Tris­(ethyl­enedi­amine-N,N')cobalt(III) oxalate perchlorate dihydrate

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.

Computing details

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

Crystal data

[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) Å^3	Block, red
Z = 4	0.30 × 0.30 × 0.20 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0652P)^2 + 0.2357P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4^i	0.90	2.16	2.848 (2)	133
N1—H1A···O7	0.90	2.59	3.276 (4)	133
N1—H1B···O1^ii	0.90	2.23	3.112 (3)	165
N2—H2A···O2	0.90	2.10	2.887 (2)	146
N2—H2A···O8^iii	0.90	2.50	3.130 (3)	128
N2—H2B···OW1^iv	0.90	2.17	3.045 (3)	165
N3—H3A···O3	0.90	2.24	2.960 (2)	137
N3—H3A···O8^iii	0.90	2.55	3.270 (3)	138
N3—H3B···O3^v	0.90	1.97	2.852 (2)	166
N4—H4A···O1^i	0.90	2.34	3.127 (2)	146
N4—H4B···OW1^iv	0.90	2.21	3.043 (3)	154
N5—H5A···O1^i	0.90	2.11	2.885 (2)	143
N5—H5A···O4^i	0.90	2.32	3.079 (2)	141
N5—H5B···O4^v	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···O2^ii	0.90	2.02	2.908 (2)	167
OW1—HW1···OW2	0.95	1.79	2.732 (3)	172
OW1—HW2···O6^vi	0.84	2.37	3.071 (4)	141
OW2—HW3···O1	0.91	1.96	2.850 (3)	167
OW2—HW4···O6^vii	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.