A redetermination of cis-aqua­bis­(glycinato-κ²N,O)copper(II)

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 Cu^II coordination network self-resolved into a pure enantiomeric phase.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](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

---

Computing details

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(glycinatoκ²N,O)copper(II)

Crystal data

[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) Å^3	Needle, light blue
Z = 4	0.24 × 0.03 × 0.02 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0465P)^2] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

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

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—O4^i	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—O4^i	82.67 (12)	Cu—N1—H1N1	102 (5)
O3—Cu—O4^i	92.32 (11)	C2—N1—H2N1	110 (4)
N2—Cu—O4^i	92.58 (14)	Cu—N1—H2N1	111 (4)
N1—Cu—O4^i	86.74 (17)	H1N1—N1—H2N1	114 (6)
O5—Cu—O4^i	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)	O4^i—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)	O4^i—Cu—O1—C1	88.0 (3)
O5—Cu—N1—C2	83.8 (4)	O4—C3—O3—Cu	178.3 (3)
O4^i—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)	O4^i—Cu—O3—C3	−93.8 (3)

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1^ii	0.76 (6)	2.37 (6)	3.093 (5)	159 (6)
N2—H1N2···O3^ii	0.79 (5)	2.24 (5)	2.992 (5)	159 (5)
N2—H2N2···O2^iii	0.84 (6)	2.12 (6)	2.950 (5)	170 (5)
O5—H1O5···O2^iv	0.69 (6)	2.13 (6)	2.808 (5)	171 (7)
O5—H2O5···O4^v	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.