The crystal structure of the title compound, [Cu(C2H4NO2)2(H2O)], reported by Freeman et al. [(1964). Acta Cryst. 17, 1463–1470], has been reinvestigated and its absolute configuration established by anomalous dispersion effects. The origin of chirality in the crystalline state of this compound is the formation of right-handed helices from a CuII coordination network self-resolved into a pure enantiomeric phase.
Supporting information
CCDC reference: 259076
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.006 Å
- R factor = 0.046
- wR factor = 0.097
- Data-to-parameter ratio = 17.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT352_ALERT_3_C Short N-H Bond (0.87A) N1 - H1N1 ... 0.76 Ang.
PLAT354_ALERT_3_C Short O-H Bond (0.82A) O5 - H1O5 ... 0.69 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor N1 - H2N1 ... ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 10
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 30.52
From the CIF: _reflns_number_total 2301
Count of symmetry unique reflns 1358
Completeness (_total/calc) 169.44%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 943
Fraction of Friedel pairs measured 0.694
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL.
cis-aquabis(glycinato
κ2N,
O)copper(II)
top
Crystal data top
[Cu(C2H4NO2)2(H2O) | F(000) = 468 |
Mr = 229.68 | Dx = 2.029 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3850 reflections |
a = 5.1920 (3) Å | θ = 2.4–30.5° |
b = 10.6850 (6) Å | µ = 2.89 mm−1 |
c = 13.5535 (8) Å | T = 173 K |
V = 751.90 (8) Å3 | Needle, light blue |
Z = 4 | 0.24 × 0.03 × 0.02 mm |
Data collection top
Siemens SMART CCD area-detector diffractometer | 2301 independent reflections |
Radiation source: fine-focus sealed tube | 1775 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.083 |
ω scans | θmax = 30.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −7→7 |
Tmin = 0.544, Tmax = 0.944 | k = −15→14 |
10748 measured reflections | l = −19→19 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0465P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2301 reflections | Δρmax = 0.53 e Å−3 |
134 parameters | Δρmin = −0.66 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1358 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (3) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu | 0.91404 (9) | 0.14588 (5) | 0.34968 (4) | 0.01598 (13) | |
C1 | 0.7801 (8) | 0.2516 (4) | 0.1712 (3) | 0.0166 (9) | |
C2 | 1.0282 (8) | 0.1826 (4) | 0.1457 (3) | 0.0194 (9) | |
H1C2 | 0.9894 | 0.1148 | 0.0981 | 0.023 (10)* | |
H2C2 | 1.1494 | 0.2414 | 0.1135 | 0.023 (10)* | |
C3 | 0.7518 (8) | 0.1231 (4) | 0.5430 (3) | 0.0143 (8) | |
C4 | 1.0076 (8) | 0.0548 (4) | 0.5443 (3) | 0.0178 (9) | |
H1C4 | 1.1180 | 0.0907 | 0.5967 | 0.033 (10)* | |
H2C4 | 0.9777 | −0.0345 | 0.5603 | 0.033 (10)* | |
N1 | 1.1510 (8) | 0.1288 (5) | 0.2335 (3) | 0.0223 (9) | |
N2 | 1.1423 (7) | 0.0638 (4) | 0.4489 (3) | 0.0146 (8) | |
O1 | 0.6967 (6) | 0.2405 (3) | 0.2585 (2) | 0.0218 (7) | |
O2 | 0.6711 (6) | 0.3122 (3) | 0.1053 (2) | 0.0239 (8) | |
O3 | 0.6763 (5) | 0.1680 (3) | 0.4602 (2) | 0.0158 (7) | |
O4 | 0.6276 (6) | 0.1314 (3) | 0.6209 (2) | 0.0215 (7) | |
O5 | 0.7008 (9) | −0.0400 (4) | 0.2996 (3) | 0.0388 (11) | |
H1N1 | 1.265 (11) | 0.168 (5) | 0.249 (4) | 0.036 (18)* | |
H2N1 | 1.186 (11) | 0.056 (6) | 0.224 (4) | 0.029 (17)* | |
H1N2 | 1.263 (10) | 0.108 (5) | 0.451 (4) | 0.015 (13)* | |
H2N2 | 1.181 (10) | −0.008 (6) | 0.429 (4) | 0.031 (16)* | |
H1O5 | 0.600 (13) | −0.070 (6) | 0.323 (4) | 0.036 (12)* | |
H2O5 | 0.735 (11) | −0.060 (6) | 0.248 (4) | 0.036 (12)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.01031 (19) | 0.0233 (3) | 0.0144 (2) | 0.0031 (2) | 0.0007 (2) | 0.0009 (2) |
C1 | 0.016 (2) | 0.013 (2) | 0.021 (2) | −0.0048 (17) | −0.0035 (16) | −0.0007 (17) |
C2 | 0.020 (2) | 0.023 (2) | 0.0160 (19) | 0.0010 (15) | 0.0033 (18) | −0.002 (2) |
C3 | 0.0124 (17) | 0.011 (2) | 0.0195 (19) | −0.0033 (16) | 0.0007 (16) | −0.0022 (17) |
C4 | 0.0155 (19) | 0.017 (2) | 0.021 (2) | 0.0037 (16) | 0.0024 (16) | 0.0010 (19) |
N1 | 0.015 (2) | 0.027 (3) | 0.025 (2) | 0.0069 (18) | 0.0030 (14) | 0.003 (2) |
N2 | 0.0099 (18) | 0.012 (2) | 0.0215 (18) | −0.0009 (14) | −0.0012 (14) | 0.0009 (16) |
O1 | 0.0172 (15) | 0.034 (2) | 0.0145 (15) | 0.0075 (15) | 0.0003 (12) | 0.0041 (14) |
O2 | 0.0199 (16) | 0.0300 (19) | 0.0219 (16) | 0.0021 (13) | 0.0000 (13) | 0.0098 (14) |
O3 | 0.0123 (12) | 0.0195 (19) | 0.0157 (14) | 0.0031 (12) | −0.0023 (11) | −0.0010 (12) |
O4 | 0.0181 (16) | 0.0294 (18) | 0.0170 (14) | 0.0028 (14) | 0.0053 (11) | 0.0020 (13) |
O5 | 0.050 (3) | 0.038 (3) | 0.029 (2) | −0.023 (2) | 0.014 (2) | −0.0165 (19) |
Geometric parameters (Å, º) top
Cu—O1 | 1.955 (3) | C3—O4 | 1.241 (5) |
Cu—O3 | 1.956 (3) | C3—O3 | 1.281 (5) |
Cu—N2 | 1.996 (4) | C3—C4 | 1.516 (6) |
Cu—N1 | 2.006 (4) | C4—N2 | 1.473 (6) |
Cu—O5 | 2.373 (4) | C4—H1C4 | 0.9900 |
Cu—O4i | 2.655 (3) | C4—H2C4 | 0.9900 |
C1—O2 | 1.239 (5) | N1—H1N1 | 0.76 (6) |
C1—O1 | 1.265 (5) | N1—H2N1 | 0.81 (6) |
C1—C2 | 1.524 (6) | N2—H1N2 | 0.79 (5) |
C2—N1 | 1.468 (6) | N2—H2N2 | 0.84 (6) |
C2—H1C2 | 0.9900 | O5—H1O5 | 0.69 (6) |
C2—H2C2 | 0.9900 | O5—H2O5 | 0.76 (6) |
| | | |
O1—Cu—O3 | 93.32 (12) | O4—C3—C4 | 118.7 (4) |
O1—Cu—N2 | 174.87 (16) | O3—C3—C4 | 117.3 (4) |
O3—Cu—N2 | 84.91 (13) | N2—C4—C3 | 112.0 (4) |
O1—Cu—N1 | 84.54 (15) | N2—C4—H1C4 | 109.2 |
O3—Cu—N1 | 177.75 (16) | C3—C4—H1C4 | 109.2 |
N2—Cu—N1 | 97.17 (16) | N2—C4—H2C4 | 109.2 |
O1—Cu—O5 | 89.01 (16) | C3—C4—H2C4 | 109.2 |
O3—Cu—O5 | 91.47 (13) | H1C4—C4—H2C4 | 107.9 |
N2—Cu—O5 | 95.84 (17) | C2—N1—Cu | 109.5 (3) |
N1—Cu—O5 | 89.17 (18) | C2—N1—H1N1 | 110 (5) |
O1—Cu—O4i | 82.67 (12) | Cu—N1—H1N1 | 102 (5) |
O3—Cu—O4i | 92.32 (11) | C2—N1—H2N1 | 110 (4) |
N2—Cu—O4i | 92.58 (14) | Cu—N1—H2N1 | 111 (4) |
N1—Cu—O4i | 86.74 (17) | H1N1—N1—H2N1 | 114 (6) |
O5—Cu—O4i | 171.04 (13) | C4—N2—Cu | 109.8 (3) |
O2—C1—O1 | 124.5 (4) | C4—N2—H1N2 | 113 (4) |
O2—C1—C2 | 118.4 (4) | Cu—N2—H1N2 | 103 (4) |
O1—C1—C2 | 117.1 (4) | C4—N2—H2N2 | 110 (4) |
N1—C2—C1 | 111.9 (4) | Cu—N2—H2N2 | 109 (4) |
N1—C2—H1C2 | 109.2 | H1N2—N2—H2N2 | 112 (5) |
C1—C2—H1C2 | 109.2 | C1—O1—Cu | 116.3 (3) |
N1—C2—H2C2 | 109.2 | C3—O3—Cu | 115.6 (3) |
C1—C2—H2C2 | 109.2 | Cu—O5—H1O5 | 128 (5) |
H1C2—C2—H2C2 | 107.9 | Cu—O5—H2O5 | 113 (5) |
O4—C3—O3 | 124.0 (4) | H1O5—O5—H2O5 | 118 (7) |
| | | |
O2—C1—C2—N1 | 172.8 (4) | O4i—Cu—N2—C4 | 96.7 (3) |
O1—C1—C2—N1 | −8.7 (5) | O2—C1—O1—Cu | −177.3 (3) |
O4—C3—C4—N2 | −174.4 (4) | C2—C1—O1—Cu | 4.3 (5) |
O3—C3—C4—N2 | 6.2 (5) | O3—Cu—O1—C1 | 180.0 (3) |
C1—C2—N1—Cu | 8.5 (5) | N1—Cu—O1—C1 | 0.6 (3) |
O1—Cu—N1—C2 | −5.3 (3) | O5—Cu—O1—C1 | −88.6 (3) |
N2—Cu—N1—C2 | 179.6 (3) | O4i—Cu—O1—C1 | 88.0 (3) |
O5—Cu—N1—C2 | 83.8 (4) | O4—C3—O3—Cu | 178.3 (3) |
O4i—Cu—N1—C2 | −88.2 (3) | C4—C3—O3—Cu | −2.3 (4) |
C3—C4—N2—Cu | −6.7 (4) | O1—Cu—O3—C3 | −176.6 (3) |
O3—Cu—N2—C4 | 4.6 (3) | N2—Cu—O3—C3 | −1.4 (3) |
N1—Cu—N2—C4 | −176.3 (3) | O5—Cu—O3—C3 | 94.4 (3) |
O5—Cu—N2—C4 | −86.4 (3) | O4i—Cu—O3—C3 | −93.8 (3) |
Symmetry code: (i) x+1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O1ii | 0.76 (6) | 2.37 (6) | 3.093 (5) | 159 (6) |
N2—H1N2···O3ii | 0.79 (5) | 2.24 (5) | 2.992 (5) | 159 (5) |
N2—H2N2···O2iii | 0.84 (6) | 2.12 (6) | 2.950 (5) | 170 (5) |
O5—H1O5···O2iv | 0.69 (6) | 2.13 (6) | 2.808 (5) | 171 (7) |
O5—H2O5···O4v | 0.76 (6) | 2.01 (6) | 2.759 (5) | 170 (6) |
Symmetry codes: (ii) x+1, y, z; (iii) −x+2, y−1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) −x+3/2, −y, z−1/2. |