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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009885/ob1068sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009885/ob1068I_293Ksup2.hkl
Contains datablock I_293K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009885/ob1068I_100Ksup3.hkl
Contains datablock I_100K

CCDC references: 181328; 181329

Comment top

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.

Experimental top

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%.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A perspective view of the complex cation in (I) at 293 K. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram (viewed from the b axis) showing the hydrogen-bonding interactions between the ethylenediammonium dications, bis[N-(2-aminoethyl)glycinato]chromium(III) monocations, Cl- anions and hydrated water molecules of (I) at 293 K.
(I_293K) Ethylenediammonium bis{bis[N-(2-aminoethyl)glycinato-κ3N,N',O]chromium(III)} tetrachloride dihydrate top
Crystal data top
(C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2OF(000) = 848
Mr = 812.48Dx = 1.569 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
a = 12.5921 (3) ÅCell parameters from 12402 reflections
b = 7.5227 (1) Åθ = 2.7–27.4°
c = 18.2511 (4) ŵ = 1.00 mm1
β = 95.915 (1)°T = 293 K
V = 1719.66 (6) Å3Hexagonal column, red
Z = 20.22 × 0.22 × 0.18 mm
Data collection top
Rigaku R-AXIS RAPID imaging-plate
diffractometer
3932 independent reflections
Radiation source: fine-focus sealed tube3482 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 2.2°
ω scansh = 1616
Absorption correction: multi-scan
(Higashi, 1995)
k = 99
Tmin = 0.725, Tmax = 0.835l = 2323
16059 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H 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 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
(C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2OV = 1719.66 (6) Å3
Mr = 812.48Z = 2
Monoclinic, P21/cMo Kα radiation
a = 12.5921 (3) ŵ = 1.00 mm1
b = 7.5227 (1) ÅT = 293 K
c = 18.2511 (4) Å0.22 × 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 = 0.835Rint = 0.023
16059 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.30 e Å3
3932 reflectionsΔρmin = 0.40 e Å3
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
xyzUiso*/Ueq
Cr0.816128 (17)0.21824 (3)0.836523 (12)0.02069 (7)
Cl10.50163 (3)0.09151 (6)0.40119 (2)0.04079 (11)
Cl20.82947 (3)0.36678 (6)0.55803 (2)0.04080 (11)
O10.90990 (8)0.41282 (13)0.81360 (6)0.0296 (2)
O20.94504 (10)0.70047 (14)0.82646 (7)0.0407 (3)
O30.71554 (8)0.03513 (13)0.86037 (5)0.0262 (2)
O40.55481 (10)0.08033 (18)0.83202 (6)0.0439 (3)
O60.68352 (12)0.37757 (18)0.69518 (8)0.0478 (3)
N10.75558 (10)0.41252 (16)0.90261 (6)0.0254 (2)
N20.91135 (10)0.15211 (18)0.93142 (7)0.0329 (3)
N30.70635 (11)0.25397 (17)0.74465 (6)0.0286 (3)
N40.89114 (11)0.05402 (17)0.76814 (8)0.0358 (3)
N50.40311 (10)0.32169 (18)0.52032 (7)0.0327 (3)
C10.79232 (12)0.58811 (19)0.87839 (9)0.0297 (3)
C20.89039 (12)0.57047 (19)0.83673 (8)0.0267 (3)
C30.79455 (15)0.3689 (2)0.98044 (8)0.0379 (4)
C40.90774 (15)0.3012 (2)0.98435 (10)0.0429 (4)
C50.60733 (12)0.1560 (2)0.75696 (8)0.0317 (3)
C60.62503 (12)0.0255 (2)0.81997 (8)0.0271 (3)
C70.75792 (16)0.1865 (3)0.68002 (9)0.0430 (4)
C80.81740 (17)0.0181 (3)0.70159 (10)0.0472 (5)
C90.44016 (11)0.4925 (2)0.49193 (9)0.0317 (3)
H010.68300.40880.89680.041*
H02A0.88730.05170.95090.041*
H02B0.97890.13380.92120.041*
H030.69140.37170.73860.041*
H04A0.95090.10640.75550.041*
H04B0.90960.04860.79140.041*
H05A0.33320.31030.50780.041*
H05B0.41640.31950.56920.041*
H05C0.43740.23240.50110.041*
H1A0.80920.66360.92110.041*
H1B0.73530.64440.84690.041*
H3A0.74900.27910.99900.041*
H3B0.79180.47431.01080.041*
H4A0.95510.39580.97200.041*
H4B0.93090.26061.03390.041*
H5A0.58180.09240.71240.041*
H5B0.55260.24040.76740.041*
H7A0.80690.27500.66440.041*
H7B0.70400.16340.63920.041*
H8A0.76750.07490.71160.041*
H8B0.85720.02110.66180.041*
H9A0.40600.59020.51500.041*
H9B0.42060.49930.43920.041*
H06A0.7219 (17)0.371 (3)0.6603 (12)0.041*
H06B0.6255 (17)0.323 (3)0.6787 (11)0.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr0.02123 (12)0.01789 (11)0.02363 (12)0.00207 (8)0.00559 (8)0.00053 (8)
Cl10.0366 (2)0.0475 (2)0.0394 (2)0.00423 (17)0.00896 (16)0.01310 (18)
Cl20.0284 (2)0.0519 (2)0.0419 (2)0.00055 (17)0.00220 (15)0.00635 (18)
O10.0302 (5)0.0211 (5)0.0402 (6)0.0032 (4)0.0167 (4)0.0022 (4)
O20.0421 (7)0.0229 (5)0.0600 (8)0.0057 (5)0.0188 (6)0.0021 (5)
O30.0255 (5)0.0264 (5)0.0265 (5)0.0056 (4)0.0011 (4)0.0039 (4)
O40.0402 (7)0.0555 (8)0.0345 (6)0.0263 (6)0.0029 (5)0.0052 (5)
O60.0469 (8)0.0451 (7)0.0517 (8)0.0005 (6)0.0064 (6)0.0070 (6)
N10.0249 (6)0.0269 (6)0.0253 (6)0.0038 (5)0.0067 (4)0.0038 (5)
N20.0230 (6)0.0335 (7)0.0410 (7)0.0041 (5)0.0028 (5)0.0078 (6)
N30.0396 (7)0.0257 (6)0.0209 (6)0.0038 (5)0.0047 (5)0.0013 (5)
N40.0404 (8)0.0207 (6)0.0501 (8)0.0007 (5)0.0233 (6)0.0014 (6)
N50.0257 (6)0.0392 (7)0.0339 (7)0.0025 (5)0.0064 (5)0.0067 (6)
C10.0334 (8)0.0221 (7)0.0354 (8)0.0007 (6)0.0119 (6)0.0032 (6)
C20.0290 (7)0.0219 (7)0.0297 (7)0.0009 (5)0.0059 (6)0.0020 (6)
C30.0537 (10)0.0377 (9)0.0232 (7)0.0098 (8)0.0082 (7)0.0037 (6)
C40.0476 (10)0.0441 (10)0.0335 (8)0.0157 (8)0.0123 (7)0.0033 (7)
C50.0310 (8)0.0389 (8)0.0241 (7)0.0046 (6)0.0018 (6)0.0024 (6)
C60.0293 (7)0.0298 (7)0.0223 (6)0.0071 (6)0.0027 (5)0.0027 (6)
C70.0572 (11)0.0514 (11)0.0224 (7)0.0108 (9)0.0135 (7)0.0035 (7)
C80.0627 (12)0.0394 (9)0.0444 (10)0.0125 (8)0.0282 (9)0.0190 (8)
C90.0235 (8)0.0372 (8)0.0342 (8)0.0015 (6)0.0020 (6)0.0046 (6)
Geometric parameters (Å, º) top
Cr—O11.9529 (10)N5—C91.479 (2)
Cr—O31.9506 (10)N5—H05A0.8900
Cr—N12.0885 (12)N5—H05B0.8900
Cr—N22.0633 (13)N5—H05C0.8900
Cr—N32.0777 (13)C1—C21.521 (2)
Cr—N42.0541 (13)C1—H1A0.9700
O1—C21.2909 (17)C1—H1B0.9700
O2—C21.2213 (18)C3—C41.508 (3)
O3—C61.2940 (17)C3—H3A0.9700
O4—C61.2267 (18)C3—H3B0.9700
O6—H06A0.84 (2)C4—H4A0.9700
O6—H06B0.87 (2)C4—H4B0.9700
N1—C11.4820 (18)C5—C61.511 (2)
N1—C31.4908 (19)C5—H5A0.9700
N1—H010.9100C5—H5B0.9700
N2—C41.484 (2)C7—C81.503 (3)
N2—H02A0.9000C7—H7A0.9700
N2—H02B0.9000C7—H7B0.9700
N3—C51.485 (2)C8—H8A0.9700
N3—C71.493 (2)C8—H8B0.9700
N3—H030.9100C9—C9i1.510 (3)
N4—C81.476 (2)C9—H9A0.9700
N4—H04A0.9000C9—H9B0.9700
N4—H04B0.9000
O1—Cr—O3176.36 (4)N1—C1—C2111.46 (11)
O1—Cr—N182.19 (4)N1—C1—H1A109.3
O1—Cr—N292.79 (5)C2—C1—H1A109.3
O1—Cr—N395.56 (5)N1—C1—H1B109.3
O1—Cr—N489.69 (5)C2—C1—H1B109.3
O3—Cr—N194.66 (5)H1A—C1—H1B108.0
O3—Cr—N288.68 (5)O2—C2—O1123.80 (14)
O3—Cr—N383.00 (4)O2—C2—C1120.40 (13)
O3—Cr—N493.48 (5)O1—C2—C1115.80 (12)
N1—Cr—N284.21 (5)N1—C3—C4109.64 (13)
N1—Cr—N397.09 (5)N1—C3—H3A109.7
N1—Cr—N4171.86 (5)C4—C3—H3A109.7
N2—Cr—N3171.65 (5)N1—C3—H3B109.7
N2—Cr—N495.81 (6)C4—C3—H3B109.7
N3—Cr—N484.08 (6)H3A—C3—H3B108.2
C2—O1—Cr118.61 (9)N2—C4—C3108.47 (13)
C6—O3—Cr117.79 (9)N2—C4—H4A110.0
H06A—O6—H06B103.8 (19)C3—C4—H4A110.0
C1—N1—C3113.45 (12)N2—C4—H4B110.0
C1—N1—Cr107.92 (8)C3—C4—H4B110.0
C3—N1—Cr107.01 (10)H4A—C4—H4B108.4
C1—N1—H01109.5N3—C5—C6112.16 (12)
C3—N1—H01109.5N3—C5—H5A109.2
Cr—N1—H01109.5C6—C5—H5A109.2
C4—N2—Cr108.07 (10)N3—C5—H5B109.2
C4—N2—H02A110.1C6—C5—H5B109.2
Cr—N2—H02A110.1H5A—C5—H5B107.9
C4—N2—H02B110.1O4—C6—O3122.87 (14)
Cr—N2—H02B110.1O4—C6—C5120.38 (13)
H02A—N2—H02B108.4O3—C6—C5116.73 (12)
C5—N3—C7113.02 (13)N3—C7—C8108.97 (13)
C5—N3—Cr108.23 (9)N3—C7—H7A109.9
C7—N3—Cr106.64 (11)C8—C7—H7A109.9
C5—N3—H03109.6N3—C7—H7B109.9
C7—N3—H03109.6C8—C7—H7B109.9
Cr—N3—H03109.6H7A—C7—H7B108.3
C8—N4—Cr108.69 (10)N4—C8—C7108.40 (14)
C8—N4—H04A110.0N4—C8—H8A110.0
Cr—N4—H04A110.0C7—C8—H8A110.0
C8—N4—H04B110.0N4—C8—H8B110.0
Cr—N4—H04B110.0C7—C8—H8B110.0
H04A—N4—H04B108.3H8A—C8—H8B108.4
C9—N5—H05A109.5N5—C9—C9i109.97 (17)
C9—N5—H05B109.5N5—C9—H9A109.7
H05A—N5—H05B109.5C9i—C9—H9A109.7
C9—N5—H05C109.5N5—C9—H9B109.7
H05A—N5—H05C109.5C9i—C9—H9B109.7
H05B—N5—H05C109.5H9A—C9—H9B108.2
N4—Cr—O1—C2171.76 (12)N4—Cr—N3—C715.18 (10)
N2—Cr—O1—C292.44 (12)N1—Cr—N3—C7156.71 (10)
N3—Cr—O1—C287.74 (11)O3—Cr—N4—C869.38 (11)
N1—Cr—O1—C28.68 (11)O1—Cr—N4—C8108.82 (11)
N4—Cr—O3—C691.63 (11)N2—Cr—N4—C8158.41 (11)
N2—Cr—O3—C6172.63 (11)N3—Cr—N4—C813.20 (11)
N3—Cr—O3—C68.04 (11)C3—N1—C1—C297.20 (15)
N1—Cr—O3—C688.55 (11)Cr—N1—C1—C221.18 (14)
O3—Cr—N1—C1161.79 (9)Cr—O1—C2—O2178.73 (12)
O1—Cr—N1—C116.39 (10)Cr—O1—C2—C11.70 (17)
N2—Cr—N1—C1110.02 (10)N1—C1—C2—O2164.22 (14)
N3—Cr—N1—C178.28 (10)N1—C1—C2—O116.19 (18)
O3—Cr—N1—C375.79 (10)C1—N1—C3—C480.62 (16)
O1—Cr—N1—C3106.04 (10)Cr—N1—C3—C438.29 (14)
N2—Cr—N1—C312.41 (10)Cr—N2—C4—C340.67 (15)
N3—Cr—N1—C3159.29 (10)N1—C3—C4—N253.50 (17)
O3—Cr—N2—C4110.41 (11)C7—N3—C5—C6102.96 (15)
O1—Cr—N2—C466.26 (11)Cr—N3—C5—C614.91 (15)
N4—Cr—N2—C4156.23 (11)Cr—O3—C6—O4177.22 (12)
N1—Cr—N2—C415.59 (10)Cr—O3—C6—C51.21 (17)
O3—Cr—N3—C512.44 (10)N3—C5—C6—O4171.63 (14)
O1—Cr—N3—C5164.20 (10)N3—C5—C6—O39.9 (2)
N4—Cr—N3—C5106.69 (10)C5—N3—C7—C877.96 (18)
N1—Cr—N3—C581.41 (10)Cr—N3—C7—C840.84 (16)
O3—Cr—N3—C7109.44 (10)Cr—N4—C8—C739.19 (15)
O1—Cr—N3—C773.92 (10)N3—C7—C8—N454.03 (18)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H01···Cl1ii0.912.293.195 (1)171
N2—H02A···Cl2iii0.902.573.391 (1)153
N2—H02B···Cl2iv0.902.403.253 (1)157
N3—H03···O6v0.912.042.920 (2)161
N4—H04A···O2vi0.902.213.030 (2)152
N4—H04B···O2vii0.902.032.919 (2)170
N5—H05A···Cl2viii0.892.313.142 (1)157
N5—H05B···O4ix0.891.952.791 (2)156
N5—H05C···Cl10.892.333.134 (1)151
O6—H06A···Cl20.84 (2)2.42 (2)3.255 (2)177 (2)
O6—H06B···Cl1viii0.87 (2)2.69 (2)3.509 (2)159 (2)
Symmetry codes: (ii) x, y+1/2, z+1/2; (iii) x, y1/2, z+1/2; (iv) x+2, y+1/2, z+3/2; (v) x, y+1, z; (vi) x+2, y1/2, z+3/2; (vii) x, y1, 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]2Cl4·2H2OF(000) = 848
Mr = 812.48Dx = 1.592 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
a = 12.5546 (4) ÅCell parameters from 12063 reflections
b = 7.4907 (1) Åθ = 2.9–27.5°
c = 18.1157 (4) ŵ = 1.02 mm1
β = 95.939 (1)°T = 100 K
V = 1694.51 (7) Å3Hexagonal column, orange
Z = 20.22 × 0.22 × 0.18 mm
Data collection top
Rigaku R-AXIS RAPID imaging-plate
diffractometer
3894 independent reflections
Radiation source: fine-focus sealed tube3514 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 2.3°
ω scansh = 1616
Absorption correction: multi-scan
(Higashi, 1995)
k = 99
Tmin = 0.733, Tmax = 0.832l = 2323
15950 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: difference Fourier map
wR(F2) = 0.059H 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 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
(C2H10N2)[Cr(C4H9N2O2)2]2Cl4·2H2OV = 1694.51 (7) Å3
Mr = 812.48Z = 2
Monoclinic, P21/cMo Kα radiation
a = 12.5546 (4) ŵ = 1.02 mm1
b = 7.4907 (1) ÅT = 100 K
c = 18.1157 (4) Å0.22 × 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 = 0.832Rint = 0.023
15950 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.059H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.39 e Å3
3894 reflectionsΔρmin = 0.42 e Å3
202 parameters
Special details top

Experimental. none

Refinement. None

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cr0.815487 (15)0.22047 (3)0.835642 (11)0.00845 (6)
Cl10.50086 (3)0.09497 (4)0.401175 (17)0.01568 (8)
Cl20.82955 (2)0.36846 (4)0.557911 (17)0.01550 (8)
O10.91017 (7)0.41583 (12)0.81304 (5)0.01257 (18)
O20.94615 (8)0.70537 (12)0.82684 (5)0.0158 (2)
O30.71535 (7)0.03559 (12)0.85984 (5)0.01133 (18)
O40.55393 (8)0.08189 (13)0.83089 (5)0.0170 (2)
O60.68346 (8)0.37226 (13)0.69411 (6)0.0181 (2)
N10.75537 (9)0.41489 (14)0.90299 (6)0.0109 (2)
H010.68090.41080.89750.017*
N20.91146 (9)0.15156 (15)0.93086 (6)0.0139 (2)
H02A0.88620.04910.95100.017*
H02B0.98040.13120.92000.017*
N30.70436 (9)0.25849 (15)0.74354 (6)0.0118 (2)
H030.68880.37940.73790.017*
N40.89034 (9)0.05716 (15)0.76620 (6)0.0145 (2)
H04A0.95130.11150.75300.017*
H04B0.90970.04840.78990.017*
N50.40289 (9)0.32104 (15)0.52178 (6)0.0133 (2)
H05A0.43890.22920.50280.017*
H05B0.33140.30780.50860.017*
H05C0.41590.32080.57210.017*
C10.79186 (10)0.59218 (17)0.87838 (7)0.0127 (3)
H1A0.80850.67010.92220.017*
H1B0.73350.64900.84560.017*
C20.89081 (10)0.57460 (17)0.83680 (7)0.0114 (2)
C30.79574 (11)0.37062 (19)0.98120 (7)0.0160 (3)
H3A0.74930.27871.00060.017*
H3B0.79370.47851.01260.017*
C40.90950 (12)0.30160 (19)0.98427 (8)0.0178 (3)
H4A0.95800.39810.97100.017*
H4B0.93400.26001.03510.017*
C50.60531 (11)0.15850 (18)0.75596 (7)0.0133 (3)
H5A0.57900.09420.70990.017*
H5B0.54920.24420.76720.017*
C60.62410 (10)0.02565 (17)0.81911 (7)0.0116 (2)
C70.75585 (12)0.19248 (19)0.67789 (7)0.0171 (3)
H7A0.80620.28340.66230.017*
H7B0.70050.17030.63590.017*
C80.81542 (12)0.02128 (19)0.69897 (8)0.0184 (3)
H8A0.76420.07380.70930.017*
H8B0.85570.01880.65780.017*
C90.43963 (10)0.49316 (18)0.49209 (7)0.0135 (3)
H9A0.40520.59400.51580.017*
H9B0.41890.49930.43790.017*
H06A0.7253 (14)0.36230.65830.017*
H06B0.6261 (14)0.32010.67660.017*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr0.00883 (10)0.00766 (10)0.00905 (10)0.00073 (7)0.00184 (7)0.00010 (7)
Cl10.01474 (16)0.01790 (16)0.01471 (15)0.00112 (12)0.00298 (11)0.00408 (12)
Cl20.01152 (15)0.01959 (16)0.01525 (15)0.00006 (12)0.00078 (11)0.00217 (12)
O10.0137 (4)0.0095 (4)0.0153 (4)0.0009 (3)0.0054 (4)0.0009 (4)
O20.0162 (5)0.0109 (4)0.0209 (5)0.0021 (4)0.0054 (4)0.0002 (4)
O30.0106 (4)0.0116 (4)0.0116 (4)0.0017 (3)0.0000 (3)0.0012 (3)
O40.0161 (5)0.0204 (5)0.0142 (4)0.0082 (4)0.0006 (4)0.0012 (4)
O60.0172 (5)0.0178 (5)0.0196 (5)0.0003 (4)0.0036 (4)0.0032 (4)
N10.0109 (5)0.0114 (5)0.0106 (5)0.0023 (4)0.0022 (4)0.0011 (4)
N20.0102 (5)0.0144 (5)0.0167 (5)0.0016 (4)0.0009 (4)0.0022 (5)
N30.0160 (6)0.0105 (5)0.0092 (5)0.0009 (4)0.0021 (4)0.0006 (4)
N40.0160 (6)0.0097 (5)0.0191 (6)0.0003 (4)0.0077 (5)0.0000 (4)
N50.0111 (5)0.0154 (5)0.0135 (5)0.0010 (4)0.0020 (4)0.0022 (4)
C10.0138 (6)0.0100 (6)0.0150 (6)0.0003 (5)0.0050 (5)0.0014 (5)
C20.0124 (6)0.0114 (6)0.0104 (5)0.0012 (5)0.0003 (5)0.0009 (5)
C30.0227 (7)0.0166 (6)0.0088 (6)0.0039 (5)0.0027 (5)0.0005 (5)
C40.0202 (7)0.0188 (7)0.0131 (6)0.0064 (5)0.0045 (5)0.0004 (5)
C50.0131 (6)0.0157 (6)0.0107 (6)0.0017 (5)0.0010 (5)0.0014 (5)
C60.0133 (6)0.0124 (6)0.0092 (5)0.0008 (5)0.0018 (4)0.0021 (5)
C70.0230 (7)0.0201 (7)0.0089 (6)0.0036 (6)0.0052 (5)0.0006 (5)
C80.0241 (7)0.0163 (7)0.0161 (6)0.0032 (5)0.0088 (5)0.0068 (5)
C90.0114 (6)0.0146 (6)0.0143 (6)0.0008 (5)0.0007 (5)0.0006 (5)
Geometric parameters (Å, º) top
Cr—O11.9552 (9)N5—C91.4885 (17)
Cr—O31.9505 (9)N5—H05A0.9100
Cr—N12.0904 (11)N5—H05B0.9100
Cr—N22.0649 (11)N5—H05C0.9100
Cr—N32.0807 (11)C1—C21.5237 (18)
Cr—N42.0511 (11)C1—H1A0.9900
O1—C21.2963 (15)C1—H1B0.9900
O2—C21.2250 (16)C3—C41.515 (2)
O3—C61.2991 (15)C3—H3A0.9900
O4—C61.2286 (16)C3—H3B0.9900
O6—H06A0.879 (12)C4—H4A0.9900
O6—H06B0.851 (14)C4—H4B0.9900
N1—C11.4882 (16)C5—C61.5162 (18)
N1—C31.4917 (16)C5—H5A0.9900
N1—H010.9300C5—H5B0.9900
N2—C41.4849 (18)C7—C81.514 (2)
N2—H02A0.9200C7—H7A0.9900
N2—H02B0.9200C7—H7B0.9900
N3—C51.4886 (17)C8—H8A0.9900
N3—C71.4953 (17)C8—H8B0.9900
N3—H030.9300C9—C9i1.517 (2)
N4—C81.4843 (18)C9—H9A0.9900
N4—H04A0.9200C9—H9B0.9900
N4—H04B0.9200
O1—Cr—O3176.77 (4)N1—C1—C2111.29 (10)
O1—Cr—N182.23 (4)N1—C1—H1A109.4
O1—Cr—N292.70 (4)C2—C1—H1A109.4
O1—Cr—N395.82 (4)N1—C1—H1B109.4
O1—Cr—N489.48 (4)C2—C1—H1B109.4
O3—Cr—N194.79 (4)H1A—C1—H1B108.0
O3—Cr—N288.21 (4)O2—C2—O1123.79 (12)
O3—Cr—N383.29 (4)O2—C2—C1120.50 (11)
O3—Cr—N493.51 (4)O1—C2—C1115.71 (11)
N1—Cr—N284.33 (4)N1—C3—C4109.70 (11)
N1—Cr—N396.89 (4)N1—C3—H3A109.7
N1—Cr—N4171.70 (4)C4—C3—H3A109.7
N2—Cr—N3171.48 (4)N1—C3—H3B109.7
N2—Cr—N495.65 (5)C4—C3—H3B109.7
N3—Cr—N484.35 (5)H3A—C3—H3B108.2
C2—O1—Cr118.57 (8)N2—C4—C3108.27 (11)
C6—O3—Cr117.65 (8)N2—C4—H4A110.0
H06A—O6—H06B103.5 (9)C3—C4—H4A110.0
C1—N1—C3113.46 (10)N2—C4—H4B110.0
C1—N1—Cr107.81 (8)C3—C4—H4B110.0
C3—N1—Cr106.96 (8)H4A—C4—H4B108.4
C1—N1—H01109.5N3—C5—C6112.15 (10)
C3—N1—H01109.5N3—C5—H5A109.2
Cr—N1—H01109.5C6—C5—H5A109.2
C4—N2—Cr107.91 (8)N3—C5—H5B109.2
C4—N2—H02A110.1C6—C5—H5B109.2
Cr—N2—H02A110.1H5A—C5—H5B107.9
C4—N2—H02B110.1O4—C6—O3123.02 (12)
Cr—N2—H02B110.1O4—C6—C5120.20 (11)
H02A—N2—H02B108.4O3—C6—C5116.76 (11)
C5—N3—C7112.98 (10)N3—C7—C8108.82 (11)
C5—N3—Cr108.14 (7)N3—C7—H7A109.9
C7—N3—Cr106.46 (8)C8—C7—H7A109.9
C5—N3—H03109.7N3—C7—H7B109.9
C7—N3—H03109.7C8—C7—H7B109.9
Cr—N3—H03109.7H7A—C7—H7B108.3
C8—N4—Cr108.64 (8)N4—C8—C7107.95 (11)
C8—N4—H04A110.0N4—C8—H8A110.1
Cr—N4—H04A110.0C7—C8—H8A110.1
C8—N4—H04B110.0N4—C8—H8B110.1
Cr—N4—H04B110.0C7—C8—H8B110.1
H04A—N4—H04B108.3H8A—C8—H8B108.4
C9—N5—H05A109.5N5—C9—C9i109.35 (13)
C9—N5—H05B109.5N5—C9—H9A109.8
H05A—N5—H05B109.5C9i—C9—H9A109.8
C9—N5—H05C109.5N5—C9—H9B109.8
H05A—N5—H05C109.5C9i—C9—H9B109.8
H05B—N5—H05C109.5H9A—C9—H9B108.3
N4—Cr—O1—C2171.58 (10)N4—Cr—N3—C715.33 (8)
N2—Cr—O1—C292.79 (9)N1—Cr—N3—C7156.41 (8)
N3—Cr—O1—C287.31 (9)O3—Cr—N4—C869.44 (9)
N1—Cr—O1—C28.89 (9)O1—Cr—N4—C8109.35 (9)
N4—Cr—O3—C691.43 (9)N2—Cr—N4—C8157.98 (9)
N2—Cr—O3—C6173.02 (9)N3—Cr—N4—C813.46 (8)
N3—Cr—O3—C67.54 (9)C3—N1—C1—C296.15 (12)
N1—Cr—O3—C688.86 (9)Cr—N1—C1—C222.11 (12)
O3—Cr—N1—C1161.74 (8)Cr—O1—C2—O2178.66 (10)
O1—Cr—N1—C117.03 (8)Cr—O1—C2—C12.03 (14)
N2—Cr—N1—C1110.55 (8)N1—C1—C2—O2163.63 (12)
N3—Cr—N1—C177.94 (8)N1—C1—C2—O117.04 (15)
O3—Cr—N1—C375.91 (8)C1—N1—C3—C480.87 (13)
O1—Cr—N1—C3105.33 (8)Cr—N1—C3—C437.88 (12)
N2—Cr—N1—C311.81 (8)Cr—N2—C4—C341.28 (12)
N3—Cr—N1—C3159.71 (8)N1—C3—C4—N253.69 (14)
O3—Cr—N2—C4111.34 (9)C7—N3—C5—C6102.84 (12)
O1—Cr—N2—C465.57 (9)Cr—N3—C5—C614.72 (12)
N4—Cr—N2—C4155.31 (9)Cr—O3—C6—O4177.64 (10)
N1—Cr—N2—C416.35 (9)Cr—O3—C6—C50.67 (15)
O3—Cr—N3—C512.12 (8)N3—C5—C6—O4171.52 (11)
O1—Cr—N3—C5164.76 (8)N3—C5—C6—O310.12 (16)
N4—Cr—N3—C5106.35 (8)C5—N3—C7—C877.30 (14)
N1—Cr—N3—C581.91 (8)Cr—N3—C7—C841.25 (12)
O3—Cr—N3—C7109.56 (8)Cr—N4—C8—C739.56 (12)
O1—Cr—N3—C773.56 (8)N3—C7—C8—N454.53 (14)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H01···Cl1ii0.932.273.193 (1)172
N2—H02A···Cl2iii0.922.533.368 (1)152
N2—H02B···Cl2iv0.922.383.240 (1)156
N3—H03···O6v0.932.022.911 (2)160
N4—H04A···O2vi0.922.153.001 (2)153
N4—H04A···O1vi0.922.653.193 (1)118
N4—H04B···O2vii0.922.002.913 (1)172
N5—H05A···Cl10.912.303.116 (1)149
N5—H05B···Cl2viii0.912.293.139 (1)155
N5—H05C···O4ix0.911.902.765 (1)157
O6—H06A···Cl20.879 (12)2.349 (11)3.223 (1)173.3 (5)
O6—H06B···Cl1viii0.851 (14)2.628 (10)3.438 (1)160 (1)
Symmetry codes: (ii) x, y+1/2, z+1/2; (iii) x, y1/2, z+1/2; (iv) x+2, y+1/2, z+3/2; (v) x, y+1, z; (vi) x+2, y1/2, z+3/2; (vii) x, y1, 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
Mr812.48812.48
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)293100
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)
V3)1719.66 (6)1694.51 (7)
Z22
Radiation typeMo KαMo Kα
µ (mm1)1.001.02
Crystal size (mm)0.22 × 0.22 × 0.180.22 × 0.22 × 0.18
Data collection
DiffractometerRigaku R-AXIS RAPID imaging-plate
diffractometer
Rigaku R-AXIS RAPID imaging-plate
diffractometer
Absorption correctionMulti-scan
(Higashi, 1995)
Multi-scan
(Higashi, 1995)
Tmin, Tmax0.725, 0.8350.733, 0.832
No. of measured, independent and
observed [I > 2σ(I)] reflections
16059, 3932, 3482 15950, 3894, 3514
Rint0.0230.023
(sin θ/λ)max1)0.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.070, 1.01 0.022, 0.059, 1.06
No. of reflections39323894
No. of parameters206202
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.30, 0.400.39, 0.42

Computer programs: PROCESS-AUTO (Rigaku Corporation, 1998), PROCESS-AUTO, TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP (Johnson, 1970), SHELXL97.

Selected geometric parameters (Å, º) for (I_293K) top
Cr—O11.9529 (10)Cr—N22.0633 (13)
Cr—O31.9506 (10)Cr—N32.0777 (13)
Cr—N12.0885 (12)Cr—N42.0541 (13)
O1—Cr—O3176.36 (4)O3—Cr—N493.48 (5)
O1—Cr—N182.19 (4)N1—Cr—N284.21 (5)
O1—Cr—N292.79 (5)N1—Cr—N397.09 (5)
O1—Cr—N395.56 (5)N1—Cr—N4171.86 (5)
O1—Cr—N489.69 (5)N2—Cr—N3171.65 (5)
O3—Cr—N194.66 (5)N2—Cr—N495.81 (6)
O3—Cr—N288.68 (5)N3—Cr—N484.08 (6)
O3—Cr—N383.00 (4)
Hydrogen-bond geometry (Å, º) for (I_293K) top
D—H···AD—HH···AD···AD—H···A
N1—H01···Cl1i0.912.293.195 (1)171
N2—H02A···Cl2ii0.902.573.391 (1)153
N2—H02B···Cl2iii0.902.403.253 (1)157
N3—H03···O6iv0.912.042.920 (2)161
N4—H04A···O2v0.902.213.030 (2)152
N4—H04B···O2vi0.902.032.919 (2)170
N5—H05A···Cl2vii0.892.313.142 (1)157
N5—H05B···O4viii0.891.952.791 (2)156
N5—H05C···Cl10.892.333.134 (1)151
O6—H06A···Cl20.84 (2)2.42 (2)3.255 (2)177 (2)
O6—H06B···Cl1vii0.87 (2)2.69 (2)3.509 (2)159 (2)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y1/2, z+1/2; (iii) x+2, y+1/2, z+3/2; (iv) x, y+1, z; (v) x+2, y1/2, z+3/2; (vi) x, y1, z; (vii) x+1, y, z+1; (viii) x+1, y+1/2, z+3/2.
Selected geometric parameters (Å, º) for (I_100K) top
Cr—O11.9552 (9)Cr—N22.0649 (11)
Cr—O31.9505 (9)Cr—N32.0807 (11)
Cr—N12.0904 (11)Cr—N42.0511 (11)
O1—Cr—O3176.77 (4)O3—Cr—N493.51 (4)
O1—Cr—N182.23 (4)N1—Cr—N284.33 (4)
O1—Cr—N292.70 (4)N1—Cr—N396.89 (4)
O1—Cr—N395.82 (4)N1—Cr—N4171.70 (4)
O1—Cr—N489.48 (4)N2—Cr—N3171.48 (4)
O3—Cr—N194.79 (4)N2—Cr—N495.65 (5)
O3—Cr—N288.21 (4)N3—Cr—N484.35 (5)
O3—Cr—N383.29 (4)
Hydrogen-bond geometry (Å, º) for (I_100K) top
D—H···AD—HH···AD···AD—H···A
N1—H01···Cl1i0.932.273.193 (1)172
N2—H02A···Cl2ii0.922.533.368 (1)152
N2—H02B···Cl2iii0.922.383.240 (1)156
N3—H03···O6iv0.932.022.911 (2)160
N4—H04A···O2v0.922.153.001 (2)153
N4—H04A···O1v0.922.653.193 (1)118
N4—H04B···O2vi0.922.002.913 (1)172
N5—H05A···Cl10.912.303.116 (1)149
N5—H05B···Cl2vii0.912.293.139 (1)155
N5—H05C···O4viii0.911.902.765 (1)157
O6—H06A···Cl20.879 (12)2.349 (11)3.223 (1)173.3 (5)
O6—H06B···Cl1vii0.851 (14)2.628 (10)3.438 (1)160 (1)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y1/2, z+1/2; (iii) x+2, y+1/2, z+3/2; (iv) x, y+1, z; (v) x+2, y1/2, z+3/2; (vi) x, y1, z; (vii) x+1, y, z+1; (viii) x+1, y+1/2, z+3/2.
 

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