | −0.039 (5) |
Cu—N4i | 1.984 (4) | C3—N4 | 1.364 (7) |
Cu—N4 | 1.984 (4) | C3—H3B | 0.9300 |
Cu—N3i | 1.988 (5) | C4—C5 | 1.307 (7) |
Cu—N3 | 1.988 (5) | C4—N5 | 1.340 (8) |
C1—N1 | 1.153 (6) | C4—H4A | 0.9243 |
C1—N2 | 1.300 (7) | C5—N4 | 1.316 (7) |
C2—N3 | 1.155 (7) | C5—H5B | 0.9282 |
C2—N2 | 1.309 (7) | N5—H5A | 0.8688 |
C3—N5 | 1.363 (8) | ||
N4i—Cu—N4 | 180.0 (3) | N5—C4—H4A | 126.8 |
N4i—Cu—N3i | 89.85 (18) | C4—C5—N4 | 112.9 (5) |
N4—Cu—N3i | 90.15 (18) | C4—C5—H5B | 123.6 |
N4i—Cu—N3 | 90.15 (18) | N4—C5—H5B | 123.5 |
N4—Cu—N3 | 89.85 (18) | C1—N2—C2 | 120.1 (5) |
N3i—Cu—N3 | 180.0 (3) | C2—N3—Cu | 168.8 (5) |
N1—C1—N2 | 174.0 (6) | C5—N4—C3 | 105.4 (5) |
N3—C2—N2 | 174.3 (6) | C5—N4—Cu | 128.1 (4) |
N5—C3—N4 | 107.2 (5) | C3—N4—Cu | 126.5 (4) |
N5—C3—H3B | 126.4 | C4—N5—C3 | 108.2 (5) |
N4—C3—H3B | 126.4 | C4—N5—H5A | 126.1 |
C5—C4—N5 | 106.2 (5) | C3—N5—H5A | 125.6 |
C5—C4—H4A | 127.0 |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2N3)2(C3H4N2)2] |
Mr | 165.90 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.2024 (11), 7.5897 (9), 9.7251 (11) |
β (°) | 101.790 (2) |
V (Å3) | 664.90 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.65 |
Crystal size (mm) | 0.28 × 0.21 × 0.18 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.502, 0.549 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3295, 1173, 817 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.133, 1.02 |
No. of reflections | 1173 |
No. of parameters | 97 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.50 |
Computer programs: SMART (Siemens, 1994), SMART, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Cu—N4 | 1.984 (4) | C3—N5 | 1.363 (8) |
Cu—N3 | 1.988 (5) | C3—N4 | 1.364 (7) |
C1—N1 | 1.153 (6) | C4—C5 | 1.307 (7) |
C1—N2 | 1.300 (7) | C4—N5 | 1.340 (8) |
C2—N3 | 1.155 (7) | C5—N4 | 1.316 (7) |
C2—N2 | 1.309 (7) | ||
N4i—Cu—N4 | 180.0 (3) | C4—C5—N4 | 112.9 (5) |
N4i—Cu—N3 | 90.15 (18) | C1—N2—C2 | 120.1 (5) |
N4—Cu—N3 | 89.85 (18) | C2—N3—Cu | 168.8 (5) |
N3i—Cu—N3 | 180.0 (3) | C5—N4—C3 | 105.4 (5) |
N1—C1—N2 | 174.0 (6) | C5—N4—Cu | 128.1 (4) |
N3—C2—N2 | 174.3 (6) | C3—N4—Cu | 126.5 (4) |
N5—C3—N4 | 107.2 (5) | C4—N5—C3 | 108.2 (5) |
C5—C4—N5 | 106.2 (5) |
Symmetry code: (i) −x, −y, −z. |
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Dicyanamide, [N(CN)2]-, was selected since its coordination versatility ranges from being monodentate to µ4-coordination. Also, many complexes containing dicyanamide have been reported, such as (CH3)2Tl[[N(CN)2] (Chow & Britton, 1975), [Cu(phen)2{N(CN)2}2] (Potocnák et al., 1995), [Ni{N(CN)2}2(C4H6N2)4] (Kozísek et al., 1996), [Ag2{N(CN)2}2{P(Ph)3}2] (Bessler et al., 2000), [Zn{N(CN)2}2] (Manson et al., 1998) and [Mn{N(CN)2}2] (Batten et al., 1999). We report here the crystal structure of the title compound, [Cu(N(CN)2)2(C3H4N2)2], (I), whose structure is composed of discrete molecules.
The Cu atom is four-coordinated by two N atoms from two trans-bonded dicyanamide anions and two N atoms of two trans-bonded imidazole ligands. The Cu—Ndca (Cu1—N3) bond length is 1.988 (5) Å, which is comparable to the corresponding values in [Cu(C12H8N2){N(CN)2}][C(CN)3] (Potocnák et al., 1996) and the Cu—Niz (Cu1—N4) bond length is 1.984 (4) Å. The Niz—Cu1—Niz and Ndca—Cu1—Ndca bond angles are very close to 180°. The Niz—Cu1—Ndca bond angles are almost exactly 90°. The five atoms Cu1, N3, N3i, N4 and N4i are coplanar [symmetry code: (i) -x, -y, -z]. In summary, the Cu atom exhibits almost perfect tetragonal coordination.