The title compound, [Cu(C2O4)2(C6H9N2)2], crystallizes in the space group P21/c, with the Cu atom located at a centre of symmetry. It is a neutral coordination complex in which the metal exhibits a tetragonally elongated octahedral trans-CuO4N2 coordination environment. Extensive intermolecular hydrogen bonding between the oxalate anions and the ammonium cations determines the molecular packing in the crystal.
Supporting information
CCDC reference: 227750
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- R factor = 0.035
- wR factor = 0.091
- Data-to-parameter ratio = 14.2
checkCIF/PLATON results
No syntax errors found
Alert level C
ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
Tmin and Tmax reported: 0.605 0.880
Tmin' and Tmax expected: 0.771 0.880
RR' = 0.785
Please check that your absorption correction is appropriate.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.99
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.78
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for O3 - C2 = 5.05 su
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C2 = 1.56 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 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
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: DENZO (Otwinowski and Minor, 1997); cell refinement: DENZO and COLLECT (Hooft, 1998); data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) in WinGX (Farrugia, 1999); program(s) used to refine structure: SHELXS97 (Sheldrick, 1997) in WinGX; molecular graphics: DIAMOND (Brandenburg, 1999).
Crystal data top
[Cu(C2O4)2(C6H9N2)2] | Dx = 1.709 Mg m−3 |
Mr = 457.89 | Melting point: N/A K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.5768 (4) Å | Cell parameters from 4249 reflections |
b = 10.6642 (3) Å | θ = 2.9–27.5° |
c = 7.5782 (2) Å | µ = 1.28 mm−1 |
β = 108.013 (1)° | T = 120 K |
V = 889.73 (5) Å3 | Block, pale green |
Z = 2 | 0.2 × 0.1 × 0.1 mm |
F(000) = 470 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1765 reflections with I > 2σ(I) |
φ and ω scans to fill Ewald sphere | Rint = 0.086 |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | θmax = 27.5°, θmin = 2.9° |
Tmin = 0.605, Tmax = 0.880 | h = −15→15 |
8409 measured reflections | k = −13→13 |
2023 independent reflections | l = −9→9 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.0263P)2 + 0.8605P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.091 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.47 e Å−3 |
2023 reflections | Δρmin = −0.56 e Å−3 |
142 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. Amine H atoms were freely refined. Ammonium H atoms were fixed in
calculated positions and refined in riding mode with the group allowed to
rotate freely along the N2—C4 bond. Aryl H atoms were fixed in calculated
positions and refined in riding mode |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
H1B | 0.139 (2) | 0.118 (3) | 0.348 (4) | 0.025 (7)* | |
H1A | 0.148 (2) | 0.197 (3) | 0.188 (4) | 0.021 (7)* | |
Cu1 | 0 | 0 | 0 | 0.01258 (13) | |
O1 | −0.24205 (13) | 0.13669 (14) | 0.2149 (2) | 0.0157 (3) | |
O4 | −0.03181 (13) | −0.09760 (14) | 0.2004 (2) | 0.0139 (3) | |
O2 | −0.12189 (12) | 0.11570 (14) | 0.0367 (2) | 0.0136 (3) | |
O3 | −0.15409 (14) | −0.09020 (15) | 0.3788 (2) | 0.0183 (3) | |
N2 | 0.22712 (15) | −0.11713 (17) | 0.4045 (3) | 0.0137 (4) | |
H2A | 0.2389 | −0.1985 | 0.3901 | 0.021* | |
H2B | 0.1503 | −0.0975 | 0.3441 | 0.021* | |
H2C | 0.2428 | −0.1002 | 0.5246 | 0.021* | |
N1 | 0.15697 (16) | 0.12297 (18) | 0.2376 (3) | 0.0152 (4) | |
C5 | 0.4172 (2) | −0.0972 (2) | 0.3323 (3) | 0.0188 (5) | |
H5 | 0.4392 | −0.1753 | 0.3872 | 0.023* | |
C1 | −0.16504 (18) | 0.07888 (19) | 0.1619 (3) | 0.0123 (4) | |
C8 | 0.3508 (2) | 0.1354 (2) | 0.1705 (3) | 0.0183 (5) | |
H8 | 0.3295 | 0.2136 | 0.1158 | 0.022* | |
C4 | 0.30838 (19) | −0.0435 (2) | 0.3299 (3) | 0.0145 (4) | |
C2 | −0.11398 (18) | −0.0473 (2) | 0.2586 (3) | 0.0135 (4) | |
C6 | 0.4940 (2) | −0.0348 (2) | 0.2527 (4) | 0.0224 (5) | |
H6 | 0.5676 | −0.0704 | 0.2543 | 0.027* | |
C3 | 0.27242 (18) | 0.0743 (2) | 0.2512 (3) | 0.0140 (4) | |
C7 | 0.4598 (2) | 0.0807 (2) | 0.1711 (4) | 0.0226 (5) | |
H7 | 0.5103 | 0.1224 | 0.116 | 0.027* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0129 (2) | 0.0124 (2) | 0.0140 (2) | 0.00294 (12) | 0.00640 (16) | 0.00287 (13) |
O1 | 0.0149 (7) | 0.0144 (8) | 0.0196 (8) | 0.0023 (6) | 0.0080 (6) | 0.0000 (6) |
O4 | 0.0157 (7) | 0.0122 (8) | 0.0153 (8) | 0.0022 (6) | 0.0071 (6) | 0.0021 (6) |
O2 | 0.0142 (7) | 0.0122 (7) | 0.0156 (8) | 0.0013 (6) | 0.0063 (6) | 0.0021 (6) |
O3 | 0.0235 (8) | 0.0167 (8) | 0.0192 (8) | 0.0027 (6) | 0.0130 (7) | 0.0038 (6) |
N2 | 0.0137 (8) | 0.0116 (9) | 0.0154 (9) | 0.0004 (7) | 0.0039 (7) | 0.0005 (7) |
N1 | 0.0173 (9) | 0.0117 (9) | 0.0171 (10) | 0.0022 (7) | 0.0060 (8) | 0.0026 (7) |
C5 | 0.0175 (10) | 0.0151 (11) | 0.0231 (12) | 0.0025 (8) | 0.0053 (9) | −0.0006 (9) |
C1 | 0.0118 (9) | 0.0111 (10) | 0.0122 (10) | −0.0018 (7) | 0.0012 (8) | −0.0002 (8) |
C8 | 0.0219 (11) | 0.0120 (11) | 0.0215 (12) | −0.0028 (8) | 0.0075 (9) | −0.0005 (9) |
C4 | 0.0143 (10) | 0.0136 (10) | 0.0146 (11) | −0.0039 (8) | 0.0029 (8) | −0.0022 (9) |
C2 | 0.0131 (9) | 0.0120 (10) | 0.0134 (10) | −0.0010 (8) | 0.0012 (8) | −0.0027 (8) |
C6 | 0.0139 (10) | 0.0241 (12) | 0.0309 (14) | 0.0007 (9) | 0.0093 (10) | −0.0020 (11) |
C3 | 0.0143 (9) | 0.0134 (10) | 0.0134 (11) | −0.0006 (8) | 0.0028 (8) | −0.0034 (8) |
C7 | 0.0214 (11) | 0.0214 (12) | 0.0283 (13) | −0.0064 (9) | 0.0122 (10) | −0.0011 (10) |
Geometric parameters (Å, º) top
Cu1—O2 | 1.9579 (14) | N1—H1B | 0.92 (3) |
Cu1—O2i | 1.9579 (14) | N1—H1A | 0.86 (3) |
Cu1—O4i | 1.9675 (14) | C5—C4 | 1.379 (3) |
Cu1—O4 | 1.9675 (14) | C5—C6 | 1.389 (3) |
Cu1—N1 | 2.4980 (19) | C5—H5 | 0.9300 |
O1—C1 | 1.248 (2) | C1—C2 | 1.559 (3) |
O4—C2 | 1.283 (2) | C8—C7 | 1.389 (3) |
O2—C1 | 1.264 (3) | C8—C3 | 1.402 (3) |
O3—C2 | 1.231 (3) | C8—H8 | 0.9300 |
N2—C4 | 1.466 (3) | C4—C3 | 1.398 (3) |
N2—H2A | 0.8900 | C6—C7 | 1.380 (4) |
N2—H2B | 0.8900 | C6—H6 | 0.9300 |
N2—H2C | 0.8900 | C7—H7 | 0.9300 |
N1—C3 | 1.407 (3) | | |
| | | |
O2—Cu1—O2i | 180.00 (8) | C4—C5—C6 | 120.0 (2) |
O2—Cu1—O4i | 95.24 (6) | C4—C5—H5 | 120.0 |
O2i—Cu1—O4i | 84.76 (6) | C6—C5—H5 | 120.0 |
O2—Cu1—O4 | 84.76 (6) | O1—C1—O2 | 125.13 (19) |
O2i—Cu1—O4 | 95.24 (6) | O1—C1—C2 | 118.71 (18) |
O4i—Cu1—O4 | 180.00 (11) | O2—C1—C2 | 116.14 (17) |
O2—Cu1—N1 | 87.85 (6) | C7—C8—C3 | 120.9 (2) |
O2i—Cu1—N1 | 92.15 (6) | C7—C8—H8 | 119.6 |
O4i—Cu1—N1 | 90.60 (6) | C3—C8—H8 | 119.6 |
O4—Cu1—N1 | 89.40 (6) | C5—C4—C3 | 122.0 (2) |
C2—O4—Cu1 | 112.33 (13) | C5—C4—N2 | 117.7 (2) |
C1—O2—Cu1 | 112.36 (13) | C3—C4—N2 | 120.28 (18) |
C4—N2—H2A | 109.5 | O3—C2—O4 | 126.0 (2) |
C4—N2—H2B | 109.5 | O3—C2—C1 | 119.57 (18) |
H2A—N2—H2B | 109.5 | O4—C2—C1 | 114.39 (18) |
C4—N2—H2C | 109.5 | C7—C6—C5 | 119.3 (2) |
H2A—N2—H2C | 109.5 | C7—C6—H6 | 120.3 |
H2B—N2—H2C | 109.5 | C5—C6—H6 | 120.3 |
C3—N1—Cu1 | 108.78 (13) | C4—C3—C8 | 117.16 (19) |
C3—N1—H1B | 112.9 (17) | C4—C3—N1 | 120.87 (19) |
Cu1—N1—H1B | 107.8 (17) | C8—C3—N1 | 121.7 (2) |
C3—N1—H1A | 110.3 (17) | C6—C7—C8 | 120.7 (2) |
Cu1—N1—H1A | 101.9 (18) | C6—C7—H7 | 119.7 |
H1B—N1—H1A | 114 (2) | C8—C7—H7 | 119.7 |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3ii | 0.86 (3) | 2.33 (3) | 3.181 (2) | 167 (2) |
N2—H2A···O1iii | 0.89 | 1.93 | 2.799 (2) | 164 |
N2—H2A···O2iii | 0.89 | 2.56 | 3.184 (2) | 128 |
N2—H2B···O4 | 0.89 | 2.05 | 2.925 (2) | 166 |
N2—H2C···O1iv | 0.89 | 2.01 | 2.843 (2) | 154 |
N2—H2C···O3iv | 0.89 | 2.49 | 3.026 (2) | 120 |
N1—H1B···O3iv | 0.92 (3) | 2.05 (3) | 2.938 (3) | 162 (2) |
Symmetry codes: (ii) −x, y+1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x, −y, −z+1. |