The crystallization behavior of the title compound, [Co(C2H8N2)3](C2O4)(ClO4)·2H2O, has been studied in order to evaluate the effect of the counter-anion on the crystalline structures of [Co(en)3](C2O4)·X (en = ethylenediamine). Two-dimensional intermolecular hydrogen-bonding networks are formed between the amine protons of the [Co(en)3]3+ cations and the O atoms of the oxalate anions. Perchlorate and water molecules fill in the channels between the two-dimensional networks and form hydrogen-bonding interactions with the two-dimensional layers, thus constructing a three-dimensional hydrogen-bonding network.
Supporting information
CCDC reference: 146044
Data collection: SMART (Bruker, 1998a); cell refinement: SMART; data reduction: SAINT+ (Bruker,1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998b); software used to prepare material for publication: SHELXTL.
Tris(ethylenediamine) cobalt (III) oxalato perchlorate dihydrate
top
Crystal data top
[Co(C2H8N2)3](C2O4)(ClO4)·2H2O | F(000) = 968 |
Mr = 462.74 | Dx = 1.668 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.5502 (7) Å | Cell parameters from global unit cell refinement reflections |
b = 9.5832 (5) Å | θ = 2.0–27.0° |
c = 15.3950 (8) Å | µ = 1.14 mm−1 |
β = 95.734 (1)° | T = 293 K |
V = 1842.31 (17) Å3 | Block, red |
Z = 4 | 0.30 × 0.30 × 0.20 mm |
Data collection top
Bruker SMART CCD area detector diffractometer | 4017 independent reflections |
Radiation source: fine-focus sealed tube | 3256 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
φ and ω scans | θmax = 27.0°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (Blessing, 1995) | h = −15→16 |
Tmin = 0.727, Tmax = 0.804 | k = −5→12 |
10764 measured reflections | l = −19→19 |
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)] = 0.031 | w = 1/[σ2(Fo2) + (0.0652P)2 + 0.2357P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.090 | (Δ/σ)max = 0.006 |
S = 1.02 | Δρmax = 0.46 e Å−3 |
4017 reflections | Δρmin = −0.37 e Å−3 |
235 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.204189 (19) | 0.25769 (2) | 0.069605 (15) | 0.02170 (9) | |
Cl | 0.62348 (5) | 0.13933 (7) | 0.21236 (4) | 0.05170 (17) | |
C1 | 0.29927 (19) | −0.0104 (2) | 0.07421 (14) | 0.0383 (5) | |
H1C | 0.3001 | −0.1034 | 0.0991 | 0.046* | |
H1D | 0.3717 | 0.0139 | 0.0630 | 0.046* | |
C2 | 0.22575 (18) | −0.0056 (2) | −0.00915 (13) | 0.0352 (5) | |
H2C | 0.2560 | −0.0587 | −0.0544 | 0.042* | |
H2D | 0.1566 | −0.0453 | −0.0001 | 0.042* | |
C3 | 0.25658 (18) | 0.4870 (3) | −0.03350 (15) | 0.0415 (5) | |
H3C | 0.2414 | 0.5835 | −0.0492 | 0.050* | |
H3D | 0.2775 | 0.4385 | −0.0844 | 0.050* | |
C4 | 0.34462 (18) | 0.4789 (2) | 0.04016 (16) | 0.0417 (5) | |
H4C | 0.4121 | 0.5083 | 0.0204 | 0.050* | |
H4D | 0.3286 | 0.5392 | 0.0878 | 0.050* | |
C5 | 0.08770 (17) | 0.3098 (2) | 0.21409 (13) | 0.0340 (5) | |
H5C | 0.0646 | 0.3791 | 0.2541 | 0.041* | |
H5D | 0.0991 | 0.2222 | 0.2452 | 0.041* | |
C6 | 0.00432 (16) | 0.2921 (2) | 0.13724 (13) | 0.0312 (4) | |
H6C | −0.0589 | 0.2467 | 0.1554 | 0.037* | |
H6D | −0.0164 | 0.3823 | 0.1123 | 0.037* | |
C7 | −0.06625 (15) | 0.1440 (2) | −0.16222 (12) | 0.0266 (4) | |
C8 | −0.10735 (16) | 0.2912 (2) | −0.14048 (12) | 0.0267 (4) | |
N1 | 0.25802 (14) | 0.09149 (17) | 0.13512 (10) | 0.0310 (4) | |
H1A | 0.3107 | 0.1161 | 0.1762 | 0.037* | |
H1B | 0.2049 | 0.0525 | 0.1619 | 0.037* | |
N2 | 0.21358 (14) | 0.14248 (17) | −0.03524 (10) | 0.0296 (4) | |
H2A | 0.1539 | 0.1533 | −0.0722 | 0.035* | |
H2B | 0.2701 | 0.1695 | −0.0628 | 0.035* | |
N3 | 0.16109 (13) | 0.42020 (17) | −0.00236 (10) | 0.0285 (3) | |
H3A | 0.1158 | 0.3935 | −0.0484 | 0.034* | |
H3B | 0.1268 | 0.4818 | 0.0291 | 0.034* | |
N4 | 0.35136 (13) | 0.33129 (18) | 0.06955 (12) | 0.0339 (4) | |
H4A | 0.3858 | 0.3260 | 0.1236 | 0.041* | |
H4B | 0.3880 | 0.2806 | 0.0333 | 0.041* | |
N5 | 0.18740 (13) | 0.35532 (17) | 0.17921 (10) | 0.0278 (3) | |
H5A | 0.2438 | 0.3368 | 0.2183 | 0.033* | |
H5B | 0.1852 | 0.4480 | 0.1698 | 0.033* | |
N6 | 0.05353 (13) | 0.20486 (17) | 0.07223 (10) | 0.0265 (3) | |
H6A | 0.0180 | 0.2172 | 0.0190 | 0.032* | |
H6B | 0.0491 | 0.1142 | 0.0866 | 0.032* | |
O1 | −0.10277 (12) | 0.08980 (16) | −0.23318 (9) | 0.0408 (4) | |
O2 | −0.00388 (12) | 0.08533 (14) | −0.10582 (9) | 0.0359 (3) | |
O3 | −0.05980 (12) | 0.35217 (15) | −0.07590 (9) | 0.0389 (4) | |
O4 | −0.18755 (12) | 0.33671 (15) | −0.18644 (10) | 0.0395 (4) | |
O5 | 0.6656 (4) | 0.2351 (3) | 0.1580 (3) | 0.172 (2) | |
O6 | 0.6814 (3) | 0.0136 (3) | 0.21203 (19) | 0.1154 (11) | |
O7 | 0.5180 (3) | 0.1149 (4) | 0.1808 (2) | 0.1477 (15) | |
O8 | 0.6278 (3) | 0.1933 (4) | 0.29642 (16) | 0.1218 (12) | |
OW1 | 0.07009 (19) | −0.2845 (2) | −0.40327 (14) | 0.0707 (6) | |
HW1 | 0.0632 | −0.2035 | −0.3689 | 0.085* | |
HW2 | 0.0677 | −0.3566 | −0.3723 | 0.085* | |
OW2 | 0.0709 (2) | −0.0522 (3) | −0.30038 (16) | 0.0898 (8) | |
HW3 | 0.0197 | −0.0122 | −0.2706 | 0.108* | |
HW4 | 0.1327 | −0.0195 | −0.2665 | 0.108* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.02281 (15) | 0.02197 (14) | 0.01947 (14) | −0.00003 (9) | −0.00213 (9) | −0.00024 (9) |
Cl | 0.0584 (4) | 0.0520 (4) | 0.0464 (3) | −0.0021 (3) | 0.0138 (3) | −0.0093 (3) |
C1 | 0.0417 (12) | 0.0327 (11) | 0.0396 (11) | 0.0117 (9) | −0.0005 (9) | −0.0012 (9) |
C2 | 0.0446 (12) | 0.0293 (11) | 0.0315 (10) | 0.0032 (9) | 0.0034 (9) | −0.0065 (8) |
C3 | 0.0417 (13) | 0.0384 (12) | 0.0459 (13) | −0.0016 (9) | 0.0110 (10) | 0.0133 (10) |
C4 | 0.0328 (11) | 0.0360 (12) | 0.0573 (14) | −0.0091 (9) | 0.0088 (10) | 0.0003 (10) |
C5 | 0.0381 (12) | 0.0385 (12) | 0.0257 (9) | −0.0023 (9) | 0.0044 (8) | −0.0053 (9) |
C6 | 0.0262 (10) | 0.0343 (11) | 0.0331 (11) | 0.0021 (8) | 0.0032 (8) | −0.0021 (8) |
C7 | 0.0248 (9) | 0.0259 (10) | 0.0282 (9) | −0.0029 (7) | −0.0014 (7) | −0.0002 (8) |
C8 | 0.0298 (10) | 0.0249 (9) | 0.0247 (9) | −0.0007 (8) | −0.0009 (8) | 0.0014 (7) |
N1 | 0.0344 (9) | 0.0298 (9) | 0.0273 (8) | 0.0015 (7) | −0.0046 (7) | −0.0001 (7) |
N2 | 0.0322 (9) | 0.0323 (9) | 0.0236 (8) | 0.0015 (7) | −0.0003 (6) | −0.0018 (7) |
N3 | 0.0320 (9) | 0.0265 (8) | 0.0266 (8) | −0.0003 (7) | 0.0009 (7) | 0.0027 (6) |
N4 | 0.0272 (9) | 0.0360 (10) | 0.0379 (9) | −0.0019 (7) | −0.0003 (7) | −0.0003 (8) |
N5 | 0.0294 (8) | 0.0276 (8) | 0.0251 (8) | −0.0003 (7) | −0.0038 (6) | −0.0019 (6) |
N6 | 0.0278 (8) | 0.0258 (8) | 0.0249 (8) | −0.0023 (6) | −0.0023 (6) | 0.0008 (6) |
O1 | 0.0438 (9) | 0.0391 (9) | 0.0362 (8) | 0.0073 (7) | −0.0125 (7) | −0.0149 (7) |
O2 | 0.0419 (8) | 0.0279 (7) | 0.0350 (8) | 0.0031 (6) | −0.0101 (6) | 0.0037 (6) |
O3 | 0.0442 (9) | 0.0329 (8) | 0.0359 (8) | 0.0079 (6) | −0.0137 (7) | −0.0119 (6) |
O4 | 0.0447 (9) | 0.0338 (8) | 0.0365 (8) | 0.0107 (7) | −0.0135 (7) | −0.0032 (6) |
O5 | 0.268 (6) | 0.083 (2) | 0.190 (4) | −0.022 (2) | 0.150 (4) | 0.016 (2) |
O6 | 0.148 (3) | 0.0859 (19) | 0.112 (2) | 0.0424 (18) | 0.0125 (19) | −0.0161 (16) |
O7 | 0.102 (2) | 0.161 (3) | 0.164 (3) | −0.032 (2) | −0.065 (2) | 0.007 (2) |
O8 | 0.132 (3) | 0.169 (3) | 0.0617 (15) | 0.047 (2) | −0.0032 (16) | −0.0489 (18) |
OW1 | 0.0858 (16) | 0.0592 (12) | 0.0736 (14) | 0.0006 (11) | 0.0402 (12) | 0.0032 (10) |
OW2 | 0.0829 (16) | 0.0863 (18) | 0.1072 (17) | −0.0126 (13) | 0.0440 (13) | −0.0409 (15) |
Geometric parameters (Å, º) top
Co1—N3 | 1.9560 (15) | C2—N2 | 1.479 (3) |
Co1—N5 | 1.9590 (16) | C3—N3 | 1.480 (3) |
Co1—N6 | 1.9617 (16) | C3—C4 | 1.504 (3) |
Co1—N1 | 1.9683 (16) | C4—N4 | 1.485 (3) |
Co1—N2 | 1.9688 (16) | C5—N5 | 1.476 (3) |
Co1—N4 | 1.9772 (17) | C5—C6 | 1.509 (3) |
Cl—O5 | 1.382 (3) | C6—N6 | 1.485 (3) |
Cl—O7 | 1.384 (3) | C7—O2 | 1.244 (2) |
Cl—O8 | 1.390 (2) | C7—O1 | 1.254 (2) |
Cl—O6 | 1.407 (3) | C7—C8 | 1.551 (3) |
C1—N1 | 1.483 (3) | C8—O4 | 1.249 (2) |
C1—C2 | 1.505 (3) | C8—O3 | 1.252 (2) |
| | | |
N3—Co1—N5 | 93.45 (7) | O8—Cl—O6 | 110.45 (19) |
N3—Co1—N6 | 90.26 (7) | N1—C1—C2 | 107.23 (17) |
N5—Co1—N6 | 85.34 (7) | N2—C2—C1 | 107.39 (16) |
N3—Co1—N1 | 174.79 (7) | N3—C3—C4 | 106.94 (17) |
N5—Co1—N1 | 90.35 (7) | N4—C4—C3 | 107.07 (17) |
N6—Co1—N1 | 93.60 (7) | N5—C5—C6 | 107.13 (16) |
N3—Co1—N2 | 91.03 (7) | N6—C6—C5 | 106.80 (16) |
N5—Co1—N2 | 173.90 (7) | O2—C7—O1 | 124.81 (19) |
N6—Co1—N2 | 90.51 (7) | O2—C7—C8 | 117.41 (16) |
N1—Co1—N2 | 85.45 (7) | O1—C7—C8 | 117.66 (16) |
N3—Co1—N4 | 85.48 (7) | O4—C8—O3 | 125.47 (19) |
N5—Co1—N4 | 90.62 (7) | O4—C8—C7 | 117.49 (16) |
N6—Co1—N4 | 173.95 (7) | O3—C8—C7 | 116.97 (16) |
N1—Co1—N4 | 90.92 (7) | C1—N1—Co1 | 109.43 (12) |
N2—Co1—N4 | 93.86 (7) | C2—N2—Co1 | 109.18 (12) |
O5—Cl—O7 | 108.0 (3) | C3—N3—Co1 | 109.92 (13) |
O5—Cl—O8 | 109.6 (2) | C4—N4—Co1 | 108.37 (12) |
O7—Cl—O8 | 109.7 (2) | C5—N5—Co1 | 109.89 (12) |
O5—Cl—O6 | 109.7 (2) | C6—N6—Co1 | 109.57 (12) |
O7—Cl—O6 | 109.3 (2) | | |
| | | |
N1—C1—C2—N2 | 50.3 (2) | N1—Co1—N3—C3 | −33.7 (8) |
N3—C3—C4—N4 | 51.2 (2) | N2—Co1—N3—C3 | −81.07 (15) |
N5—C5—C6—N6 | 50.0 (2) | N4—Co1—N3—C3 | 12.71 (14) |
O2—C7—C8—O4 | −163.65 (19) | C3—C4—N4—Co1 | −40.5 (2) |
O1—C7—C8—O4 | 12.6 (3) | N3—Co1—N4—C4 | 15.81 (14) |
O2—C7—C8—O3 | 13.5 (3) | N5—Co1—N4—C4 | −77.60 (15) |
O1—C7—C8—O3 | −170.29 (19) | N6—Co1—N4—C4 | −29.6 (7) |
C2—C1—N1—Co1 | −38.0 (2) | N1—Co1—N4—C4 | −167.96 (14) |
N3—Co1—N1—C1 | −34.3 (8) | N2—Co1—N4—C4 | 106.54 (14) |
N5—Co1—N1—C1 | −171.11 (14) | C6—C5—N5—Co1 | −38.49 (18) |
N6—Co1—N1—C1 | 103.54 (14) | N3—Co1—N5—C5 | 103.83 (13) |
N2—Co1—N1—C1 | 13.31 (14) | N6—Co1—N5—C5 | 13.85 (13) |
N4—Co1—N1—C1 | −80.48 (15) | N1—Co1—N5—C5 | −79.73 (14) |
C1—C2—N2—Co1 | −39.2 (2) | N2—Co1—N5—C5 | −33.3 (7) |
N3—Co1—N2—C2 | −169.12 (14) | N4—Co1—N5—C5 | −170.66 (14) |
N5—Co1—N2—C2 | −31.9 (7) | C5—C6—N6—Co1 | −38.68 (18) |
N6—Co1—N2—C2 | −78.85 (14) | N3—Co1—N6—C6 | −79.10 (13) |
N1—Co1—N2—C2 | 14.72 (14) | N5—Co1—N6—C6 | 14.34 (13) |
N4—Co1—N2—C2 | 105.34 (14) | N1—Co1—N6—C6 | 104.40 (13) |
C4—C3—N3—Co1 | −38.1 (2) | N2—Co1—N6—C6 | −170.13 (13) |
N5—Co1—N3—C3 | 103.07 (14) | N4—Co1—N6—C6 | −33.9 (7) |
N6—Co1—N3—C3 | −171.59 (14) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.90 | 2.16 | 2.848 (2) | 133 |
N1—H1A···O7 | 0.90 | 2.59 | 3.276 (4) | 133 |
N1—H1B···O1ii | 0.90 | 2.23 | 3.112 (3) | 165 |
N2—H2A···O2 | 0.90 | 2.10 | 2.887 (2) | 146 |
N2—H2A···O8iii | 0.90 | 2.50 | 3.130 (3) | 128 |
N2—H2B···OW1iv | 0.90 | 2.17 | 3.045 (3) | 165 |
N3—H3A···O3 | 0.90 | 2.24 | 2.960 (2) | 137 |
N3—H3A···O8iii | 0.90 | 2.55 | 3.270 (3) | 138 |
N3—H3B···O3v | 0.90 | 1.97 | 2.852 (2) | 166 |
N4—H4A···O1i | 0.90 | 2.34 | 3.127 (2) | 146 |
N4—H4B···OW1iv | 0.90 | 2.21 | 3.043 (3) | 154 |
N5—H5A···O1i | 0.90 | 2.11 | 2.885 (2) | 143 |
N5—H5A···O4i | 0.90 | 2.32 | 3.079 (2) | 141 |
N5—H5B···O4v | 0.90 | 2.08 | 2.953 (2) | 164 |
N6—H6A···O3 | 0.90 | 2.12 | 2.927 (2) | 149 |
N6—H6A···O2 | 0.90 | 2.29 | 2.992 (2) | 134 |
N6—H6B···O2ii | 0.90 | 2.02 | 2.908 (2) | 167 |
OW1—HW1···OW2 | 0.95 | 1.79 | 2.732 (3) | 172 |
OW1—HW2···O6vi | 0.84 | 2.37 | 3.071 (4) | 141 |
OW2—HW3···O1 | 0.91 | 1.96 | 2.850 (3) | 167 |
OW2—HW4···O6vii | 0.94 | 2.40 | 3.287 (4) | 157 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x, −y, −z; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, −z−1/2; (v) −x, −y+1, −z; (vi) x−1/2, −y−1/2, z−1/2; (vii) −x+1, −y, −z. |