The crystal structure of the title compound, (C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2O, has been determined by single-crystal X-ray diffraction studies at 293 and 100 K. The analyses demonstrated that the crystal consists of ethylenediammonium dications (which lie about inversion centres), bis[N-(2-aminoethyl)glycinato]chromium(III) monocations, Cl- anions and hydrate water molecules, in a molecular ratio of 1:2:4:2. The complex cation unit has a slightly distorted octahedrally coordinated Cr atom, with two Cr-O and four Cr-N bonds in the ranges 1.951 (1)-1.953 (1) and 2.054 (1)-2.089 (2) Å, respectively, at 293 K. The geometry of the bis[N-(2-aminoethyl)glycinato]chromium(III) moiety was found to be trans,cis,cis with respect to the carboxylate O atom and the primary and secondary amine N atoms. The two analyses, at 293 and 100 K, exhibited no remarkable structural differences, although the colour of the crystals did differ, being red at 293 K and orange at 100 K.
Supporting information
CCDC references: 181328; 181329
The ligand, Hedma·2HCl·H2O, and the title complex were prepared by
the literature method of Fujii et al. (1970). Recrystallization of the
complex from 10% ethanol solution gave bright-red crystals of (I) that were
suitable for crystallographic analysis. Analysis found: C 26.52, H 6.21, N
17.21%; calculated for C18H50Cl4Cr2N10O10: C 26.61, H 6.20, N
17.24%.
The H atoms of the hydrated water molecules were located from difference Fourier
syntheses and their positions were refined. The other H atoms were placed
geometrically, with N—H = 0.89–0.93 Å and C—H = 0.97–0.99 Å, and
refined using a riding model. For all H atoms, Uiso(H) was set to be
0.041 (for 293 K) or 0.017 Å2 (for 100 K).
For both compounds, data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1970); software used to prepare material for publication: SHELXL97.
(I_293K) Ethylenediammonium
bis{bis[
N-(2-aminoethyl)glycinato-
κ3N,
N',
O]chromium(III)} tetrachloride dihydrate
top
Crystal data top
(C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2O | F(000) = 848 |
Mr = 812.48 | Dx = 1.569 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 12.5921 (3) Å | Cell parameters from 12402 reflections |
b = 7.5227 (1) Å | θ = 2.7–27.4° |
c = 18.2511 (4) Å | µ = 1.00 mm−1 |
β = 95.915 (1)° | T = 293 K |
V = 1719.66 (6) Å3 | Hexagonal column, red |
Z = 2 | 0.22 × 0.22 × 0.18 mm |
Data collection top
Rigaku R-AXIS RAPID imaging-plate diffractometer | 3932 independent reflections |
Radiation source: fine-focus sealed tube | 3482 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 2.2° |
ω scans | h = −16→16 |
Absorption correction: multi-scan (Higashi, 1995) | k = −9→9 |
Tmin = 0.725, Tmax = 0.835 | l = −23→23 |
16059 measured reflections | |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0437P)2 + 0.4474P] where P = (Fo2 + 2Fc2)/3 |
3932 reflections | (Δ/σ)max = 0.002 |
206 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Crystal data top
(C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2O | V = 1719.66 (6) Å3 |
Mr = 812.48 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.5921 (3) Å | µ = 1.00 mm−1 |
b = 7.5227 (1) Å | T = 293 K |
c = 18.2511 (4) Å | 0.22 × 0.22 × 0.18 mm |
β = 95.915 (1)° | |
Data collection top
Rigaku R-AXIS RAPID imaging-plate diffractometer | 3932 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 3482 reflections with I > 2σ(I) |
Tmin = 0.725, Tmax = 0.835 | Rint = 0.023 |
16059 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.30 e Å−3 |
3932 reflections | Δρmin = −0.40 e Å−3 |
206 parameters | |
Special details top
Experimental. none |
Refinement. There was an unusually short intermolecular distance between atoms H4A and H4A(2
- x, 1 - y, 2 - z), of 2.13 Å at 293 K (2.08 Å at 100 K), but we believe that there is not a substantial interaction between them,
because the position of this H atom may be distorted from the ideal position
presumed in these analyses, to reduce such steric congestion. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cr | 0.816128 (17) | 0.21824 (3) | 0.836523 (12) | 0.02069 (7) | |
Cl1 | 0.50163 (3) | 0.09151 (6) | 0.40119 (2) | 0.04079 (11) | |
Cl2 | 0.82947 (3) | −0.36678 (6) | 0.55803 (2) | 0.04080 (11) | |
O1 | 0.90990 (8) | 0.41282 (13) | 0.81360 (6) | 0.0296 (2) | |
O2 | 0.94504 (10) | 0.70047 (14) | 0.82646 (7) | 0.0407 (3) | |
O3 | 0.71554 (8) | 0.03513 (13) | 0.86037 (5) | 0.0262 (2) | |
O4 | 0.55481 (10) | −0.08033 (18) | 0.83202 (6) | 0.0439 (3) | |
O6 | 0.68352 (12) | −0.37757 (18) | 0.69518 (8) | 0.0478 (3) | |
N1 | 0.75558 (10) | 0.41252 (16) | 0.90261 (6) | 0.0254 (2) | |
N2 | 0.91135 (10) | 0.15211 (18) | 0.93142 (7) | 0.0329 (3) | |
N3 | 0.70635 (11) | 0.25397 (17) | 0.74465 (6) | 0.0286 (3) | |
N4 | 0.89114 (11) | 0.05402 (17) | 0.76814 (8) | 0.0358 (3) | |
N5 | 0.40311 (10) | 0.32169 (18) | 0.52032 (7) | 0.0327 (3) | |
C1 | 0.79232 (12) | 0.58811 (19) | 0.87839 (9) | 0.0297 (3) | |
C2 | 0.89039 (12) | 0.57047 (19) | 0.83673 (8) | 0.0267 (3) | |
C3 | 0.79455 (15) | 0.3689 (2) | 0.98044 (8) | 0.0379 (4) | |
C4 | 0.90774 (15) | 0.3012 (2) | 0.98435 (10) | 0.0429 (4) | |
C5 | 0.60733 (12) | 0.1560 (2) | 0.75696 (8) | 0.0317 (3) | |
C6 | 0.62503 (12) | 0.0255 (2) | 0.81997 (8) | 0.0271 (3) | |
C7 | 0.75792 (16) | 0.1865 (3) | 0.68002 (9) | 0.0430 (4) | |
C8 | 0.81740 (17) | 0.0181 (3) | 0.70159 (10) | 0.0472 (5) | |
C9 | 0.44016 (11) | 0.4925 (2) | 0.49193 (9) | 0.0317 (3) | |
H01 | 0.6830 | 0.4088 | 0.8968 | 0.041* | |
H02A | 0.8873 | 0.0517 | 0.9509 | 0.041* | |
H02B | 0.9789 | 0.1338 | 0.9212 | 0.041* | |
H03 | 0.6914 | 0.3717 | 0.7386 | 0.041* | |
H04A | 0.9509 | 0.1064 | 0.7555 | 0.041* | |
H04B | 0.9096 | −0.0486 | 0.7914 | 0.041* | |
H05A | 0.3332 | 0.3103 | 0.5078 | 0.041* | |
H05B | 0.4164 | 0.3195 | 0.5692 | 0.041* | |
H05C | 0.4374 | 0.2324 | 0.5011 | 0.041* | |
H1A | 0.8092 | 0.6636 | 0.9211 | 0.041* | |
H1B | 0.7353 | 0.6444 | 0.8469 | 0.041* | |
H3A | 0.7490 | 0.2791 | 0.9990 | 0.041* | |
H3B | 0.7918 | 0.4743 | 1.0108 | 0.041* | |
H4A | 0.9551 | 0.3958 | 0.9720 | 0.041* | |
H4B | 0.9309 | 0.2606 | 1.0339 | 0.041* | |
H5A | 0.5818 | 0.0924 | 0.7124 | 0.041* | |
H5B | 0.5526 | 0.2404 | 0.7674 | 0.041* | |
H7A | 0.8069 | 0.2750 | 0.6644 | 0.041* | |
H7B | 0.7040 | 0.1634 | 0.6392 | 0.041* | |
H8A | 0.7675 | −0.0749 | 0.7116 | 0.041* | |
H8B | 0.8572 | −0.0211 | 0.6618 | 0.041* | |
H9A | 0.4060 | 0.5902 | 0.5150 | 0.041* | |
H9B | 0.4206 | 0.4993 | 0.4392 | 0.041* | |
H06A | 0.7219 (17) | −0.371 (3) | 0.6603 (12) | 0.041* | |
H06B | 0.6255 (17) | −0.323 (3) | 0.6787 (11) | 0.041* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cr | 0.02123 (12) | 0.01789 (11) | 0.02363 (12) | −0.00207 (8) | 0.00559 (8) | −0.00053 (8) |
Cl1 | 0.0366 (2) | 0.0475 (2) | 0.0394 (2) | −0.00423 (17) | 0.00896 (16) | −0.01310 (18) |
Cl2 | 0.0284 (2) | 0.0519 (2) | 0.0419 (2) | 0.00055 (17) | 0.00220 (15) | −0.00635 (18) |
O1 | 0.0302 (5) | 0.0211 (5) | 0.0402 (6) | −0.0032 (4) | 0.0167 (4) | −0.0022 (4) |
O2 | 0.0421 (7) | 0.0229 (5) | 0.0600 (8) | −0.0057 (5) | 0.0188 (6) | 0.0021 (5) |
O3 | 0.0255 (5) | 0.0264 (5) | 0.0265 (5) | −0.0056 (4) | 0.0011 (4) | 0.0039 (4) |
O4 | 0.0402 (7) | 0.0555 (8) | 0.0345 (6) | −0.0263 (6) | −0.0029 (5) | 0.0052 (5) |
O6 | 0.0469 (8) | 0.0451 (7) | 0.0517 (8) | 0.0005 (6) | 0.0064 (6) | 0.0070 (6) |
N1 | 0.0249 (6) | 0.0269 (6) | 0.0253 (6) | −0.0038 (5) | 0.0067 (4) | −0.0038 (5) |
N2 | 0.0230 (6) | 0.0335 (7) | 0.0410 (7) | −0.0041 (5) | −0.0028 (5) | 0.0078 (6) |
N3 | 0.0396 (7) | 0.0257 (6) | 0.0209 (6) | −0.0038 (5) | 0.0047 (5) | 0.0013 (5) |
N4 | 0.0404 (8) | 0.0207 (6) | 0.0501 (8) | 0.0007 (5) | 0.0233 (6) | −0.0014 (6) |
N5 | 0.0257 (6) | 0.0392 (7) | 0.0339 (7) | −0.0025 (5) | 0.0064 (5) | −0.0067 (6) |
C1 | 0.0334 (8) | 0.0221 (7) | 0.0354 (8) | 0.0007 (6) | 0.0119 (6) | −0.0032 (6) |
C2 | 0.0290 (7) | 0.0219 (7) | 0.0297 (7) | −0.0009 (5) | 0.0059 (6) | 0.0020 (6) |
C3 | 0.0537 (10) | 0.0377 (9) | 0.0232 (7) | −0.0098 (8) | 0.0082 (7) | −0.0037 (6) |
C4 | 0.0476 (10) | 0.0441 (10) | 0.0335 (8) | −0.0157 (8) | −0.0123 (7) | 0.0033 (7) |
C5 | 0.0310 (8) | 0.0389 (8) | 0.0241 (7) | −0.0046 (6) | −0.0018 (6) | 0.0024 (6) |
C6 | 0.0293 (7) | 0.0298 (7) | 0.0223 (6) | −0.0071 (6) | 0.0027 (5) | −0.0027 (6) |
C7 | 0.0572 (11) | 0.0514 (11) | 0.0224 (7) | −0.0108 (9) | 0.0135 (7) | −0.0035 (7) |
C8 | 0.0627 (12) | 0.0394 (9) | 0.0444 (10) | −0.0125 (8) | 0.0282 (9) | −0.0190 (8) |
C9 | 0.0235 (8) | 0.0372 (8) | 0.0342 (8) | −0.0015 (6) | 0.0020 (6) | −0.0046 (6) |
Geometric parameters (Å, º) top
Cr—O1 | 1.9529 (10) | N5—C9 | 1.479 (2) |
Cr—O3 | 1.9506 (10) | N5—H05A | 0.8900 |
Cr—N1 | 2.0885 (12) | N5—H05B | 0.8900 |
Cr—N2 | 2.0633 (13) | N5—H05C | 0.8900 |
Cr—N3 | 2.0777 (13) | C1—C2 | 1.521 (2) |
Cr—N4 | 2.0541 (13) | C1—H1A | 0.9700 |
O1—C2 | 1.2909 (17) | C1—H1B | 0.9700 |
O2—C2 | 1.2213 (18) | C3—C4 | 1.508 (3) |
O3—C6 | 1.2940 (17) | C3—H3A | 0.9700 |
O4—C6 | 1.2267 (18) | C3—H3B | 0.9700 |
O6—H06A | 0.84 (2) | C4—H4A | 0.9700 |
O6—H06B | 0.87 (2) | C4—H4B | 0.9700 |
N1—C1 | 1.4820 (18) | C5—C6 | 1.511 (2) |
N1—C3 | 1.4908 (19) | C5—H5A | 0.9700 |
N1—H01 | 0.9100 | C5—H5B | 0.9700 |
N2—C4 | 1.484 (2) | C7—C8 | 1.503 (3) |
N2—H02A | 0.9000 | C7—H7A | 0.9700 |
N2—H02B | 0.9000 | C7—H7B | 0.9700 |
N3—C5 | 1.485 (2) | C8—H8A | 0.9700 |
N3—C7 | 1.493 (2) | C8—H8B | 0.9700 |
N3—H03 | 0.9100 | C9—C9i | 1.510 (3) |
N4—C8 | 1.476 (2) | C9—H9A | 0.9700 |
N4—H04A | 0.9000 | C9—H9B | 0.9700 |
N4—H04B | 0.9000 | | |
| | | |
O1—Cr—O3 | 176.36 (4) | N1—C1—C2 | 111.46 (11) |
O1—Cr—N1 | 82.19 (4) | N1—C1—H1A | 109.3 |
O1—Cr—N2 | 92.79 (5) | C2—C1—H1A | 109.3 |
O1—Cr—N3 | 95.56 (5) | N1—C1—H1B | 109.3 |
O1—Cr—N4 | 89.69 (5) | C2—C1—H1B | 109.3 |
O3—Cr—N1 | 94.66 (5) | H1A—C1—H1B | 108.0 |
O3—Cr—N2 | 88.68 (5) | O2—C2—O1 | 123.80 (14) |
O3—Cr—N3 | 83.00 (4) | O2—C2—C1 | 120.40 (13) |
O3—Cr—N4 | 93.48 (5) | O1—C2—C1 | 115.80 (12) |
N1—Cr—N2 | 84.21 (5) | N1—C3—C4 | 109.64 (13) |
N1—Cr—N3 | 97.09 (5) | N1—C3—H3A | 109.7 |
N1—Cr—N4 | 171.86 (5) | C4—C3—H3A | 109.7 |
N2—Cr—N3 | 171.65 (5) | N1—C3—H3B | 109.7 |
N2—Cr—N4 | 95.81 (6) | C4—C3—H3B | 109.7 |
N3—Cr—N4 | 84.08 (6) | H3A—C3—H3B | 108.2 |
C2—O1—Cr | 118.61 (9) | N2—C4—C3 | 108.47 (13) |
C6—O3—Cr | 117.79 (9) | N2—C4—H4A | 110.0 |
H06A—O6—H06B | 103.8 (19) | C3—C4—H4A | 110.0 |
C1—N1—C3 | 113.45 (12) | N2—C4—H4B | 110.0 |
C1—N1—Cr | 107.92 (8) | C3—C4—H4B | 110.0 |
C3—N1—Cr | 107.01 (10) | H4A—C4—H4B | 108.4 |
C1—N1—H01 | 109.5 | N3—C5—C6 | 112.16 (12) |
C3—N1—H01 | 109.5 | N3—C5—H5A | 109.2 |
Cr—N1—H01 | 109.5 | C6—C5—H5A | 109.2 |
C4—N2—Cr | 108.07 (10) | N3—C5—H5B | 109.2 |
C4—N2—H02A | 110.1 | C6—C5—H5B | 109.2 |
Cr—N2—H02A | 110.1 | H5A—C5—H5B | 107.9 |
C4—N2—H02B | 110.1 | O4—C6—O3 | 122.87 (14) |
Cr—N2—H02B | 110.1 | O4—C6—C5 | 120.38 (13) |
H02A—N2—H02B | 108.4 | O3—C6—C5 | 116.73 (12) |
C5—N3—C7 | 113.02 (13) | N3—C7—C8 | 108.97 (13) |
C5—N3—Cr | 108.23 (9) | N3—C7—H7A | 109.9 |
C7—N3—Cr | 106.64 (11) | C8—C7—H7A | 109.9 |
C5—N3—H03 | 109.6 | N3—C7—H7B | 109.9 |
C7—N3—H03 | 109.6 | C8—C7—H7B | 109.9 |
Cr—N3—H03 | 109.6 | H7A—C7—H7B | 108.3 |
C8—N4—Cr | 108.69 (10) | N4—C8—C7 | 108.40 (14) |
C8—N4—H04A | 110.0 | N4—C8—H8A | 110.0 |
Cr—N4—H04A | 110.0 | C7—C8—H8A | 110.0 |
C8—N4—H04B | 110.0 | N4—C8—H8B | 110.0 |
Cr—N4—H04B | 110.0 | C7—C8—H8B | 110.0 |
H04A—N4—H04B | 108.3 | H8A—C8—H8B | 108.4 |
C9—N5—H05A | 109.5 | N5—C9—C9i | 109.97 (17) |
C9—N5—H05B | 109.5 | N5—C9—H9A | 109.7 |
H05A—N5—H05B | 109.5 | C9i—C9—H9A | 109.7 |
C9—N5—H05C | 109.5 | N5—C9—H9B | 109.7 |
H05A—N5—H05C | 109.5 | C9i—C9—H9B | 109.7 |
H05B—N5—H05C | 109.5 | H9A—C9—H9B | 108.2 |
| | | |
N4—Cr—O1—C2 | 171.76 (12) | N4—Cr—N3—C7 | −15.18 (10) |
N2—Cr—O1—C2 | −92.44 (12) | N1—Cr—N3—C7 | 156.71 (10) |
N3—Cr—O1—C2 | 87.74 (11) | O3—Cr—N4—C8 | 69.38 (11) |
N1—Cr—O1—C2 | −8.68 (11) | O1—Cr—N4—C8 | −108.82 (11) |
N4—Cr—O3—C6 | −91.63 (11) | N2—Cr—N4—C8 | 158.41 (11) |
N2—Cr—O3—C6 | 172.63 (11) | N3—Cr—N4—C8 | −13.20 (11) |
N3—Cr—O3—C6 | −8.04 (11) | C3—N1—C1—C2 | 97.20 (15) |
N1—Cr—O3—C6 | 88.55 (11) | Cr—N1—C1—C2 | −21.18 (14) |
O3—Cr—N1—C1 | −161.79 (9) | Cr—O1—C2—O2 | 178.73 (12) |
O1—Cr—N1—C1 | 16.39 (10) | Cr—O1—C2—C1 | −1.70 (17) |
N2—Cr—N1—C1 | 110.02 (10) | N1—C1—C2—O2 | −164.22 (14) |
N3—Cr—N1—C1 | −78.28 (10) | N1—C1—C2—O1 | 16.19 (18) |
O3—Cr—N1—C3 | 75.79 (10) | C1—N1—C3—C4 | −80.62 (16) |
O1—Cr—N1—C3 | −106.04 (10) | Cr—N1—C3—C4 | 38.29 (14) |
N2—Cr—N1—C3 | −12.41 (10) | Cr—N2—C4—C3 | 40.67 (15) |
N3—Cr—N1—C3 | 159.29 (10) | N1—C3—C4—N2 | −53.50 (17) |
O3—Cr—N2—C4 | −110.41 (11) | C7—N3—C5—C6 | 102.96 (15) |
O1—Cr—N2—C4 | 66.26 (11) | Cr—N3—C5—C6 | −14.91 (15) |
N4—Cr—N2—C4 | 156.23 (11) | Cr—O3—C6—O4 | −177.22 (12) |
N1—Cr—N2—C4 | −15.59 (10) | Cr—O3—C6—C5 | 1.21 (17) |
O3—Cr—N3—C5 | 12.44 (10) | N3—C5—C6—O4 | −171.63 (14) |
O1—Cr—N3—C5 | −164.20 (10) | N3—C5—C6—O3 | 9.9 (2) |
N4—Cr—N3—C5 | 106.69 (10) | C5—N3—C7—C8 | −77.96 (18) |
N1—Cr—N3—C5 | −81.41 (10) | Cr—N3—C7—C8 | 40.84 (16) |
O3—Cr—N3—C7 | −109.44 (10) | Cr—N4—C8—C7 | 39.19 (15) |
O1—Cr—N3—C7 | 73.92 (10) | N3—C7—C8—N4 | −54.03 (18) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···Cl1ii | 0.91 | 2.29 | 3.195 (1) | 171 |
N2—H02A···Cl2iii | 0.90 | 2.57 | 3.391 (1) | 153 |
N2—H02B···Cl2iv | 0.90 | 2.40 | 3.253 (1) | 157 |
N3—H03···O6v | 0.91 | 2.04 | 2.920 (2) | 161 |
N4—H04A···O2vi | 0.90 | 2.21 | 3.030 (2) | 152 |
N4—H04B···O2vii | 0.90 | 2.03 | 2.919 (2) | 170 |
N5—H05A···Cl2viii | 0.89 | 2.31 | 3.142 (1) | 157 |
N5—H05B···O4ix | 0.89 | 1.95 | 2.791 (2) | 156 |
N5—H05C···Cl1 | 0.89 | 2.33 | 3.134 (1) | 151 |
O6—H06A···Cl2 | 0.84 (2) | 2.42 (2) | 3.255 (2) | 177 (2) |
O6—H06B···Cl1viii | 0.87 (2) | 2.69 (2) | 3.509 (2) | 159 (2) |
Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) x, −y−1/2, z+1/2; (iv) −x+2, y+1/2, −z+3/2; (v) x, y+1, z; (vi) −x+2, y−1/2, −z+3/2; (vii) x, y−1, z; (viii) −x+1, −y, −z+1; (ix) −x+1, y+1/2, −z+3/2. |
(I_100K) Ethylenediammonium
bis{bis[
N-(2-aminoethyl)glycinato-
κ3N,
N',
O]chromium(III)} tetrachloride dihydrate
top
Crystal data top
(C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2O | F(000) = 848 |
Mr = 812.48 | Dx = 1.592 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 12.5546 (4) Å | Cell parameters from 12063 reflections |
b = 7.4907 (1) Å | θ = 2.9–27.5° |
c = 18.1157 (4) Å | µ = 1.02 mm−1 |
β = 95.939 (1)° | T = 100 K |
V = 1694.51 (7) Å3 | Hexagonal column, orange |
Z = 2 | 0.22 × 0.22 × 0.18 mm |
Data collection top
Rigaku R-AXIS RAPID imaging-plate diffractometer | 3894 independent reflections |
Radiation source: fine-focus sealed tube | 3514 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
ω scans | h = −16→16 |
Absorption correction: multi-scan (Higashi, 1995) | k = −9→9 |
Tmin = 0.733, Tmax = 0.832 | l = −23→23 |
15950 measured reflections | |
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)] = 0.022 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.035P)2 + 0.5214P] where P = (Fo2 + 2Fc2)/3 |
3894 reflections | (Δ/σ)max = 0.004 |
202 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Crystal data top
(C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2O | V = 1694.51 (7) Å3 |
Mr = 812.48 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.5546 (4) Å | µ = 1.02 mm−1 |
b = 7.4907 (1) Å | T = 100 K |
c = 18.1157 (4) Å | 0.22 × 0.22 × 0.18 mm |
β = 95.939 (1)° | |
Data collection top
Rigaku R-AXIS RAPID imaging-plate diffractometer | 3894 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 3514 reflections with I > 2σ(I) |
Tmin = 0.733, Tmax = 0.832 | Rint = 0.023 |
15950 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.39 e Å−3 |
3894 reflections | Δρmin = −0.42 e Å−3 |
202 parameters | |
Special details top
Experimental. none |
Refinement. None |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cr | 0.815487 (15) | 0.22047 (3) | 0.835642 (11) | 0.00845 (6) | |
Cl1 | 0.50086 (3) | 0.09497 (4) | 0.401175 (17) | 0.01568 (8) | |
Cl2 | 0.82955 (2) | −0.36846 (4) | 0.557911 (17) | 0.01550 (8) | |
O1 | 0.91017 (7) | 0.41583 (12) | 0.81304 (5) | 0.01257 (18) | |
O2 | 0.94615 (8) | 0.70537 (12) | 0.82684 (5) | 0.0158 (2) | |
O3 | 0.71535 (7) | 0.03559 (12) | 0.85984 (5) | 0.01133 (18) | |
O4 | 0.55393 (8) | −0.08189 (13) | 0.83089 (5) | 0.0170 (2) | |
O6 | 0.68346 (8) | −0.37226 (13) | 0.69411 (6) | 0.0181 (2) | |
N1 | 0.75537 (9) | 0.41489 (14) | 0.90299 (6) | 0.0109 (2) | |
H01 | 0.6809 | 0.4108 | 0.8975 | 0.017* | |
N2 | 0.91146 (9) | 0.15156 (15) | 0.93086 (6) | 0.0139 (2) | |
H02A | 0.8862 | 0.0491 | 0.9510 | 0.017* | |
H02B | 0.9804 | 0.1312 | 0.9200 | 0.017* | |
N3 | 0.70436 (9) | 0.25849 (15) | 0.74354 (6) | 0.0118 (2) | |
H03 | 0.6888 | 0.3794 | 0.7379 | 0.017* | |
N4 | 0.89034 (9) | 0.05716 (15) | 0.76620 (6) | 0.0145 (2) | |
H04A | 0.9513 | 0.1115 | 0.7530 | 0.017* | |
H04B | 0.9097 | −0.0484 | 0.7899 | 0.017* | |
N5 | 0.40289 (9) | 0.32104 (15) | 0.52178 (6) | 0.0133 (2) | |
H05A | 0.4389 | 0.2292 | 0.5028 | 0.017* | |
H05B | 0.3314 | 0.3078 | 0.5086 | 0.017* | |
H05C | 0.4159 | 0.3208 | 0.5721 | 0.017* | |
C1 | 0.79186 (10) | 0.59218 (17) | 0.87838 (7) | 0.0127 (3) | |
H1A | 0.8085 | 0.6701 | 0.9222 | 0.017* | |
H1B | 0.7335 | 0.6490 | 0.8456 | 0.017* | |
C2 | 0.89081 (10) | 0.57460 (17) | 0.83680 (7) | 0.0114 (2) | |
C3 | 0.79574 (11) | 0.37062 (19) | 0.98120 (7) | 0.0160 (3) | |
H3A | 0.7493 | 0.2787 | 1.0006 | 0.017* | |
H3B | 0.7937 | 0.4785 | 1.0126 | 0.017* | |
C4 | 0.90950 (12) | 0.30160 (19) | 0.98427 (8) | 0.0178 (3) | |
H4A | 0.9580 | 0.3981 | 0.9710 | 0.017* | |
H4B | 0.9340 | 0.2600 | 1.0351 | 0.017* | |
C5 | 0.60531 (11) | 0.15850 (18) | 0.75596 (7) | 0.0133 (3) | |
H5A | 0.5790 | 0.0942 | 0.7099 | 0.017* | |
H5B | 0.5492 | 0.2442 | 0.7672 | 0.017* | |
C6 | 0.62410 (10) | 0.02565 (17) | 0.81911 (7) | 0.0116 (2) | |
C7 | 0.75585 (12) | 0.19248 (19) | 0.67789 (7) | 0.0171 (3) | |
H7A | 0.8062 | 0.2834 | 0.6623 | 0.017* | |
H7B | 0.7005 | 0.1703 | 0.6359 | 0.017* | |
C8 | 0.81542 (12) | 0.02128 (19) | 0.69897 (8) | 0.0184 (3) | |
H8A | 0.7642 | −0.0738 | 0.7093 | 0.017* | |
H8B | 0.8557 | −0.0188 | 0.6578 | 0.017* | |
C9 | 0.43963 (10) | 0.49316 (18) | 0.49209 (7) | 0.0135 (3) | |
H9A | 0.4052 | 0.5940 | 0.5158 | 0.017* | |
H9B | 0.4189 | 0.4993 | 0.4379 | 0.017* | |
H06A | 0.7253 (14) | −0.3623 | 0.6583 | 0.017* | |
H06B | 0.6261 (14) | −0.3201 | 0.6766 | 0.017* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cr | 0.00883 (10) | 0.00766 (10) | 0.00905 (10) | −0.00073 (7) | 0.00184 (7) | −0.00010 (7) |
Cl1 | 0.01474 (16) | 0.01790 (16) | 0.01471 (15) | −0.00112 (12) | 0.00298 (11) | −0.00408 (12) |
Cl2 | 0.01152 (15) | 0.01959 (16) | 0.01525 (15) | 0.00006 (12) | 0.00078 (11) | −0.00217 (12) |
O1 | 0.0137 (4) | 0.0095 (4) | 0.0153 (4) | −0.0009 (3) | 0.0054 (4) | −0.0009 (4) |
O2 | 0.0162 (5) | 0.0109 (4) | 0.0209 (5) | −0.0021 (4) | 0.0054 (4) | 0.0002 (4) |
O3 | 0.0106 (4) | 0.0116 (4) | 0.0116 (4) | −0.0017 (3) | 0.0000 (3) | 0.0012 (3) |
O4 | 0.0161 (5) | 0.0204 (5) | 0.0142 (4) | −0.0082 (4) | −0.0006 (4) | 0.0012 (4) |
O6 | 0.0172 (5) | 0.0178 (5) | 0.0196 (5) | 0.0003 (4) | 0.0036 (4) | 0.0032 (4) |
N1 | 0.0109 (5) | 0.0114 (5) | 0.0106 (5) | −0.0023 (4) | 0.0022 (4) | −0.0011 (4) |
N2 | 0.0102 (5) | 0.0144 (5) | 0.0167 (5) | −0.0016 (4) | −0.0009 (4) | 0.0022 (5) |
N3 | 0.0160 (6) | 0.0105 (5) | 0.0092 (5) | −0.0009 (4) | 0.0021 (4) | 0.0006 (4) |
N4 | 0.0160 (6) | 0.0097 (5) | 0.0191 (6) | −0.0003 (4) | 0.0077 (5) | 0.0000 (4) |
N5 | 0.0111 (5) | 0.0154 (5) | 0.0135 (5) | −0.0010 (4) | 0.0020 (4) | −0.0022 (4) |
C1 | 0.0138 (6) | 0.0100 (6) | 0.0150 (6) | −0.0003 (5) | 0.0050 (5) | −0.0014 (5) |
C2 | 0.0124 (6) | 0.0114 (6) | 0.0104 (5) | 0.0012 (5) | 0.0003 (5) | 0.0009 (5) |
C3 | 0.0227 (7) | 0.0166 (6) | 0.0088 (6) | −0.0039 (5) | 0.0027 (5) | −0.0005 (5) |
C4 | 0.0202 (7) | 0.0188 (7) | 0.0131 (6) | −0.0064 (5) | −0.0045 (5) | 0.0004 (5) |
C5 | 0.0131 (6) | 0.0157 (6) | 0.0107 (6) | −0.0017 (5) | −0.0010 (5) | 0.0014 (5) |
C6 | 0.0133 (6) | 0.0124 (6) | 0.0092 (5) | −0.0008 (5) | 0.0018 (4) | −0.0021 (5) |
C7 | 0.0230 (7) | 0.0201 (7) | 0.0089 (6) | −0.0036 (6) | 0.0052 (5) | −0.0006 (5) |
C8 | 0.0241 (7) | 0.0163 (7) | 0.0161 (6) | −0.0032 (5) | 0.0088 (5) | −0.0068 (5) |
C9 | 0.0114 (6) | 0.0146 (6) | 0.0143 (6) | −0.0008 (5) | 0.0007 (5) | −0.0006 (5) |
Geometric parameters (Å, º) top
Cr—O1 | 1.9552 (9) | N5—C9 | 1.4885 (17) |
Cr—O3 | 1.9505 (9) | N5—H05A | 0.9100 |
Cr—N1 | 2.0904 (11) | N5—H05B | 0.9100 |
Cr—N2 | 2.0649 (11) | N5—H05C | 0.9100 |
Cr—N3 | 2.0807 (11) | C1—C2 | 1.5237 (18) |
Cr—N4 | 2.0511 (11) | C1—H1A | 0.9900 |
O1—C2 | 1.2963 (15) | C1—H1B | 0.9900 |
O2—C2 | 1.2250 (16) | C3—C4 | 1.515 (2) |
O3—C6 | 1.2991 (15) | C3—H3A | 0.9900 |
O4—C6 | 1.2286 (16) | C3—H3B | 0.9900 |
O6—H06A | 0.879 (12) | C4—H4A | 0.9900 |
O6—H06B | 0.851 (14) | C4—H4B | 0.9900 |
N1—C1 | 1.4882 (16) | C5—C6 | 1.5162 (18) |
N1—C3 | 1.4917 (16) | C5—H5A | 0.9900 |
N1—H01 | 0.9300 | C5—H5B | 0.9900 |
N2—C4 | 1.4849 (18) | C7—C8 | 1.514 (2) |
N2—H02A | 0.9200 | C7—H7A | 0.9900 |
N2—H02B | 0.9200 | C7—H7B | 0.9900 |
N3—C5 | 1.4886 (17) | C8—H8A | 0.9900 |
N3—C7 | 1.4953 (17) | C8—H8B | 0.9900 |
N3—H03 | 0.9300 | C9—C9i | 1.517 (2) |
N4—C8 | 1.4843 (18) | C9—H9A | 0.9900 |
N4—H04A | 0.9200 | C9—H9B | 0.9900 |
N4—H04B | 0.9200 | | |
| | | |
O1—Cr—O3 | 176.77 (4) | N1—C1—C2 | 111.29 (10) |
O1—Cr—N1 | 82.23 (4) | N1—C1—H1A | 109.4 |
O1—Cr—N2 | 92.70 (4) | C2—C1—H1A | 109.4 |
O1—Cr—N3 | 95.82 (4) | N1—C1—H1B | 109.4 |
O1—Cr—N4 | 89.48 (4) | C2—C1—H1B | 109.4 |
O3—Cr—N1 | 94.79 (4) | H1A—C1—H1B | 108.0 |
O3—Cr—N2 | 88.21 (4) | O2—C2—O1 | 123.79 (12) |
O3—Cr—N3 | 83.29 (4) | O2—C2—C1 | 120.50 (11) |
O3—Cr—N4 | 93.51 (4) | O1—C2—C1 | 115.71 (11) |
N1—Cr—N2 | 84.33 (4) | N1—C3—C4 | 109.70 (11) |
N1—Cr—N3 | 96.89 (4) | N1—C3—H3A | 109.7 |
N1—Cr—N4 | 171.70 (4) | C4—C3—H3A | 109.7 |
N2—Cr—N3 | 171.48 (4) | N1—C3—H3B | 109.7 |
N2—Cr—N4 | 95.65 (5) | C4—C3—H3B | 109.7 |
N3—Cr—N4 | 84.35 (5) | H3A—C3—H3B | 108.2 |
C2—O1—Cr | 118.57 (8) | N2—C4—C3 | 108.27 (11) |
C6—O3—Cr | 117.65 (8) | N2—C4—H4A | 110.0 |
H06A—O6—H06B | 103.5 (9) | C3—C4—H4A | 110.0 |
C1—N1—C3 | 113.46 (10) | N2—C4—H4B | 110.0 |
C1—N1—Cr | 107.81 (8) | C3—C4—H4B | 110.0 |
C3—N1—Cr | 106.96 (8) | H4A—C4—H4B | 108.4 |
C1—N1—H01 | 109.5 | N3—C5—C6 | 112.15 (10) |
C3—N1—H01 | 109.5 | N3—C5—H5A | 109.2 |
Cr—N1—H01 | 109.5 | C6—C5—H5A | 109.2 |
C4—N2—Cr | 107.91 (8) | N3—C5—H5B | 109.2 |
C4—N2—H02A | 110.1 | C6—C5—H5B | 109.2 |
Cr—N2—H02A | 110.1 | H5A—C5—H5B | 107.9 |
C4—N2—H02B | 110.1 | O4—C6—O3 | 123.02 (12) |
Cr—N2—H02B | 110.1 | O4—C6—C5 | 120.20 (11) |
H02A—N2—H02B | 108.4 | O3—C6—C5 | 116.76 (11) |
C5—N3—C7 | 112.98 (10) | N3—C7—C8 | 108.82 (11) |
C5—N3—Cr | 108.14 (7) | N3—C7—H7A | 109.9 |
C7—N3—Cr | 106.46 (8) | C8—C7—H7A | 109.9 |
C5—N3—H03 | 109.7 | N3—C7—H7B | 109.9 |
C7—N3—H03 | 109.7 | C8—C7—H7B | 109.9 |
Cr—N3—H03 | 109.7 | H7A—C7—H7B | 108.3 |
C8—N4—Cr | 108.64 (8) | N4—C8—C7 | 107.95 (11) |
C8—N4—H04A | 110.0 | N4—C8—H8A | 110.1 |
Cr—N4—H04A | 110.0 | C7—C8—H8A | 110.1 |
C8—N4—H04B | 110.0 | N4—C8—H8B | 110.1 |
Cr—N4—H04B | 110.0 | C7—C8—H8B | 110.1 |
H04A—N4—H04B | 108.3 | H8A—C8—H8B | 108.4 |
C9—N5—H05A | 109.5 | N5—C9—C9i | 109.35 (13) |
C9—N5—H05B | 109.5 | N5—C9—H9A | 109.8 |
H05A—N5—H05B | 109.5 | C9i—C9—H9A | 109.8 |
C9—N5—H05C | 109.5 | N5—C9—H9B | 109.8 |
H05A—N5—H05C | 109.5 | C9i—C9—H9B | 109.8 |
H05B—N5—H05C | 109.5 | H9A—C9—H9B | 108.3 |
| | | |
N4—Cr—O1—C2 | 171.58 (10) | N4—Cr—N3—C7 | −15.33 (8) |
N2—Cr—O1—C2 | −92.79 (9) | N1—Cr—N3—C7 | 156.41 (8) |
N3—Cr—O1—C2 | 87.31 (9) | O3—Cr—N4—C8 | 69.44 (9) |
N1—Cr—O1—C2 | −8.89 (9) | O1—Cr—N4—C8 | −109.35 (9) |
N4—Cr—O3—C6 | −91.43 (9) | N2—Cr—N4—C8 | 157.98 (9) |
N2—Cr—O3—C6 | 173.02 (9) | N3—Cr—N4—C8 | −13.46 (8) |
N3—Cr—O3—C6 | −7.54 (9) | C3—N1—C1—C2 | 96.15 (12) |
N1—Cr—O3—C6 | 88.86 (9) | Cr—N1—C1—C2 | −22.11 (12) |
O3—Cr—N1—C1 | −161.74 (8) | Cr—O1—C2—O2 | 178.66 (10) |
O1—Cr—N1—C1 | 17.03 (8) | Cr—O1—C2—C1 | −2.03 (14) |
N2—Cr—N1—C1 | 110.55 (8) | N1—C1—C2—O2 | −163.63 (12) |
N3—Cr—N1—C1 | −77.94 (8) | N1—C1—C2—O1 | 17.04 (15) |
O3—Cr—N1—C3 | 75.91 (8) | C1—N1—C3—C4 | −80.87 (13) |
O1—Cr—N1—C3 | −105.33 (8) | Cr—N1—C3—C4 | 37.88 (12) |
N2—Cr—N1—C3 | −11.81 (8) | Cr—N2—C4—C3 | 41.28 (12) |
N3—Cr—N1—C3 | 159.71 (8) | N1—C3—C4—N2 | −53.69 (14) |
O3—Cr—N2—C4 | −111.34 (9) | C7—N3—C5—C6 | 102.84 (12) |
O1—Cr—N2—C4 | 65.57 (9) | Cr—N3—C5—C6 | −14.72 (12) |
N4—Cr—N2—C4 | 155.31 (9) | Cr—O3—C6—O4 | −177.64 (10) |
N1—Cr—N2—C4 | −16.35 (9) | Cr—O3—C6—C5 | 0.67 (15) |
O3—Cr—N3—C5 | 12.12 (8) | N3—C5—C6—O4 | −171.52 (11) |
O1—Cr—N3—C5 | −164.76 (8) | N3—C5—C6—O3 | 10.12 (16) |
N4—Cr—N3—C5 | 106.35 (8) | C5—N3—C7—C8 | −77.30 (14) |
N1—Cr—N3—C5 | −81.91 (8) | Cr—N3—C7—C8 | 41.25 (12) |
O3—Cr—N3—C7 | −109.56 (8) | Cr—N4—C8—C7 | 39.56 (12) |
O1—Cr—N3—C7 | 73.56 (8) | N3—C7—C8—N4 | −54.53 (14) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···Cl1ii | 0.93 | 2.27 | 3.193 (1) | 172 |
N2—H02A···Cl2iii | 0.92 | 2.53 | 3.368 (1) | 152 |
N2—H02B···Cl2iv | 0.92 | 2.38 | 3.240 (1) | 156 |
N3—H03···O6v | 0.93 | 2.02 | 2.911 (2) | 160 |
N4—H04A···O2vi | 0.92 | 2.15 | 3.001 (2) | 153 |
N4—H04A···O1vi | 0.92 | 2.65 | 3.193 (1) | 118 |
N4—H04B···O2vii | 0.92 | 2.00 | 2.913 (1) | 172 |
N5—H05A···Cl1 | 0.91 | 2.30 | 3.116 (1) | 149 |
N5—H05B···Cl2viii | 0.91 | 2.29 | 3.139 (1) | 155 |
N5—H05C···O4ix | 0.91 | 1.90 | 2.765 (1) | 157 |
O6—H06A···Cl2 | 0.879 (12) | 2.349 (11) | 3.223 (1) | 173.3 (5) |
O6—H06B···Cl1viii | 0.851 (14) | 2.628 (10) | 3.438 (1) | 160 (1) |
Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) x, −y−1/2, z+1/2; (iv) −x+2, y+1/2, −z+3/2; (v) x, y+1, z; (vi) −x+2, y−1/2, −z+3/2; (vii) x, y−1, z; (viii) −x+1, −y, −z+1; (ix) −x+1, y+1/2, −z+3/2. |
Experimental details
| (I_293K) | (I_100K) |
Crystal data |
Chemical formula | (C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2O | (C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2O |
Mr | 812.48 | 812.48 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 100 |
a, b, c (Å) | 12.5921 (3), 7.5227 (1), 18.2511 (4) | 12.5546 (4), 7.4907 (1), 18.1157 (4) |
β (°) | 95.915 (1) | 95.939 (1) |
V (Å3) | 1719.66 (6) | 1694.51 (7) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.00 | 1.02 |
Crystal size (mm) | 0.22 × 0.22 × 0.18 | 0.22 × 0.22 × 0.18 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID imaging-plate diffractometer | Rigaku R-AXIS RAPID imaging-plate diffractometer |
Absorption correction | Multi-scan (Higashi, 1995) | Multi-scan (Higashi, 1995) |
Tmin, Tmax | 0.725, 0.835 | 0.733, 0.832 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16059, 3932, 3482 | 15950, 3894, 3514 |
Rint | 0.023 | 0.023 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.070, 1.01 | 0.022, 0.059, 1.06 |
No. of reflections | 3932 | 3894 |
No. of parameters | 206 | 202 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.40 | 0.39, −0.42 |
Selected geometric parameters (Å, º) for (I_293K) topCr—O1 | 1.9529 (10) | Cr—N2 | 2.0633 (13) |
Cr—O3 | 1.9506 (10) | Cr—N3 | 2.0777 (13) |
Cr—N1 | 2.0885 (12) | Cr—N4 | 2.0541 (13) |
| | | |
O1—Cr—O3 | 176.36 (4) | O3—Cr—N4 | 93.48 (5) |
O1—Cr—N1 | 82.19 (4) | N1—Cr—N2 | 84.21 (5) |
O1—Cr—N2 | 92.79 (5) | N1—Cr—N3 | 97.09 (5) |
O1—Cr—N3 | 95.56 (5) | N1—Cr—N4 | 171.86 (5) |
O1—Cr—N4 | 89.69 (5) | N2—Cr—N3 | 171.65 (5) |
O3—Cr—N1 | 94.66 (5) | N2—Cr—N4 | 95.81 (6) |
O3—Cr—N2 | 88.68 (5) | N3—Cr—N4 | 84.08 (6) |
O3—Cr—N3 | 83.00 (4) | | |
Hydrogen-bond geometry (Å, º) for (I_293K) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···Cl1i | 0.91 | 2.29 | 3.195 (1) | 171 |
N2—H02A···Cl2ii | 0.90 | 2.57 | 3.391 (1) | 153 |
N2—H02B···Cl2iii | 0.90 | 2.40 | 3.253 (1) | 157 |
N3—H03···O6iv | 0.91 | 2.04 | 2.920 (2) | 161 |
N4—H04A···O2v | 0.90 | 2.21 | 3.030 (2) | 152 |
N4—H04B···O2vi | 0.90 | 2.03 | 2.919 (2) | 170 |
N5—H05A···Cl2vii | 0.89 | 2.31 | 3.142 (1) | 157 |
N5—H05B···O4viii | 0.89 | 1.95 | 2.791 (2) | 156 |
N5—H05C···Cl1 | 0.89 | 2.33 | 3.134 (1) | 151 |
O6—H06A···Cl2 | 0.84 (2) | 2.42 (2) | 3.255 (2) | 177 (2) |
O6—H06B···Cl1vii | 0.87 (2) | 2.69 (2) | 3.509 (2) | 159 (2) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y−1/2, z+1/2; (iii) −x+2, y+1/2, −z+3/2; (iv) x, y+1, z; (v) −x+2, y−1/2, −z+3/2; (vi) x, y−1, z; (vii) −x+1, −y, −z+1; (viii) −x+1, y+1/2, −z+3/2. |
Selected geometric parameters (Å, º) for (I_100K) topCr—O1 | 1.9552 (9) | Cr—N2 | 2.0649 (11) |
Cr—O3 | 1.9505 (9) | Cr—N3 | 2.0807 (11) |
Cr—N1 | 2.0904 (11) | Cr—N4 | 2.0511 (11) |
| | | |
O1—Cr—O3 | 176.77 (4) | O3—Cr—N4 | 93.51 (4) |
O1—Cr—N1 | 82.23 (4) | N1—Cr—N2 | 84.33 (4) |
O1—Cr—N2 | 92.70 (4) | N1—Cr—N3 | 96.89 (4) |
O1—Cr—N3 | 95.82 (4) | N1—Cr—N4 | 171.70 (4) |
O1—Cr—N4 | 89.48 (4) | N2—Cr—N3 | 171.48 (4) |
O3—Cr—N1 | 94.79 (4) | N2—Cr—N4 | 95.65 (5) |
O3—Cr—N2 | 88.21 (4) | N3—Cr—N4 | 84.35 (5) |
O3—Cr—N3 | 83.29 (4) | | |
Hydrogen-bond geometry (Å, º) for (I_100K) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···Cl1i | 0.93 | 2.27 | 3.193 (1) | 172 |
N2—H02A···Cl2ii | 0.92 | 2.53 | 3.368 (1) | 152 |
N2—H02B···Cl2iii | 0.92 | 2.38 | 3.240 (1) | 156 |
N3—H03···O6iv | 0.93 | 2.02 | 2.911 (2) | 160 |
N4—H04A···O2v | 0.92 | 2.15 | 3.001 (2) | 153 |
N4—H04A···O1v | 0.92 | 2.65 | 3.193 (1) | 118 |
N4—H04B···O2vi | 0.92 | 2.00 | 2.913 (1) | 172 |
N5—H05A···Cl1 | 0.91 | 2.30 | 3.116 (1) | 149 |
N5—H05B···Cl2vii | 0.91 | 2.29 | 3.139 (1) | 155 |
N5—H05C···O4viii | 0.91 | 1.90 | 2.765 (1) | 157 |
O6—H06A···Cl2 | 0.879 (12) | 2.349 (11) | 3.223 (1) | 173.3 (5) |
O6—H06B···Cl1vii | 0.851 (14) | 2.628 (10) | 3.438 (1) | 160 (1) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y−1/2, z+1/2; (iii) −x+2, y+1/2, −z+3/2; (iv) x, y+1, z; (v) −x+2, y−1/2, −z+3/2; (vi) x, y−1, z; (vii) −x+1, −y, −z+1; (viii) −x+1, y+1/2, −z+3/2. |
N-[2-Aminoethyl)glycinate, or ethylenediaminemonoacetate or 4-amino-2-aza-butanecarboxylate (edma), has one acetate group and two amino groups, and can act as a tridentate ligand in complexation with cobalt(III) or chromium(III) ions (Fujii et al., 1970; Battaglia et al., 1974; Ama et al., 1985; Okamoto et al., 1991; Yasui et al., 1994). On the basis of elemental analysis and visible absorption, 13C NMR and CD (please define) spectra, the molecular structure of the cobalt(III) complex with the edma ligand has been determined (Igi & Douglas, 1974; Yasui et al., 1983).
A tridentate ligand can take on various coordination forms in an octahedral environment, depending upon the steric requirements of the ligand and the character of the central metal ion. There are six possible geometric diastereomers of the bis[N-(2-aminoethyl)glycinato-κ3N,N',O]chromium(III) moiety, as shown in the Scheme below. These may be further identified as (a) C2-trans(O), (b) Ci-trans(O), (c) mer, (d) C1-cis(O), (e) C2-trans(NH2) and (f) C2-trans(NH), where O, NH2, and NH refer to the carboxylate O atom, and the primary and secondary amine N atoms, respectively. Of these, only a trans form with respect to the coordinated carboxylate O atoms has been isolated and its spectroscopic properties reported (Fujii et al., 1970; Yuen, 1981). However, two configurations are possible for a trans(O)-type complex, namely, the chiral configuration C2-trans(O) and the achiral configuration Ci-trans(O). The choice of cis or trans configuration with respect to the primary and secondary amine N atoms is not clear. Scheme1. \sch
The electronic absorption and IR spectra can be used diagnostically to identify the geometric isomers of chromium(III) complexes with tridentate ligands (Choi & Hoggard, 1992). However, it should be noted that the assignments based on spectroscopic investigations are not always conclusive (Stearns & Armstrong, 1992). Recently, we have been interested in the emission and excitation spectroscopic measurements of chromium(III) complexes at low temperature (Choi, 2000a,b). A notable feature is that, on cooling single crystals of the title complex, (I), to liquid nitrogen temperature, its colour is changed from bright red to orange-yellow. The colour change is reversible on warming to room temperature. A similar thermochromism was also observed for trans- and cis-[Cr(NCS)2(cyclam)](ClO4) (cyclam is 1,4,8,11-tetraazacyclotetradecane; Friesen et al., 1997). In order to establish the details of the coordination, to verify the spectroscopic structural assignment previously described, and to help in studying the temperature-dependent occurrence of geometric isomerism, an X-ray crystal analysis of the title chromium(III) complex with edma has been undertaken at room (293 K) and low (100 K) temperatures. We used the same single-crystal for both measurements. The colour of crystal was red at room temperature, and orange at 100 K. Scheme2.
The structural analysis indicated that the crystal of (I) consists of ethylenediammonium dications, bis[N-(2-aminoethyl)glycinato]chromium(III) monocations, Cl- anions and hydrated water molecules, in a molecular ratio of 1:2:4:2, so that it can be formulated as (H2en)[Cr(edma)2]2Cl4·2H2O. This is in agreement with the elemental analysis. The chemical formula is different from that previously suggested by Fujii et al. (1970).
The [Cr(edma)2]+ moiety has a trans,cis,cis configuration with respect to the carboxylate O atom, and the primary and secondary amine N atoms (Fig. 1). At 293 K, the Cr—O bond length of 1.953 (1) Å is relatively short, and can be compared with the distance of 1.972 (5) Å found in [Cr(dpt)(glygly)]+ [dpt is bis(3-aminopropyl)amine and H2glygly is glycylglycine; Choi et al., 1995]. The Cr—N bond lengths are in the range 2.054 (1)–2.089 (1) Å, and the O—Cr—O angle is 176.36 (4)° (Table 1). Both ethylendiamine rings have λ conformations for the Δ stereoisomer (two acetate chelates are used to determine the absolute configuration around Cr) and δ conformations for the Λ stereoisomer.
The ethylenediammonium dication, H2en2+, has a centre of symmetry. In the crystal of (I), there are hydrogen bonds between ethylenediammonium dications, bis[N-(2-aminoethyl)glycinato]chromium(III) monocations, Cl- anions and hydrated water molecules, forming a three-dimensional hydrogen-bonding network (Fig. 2 and Table 2). There are no remarkable differences between the 293 K and 100 K structures, either in the molecular structure of the complex cation or in the crystal packing, although the cell lengths and volume are slightly reduced from 293 K to 100 K.
This crystallographic study indicated that the observed colour change of the crystal does not originate from a structural change of the complex.