Disodium μ-triethyl­enetetra­amine­hexaacetato-bis­[oxovanadate(IV)] hexahydrate

The crystals structure of the title heterometallic coordination compound, Na₂[(C₁₈H₂₄N₄O₁₂)(VO)₂]·6H₂O, is built of Na⁺ cations, binuclear [C₁₈H₂₄N₄O₁₂(VO)₂]²⁻ dianions and water mol­ecules. The cations and anion occupy special positions at inversion centers. The V atom has an octahedral coordination environment formed by the vanadyl oxo atom [V=O 1.618 (3) Å], two N [V—N 2.174 (4) and 2.289 (4) Å] and three O atoms [V—O 1.993 (3), 1.998 (3) and 2.001 (3) Å] of the amino-carboxyl­ato group.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.067
• wR factor = 0.151
• Data-to-parameter ratio = 10.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



ABSTM_02  Alert B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
          Tmin and Tmax reported:      0.390     0.862
          Tmin' and Tmax expected:      0.786     0.899
          RR' =      0.517
          Please check that your absorption correction is appropriate.


 Alert Level C:



PLAT_731  Alert C Bond    Calc     0.87(3), Rep   0.860(10) ......       3.00 su-Rat
                     O1W  -H1W2    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
                     O2W  -H2W1    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Rat
                     O2W  -H2W2    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
                     O3W  -H3W1    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
                     O3W  -H3W2    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.87(3), Rep   0.860(10) ......       3.00 su-Rat
                     O1W  -H1W2    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
                     O1W  -H1W1    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
                     O2W  -H2W1    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Rat
                     O2W  -H2W2    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
                     O3W  -H3W1    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
                     O3W  -H3W2    1.555   1.555

PLAT_736  Alert C H...A   Calc     1.94(3), Rep   1.940(10) ......       3.00 su-Rat
                     H1W1 -O5      1.555   1.545

PLAT_736  Alert C H...A   Calc     1.87(3), Rep   1.870(10) ......       3.00 su-Rat
                     H2W1 -O2      1.555   1.655


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 13 Alert Level C = Please check

---

S1. Comment

We have recently reported several heterometallic coordination compounds in which main-group metal atoms are linked to transition metals through carboxylato groups (Long et al., 2002; Ren et al., 2002). Sodium µ-triethylenetetraaminehexaacetatodi[oxovanadate] was reported earlier as a decahydrate (Fallon & Gatehouse, 1976). In this paper, we report the structure of the hexahydrate form, (I), of this complex,

The dinuclear anion and both Na⁺ cations occupy special positions at inversion centers (one of the Na⁺ cations is disordered in the vicinity of the inversion center). The V(IV) atom has an octahedral coordination environment, defined by the vanadyl oxo atom, two N and three O atoms of the aminoacetato anion (Fig. 1). The V=O double-bond distance [V1=O7 1.618 (3) Å] is significantly shorter than the other three covalent V—O bonds [1.993 (3), 1.998 (3), 2.001 (3) Å]. The V—N bond trans to the V=O bond [V1—N2 2.289 (4) Å] is somewhat longer than the other V—N bond [V1—N1 2.174 (4) Å]. The distances are similar to those found in the decahydrate, and the geometry of the V atom is also the same. In the decahydrate, the V=O double bond is 1.605 (8) Å; the V—N bond trans to the vanadyl bond is 2.294 (7) Å (Fallon & Gatehouse, 1976).

One of the Na⁺ cations (Na2) is coordinated by six water molecules whereas the other (Na1) is only penta-coordinate. Four of the neighbors of the Na1 atom are water O atoms bridging it to the Na2 atom, the fifth being a carbonyl O atom belonging to the aminoacid ligand (Fig. 2). The bridging pattern gives rise to a tightly-held network structure. The packing of the hexahydrate is more compact than that of the decahydrate, as noted from the higher density.

The blue colour of the title complex leaves no doubt that the V atom oxidation state is 4+. It is not clear, however, what is the exact nature of the reducing agent in the process of its synthesis from metavanadate where V has an oxidation state of 5. One may guess, though, that under hydrothermal condition the carboxylate group or even water may exhibit redox activity.

S2. Experimental

The compound was synthesized hydrothermally from the reaction of ammonium metavanadate (0.12 g, 1 mmol), triethylenetetraaminehexaacetic acid (0.15 g, 0.5 mmol) and sodium hydroxide (0.12 g, 3 mmol); the pH of the solution was approximately 7. The solution was heated in a steel bomb to 453 K and was kept at this temperature for 72 h. The bomb was then cooled to room temperature at the rate of 5 K per hour. Blue polyhedral crystals separated from the solution in about 50% yield.

S3. Refinement

One of the two independent Na atoms (Na1) is disordered over an inversion center at (1/2,0,1/2); the PART −1 command in SHELXL97 was used for its refinement. The water H atoms were located and refined subject to the O—H = 0.85 (1) and H···H = 1.39 (1) Å constraints; their temperature factors were set to 1.2 times those of the equivalent isotropic temperature factors of the parent O atoms. The C-bound H atoms were positioned geometrically (C—H = 0.97 Å) and were included in the refinement in the riding model approximation; their temperature factors were treated similarly as those of the water H atoms.

Although the diffraction data were collected up to a 2θ of 55°, the use of the reflections with 2θ > 50° led to an R-index higher than 0.070. The 2θ limit was therefore set to 50° in the final refinement.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-II (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. ORTEP (Johnson, 1976) plot of the fragment of the structure of sodium µ-triethylenetetraaminehexaacetatodi[oxovanadate(IV)] hexahydrate with displacement ellipsoids drawn at the 50% probability level. Only one component of the disordered Na1 atom is shown.
	Fig. 2. ORTEP (Johnson, 1976) plot of the water- and carbonyl O-linked cationic chain. H atoms are drawn as spheres of arbitrary radii.

Disodium µ-triethylenetetraaminehexaacetatodi[oxovanadate(IV)] hexahydrate

Crystal data

(Na^+)2·C18H24N4O14V2^2^−·6(H2O)	F(000) = 800
Mr = 776.37	Dx = 1.756 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.7086 (2) Å	Cell parameters from 2808 reflections
b = 10.5746 (3) Å	θ = 2.0–27.0°
c = 20.9333 (5) Å	µ = 0.76 mm^−1
β = 98.678 (1)°	T = 298 K
V = 1468.02 (7) Å^3	Block, blue
Z = 2	0.31 × 0.21 × 0.14 mm

Data collection

Bruker APEX area-detector diffractometer	2485 independent reflections
Radiation source: fine-focus sealed tube	2162 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ϕ and ω scan	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −5→7
Tmin = 0.390, Tmax = 0.862	k = −12→11
7204 measured reflections	l = −13→24

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ^2(Fo^2) + (0.0674P)^2] where P = (Fo^2 + 2Fc^2)/3
2485 reflections	(Δ/σ)max < 0.001
232 parameters	Δρmax = 0.58 e Å^−3
9 restraints	Δρmin = −0.35 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
V1	0.6958 (1)	0.57000 (7)	0.63400 (3)	0.0230 (3)
Na1	0.497 (1)	0.0280 (5)	0.5121 (3)	0.047 (2)	0.50
Na2	1.0000	0.0000	0.5000	0.0411 (7)
O1	0.5956 (5)	0.3946 (3)	0.6452 (2)	0.033 (1)
O2	0.5411 (5)	0.2105 (4)	0.5934 (2)	0.052 (1)
O3	0.5910 (5)	0.6197 (3)	0.7146 (1)	0.035 (1)
O4	0.5859 (5)	0.5860 (4)	0.8190 (2)	0.043 (1)
O5	0.8826 (5)	0.7178 (3)	0.6355 (1)	0.029 (1)
O6	1.1590 (6)	0.8212 (4)	0.6765 (2)	0.048 (1)
O7	0.5294 (5)	0.6239 (3)	0.5764 (2)	0.036 (1)
O1w	0.7775 (6)	−0.0575 (3)	0.5700 (1)	0.035 (1)
O2w	1.1582 (6)	0.1229 (4)	0.5877 (2)	0.047 (1)
O3w	1.2957 (6)	−0.1370 (4)	0.5565 (2)	0.049 (1)
N1	0.8947 (5)	0.4670 (3)	0.5796 (2)	0.020 (1)
N2	0.9500 (6)	0.5210 (3)	0.7160 (2)	0.023 (1)
C1	0.7892 (7)	0.3451 (4)	0.5614 (2)	0.027 (1)
C2	0.6302 (7)	0.3125 (5)	0.6032 (2)	0.030 (1)
C3	0.8445 (7)	0.4848 (5)	0.7710 (2)	0.031 (1)
C4	0.6604 (8)	0.5687 (5)	0.7694 (2)	0.033 (1)
C5	1.0730 (7)	0.6363 (5)	0.7310 (2)	0.028 (1)
C6	1.0411 (7)	0.7339 (5)	0.6778 (2)	0.029 (1)
C7	1.0941 (7)	0.4463 (4)	0.6227 (2)	0.022 (1)
C8	1.0664 (7)	0.4166 (4)	0.6918 (2)	0.028 (1)
C9	0.9310 (7)	0.5359 (4)	0.5199 (2)	0.024 (1)
H1w1	0.807 (7)	−0.131 (2)	0.585 (2)	0.042*
H1w2	0.803 (7)	−0.003 (3)	0.601 (1)	0.042*
H2w1	1.277 (4)	0.152 (5)	0.591 (2)	0.057*
H2w2	1.132 (7)	0.099 (5)	0.624 (1)	0.057*
H3w1	1.373 (7)	−0.201 (4)	0.562 (2)	0.058*
H3w2	1.239 (7)	−0.128 (5)	0.590 (2)	0.058*
H1a	0.8881	0.2776	0.5648	0.032*
H1b	0.7256	0.3498	0.5167	0.032*
H3a	0.9339	0.4958	0.8116	0.037*
H3b	0.8040	0.3967	0.7672	0.037*
H5a	1.2144	0.6128	0.7388	0.034*
H5b	1.0400	0.6736	0.7704	0.034*
H7a	1.1764	0.5216	0.6223	0.026*
H7b	1.1649	0.3769	0.6057	0.026*
H8a	0.9946	0.3373	0.6933	0.033*
H8b	1.1969	0.4085	0.7187	0.033*
H9a	0.9911	0.6175	0.5322	0.029*
H9b	0.8024	0.5512	0.4929	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0178 (5)	0.0342 (5)	0.0176 (4)	0.0054 (3)	0.0045 (3)	0.0035 (3)
Na1	0.035 (2)	0.051 (5)	0.052 (5)	0.001 (3)	−0.001 (3)	0.014 (3)
Na2	0.032 (2)	0.060 (2)	0.033 (1)	−0.010 (1)	0.011 (1)	−0.008 (1)
O1	0.026 (2)	0.040 (2)	0.035 (2)	−0.004 (2)	0.011 (2)	0.003 (2)
O2	0.037 (2)	0.048 (2)	0.072 (3)	−0.018 (2)	0.017 (2)	−0.002 (2)
O3	0.033 (2)	0.052 (2)	0.024 (2)	0.018 (2)	0.011 (2)	0.004 (2)
O4	0.040 (2)	0.068 (3)	0.026 (2)	0.007 (2)	0.017 (2)	−0.001 (2)
O5	0.031 (2)	0.032 (2)	0.024 (2)	−0.002 (2)	0.002 (1)	0.004 (1)
O6	0.053 (3)	0.052 (2)	0.035 (2)	−0.021 (2)	−0.003 (2)	0.005 (2)
O7	0.026 (2)	0.051 (2)	0.030 (2)	0.010 (2)	0.001 (2)	0.004 (2)
O1w	0.039 (2)	0.037 (2)	0.029 (2)	−0.004 (2)	0.006 (2)	0.006 (2)
O2w	0.040 (3)	0.063 (3)	0.042 (2)	−0.013 (2)	0.016 (2)	−0.006 (2)
O3w	0.049 (3)	0.053 (3)	0.047 (2)	0.010 (2)	0.013 (2)	0.005 (2)
N1	0.018 (2)	0.027 (2)	0.016 (2)	0.001 (2)	0.003 (2)	0.003 (2)
N2	0.019 (2)	0.033 (2)	0.019 (2)	0.004 (2)	0.008 (2)	0.003 (2)
C1	0.025 (3)	0.031 (3)	0.024 (2)	−0.006 (2)	0.004 (2)	−0.001 (2)
C2	0.019 (3)	0.037 (3)	0.031 (2)	−0.003 (2)	−0.003 (2)	0.009 (2)
C3	0.026 (3)	0.049 (3)	0.018 (2)	0.003 (2)	0.007 (2)	0.004 (2)
C4	0.032 (3)	0.038 (3)	0.031 (2)	0.002 (2)	0.010 (2)	−0.003 (2)
C5	0.020 (3)	0.045 (3)	0.019 (2)	0.000 (2)	−0.001 (2)	−0.003 (2)
C6	0.029 (3)	0.036 (3)	0.021 (2)	−0.005 (2)	0.003 (2)	−0.007 (2)
C7	0.014 (2)	0.030 (2)	0.022 (2)	0.003 (2)	0.004 (2)	0.000 (2)
C8	0.024 (3)	0.036 (3)	0.022 (2)	0.006 (2)	0.001 (2)	0.006 (2)
C9	0.024 (3)	0.030 (3)	0.018 (2)	0.002 (2)	0.005 (2)	0.004 (2)

Geometric parameters (Å, º)

V1—O1	1.998 (3)	N2—C5	1.479 (6)
V1—O3	1.993 (3)	N2—C8	1.485 (6)
V1—O5	2.001 (3)	N2—C3	1.489 (5)
V1—O7	1.618 (3)	C1—C2	1.518 (6)
V1—N1	2.174 (4)	C3—C4	1.517 (7)
V1—N2	2.289 (4)	C5—C6	1.511 (6)
Na1—O2	2.561 (6)	C7—C8	1.519 (6)
Na1—O1w	2.264 (8)	C9—C9^iv	1.536 (8)
Na1—O1w^i	2.344 (8)	O1w—H1w1	0.85 (1)
Na1—O3w^ii	2.475 (9)	O1w—H1w2	0.86 (1)
Na1—O3w^iii	2.433 (9)	O2w—H2w1	0.85 (1)
Na2—O1w	2.324 (3)	O2w—H2w2	0.84 (1)
Na2—O1w^iii	2.324 (3)	O3w—H3w1	0.85 (1)
Na2—O2w	2.366 (4)	O3w—H3w2	0.85 (1)
Na2—O2w^iii	2.366 (4)	C1—H1a	0.97
Na2—O3w	2.593 (4)	C1—H1b	0.97
Na2—O3w^iii	2.593 (4)	C3—H3a	0.97
O1—C2	1.281 (6)	C3—H3b	0.97
O2—C2	1.235 (6)	C5—H5a	0.97
O3—C4	1.289 (6)	C5—H5b	0.97
O4—C4	1.232 (5)	C7—H7a	0.97
O5—C6	1.288 (5)	C7—H7b	0.97
O6—C6	1.219 (6)	C8—H8a	0.97
N1—C1	1.492 (5)	C8—H8b	0.97
N1—C9	1.498 (5)	C9—H9a	0.97
N1—C7	1.513 (5)	C9—H9b	0.97
O1—V1—O3	88.7 (1)	O2—C2—O1	125.0 (5)
O1—V1—O5	160.8 (1)	O2—C2—C1	117.8 (4)
O1—V1—O7	102.0 (2)	O1—C2—C1	117.2 (4)
O1—V1—N1	80.8 (1)	N2—C3—C4	108.2 (4)
O1—V1—N2	85.9 (1)	O4—C4—O3	123.4 (5)
O3—V1—O5	94.6 (1)	O4—C4—C3	120.0 (4)
O3—V1—O7	104.2 (2)	O3—C4—C3	116.6 (4)
O3—V1—N1	154.0 (1)	N2—C5—C6	113.2 (4)
O3—V1—N2	75.1 (1)	O6—C6—O5	123.9 (4)
O5—V1—O7	95.5 (2)	O6—C6—C5	120.9 (4)
O5—V1—N1	88.1 (1)	O5—C6—C5	115.3 (4)
O5—V1—N2	76.8 (1)	N1—C7—C8	112.0 (3)
O7—V1—N1	101.2 (1)	N2—C8—C7	108.5 (3)
O7—V1—N2	172.1 (2)	N1—C9—C9^iv	113.5 (4)
N1—V1—N2	80.4 (1)	Na1—O1w—H1w1	134 (3)
O2—Na1—O1w	86.7 (2)	Na2—O1w—H1w1	110 (3)
O2—Na1—O1w^i	112.7 (3)	Na1^i—O1w—H1w1	121 (3)
O2—Na1—O3w^ii	107.2 (3)	Na1—O1w—H1w2	101 (3)
O2—Na1—O3w^iii	91.0 (2)	Na2—O1w—H1w2	103 (3)
O1w—Na1—O1w^i	160.5 (2)	Na1^i—O1w—H1w2	120 (3)
O1w—Na1—O3w^iii	90.2 (3)	H1w1—O1w—H1w2	109 (2)
O1w—Na1—O3w^ii	88.5 (3)	Na2—O2w—H2w1	125 (3)
O1w^i—Na1—O3w^ii	87.4 (3)	Na2—O2w—H2w2	114 (3)
O1w^i—Na1—O3w^iii	87.7 (3)	H2w1—O2w—H2w2	111 (2)
O3w^ii—Na1—O3w^iii	161.6 (2)	Na1^iii—O3w—H3w1	94 (3)
O1w—Na2—O1w^iii	180.0	Na1^v—O3w—H3w1	105 (4)
O1w—Na2—O2w	84.9 (1)	Na2—O3w—H3w1	156 (4)
O1w—Na2—O2w^iii	95.1 (1)	Na1^iii—O3w—H3w2	143 (4)
O1w—Na2—O3w	95.0 (1)	Na1^v—O3w—H3w2	124 (4)
O1w—Na2—O3w^iii	85.1 (1)	Na2—O3w—H3w2	85 (3)
O1w^iii—Na2—O2w	95.1 (1)	H3w1—O3w—H3w2	109 (2)
O1w^iii—Na2—O2w^iii	84.9 (1)	N1—C1—H1a	108.9
O1w^iii—Na2—O3w	85.1 (1)	C2—C1—H1a	108.9
O1w^iii—Na2—O3w^iii	95.0 (1)	N1—C1—H1b	108.9
O2w—Na2—O2w^iii	180.0 (1)	C2—C1—H1b	108.9
O2w—Na2—O3w^iii	105.6 (1)	H1a—C1—H1b	107.7
O2w—Na2—O3w	74.4 (1)	N2—C3—H3a	110.1
O2w^iii—Na2—O3w^iii	74.4 (1)	C4—C3—H3a	110.1
O2w^iii—Na2—O3w	105.6 (1)	N2—C3—H3b	110.1
O3w—Na2—O3w^iii	180.0 (2)	C4—C3—H3b	110.1
C2—O1—V1	116.8 (3)	H3a—C3—H3b	108.4
C2—O2—Na1	140.6 (4)	N2—C5—H5a	108.9
C4—O3—V1	121.1 (3)	C6—C5—H5a	108.9
C6—O5—V1	124.4 (3)	N2—C5—H5b	108.9
Na1—O1w—Na2	96.8 (2)	C6—C5—H5b	108.9
Na2—O1w—Na1^i	90.7 (2)	H5a—C5—H5b	107.7
Na1^iii—O3w—Na2	86.0 (2)	N1—C7—H7a	109.2
Na1^v—O3w—Na2	81.9 (2)	C8—C7—H7a	109.2
C1—N1—C9	109.8 (3)	N1—C7—H7b	109.2
C1—N1—C7	111.7 (3)	C8—C7—H7b	109.2
C9—N1—C7	109.2 (3)	H7a—C7—H7b	107.9
C1—N1—V1	105.1 (3)	N2—C8—H8a	110.0
C9—N1—V1	112.6 (3)	C7—C8—H8a	110.0
C7—N1—V1	108.5 (2)	N2—C8—H8b	110.0
C5—N2—C8	112.3 (4)	C7—C8—H8b	110.0
C5—N2—C3	111.3 (3)	H8a—C8—H8b	108.4
C8—N2—C3	114.1 (3)	N1—C9—H9a	108.9
C5—N2—V1	107.5 (3)	C9^iv—C9—H9a	108.9
C8—N2—V1	106.4 (2)	N1—C9—H9b	108.9
C3—N2—V1	104.5 (3)	C9^iv—C9—H9b	108.9
N1—C1—C2	113.4 (4)	H9a—C9—H9b	107.7
O7—V1—O1—C2	77.5 (3)	N2—V1—N1—C9	−131.5 (3)
O3—V1—O1—C2	−178.2 (3)	O7—V1—N1—C7	161.6 (3)
O5—V1—O1—C2	−77.7 (5)	O3—V1—N1—C7	−30.4 (5)
N1—V1—O1—C2	−22.1 (3)	O1—V1—N1—C7	−97.9 (3)
N2—V1—O1—C2	−103.1 (3)	O5—V1—N1—C7	66.3 (3)
O1w—Na1—O2—C2	86.5 (6)	N2—V1—N1—C7	−10.6 (2)
O1w^i—Na1—O2—C2	−91.6 (6)	O3—V1—N2—C5	−86.1 (3)
O3w^iii—Na1—O2—C2	−3.6 (6)	O1—V1—N2—C5	−175.9 (3)
O3w^ii—Na1—O2—C2	173.9 (5)	O5—V1—N2—C5	12.4 (3)
O7—V1—O3—C4	164.4 (4)	N1—V1—N2—C5	102.8 (3)
O1—V1—O3—C4	62.3 (4)	O3—V1—N2—C8	153.3 (3)
O5—V1—O3—C4	−98.7 (4)	O1—V1—N2—C8	63.6 (3)
N1—V1—O3—C4	−3.5 (6)	O5—V1—N2—C8	−108.1 (3)
N2—V1—O3—C4	−23.8 (4)	N1—V1—N2—C8	−17.8 (3)
O7—V1—O5—C6	173.3 (3)	O3—V1—N2—C3	32.2 (3)
O3—V1—O5—C6	68.5 (3)	O1—V1—N2—C3	−57.5 (3)
O1—V1—O5—C6	−31.0 (6)	O5—V1—N2—C3	130.8 (3)
N1—V1—O5—C6	−85.6 (3)	N1—V1—N2—C3	−138.9 (3)
N2—V1—O5—C6	−5.0 (3)	C9—N1—C1—C2	−141.3 (4)
O1w^i—Na1—O1w—Na2	73 (1)	C7—N1—C1—C2	97.5 (4)
O3w^iii—Na1—O1w—Na2	−11.2 (2)	V1—N1—C1—C2	−20.0 (4)
O3w^ii—Na1—O1w—Na2	150.5 (2)	Na1—O2—C2—O1	168.4 (4)
O2—Na1—O1w—Na2	−102.1 (2)	Na1—O2—C2—C1	−9.9 (8)
O3w^iii—Na1—O1w—Na1^i	−84 (1)	V1—O1—C2—O2	−161.9 (4)
O3w^ii—Na1—O1w—Na1^i	78 (1)	V1—O1—C2—C1	16.4 (5)
O2—Na1—O1w—Na1^i	−175 (1)	N1—C1—C2—O2	−177.1 (4)
O2w—Na2—O1w—Na1	116.7 (2)	N1—C1—C2—O1	4.6 (6)
O2w^iii—Na2—O1w—Na1	−63.3 (2)	C5—N2—C3—C4	79.3 (5)
O3w^iii—Na2—O1w—Na1	10.5 (2)	C8—N2—C3—C4	−152.4 (4)
O3w—Na2—O1w—Na1	−169.5 (2)	V1—N2—C3—C4	−36.5 (4)
O2w—Na2—O1w—Na1^i	135.3 (2)	V1—O3—C4—O4	−171.8 (4)
O2w^iii—Na2—O1w—Na1^i	−44.7 (2)	V1—O3—C4—C3	8.7 (6)
O3w^iii—Na2—O1w—Na1^i	29.1 (2)	N2—C3—C4—O4	−157.0 (4)
O3w—Na2—O1w—Na1^i	−150.9 (2)	N2—C3—C4—O3	22.4 (6)
O1w—Na2—O3w—Na1^iii	−170.3 (2)	C8—N2—C5—C6	98.8 (4)
O1w^iii—Na2—O3w—Na1^iii	9.7 (2)	C3—N2—C5—C6	−131.9 (4)
O2w—Na2—O3w—Na1^iii	−87.0 (2)	V1—N2—C5—C6	−18.0 (4)
O2w^iii—Na2—O3w—Na1^iii	93.0 (2)	V1—O5—C6—O6	176.5 (4)
O1w—Na2—O3w—Na1^v	−152.3 (2)	V1—O5—C6—C5	−4.1 (5)
O1w^iii—Na2—O3w—Na1^v	27.7 (2)	N2—C5—C6—O6	−164.7 (4)
O2w—Na2—O3w—Na1^v	−69.0 (2)	N2—C5—C6—O5	15.8 (6)
O2w^iii—Na2—O3w—Na1^v	111.0 (2)	C1—N1—C7—C8	−76.8 (4)
O7—V1—N1—C1	−78.9 (3)	C9—N1—C7—C8	161.5 (4)
O3—V1—N1—C1	89.2 (4)	V1—N1—C7—C8	38.6 (4)
O1—V1—N1—C1	21.7 (2)	C5—N2—C8—C7	−74.6 (4)
O5—V1—N1—C1	−174.1 (3)	C3—N2—C8—C7	157.6 (4)
N2—V1—N1—C1	109.0 (3)	V1—N2—C8—C7	42.8 (4)
O7—V1—N1—C9	40.7 (3)	N1—C7—C8—N2	−56.4 (5)
O3—V1—N1—C9	−151.3 (3)	C1—N1—C9—C9^iv	−62.5 (6)
O1—V1—N1—C9	141.2 (3)	C7—N1—C9—C9^iv	60.2 (6)
O5—V1—N1—C9	−54.6 (3)	V1—N1—C9—C9^iv	−179.3 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w2···O4^vi	0.86 (1)	1.98 (2)	2.811 (5)	164 (4)
O1w—H1w1···O5^vii	0.85 (1)	1.94 (1)	2.782 (4)	170 (4)
O2w—H2w1···O2^v	0.85 (1)	1.87 (1)	2.716 (5)	176 (5)
O2w—H2w2···O4^vi	0.84 (1)	2.03 (3)	2.760 (5)	145 (5)
O3w—H3w1···O7^viii	0.85 (1)	2.12 (2)	2.971 (5)	172 (5)
O3w—H3w2···O6^vii	0.85 (1)	2.04 (2)	2.836 (5)	156 (4)

Symmetry codes: (v) x+1, y, z; (vi) −x+3/2, y−1/2, −z+3/2; (vii) x, y−1, z; (viii) x+1, y−1, z.