Tripotassium (bis­{[bis­(carboxyl­atometh­yl)amino]­meth­yl}phosphinato)cuprate(II) dihydrate

Liu, L.; Zhang, R.; Fan, P.; Yu, Z.; Zhang, X.

doi:10.1107/S1600536811053608

Tripotassium (bis{[bis(carboxylatomethyl)amino]methyl}phosphinato)cuprate(II) dihydrate

L. Liu, R. Zhang, P. Fan, Z. Yu and X. Zhang

In the title compound, K₃[Cu(C₁₀H₁₂N₂O₁₀P)]·2H₂O, the Cu^II ion, one potassium cation and a P atom are situated on a twofold rotation axis. The Cu^II ion is coordinated by two N and four O atoms from one bis{[bis(carboxylatomethyl)amino]methyl}phosphinate ligand in a distorted octahedral coordination geometry. The two crystallographically independent potassium ions exhibit different coordination environments. The potassium ion in a general position is heptacoordinated by five carboxylate O atoms, one phosphinate O atom and one water molecule [K—O = 2.718 (3)–3.040 (3) Å], and the potassium ion situated on the twofold rotation axis is hexacoordinated by four carboxylate O atoms and two water molecules [K—O = 2.618 (3)–2.771 (3) Å]. The water molecules are also involved in formation of intermolecular O—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811053608/cv5214sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811053608/cv5214Isup2.hkl Contains datablock I

CCDC reference: 861709

checkCIF report

Key indicators

Single-crystal X-ray study
T = 273 K
Mean (C-C) = 0.005 Å
R factor = 0.025
wR factor = 0.065
Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    --  O3      ..       13.8 su
PLAT919_ALERT_3_B Reflection # Likely Affected by the Beamstop ...          1
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          1

Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    --  O1      ..        9.9 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    --  N1      ..        7.8 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT733_ALERT_1_C Torsion Calc     51.0(3), Rep    50.96(7) ......       4.29 su-Ra
              K2  -O6  -K1  -O6     3.656   1.555   1.555   2.665      38
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          2

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C10 H16 Cu1 K3 N2 O12 P1
            Atom count from _chemical_formula_moiety:C10 H16 Cu1 K6 N2 O12 P1
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           25.03
           From the CIF: _reflns_number_total               1686
           Count of symmetry unique reflns         1002
           Completeness (_total/calc)            168.26%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       684
           Fraction of Friedel pairs measured     0.683
           Are heavy atom types Z>Si present        yes
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT158_ALERT_4_G The Input Unitcell is NOT Standard/Reduced .....          ?
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        273 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        273 K
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            O1  -CU1 -N1  -C1     79.00  1.30   2.655   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            O1  -CU1 -N1  -C3    -38.00  1.30   2.655   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         11
            O1  -CU1 -N1  -C5   -164.50  1.20   2.655   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            N1  -CU1 -O1  -C2    113.90  1.20   2.655   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         23
            N1  -CU1 -O1  -K2   -111.00  1.20   2.655   1.555   1.555   1.554
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         30
            O3  -CU1 -O3  -C4    -66.40  0.20   2.655   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         35
            O3  -CU1 -O3  -K2    152.06  0.16   2.655   1.555   1.555   3.646
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #        117
            N1  -C3  -C4  -K2     10.00  2.00   1.555   1.555   1.555   3.646
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.34 Ratio
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu1     (II)          2.20
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          83 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   3 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  20 ALERT level G = General information/check it is not something unexpected

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
  11 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

Comment top

The most famous chelating ligands are aminopolycarboxylic acids such as the ethylenediaminetetraacetic acid (edta). In the current continuing quest for new chelating ligands, some derivatives of edta, which have both similar chelating properties as edta and special chemical fragments, are discovered. Bis{[bis(carboxymethyl)amino]methyl}phosphinic acid (H₅XT) is a good example which could be structurally looked as two equal half of edta connected by a phosphinate group. Previous research (Xu et al., 2001) has demonstrated that XT^5- is able to form stable complexes with rare earth metal and cobalt ions. Herewith we present the crystal structure of the title compound (I).

In (I) (Fig. 1), the Cu^II ion exhibits a distorted octahedral coordination geometry, where two N and two carboxylate O atoms located at the equatorial positions. Other two carboxylate O atoms occupy the axial positions. The Cu^II ion, one potassium cation and a P atom are situated on a twofold axis. Two types of potassium ions with different coodination circumstances are distributed in the title complex (Fig. 2). K1 is hexacoordinated by four carboxylate O atoms and two water molecules; while K2 is heptacoordinated by five carboxylate O atoms, one phosphinate O atom and one water molecule. The bond distances and angles in the title coupound agree well with the corresponding bond distances and angles reported in related [Co(II)XT]^3- complex (Xu et al., 2001).

Related literature top

For details of the synthesis of the ligand, see: Varga (1997); Tircsó et al. (2007). For the isotypic compound with Co(II), see: Xu et al. (2001).

Experimental top

The ligand, bis{[bis(carboxymethyl)amino]methyl}phosphinic acid(XT), was synthesized according to the known procedure (Varga, 1997; Tircsó et al., 2007).

The title complex was simply synthesized by mixing 0.4027 g XT, 0.1774 g CuCl₂ and 5 ml water in a small beaker with sufficient stirring. When the solution became clear, KOH was used to adjust the pH value to 8. Then the beaker was transferred to a closed container of methanol. After methanol vapor diffusion for one week, blue transparent crystals were observed from the solution.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A portion of the crystal structure of (I) showing a coordination environment of Cu^II, atomic numbering and 50% probability displacement ellipsoids [symmetry code: (A) 1 - x, -y, z]. H atoms omitted for clarity.
	Fig. 2. A portion of the crystal structure of (I) showing the positions of K⁺ [symmetry code: (A) 1 - x,-y, z; (B) 1/2 + x,1/2 - y, -z; (C) x,y, -1 + z; (D) -1/2 + x,1/2 - y, 1 - z; (E) 3/2 - x,-1/2 + y,1 - z; (F) 3/2 - x,1/2 + y, 1 - z; (G) x,-1 + y, z; (H) 1 - x,-y,-1 + z; (I) -1/2 + x,-1/2 - y,1 - z; (J) -1/2 + x,1/2 - y,-z]. O6 belongs to the water molecule. H atoms omitted for clarity.

Tripotassium (bis{[bis(carboxylatomethyl)amino]methyl}phosphinato)cuprate(II) dihydrate top

Crystal data top

K₃[Cu(C₁₀H₁₂N₂O₁₀P)]·2H₂O	F(000) = 574
M_r = 568.06	D_x = 1.969 Mg m⁻³
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 376 reflections
a = 11.880 (7) Å	θ = 2.6–22.8°
b = 8.332 (5) Å	µ = 1.94 mm⁻¹
c = 9.681 (6) Å	T = 273 K
V = 958.2 (10) Å³	Block, blue
Z = 2	0.25 × 0.20 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1686 independent reflections
Radiation source: fine-focus sealed tube	1553 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
phi and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −14→7
T_min = 0.643, T_max = 0.760	k = −9→9
3814 measured reflections	l = −11→11

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)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.0309P)² + 0.1108P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1686 reflections	Δρ_max = 0.42 e Å⁻³
141 parameters	Δρ_min = −0.27 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 671 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.016 (19)

Crystal data top

K₃[Cu(C₁₀H₁₂N₂O₁₀P)]·2H₂O	V = 958.2 (10) Å³
M_r = 568.06	Z = 2
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 11.880 (7) Å	µ = 1.94 mm⁻¹
b = 8.332 (5) Å	T = 273 K
c = 9.681 (6) Å	0.25 × 0.20 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1686 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	1553 reflections with I > 2σ(I)
T_min = 0.643, T_max = 0.760	R_int = 0.041
3814 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.065	Δρ_max = 0.42 e Å⁻³
S = 1.07	Δρ_min = −0.27 e Å⁻³
1686 reflections	Absolute structure: Flack (1983), 671 Friedel pairs
141 parameters	Absolute structure parameter: −0.016 (19)
2 restraints

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	U_iso*/U_eq
Cu1	0.5000	0.0000	0.24820 (5)	0.02067 (13)
N1	0.5819 (2)	0.1559 (3)	0.3846 (2)	0.0241 (5)
O1	0.56779 (19)	0.1530 (3)	0.1064 (2)	0.0350 (5)
O2	0.6252 (2)	0.4027 (3)	0.0863 (2)	0.0439 (7)
O3	0.65208 (19)	−0.1264 (3)	0.2638 (3)	0.0431 (6)
O4	0.83096 (19)	−0.0736 (3)	0.3018 (3)	0.0480 (7)
O5	0.6061 (2)	−0.0298 (3)	0.7037 (2)	0.0451 (7)
O6	0.6136 (3)	0.7735 (4)	−0.0772 (3)	0.0451 (7)
K1	0.5000	0.5000	−0.14025 (10)	0.0354 (2)
K2	0.72836 (6)	0.15198 (9)	0.89192 (7)	0.03197 (18)
P1	0.5000	0.0000	0.62460 (10)	0.0294 (3)
C1	0.5802 (3)	0.3100 (4)	0.3092 (3)	0.0309 (8)
H1A	0.6403	0.3779	0.3435	0.037*
H1B	0.5094	0.3641	0.3273	0.037*
C2	0.5938 (3)	0.2890 (4)	0.1561 (4)	0.0279 (7)
C3	0.6992 (3)	0.0996 (4)	0.4033 (4)	0.0314 (7)
H3A	0.7104	0.0719	0.4997	0.038*
H3B	0.7501	0.1871	0.3816	0.038*
C4	0.7300 (3)	−0.0441 (4)	0.3151 (3)	0.0300 (8)
C5	0.5181 (3)	0.1745 (4)	0.5159 (3)	0.0279 (7)
H5B	0.4439	0.2150	0.4930	0.033*
H5A	0.5554	0.2565	0.5703	0.033*
H6A	0.613 (3)	0.835 (5)	−0.158 (3)	0.059 (13)*
H6B	0.569 (4)	0.835 (6)	−0.017 (5)	0.10 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0246 (2)	0.0185 (2)	0.0189 (2)	−0.0019 (2)	0.000	0.000
N1	0.0280 (12)	0.0227 (13)	0.0216 (13)	0.0016 (11)	0.0028 (11)	0.0039 (13)
O1	0.0404 (13)	0.0380 (13)	0.0266 (12)	−0.0059 (11)	0.0010 (10)	−0.0022 (12)
O2	0.0466 (15)	0.0481 (16)	0.0369 (14)	−0.0133 (12)	−0.0063 (11)	0.0228 (13)
O3	0.0383 (12)	0.0399 (15)	0.0510 (16)	−0.0032 (12)	0.0113 (12)	−0.0146 (13)
O4	0.0315 (13)	0.0526 (16)	0.0599 (17)	0.0113 (13)	0.0084 (12)	0.0057 (14)
O5	0.0594 (15)	0.0483 (18)	0.0277 (11)	−0.0152 (14)	−0.0179 (11)	0.0126 (11)
O6	0.0528 (17)	0.0480 (16)	0.0346 (16)	0.0074 (13)	0.0055 (13)	0.0145 (13)
K1	0.0282 (4)	0.0441 (6)	0.0339 (5)	0.0023 (6)	0.000	0.000
K2	0.0348 (3)	0.0312 (4)	0.0299 (4)	0.0003 (3)	0.0005 (3)	−0.0034 (3)
P1	0.0408 (6)	0.0328 (6)	0.0145 (5)	−0.0103 (6)	0.000	0.000
C1	0.044 (2)	0.0214 (18)	0.0277 (17)	−0.0030 (14)	0.0002 (15)	0.0030 (14)
C2	0.0219 (15)	0.036 (2)	0.0260 (17)	−0.0021 (15)	−0.0033 (13)	0.0058 (16)
C3	0.0267 (16)	0.0380 (19)	0.0296 (18)	−0.0031 (14)	−0.0025 (13)	0.0026 (16)
C4	0.0267 (15)	0.033 (2)	0.0299 (16)	0.0030 (14)	0.0044 (14)	0.0098 (13)
C5	0.0336 (18)	0.0290 (16)	0.0209 (14)	−0.0030 (14)	0.0033 (13)	−0.0010 (13)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	2.039 (3)	K1—O4^vi	2.618 (3)
Cu1—O1	2.039 (3)	K1—O4^vii	2.618 (3)
Cu1—N1	2.092 (3)	K1—O6^viii	2.718 (3)
Cu1—N1ⁱ	2.092 (3)	K1—O2^viii	2.771 (3)
Cu1—O3ⁱ	2.097 (3)	K2—O2^iv	2.717 (3)
Cu1—O3	2.097 (3)	K2—O3ⁱⁱⁱ	2.775 (3)
N1—C1	1.478 (4)	K2—O6^iv	2.788 (3)
N1—C3	1.482 (4)	K2—O1^ix	2.819 (3)
N1—C5	1.488 (4)	K2—O4ⁱⁱⁱ	3.040 (3)
O1—C2	1.270 (4)	K2—O2^ix	3.067 (3)
O1—K2ⁱⁱ	2.819 (3)	K2—C2^ix	3.225 (4)
O2—C2	1.222 (4)	K2—C4ⁱⁱⁱ	3.267 (4)
O2—K2ⁱⁱⁱ	2.717 (3)	P1—O5ⁱ	1.496 (2)
O2—K1	2.771 (3)	P1—C5ⁱ	1.807 (3)
O2—K2ⁱⁱ	3.067 (3)	P1—C5	1.807 (3)
O3—C4	1.255 (4)	C1—C2	1.501 (5)
O3—K2^iv	2.775 (3)	C1—H1A	0.9700
O4—C4	1.231 (4)	C1—H1B	0.9700
O4—K1^v	2.618 (3)	C2—K2ⁱⁱ	3.225 (4)
O4—K2^iv	3.040 (3)	C3—C4	1.515 (5)
O5—P1	1.496 (2)	C3—H3A	0.9700
O5—K2	2.779 (3)	C3—H3B	0.9700
O6—K1	2.718 (3)	C4—K2^iv	3.267 (4)
O6—K2ⁱⁱⁱ	2.788 (3)	C5—H5B	0.9700
O6—H6A	0.932 (19)	C5—H5A	0.9700
O6—H6B	0.94 (2)

O1ⁱ—Cu1—O1	95.35 (14)	O3ⁱⁱⁱ—K2—O1^ix	138.11 (8)
O1ⁱ—Cu1—N1	175.30 (10)	O5—K2—O1^ix	97.50 (9)
O1—Cu1—N1	81.57 (10)	O6^iv—K2—O1^ix	88.91 (9)
O1ⁱ—Cu1—N1ⁱ	81.57 (10)	O2^iv—K2—O4ⁱⁱⁱ	140.46 (8)
O1—Cu1—N1ⁱ	175.30 (10)	O3ⁱⁱⁱ—K2—O4ⁱⁱⁱ	44.19 (7)
N1—Cu1—N1ⁱ	101.72 (14)	O5—K2—O4ⁱⁱⁱ	83.36 (8)
O1ⁱ—Cu1—O3ⁱ	91.27 (10)	O6^iv—K2—O4ⁱⁱⁱ	106.25 (9)
O1—Cu1—O3ⁱ	94.30 (10)	O1^ix—K2—O4ⁱⁱⁱ	107.17 (8)
N1—Cu1—O3ⁱ	92.50 (10)	O2^iv—K2—O2^ix	136.78 (5)
N1ⁱ—Cu1—O3ⁱ	82.27 (10)	O3ⁱⁱⁱ—K2—O2^ix	94.85 (8)
O1ⁱ—Cu1—O3	94.30 (10)	O5—K2—O2^ix	124.36 (8)
O1—Cu1—O3	91.27 (10)	O6^iv—K2—O2^ix	68.10 (9)
N1—Cu1—O3	82.27 (10)	O1^ix—K2—O2^ix	43.61 (7)
N1ⁱ—Cu1—O3	92.50 (10)	O4ⁱⁱⁱ—K2—O2^ix	76.91 (8)
O3ⁱ—Cu1—O3	171.73 (14)	O2^iv—K2—C2^ix	121.76 (9)
C1—N1—C3	110.4 (3)	O3ⁱⁱⁱ—K2—C2^ix	116.68 (9)
C1—N1—C5	108.9 (3)	O5—K2—C2^ix	116.98 (9)
C3—N1—C5	114.1 (2)	O6^iv—K2—C2^ix	72.25 (9)
C1—N1—Cu1	102.74 (19)	O1^ix—K2—C2^ix	23.02 (8)
C3—N1—Cu1	108.5 (2)	O4ⁱⁱⁱ—K2—C2^ix	96.20 (9)
C5—N1—Cu1	111.52 (19)	O2^ix—K2—C2^ix	22.22 (7)
C2—O1—Cu1	113.5 (2)	O2^iv—K2—C4ⁱⁱⁱ	122.90 (9)
C2—O1—K2ⁱⁱ	96.7 (2)	O3ⁱⁱⁱ—K2—C4ⁱⁱⁱ	22.10 (7)
Cu1—O1—K2ⁱⁱ	139.57 (12)	O5—K2—C4ⁱⁱⁱ	95.70 (9)
C2—O2—K2ⁱⁱⁱ	138.2 (2)	O6^iv—K2—C4ⁱⁱⁱ	90.64 (9)
C2—O2—K1	120.0 (2)	O1^ix—K2—C4ⁱⁱⁱ	123.49 (8)
K2ⁱⁱⁱ—O2—K1	100.46 (8)	O4ⁱⁱⁱ—K2—C4ⁱⁱⁱ	22.13 (7)
C2—O2—K2ⁱⁱ	86.2 (2)	O2^ix—K2—C4ⁱⁱⁱ	84.76 (8)
K2ⁱⁱⁱ—O2—K2ⁱⁱ	108.21 (9)	C2^ix—K2—C4ⁱⁱⁱ	106.68 (9)
K1—O2—K2ⁱⁱ	85.89 (8)	O2^iv—K2—K1^ix	176.86 (6)
C4—O3—Cu1	113.0 (2)	O3ⁱⁱⁱ—K2—K1^ix	79.73 (7)
C4—O3—K2^iv	101.58 (19)	O5—K2—K1^ix	89.39 (7)
Cu1—O3—K2^iv	137.40 (12)	O6^iv—K2—K1^ix	104.17 (8)
C4—O4—K1^v	139.7 (2)	O1^ix—K2—K1^ix	66.08 (6)
C4—O4—K2^iv	89.3 (2)	O4ⁱⁱⁱ—K2—K1^ix	41.09 (5)
K1^v—O4—K2^iv	89.16 (9)	O2^ix—K2—K1^ix	43.94 (5)
P1—O5—K2	133.30 (16)	C2^ix—K2—K1^ix	57.76 (7)
K1—O6—K2ⁱⁱⁱ	100.04 (10)	C4ⁱⁱⁱ—K2—K1^ix	59.39 (6)
K1—O6—H6A	106 (3)	O2^iv—K2—K1^iv	40.23 (5)
K2ⁱⁱⁱ—O6—H6A	138 (3)	O3ⁱⁱⁱ—K2—K1^iv	96.76 (7)
K1—O6—H6B	109 (4)	O5—K2—K1^iv	127.58 (7)
K2ⁱⁱⁱ—O6—H6B	100 (3)	O6^iv—K2—K1^iv	39.37 (7)
H6A—O6—H6B	102 (4)	O1^ix—K2—K1^iv	95.67 (7)
O4^vi—K1—O4^vii	106.63 (14)	O4ⁱⁱⁱ—K2—K1^iv	138.99 (5)
O4^vi—K1—O6	108.58 (9)	O2^ix—K2—K1^iv	99.24 (6)
O4^vii—K1—O6	87.12 (9)	C2^ix—K2—K1^iv	91.93 (7)
O4^vi—K1—O6^viii	87.12 (9)	C4ⁱⁱⁱ—K2—K1^iv	117.81 (7)
O4^vii—K1—O6^viii	108.58 (9)	K1^ix—K2—K1^iv	141.64 (3)
O6—K1—O6^viii	154.05 (12)	O2^iv—K2—K2^xii	125.03 (7)
O4^vi—K1—O2	162.36 (8)	O3ⁱⁱⁱ—K2—K2^xii	66.12 (7)
O4^vii—K1—O2	89.57 (9)	O5—K2—K2^xii	146.49 (6)
O6—K1—O2	78.53 (9)	O6^iv—K2—K2^xii	46.87 (7)
O6^viii—K1—O2	80.99 (9)	O1^ix—K2—K2^xii	75.11 (6)
O4^vi—K1—O2^viii	89.57 (9)	O4ⁱⁱⁱ—K2—K2^xii	68.44 (7)
O4^vii—K1—O2^viii	162.36 (8)	O2^ix—K2—K2^xii	33.39 (5)
O6—K1—O2^viii	80.99 (9)	C2^ix—K2—K2^xii	52.12 (7)
O6^viii—K1—O2^viii	78.53 (9)	C4ⁱⁱⁱ—K2—K2^xii	64.45 (7)
O2—K1—O2^viii	75.37 (12)	K1^ix—K2—K2^xii	57.52 (3)
O4^vi—K1—K2^x	49.75 (7)	K1^iv—K2—K2^xii	85.90 (3)
O4^vii—K1—K2^x	137.69 (7)	O5—P1—O5ⁱ	118.4 (2)
O6—K1—K2^x	73.15 (8)	O5—P1—C5ⁱ	105.36 (15)
O6^viii—K1—K2^x	104.76 (8)	O5ⁱ—P1—C5ⁱ	109.36 (14)
O2—K1—K2^x	121.11 (7)	O5—P1—C5	109.36 (14)
O2^viii—K1—K2^x	50.17 (6)	O5ⁱ—P1—C5	105.37 (15)
O4^vi—K1—K2ⁱⁱ	137.69 (7)	C5ⁱ—P1—C5	108.8 (2)
O4^vii—K1—K2ⁱⁱ	49.75 (7)	N1—C1—C2	112.7 (3)
O6—K1—K2ⁱⁱ	104.76 (8)	N1—C1—H1A	109.1
O6^viii—K1—K2ⁱⁱ	73.15 (8)	C2—C1—H1A	109.1
O2—K1—K2ⁱⁱ	50.17 (6)	N1—C1—H1B	109.1
O2^viii—K1—K2ⁱⁱ	121.11 (7)	C2—C1—H1B	109.1
K2^x—K1—K2ⁱⁱ	171.03 (3)	H1A—C1—H1B	107.8
O4^vi—K1—K2ⁱⁱⁱ	148.97 (7)	O2—C2—O1	123.8 (3)
O4^vii—K1—K2ⁱⁱⁱ	79.86 (7)	O2—C2—C1	119.3 (3)
O6—K1—K2ⁱⁱⁱ	40.59 (6)	O1—C2—C1	116.9 (3)
O6^viii—K1—K2ⁱⁱⁱ	120.23 (7)	O2—C2—K2ⁱⁱ	71.6 (2)
O2—K1—K2ⁱⁱⁱ	39.30 (6)	O1—C2—K2ⁱⁱ	60.27 (17)
O2^viii—K1—K2ⁱⁱⁱ	82.64 (7)	C1—C2—K2ⁱⁱ	151.4 (2)
K2^x—K1—K2ⁱⁱⁱ	104.95 (4)	N1—C3—C4	114.1 (3)
K2ⁱⁱ—K1—K2ⁱⁱⁱ	69.69 (4)	N1—C3—H3A	108.7
O4^vi—K1—K2^xi	79.86 (7)	C4—C3—H3A	108.7
O4^vii—K1—K2^xi	148.97 (7)	N1—C3—H3B	108.7
O6—K1—K2^xi	120.23 (7)	C4—C3—H3B	108.7
O6^viii—K1—K2^xi	40.59 (6)	H3A—C3—H3B	107.6
O2—K1—K2^xi	82.64 (7)	O4—C4—O3	124.7 (3)
O2^viii—K1—K2^xi	39.30 (6)	O4—C4—C3	116.8 (3)
K2^x—K1—K2^xi	69.69 (4)	O3—C4—C3	118.5 (3)
K2ⁱⁱ—K1—K2^xi	104.95 (4)	O4—C4—K2^iv	68.5 (2)
K2ⁱⁱⁱ—K1—K2^xi	110.52 (5)	O3—C4—K2^iv	56.32 (16)
O2^iv—K2—O3ⁱⁱⁱ	102.89 (9)	C3—C4—K2^iv	174.0 (2)
O2^iv—K2—O5	88.23 (9)	N1—C5—P1	118.3 (2)
O3ⁱⁱⁱ—K2—O5	105.91 (9)	N1—C5—H5B	107.7
O2^iv—K2—O6^iv	78.25 (9)	P1—C5—H5B	107.7
O3ⁱⁱⁱ—K2—O6^iv	76.29 (9)	N1—C5—H5A	107.7
O5—K2—O6^iv	166.42 (9)	P1—C5—H5A	107.7
O2^iv—K2—O1^ix	112.22 (8)	H5B—C5—H5A	107.1

O1ⁱ—Cu1—N1—C1	79.0 (13)	K2ⁱⁱⁱ—O2—K1—K2ⁱⁱ	107.77 (9)
O1—Cu1—N1—C1	29.69 (19)	C2—O2—K1—K2ⁱⁱⁱ	169.1 (3)
N1ⁱ—Cu1—N1—C1	−146.9 (2)	K2ⁱⁱ—O2—K1—K2ⁱⁱⁱ	−107.77 (9)
O3ⁱ—Cu1—N1—C1	−64.3 (2)	C2—O2—K1—K2^xi	33.3 (3)
O3—Cu1—N1—C1	122.1 (2)	K2ⁱⁱⁱ—O2—K1—K2^xi	−135.71 (8)
O1ⁱ—Cu1—N1—C3	−38.0 (13)	K2ⁱⁱ—O2—K1—K2^xi	116.52 (6)
O1—Cu1—N1—C3	−87.3 (2)	P1—O5—K2—O2^iv	179.09 (18)
N1ⁱ—Cu1—N1—C3	96.1 (2)	P1—O5—K2—O3ⁱⁱⁱ	−78.01 (19)
O3ⁱ—Cu1—N1—C3	178.8 (2)	P1—O5—K2—O6^iv	−175.5 (3)
O3—Cu1—N1—C3	5.2 (2)	P1—O5—K2—O1^ix	66.90 (19)
O1ⁱ—Cu1—N1—C5	−164.5 (12)	P1—O5—K2—O4ⁱⁱⁱ	−39.62 (17)
O1—Cu1—N1—C5	146.2 (2)	P1—O5—K2—O2^ix	29.5 (2)
N1ⁱ—Cu1—N1—C5	−30.36 (16)	P1—O5—K2—C2^ix	54.0 (2)
O3ⁱ—Cu1—N1—C5	52.3 (2)	P1—O5—K2—C4ⁱⁱⁱ	−58.02 (19)
O3—Cu1—N1—C5	−121.3 (2)	P1—O5—K2—K1^ix	1.13 (17)
O1ⁱ—Cu1—O1—C2	162.8 (3)	P1—O5—K2—K1^iv	170.04 (14)
N1—Cu1—O1—C2	−20.8 (2)	P1—O5—K2—K2^xii	−7.4 (3)
N1ⁱ—Cu1—O1—C2	113.9 (12)	K2—O5—P1—O5ⁱ	−60.87 (14)
O3ⁱ—Cu1—O1—C2	71.1 (2)	K2—O5—P1—C5ⁱ	176.51 (17)
O3—Cu1—O1—C2	−102.8 (2)	K2—O5—P1—C5	59.7 (2)
O1ⁱ—Cu1—O1—K2ⁱⁱ	−62.18 (14)	C3—N1—C1—C2	79.8 (4)
N1—Cu1—O1—K2ⁱⁱ	114.25 (17)	C5—N1—C1—C2	−154.1 (3)
N1ⁱ—Cu1—O1—K2ⁱⁱ	−111.0 (12)	Cu1—N1—C1—C2	−35.8 (3)
O3ⁱ—Cu1—O1—K2ⁱⁱ	−153.86 (17)	K2ⁱⁱⁱ—O2—C2—O1	−144.8 (3)
O3—Cu1—O1—K2ⁱⁱ	32.26 (16)	K1—O2—C2—O1	51.4 (4)
O1ⁱ—Cu1—O3—C4	161.4 (2)	K2ⁱⁱ—O2—C2—O1	−31.6 (3)
O1—Cu1—O3—C4	65.9 (2)	K2ⁱⁱⁱ—O2—C2—C1	37.7 (5)
N1—Cu1—O3—C4	−15.4 (2)	K1—O2—C2—C1	−126.1 (3)
N1ⁱ—Cu1—O3—C4	−116.9 (2)	K2ⁱⁱ—O2—C2—C1	150.9 (3)
O3ⁱ—Cu1—O3—C4	−66.4 (2)	K2ⁱⁱⁱ—O2—C2—K2ⁱⁱ	−113.2 (3)
O1ⁱ—Cu1—O3—K2^iv	19.87 (17)	K1—O2—C2—K2ⁱⁱ	83.01 (17)
O1—Cu1—O3—K2^iv	−75.59 (17)	Cu1—O1—C2—O2	−172.6 (3)
N1—Cu1—O3—K2^iv	−156.91 (18)	K2ⁱⁱ—O1—C2—O2	34.9 (3)
N1ⁱ—Cu1—O3—K2^iv	101.60 (17)	Cu1—O1—C2—C1	5.0 (4)
O3ⁱ—Cu1—O3—K2^iv	152.06 (16)	K2ⁱⁱ—O1—C2—C1	−147.5 (3)
K2ⁱⁱⁱ—O6—K1—O4^vi	175.67 (8)	Cu1—O1—C2—K2ⁱⁱ	152.51 (19)
K2ⁱⁱⁱ—O6—K1—O4^vii	−77.75 (11)	N1—C1—C2—O2	−159.6 (3)
K2ⁱⁱⁱ—O6—K1—O6^viii	50.96 (7)	N1—C1—C2—O1	22.7 (4)
K2ⁱⁱⁱ—O6—K1—O2	12.40 (8)	N1—C1—C2—K2ⁱⁱ	−53.8 (6)
K2ⁱⁱⁱ—O6—K1—O2^viii	89.18 (10)	C1—N1—C3—C4	−108.3 (3)
K2ⁱⁱⁱ—O6—K1—K2^x	140.16 (9)	C5—N1—C3—C4	128.6 (3)
K2ⁱⁱⁱ—O6—K1—K2ⁱⁱ	−30.77 (9)	Cu1—N1—C3—C4	3.6 (3)
K2ⁱⁱⁱ—O6—K1—K2^xi	86.76 (10)	K1^v—O4—C4—O3	92.5 (5)
C2—O2—K1—O4^vi	40.5 (5)	K2^iv—O4—C4—O3	4.6 (3)
K2ⁱⁱⁱ—O2—K1—O4^vi	−128.5 (3)	K1^v—O4—C4—C3	−89.3 (4)
K2ⁱⁱ—O2—K1—O4^vi	123.7 (3)	K2^iv—O4—C4—C3	−177.2 (2)
C2—O2—K1—O4^vii	−116.5 (3)	K1^v—O4—C4—K2^iv	87.9 (3)
K2ⁱⁱⁱ—O2—K1—O4^vii	74.40 (9)	Cu1—O3—C4—O4	−159.7 (3)
K2ⁱⁱ—O2—K1—O4^vii	−33.37 (7)	K2^iv—O3—C4—O4	−5.2 (4)
C2—O2—K1—O6	156.3 (3)	Cu1—O3—C4—C3	22.1 (3)
K2ⁱⁱⁱ—O2—K1—O6	−12.74 (9)	K2^iv—O3—C4—C3	176.7 (2)
K2ⁱⁱ—O2—K1—O6	−120.52 (9)	Cu1—O3—C4—K2^iv	−154.5 (2)
C2—O2—K1—O6^viii	−7.7 (3)	N1—C3—C4—O4	163.9 (3)
K2ⁱⁱⁱ—O2—K1—O6^viii	−176.70 (10)	N1—C3—C4—O3	−17.8 (4)
K2ⁱⁱ—O2—K1—O6^viii	75.52 (8)	N1—C3—C4—K2^iv	10 (2)
C2—O2—K1—O2^viii	72.7 (3)	C1—N1—C5—P1	176.6 (2)
K2ⁱⁱⁱ—O2—K1—O2^viii	−96.30 (12)	C3—N1—C5—P1	−59.6 (3)
K2ⁱⁱ—O2—K1—O2^viii	155.92 (11)	Cu1—N1—C5—P1	63.8 (3)
C2—O2—K1—K2^x	94.2 (3)	O5—P1—C5—N1	78.5 (3)
K2ⁱⁱⁱ—O2—K1—K2^x	−74.84 (9)	O5ⁱ—P1—C5—N1	−153.3 (2)
K2ⁱⁱ—O2—K1—K2^x	177.388 (15)	C5ⁱ—P1—C5—N1	−36.14 (18)
C2—O2—K1—K2ⁱⁱ	−83.2 (3)

Symmetry codes: (i) −x+1, −y, z; (ii) x, y, z−1; (iii) −x+3/2, y+1/2, −z+1; (iv) −x+3/2, y−1/2, −z+1; (v) −x+3/2, y−1/2, −z; (vi) x−1/2, −y+1/2, −z; (vii) −x+3/2, y+1/2, −z; (viii) −x+1, −y+1, z; (ix) x, y, z+1; (x) −x+1, −y+1, z−1; (xi) x−1/2, −y+1/2, −z+1; (xii) −x+3/2, y+1/2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O5^xiii	0.93 (2)	1.75 (4)	2.682 (4)	173 (4)
O6—H6B···O1^viii	0.94 (2)	2.02 (5)	2.860 (4)	148 (4)

Symmetry codes: (viii) −x+1, −y+1, z; (xiii) x, y+1, z−1.

Experimental details

Crystal data
Chemical formula	K₃[Cu(C₁₀H₁₂N₂O₁₀P)]·2H₂O
M_r	568.06
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	273
a, b, c (Å)	11.880 (7), 8.332 (5), 9.681 (6)
V (Å³)	958.2 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.94
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.643, 0.760
No. of measured, independent and observed [I > 2σ(I)] reflections	3814, 1686, 1553
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.065, 1.07
No. of reflections	1686
No. of parameters	141
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.27
Absolute structure	Flack (1983), 671 Friedel pairs
Absolute structure parameter	−0.016 (19)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).