Bis{N'-[(E)-amino­(imino)­methyl]­morpholinocarboximid­amido}copper(II)

The title complex of a deprotonated form of morpholine biguanide with Cu^II, namely bis(2-morpholinobiguanido)copper(II), [Cu(C₆H₁₂N₅O)₂], was characterized crystallographically. The Cu²⁺ ion, on a centre of symmetry, is coordinated by four N atoms from two bidentate morpholine biguanide monoanions; the biguanide groups of the two ligands and the copper ion are coplanar. The two morpholine rings of the ligands are in a trans configuration and have a chair conformation.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.028
• wR factor = 0.080
• Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O1     -   C4       =       7.29 su

Alert level C
PLAT352_ALERT_3_C Short   N-H Bond (0.87A)   N2     -   H2B      =       0.74 Ang.
PLAT352_ALERT_3_C Short   N-H Bond (0.87A)   N4     -   H4       =       0.74 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4     ...          ?

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.

Bis{N'-[(E)-amino(imino)methyl]morpholine-4-carboximidamido}copper(II)

Crystal data

[Cu(C6H12N5O)2]	F(000) = 422
Mr = 403.95	Dx = 1.582 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2289 reflections
a = 9.185 (2) Å	θ = 2.9–26.7°
b = 12.681 (3) Å	µ = 1.32 mm^−1
c = 7.7791 (17) Å	T = 293 K
β = 110.579 (3)°	Block, red
V = 848.2 (3) Å^3	0.40 × 0.40 × 0.30 mm
Z = 2

Data collection

Bruker SMART 1K CCD area-detector diffractometer	1501 independent reflections
Radiation source: fine-focus sealed tube	1290 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −10→10
Tmin = 0.602, Tmax = 0.672	k = −15→14
3429 measured reflections	l = −9→8

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0541P)^2] where P = (Fo^2 + 2Fc^2)/3
1501 reflections	(Δ/σ)max < 0.001
131 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.19 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	0.5000	0.0000	0.0000	0.03620 (16)
N1	0.5966 (2)	−0.13334 (13)	0.0812 (2)	0.0445 (4)
N4	0.5623 (2)	0.04069 (18)	0.2567 (2)	0.0496 (5)
N3	0.71007 (19)	−0.10693 (12)	0.4040 (2)	0.0391 (4)
C1	0.6759 (2)	−0.16354 (15)	0.2495 (3)	0.0368 (4)
O1	0.9448 (2)	0.17340 (14)	0.8413 (2)	0.0674 (5)
C2	0.6648 (3)	−0.00545 (14)	0.3987 (3)	0.0372 (5)
N2	0.7297 (3)	−0.26515 (15)	0.2771 (3)	0.0500 (5)
N5	0.7386 (2)	0.04864 (15)	0.5576 (2)	0.0497 (5)
C4	0.8296 (4)	0.2210 (2)	0.6889 (4)	0.0690 (7)
H4A	0.8743	0.2377	0.5963	0.083*
H4B	0.7964	0.2866	0.7279	0.083*
C5	0.8597 (3)	0.00126 (15)	0.7127 (4)	0.0531 (6)
H5A	0.8959	−0.0634	0.6746	0.064*
H5B	0.8189	−0.0157	0.8086	0.064*
C3	0.6908 (3)	0.15111 (18)	0.6061 (3)	0.0580 (6)
H3A	0.6380	0.1412	0.6932	0.070*
H3B	0.6187	0.1844	0.4971	0.070*
C6	0.9912 (3)	0.0773 (2)	0.7837 (3)	0.0621 (7)
H6A	1.0728	0.0456	0.8865	0.075*
H6B	1.0336	0.0916	0.6882	0.075*
H1	0.601 (3)	−0.1791 (17)	0.001 (3)	0.052 (6)*
H2A	0.723 (3)	−0.2983 (18)	0.174 (3)	0.046 (6)*
H2B	0.800 (3)	−0.2720 (17)	0.360 (3)	0.039 (7)*
H4	0.544 (3)	0.0962 (19)	0.270 (3)	0.044 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0385 (2)	0.0375 (2)	0.0280 (2)	0.00189 (13)	0.00592 (16)	−0.00119 (12)
N1	0.0569 (11)	0.0387 (9)	0.0335 (9)	0.0064 (8)	0.0104 (8)	−0.0052 (8)
N4	0.0641 (13)	0.0408 (11)	0.0341 (10)	0.0144 (10)	0.0051 (9)	−0.0044 (9)
N3	0.0428 (9)	0.0389 (9)	0.0320 (9)	0.0012 (7)	0.0086 (7)	0.0004 (7)
C1	0.0367 (10)	0.0374 (10)	0.0368 (11)	0.0000 (8)	0.0134 (9)	0.0021 (8)
O1	0.0726 (11)	0.0763 (12)	0.0487 (9)	−0.0258 (9)	0.0155 (9)	−0.0199 (8)
C2	0.0374 (12)	0.0411 (12)	0.0315 (11)	−0.0039 (8)	0.0103 (9)	−0.0017 (7)
N2	0.0646 (14)	0.0398 (11)	0.0413 (12)	0.0073 (9)	0.0130 (11)	0.0033 (9)
N5	0.0537 (11)	0.0468 (11)	0.0359 (10)	0.0021 (9)	0.0000 (8)	−0.0076 (8)
C4	0.102 (2)	0.0539 (15)	0.0581 (16)	−0.0198 (14)	0.0362 (15)	−0.0169 (12)
C5	0.0560 (15)	0.0541 (15)	0.0354 (14)	−0.0066 (10)	−0.0009 (11)	0.0015 (8)
C3	0.0669 (15)	0.0579 (15)	0.0448 (13)	0.0034 (12)	0.0142 (11)	−0.0129 (11)
C6	0.0501 (14)	0.0817 (19)	0.0467 (14)	−0.0125 (13)	0.0072 (11)	−0.0070 (12)

Geometric parameters (Å, º)

Cu1—N1	1.9107 (17)	N2—H2A	0.89 (2)
Cu1—N1^i	1.9107 (17)	N2—H2B	0.74 (2)
Cu1—N4^i	1.9437 (18)	N5—C5	1.453 (3)
Cu1—N4	1.9437 (18)	N5—C3	1.463 (3)
N1—C1	1.312 (3)	C4—C3	1.499 (4)
N1—H1	0.86 (2)	C4—H4A	0.970
N4—C2	1.311 (3)	C4—H4B	0.970
N4—H4	0.74 (2)	C5—C6	1.491 (3)
N3—C1	1.339 (3)	C5—H5A	0.970
N3—C2	1.348 (2)	C5—H5B	0.970
C1—N2	1.370 (3)	C3—H3A	0.970
O1—C6	1.415 (3)	C3—H3B	0.970
O1—C4	1.416 (4)	C6—H6A	0.970
C2—N5	1.367 (3)	C6—H6B	0.970
N1—Cu1—N1^i	180.00 (12)	C5—N5—C3	111.37 (17)
N1—Cu1—N4^i	92.26 (8)	O1—C4—C3	112.3 (2)
N1^i—Cu1—N4^i	87.74 (8)	O1—C4—H4A	109.1
N1—Cu1—N4	87.74 (8)	C3—C4—H4A	109.1
N1^i—Cu1—N4	92.26 (8)	O1—C4—H4B	109.1
N4^i—Cu1—N4	180.00 (12)	C3—C4—H4B	109.1
C1—N1—Cu1	128.21 (14)	H4A—C4—H4B	107.9
C1—N1—H1	112.0 (15)	N5—C5—C6	108.94 (18)
Cu1—N1—H1	119.3 (15)	N5—C5—H5A	109.9
C2—N4—Cu1	127.74 (17)	C6—C5—H5A	109.9
C2—N4—H4	116.1 (17)	N5—C5—H5B	109.9
Cu1—N4—H4	113.3 (17)	C6—C5—H5B	109.9
C1—N3—C2	120.80 (18)	H5A—C5—H5B	108.3
N1—C1—N3	127.72 (18)	N5—C3—C4	110.4 (2)
N1—C1—N2	118.31 (18)	N5—C3—H3A	109.6
N3—C1—N2	113.96 (18)	C4—C3—H3A	109.6
C6—O1—C4	108.79 (17)	N5—C3—H3B	109.6
N4—C2—N3	125.0 (2)	C4—C3—H3B	109.6
N4—C2—N5	121.26 (19)	H3A—C3—H3B	108.1
N3—C2—N5	113.69 (19)	O1—C6—C5	112.3 (2)
C1—N2—H2A	113.4 (15)	O1—C6—H6A	109.1
C1—N2—H2B	113.7 (18)	C5—C6—H6A	109.1
H2A—N2—H2B	120 (2)	O1—C6—H6B	109.1
C2—N5—C5	122.34 (19)	C5—C6—H6B	109.1
C2—N5—C3	125.51 (18)	H6A—C6—H6B	107.9
N4^i—Cu1—N1—C1	175.89 (19)	N4—C2—N5—C5	−176.0 (2)
N4—Cu1—N1—C1	−4.11 (19)	N3—C2—N5—C5	2.9 (3)
N1—Cu1—N4—C2	15.3 (2)	N4—C2—N5—C3	15.0 (4)
N1^i—Cu1—N4—C2	−164.7 (2)	N3—C2—N5—C3	−166.1 (2)
Cu1—N1—C1—N3	−1.3 (3)	C6—O1—C4—C3	58.2 (3)
Cu1—N1—C1—N2	177.28 (15)	C2—N5—C5—C6	135.0 (2)
C2—N3—C1—N1	−1.4 (3)	C3—N5—C5—C6	−54.6 (3)
C2—N3—C1—N2	179.99 (19)	C2—N5—C3—C4	−137.1 (2)
Cu1—N4—C2—N3	−22.7 (3)	C5—N5—C3—C4	52.9 (3)
Cu1—N4—C2—N5	156.06 (18)	O1—C4—C3—N5	−54.9 (3)
C1—N3—C2—N4	13.8 (3)	C4—O1—C6—C5	−60.9 (3)
C1—N3—C2—N5	−165.08 (19)	N5—C5—C6—O1	59.5 (3)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3^ii	0.89 (2)	2.39 (3)	3.274 (3)	178 (2)
N1—H1···N2^ii	0.86 (2)	2.53 (2)	3.284 (3)	146.8 (19)

Symmetry code: (ii) x, −y−1/2, z−1/2.