[4-(2-Amino­ethyl)morpholine-κ²N,N′]aqua­(oxalato-κ²O,O′)copper(II) monohydrate

The crystal structure of the title compound, [Cu(C₂O₄)(C₆H₁₄N₂O)(H₂O)]·H₂O, includes a CuN₂O₃ coordination polyhedron in the shape of a slightly distorted square pyramid with bidentate morpholine and oxalate ligands. Copper(II) is coordinated by 4-(2-amino­ethyl)morpholine (etMorph) N atoms, with Cu—N distances of 2.050 (3) and 1.985 (3) Å, and two carboxyl­ate O atoms from the oxalate ligand, with Cu—O distances of 1.955 (2) and 1.965 (2) Å; both ligands are located in the basal plane, whereas a water mol­ecule is apically positioned [Cu—O = 2.251 (3) Å]. The crystal packing is dominated by N—H...O and O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.046
• wR factor = 0.131
• Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C7     -   C8     ...       1.55 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          8

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Copper ions, present in naturally occurring systems, are involved in the biochemical reactions. Morpholine can be used as a ligand in metal complexes but it can be a component of protective coatings on fresh fruits (McGuire & Hagenmaire, 1996 or Hagenmaine?) and used as an emulsifier in the preparation of pharmaceuticals and cosmetic products (Kuchowicz & Rydzynski, 1998). Its wide application is due to its relative safety for human health. Our initial aim was to investigate the activity of the [Cu(L)₂]²⁺ complex where L is etMorph or 4-(2-aminoethyl)morpholine. In the synthesis we used different copper(II) salts, such as copper(II) chloride, nitrate and acetate using the same ligand; the products revealed to be compound (I) (Fig. 1).

The Cu^II atom is slightly distorted square pyramidal with two N atoms from etMorph ligand and two O atoms from the oxalate anion forming the basal plane, and atom O06 of the water molecule occupying the apical position (Fig. 2). The Cu—O06 apical bond (2.252 Å) is shorter than the reported values for complexes with heterocyclic amines and malonate as ligands, and significantly shorter than in oxalate complexes (Bouayad et al., 1995). The coordination geometry around the Cu^II atom is similar to those in some reported CuN₂O₃-type complexes, for example [Cu(bpym)(mal)(H₂O)]·6H₂O (Rodriguez-Martin or Rodrigez-Martin et al., 2001), [Cu(mal)(phen)(H₂O)] (Kwik et al., 1986), [Cu(mal)(bpy)(H₂O)] (Lu et al., 1996), [Cu(mal)(bpy)(H₂0)]·H₂0 (Suresh et al., 1997), [Cu(mal)(dmp)₂(H₂O)] (Xiong et al., 2001) (phen is 1,10-phenantroline, bpy is 2,2'-bipyridine, bpym is 2,2`-bipyrimidine, dmp is 3,5-dimethyl-1H-pyrazole and mal is malonic acid).

In the crystal structure, molecules are linked by: (i) N00—H···O hydrogen bonds in which the morpholine ligand is a double donor to oxalate O atoms (coordinated and uncoordinated); (ii) O—H···O hydrogen bonds in which an uncoordinated water molecule, O1W, acts as donor to oxalate O atom O5 and morpholine O atom O1; (iii) the coordinated water O06 which is a donor to the uncoodrinated water and uncoordinated oxalate O atom O3 (Table 2). Graph-set analysis (Bernstein et al., 1995) performed by the computer program RPLUTO (Motherwell et al., 2000) indicated that the unccordinated and coordinated water molecules O1W···O5 (a in Fig. 3), O1W···O1 (b in Fig. 3) and O06···O1W (c in Fig.3) form discrete D motifs. O06—H···O3 (d in Fig.3) links the complex molecules by translation along the axis a into the C (6) chain. N0···O4 (e in Fig. 3) and N0···O3 (f in Fig. 3) form the rings with graph-set motifs R₂²(8) and R₂²(12), respectively. Apart from these hydrogen bonds, in the structure of (I) there is also a weak intermolecular hydrogen bond of type C—H···O (g in Fig. 3) which connects the morpholine ring with the oxalate anion into a ring defined by the R₂²(14) descriptor.

S2. Experimental

To a warm aqueous solution of copper(II) acetate (0.05 mol, 0.998 g) dissolved in 30 ml of water, etMorph (0.34 ml, 0.1 mol) and then an ammonium oxalate (0.713 g, 0.05 mol) solution in 10 ml of water were added slowly with stirring. The mixture was wormed to 333 K and stirred for 30 min. Blue crystals of the title compound appeared within 3 d. Identical crystals were obtained using copper(II) chloride or nitrate instead of copper(II) acetate.

S3. Refinement

All H atoms bound to C atoms were treated as riding, with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C). H atoms bound to O and N atoms were located in a difference Fourier map and normalized to have the O—H and N—H distances of 0.82 and 0.87 Å, respectively.

Computing details

Data collection: KM4B8 Software (Galdecki et al., 1996); cell refinement: KM4B8 Software; data reduction: KM4B8 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia,1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing, viewed along the a axis.
	Fig. 3. The hydrogen-bond network in the structure of (I), showing O—H···O (a--d), N—H···O (e and f) and C—H···O (g, double dashed lines) interactions. H atoms not involved in these interactions have been omitted for clarity.

[4-(2-Aminoethyl)morpholine-k²N,N']aqua(oxalato-k²O,O')copper(II) monohydrate

Crystal data

[Cu(C2O4)(C6H14N2O)(H2O)]·H2O	F(000) = 660
Mr = 317.79	Dx = 1.672 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 30 reflections
a = 6.8240 (14) Å	θ = 6–25°
b = 11.916 (2) Å	µ = 2.75 mm^−1
c = 16.396 (3) Å	T = 293 K
β = 108.76 (3)°	Column, blue
V = 1262.4 (5) Å^3	0.35 × 0.10 × 0.06 mm
Z = 4

Data collection

Kuma KM-4 diffractometer	1968 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 68.5°, θmin = 4.7°
ω–2θ scans	h = −8→8
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983)	k = −14→0
Tmin = 0.755, Tmax = 0.838	l = −19→7
2315 measured reflections	3 standard reflections every 100 min
2315 independent reflections	intensity decay: 1.2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0593P)^2 + 0.8891P] where P = (Fo^2 + 2Fc^2)/3
2315 reflections	(Δ/σ)max = 0.034
187 parameters	Δρmax = 0.41 e Å^−3
6 restraints	Δρmin = −0.68 e Å^−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
Cu1	0.25912 (6)	0.16956 (4)	0.01815 (3)	0.0441 (2)
O2	−0.0252 (4)	0.21581 (19)	−0.04302 (16)	0.0516 (6)
N1	0.3263 (4)	0.3070 (2)	0.09752 (19)	0.0472 (6)
O3	−0.3153 (4)	0.1414 (2)	−0.13151 (18)	0.0649 (7)
O4	0.1791 (4)	0.03075 (19)	−0.04908 (17)	0.0525 (6)
O1	0.1569 (5)	0.5050 (2)	0.1519 (2)	0.0681 (7)
N0	0.5031 (5)	0.0972 (2)	0.1023 (2)	0.0531 (7)
O06	0.4152 (5)	0.2496 (3)	−0.0691 (2)	0.0692 (8)
C7	−0.0056 (5)	0.0337 (3)	−0.1000 (2)	0.0486 (8)
O5	−0.0886 (4)	−0.0401 (2)	−0.15155 (19)	0.0708 (8)
C8	−0.1289 (5)	0.1394 (3)	−0.0913 (2)	0.0479 (7)
C4	0.1893 (7)	0.3048 (3)	0.1525 (3)	0.0637 (10)
H4A	0.0469	0.2957	0.1158	0.076*
H4B	0.2251	0.2403	0.1905	0.076*
C1	0.2839 (6)	0.4144 (3)	0.0482 (3)	0.0564 (9)
H1A	0.3829	0.4228	0.0174	0.068*
H1B	0.1469	0.4108	0.0059	0.068*
C6	0.5962 (7)	0.1741 (3)	0.1750 (3)	0.0727 (12)
H6A	0.7447	0.1626	0.1968	0.087*
H6B	0.5401	0.1588	0.2212	0.087*
C5	0.5503 (6)	0.2936 (3)	0.1452 (3)	0.0671 (10)
H5A	0.5897	0.3434	0.1946	0.081*
H5B	0.6305	0.3137	0.1082	0.081*
C3	0.2054 (8)	0.4082 (4)	0.2054 (3)	0.0761 (12)
H3A	0.1109	0.4028	0.2385	0.091*
H3B	0.3448	0.4148	0.2454	0.091*
C2	0.2958 (6)	0.5147 (3)	0.1033 (3)	0.0647 (10)
H2A	0.4361	0.5230	0.1423	0.078*
H2B	0.2617	0.5812	0.0674	0.078*
O1W	0.1658 (9)	0.1102 (7)	0.3159 (3)	0.154 (3)
H1WA	0.171 (8)	0.075 (4)	0.275 (2)	0.081 (16)*
H0A	0.605 (5)	0.074 (3)	0.085 (3)	0.066 (12)*
H0B	0.458 (6)	0.036 (2)	0.117 (3)	0.071 (13)*
H1WB	0.052 (7)	0.132 (8)	0.317 (6)	0.19 (4)*
H06A	0.328 (7)	0.275 (4)	−0.112 (2)	0.088 (17)*
H06B	0.501 (7)	0.226 (4)	−0.090 (3)	0.100 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0362 (3)	0.0434 (3)	0.0520 (3)	0.00650 (17)	0.0134 (2)	−0.0030 (2)
O2	0.0434 (12)	0.0488 (12)	0.0597 (14)	0.0085 (10)	0.0125 (10)	−0.0065 (11)
N1	0.0441 (15)	0.0437 (14)	0.0543 (17)	0.0050 (11)	0.0163 (13)	−0.0020 (12)
O3	0.0398 (13)	0.0787 (17)	0.0677 (17)	0.0070 (12)	0.0055 (12)	−0.0094 (15)
O4	0.0446 (13)	0.0494 (12)	0.0652 (14)	0.0053 (10)	0.0202 (11)	−0.0093 (11)
O1	0.0755 (18)	0.0529 (14)	0.086 (2)	0.0136 (13)	0.0404 (16)	−0.0033 (14)
N0	0.0441 (16)	0.0494 (16)	0.0649 (19)	0.0111 (13)	0.0162 (14)	0.0024 (14)
O06	0.0712 (19)	0.0771 (18)	0.0725 (19)	0.0208 (16)	0.0417 (16)	0.0194 (16)
C7	0.0504 (19)	0.0498 (17)	0.0521 (18)	−0.0021 (15)	0.0253 (15)	−0.0035 (16)
O5	0.0704 (18)	0.0694 (16)	0.0733 (18)	−0.0106 (14)	0.0239 (14)	−0.0280 (16)
C8	0.0433 (17)	0.0546 (18)	0.0475 (17)	0.0047 (15)	0.0170 (14)	0.0017 (16)
C4	0.086 (3)	0.0509 (19)	0.069 (3)	0.0038 (18)	0.045 (2)	0.0046 (18)
C1	0.060 (2)	0.0470 (17)	0.070 (2)	0.0009 (16)	0.0310 (18)	0.0016 (18)
C6	0.064 (3)	0.070 (3)	0.068 (3)	0.0160 (19)	0.000 (2)	−0.008 (2)
C5	0.053 (2)	0.063 (2)	0.075 (3)	0.0026 (18)	0.0046 (19)	−0.013 (2)
C3	0.095 (3)	0.072 (3)	0.073 (3)	0.013 (2)	0.042 (3)	−0.004 (2)
C2	0.059 (2)	0.0494 (19)	0.088 (3)	0.0040 (17)	0.027 (2)	0.0036 (19)
O1W	0.134 (4)	0.263 (7)	0.085 (3)	−0.138 (4)	0.063 (3)	−0.076 (4)

Geometric parameters (Å, º)

Cu1—O2	1.955 (2)	C7—C8	1.547 (5)
Cu1—O4	1.965 (2)	C4—C3	1.490 (6)
Cu1—N0	1.985 (3)	C4—H4A	0.9700
Cu1—N1	2.050 (3)	C4—H4B	0.9700
Cu1—O06	2.252 (3)	C1—C2	1.484 (5)
O2—C8	1.263 (4)	C1—H1A	0.9700
N1—C5	1.485 (5)	C1—H1B	0.9700
N1—C1	1.492 (4)	C6—C5	1.504 (6)
N1—C4	1.493 (5)	C6—H6A	0.9700
O3—C8	1.230 (4)	C6—H6B	0.9700
O4—C7	1.268 (4)	C5—H5A	0.9700
O1—C3	1.422 (5)	C5—H5B	0.9700
O1—C2	1.425 (5)	C3—H3A	0.9700
N0—C6	1.475 (5)	C3—H3B	0.9700
N0—H0A	0.88 (4)	C2—H2A	0.9700
N0—H0B	0.86 (2)	C2—H2B	0.9700
O06—H06A	0.82 (2)	O1W—H1WA	0.80 (2)
O06—H06B	0.82 (5)	O1W—H1WB	0.82 (7)
C7—O5	1.225 (4)
O2—Cu1—O4	84.18 (10)	N1—C4—H4A	108.9
O2—Cu1—N0	161.99 (13)	C3—C4—H4B	108.9
O4—Cu1—N0	92.53 (12)	N1—C4—H4B	108.9
O2—Cu1—N1	94.75 (11)	H4A—C4—H4B	107.8
O4—Cu1—N1	173.50 (11)	C2—C1—N1	113.5 (3)
N0—Cu1—N1	86.52 (12)	C2—C1—H1A	108.9
O2—Cu1—O06	98.55 (11)	N1—C1—H1A	108.9
O4—Cu1—O06	95.90 (11)	C2—C1—H1B	108.9
N0—Cu1—O06	99.40 (13)	N1—C1—H1B	108.9
N1—Cu1—O06	90.60 (12)	H1A—C1—H1B	107.7
C8—O2—Cu1	112.4 (2)	N0—C6—C5	109.6 (3)
C5—N1—C1	111.4 (3)	N0—C6—H6A	109.7
C5—N1—C4	114.7 (3)	C5—C6—H6A	109.7
C1—N1—C4	107.0 (3)	N0—C6—H6B	109.7
C5—N1—Cu1	103.3 (2)	C5—C6—H6B	109.7
C1—N1—Cu1	112.1 (2)	H6A—C6—H6B	108.2
C4—N1—Cu1	108.3 (2)	N1—C5—C6	110.1 (3)
C7—O4—Cu1	112.6 (2)	N1—C5—H5A	109.6
C3—O1—C2	110.2 (3)	C6—C5—H5A	109.6
C6—N0—Cu1	109.8 (2)	N1—C5—H5B	109.6
C6—N0—H0A	106 (3)	C6—C5—H5B	109.6
Cu1—N0—H0A	119 (3)	H5A—C5—H5B	108.1
C6—N0—H0B	114 (3)	O1—C3—C4	110.7 (3)
Cu1—N0—H0B	106 (3)	O1—C3—H3A	109.5
H0A—N0—H0B	102 (4)	C4—C3—H3A	109.5
Cu1—O06—H06A	110 (4)	O1—C3—H3B	109.5
Cu1—O06—H06B	132 (4)	C4—C3—H3B	109.5
H06A—O06—H06B	101 (5)	H3A—C3—H3B	108.1
O5—C7—O4	125.1 (3)	O1—C2—C1	111.0 (3)
O5—C7—C8	120.3 (3)	O1—C2—H2A	109.4
O4—C7—C8	114.6 (3)	C1—C2—H2A	109.4
O3—C8—O2	126.6 (3)	O1—C2—H2B	109.4
O3—C8—C7	117.7 (3)	C1—C2—H2B	109.4
O2—C8—C7	115.7 (3)	H2A—C2—H2B	108.0
C3—C4—N1	113.2 (3)	H1WA—O1W—H1WB	118 (7)
C3—C4—H4A	108.9
O4—Cu1—O2—C8	3.3 (2)	Cu1—O2—C8—O3	173.4 (3)
N0—Cu1—O2—C8	−76.9 (4)	Cu1—O2—C8—C7	−6.9 (4)
N1—Cu1—O2—C8	−170.2 (2)	O5—C7—C8—O3	6.7 (5)
O06—Cu1—O2—C8	98.4 (2)	O4—C7—C8—O3	−171.8 (3)
O2—Cu1—N1—C5	−174.4 (2)	O5—C7—C8—O2	−173.1 (3)
N0—Cu1—N1—C5	23.6 (3)	O4—C7—C8—O2	8.5 (4)
O06—Cu1—N1—C5	−75.8 (2)	C5—N1—C4—C3	72.3 (4)
O2—Cu1—N1—C1	−54.3 (2)	C1—N1—C4—C3	−51.8 (5)
N0—Cu1—N1—C1	143.7 (2)	Cu1—N1—C4—C3	−172.8 (3)
O06—Cu1—N1—C1	44.3 (2)	C5—N1—C1—C2	−74.7 (4)
O2—Cu1—N1—C4	63.5 (2)	C4—N1—C1—C2	51.4 (4)
N0—Cu1—N1—C4	−98.5 (3)	Cu1—N1—C1—C2	170.0 (3)
O06—Cu1—N1—C4	162.1 (2)	Cu1—N0—C6—C5	−26.9 (5)
O2—Cu1—O4—C7	1.6 (2)	C1—N1—C5—C6	−165.3 (3)
N0—Cu1—O4—C7	163.8 (2)	C4—N1—C5—C6	72.9 (4)
O06—Cu1—O4—C7	−96.5 (2)	Cu1—N1—C5—C6	−44.7 (4)
O2—Cu1—N0—C6	−93.1 (4)	N0—C6—C5—N1	49.3 (5)
O4—Cu1—N0—C6	−172.0 (3)	C2—O1—C3—C4	−59.7 (5)
N1—Cu1—N0—C6	1.6 (3)	N1—C4—C3—O1	57.8 (5)
O06—Cu1—N0—C6	91.6 (3)	C3—O1—C2—C1	59.4 (4)
Cu1—O4—C7—O5	176.3 (3)	N1—C1—C2—O1	−56.9 (4)
Cu1—O4—C7—C8	−5.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O5^i	0.80 (2)	1.96 (3)	2.706 (5)	154 (5)
N0—H0A···O4^ii	0.88 (4)	2.15 (2)	3.002 (4)	163 (4)
N0—H0B···O3^i	0.86 (2)	2.37 (2)	3.218 (4)	170 (4)
O1W—H1WB···O1^iii	0.82 (7)	2.25 (9)	2.729 (5)	118 (8)
O06—H06A···O1W^iv	0.82 (2)	1.91 (3)	2.679 (5)	156 (5)
O06—H06B···O3^v	0.82 (5)	1.90 (5)	2.702 (4)	169 (6)
C4—H4B···O5^i	0.97	2.57	3.227 (5)	126

Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z; (iii) −x, y−1/2, −z+1/2; (iv) x, −y+1/2, z−1/2; (v) x+1, y, z.