Bis(ethyl­ene­di­ammonium) decaaqua­disodium decavanadate, (C₂H₁₀N₂)₂[Na₂(H₂O)₁₀][V₁₀O₂₈]

In the title compound, the decavanadate anion, [V₁₀O₂₈]^6-, and the bridged [Na₂(H₂O)₁₀]²⁺ dication lie across inversion centers. The charge balance is achieved by ethyl­ene­di­ammonium cations, H₃NCH₂CH₂NH₃²⁺, which are disordered. The decavanadate anions are surrounded by the [Na₂(H₂O)₁₀]²⁺ dications, thus forming layers, and the ethyl­ene­diammonium cations are located between these layers.

S1. Comment

Polyoxometalate chemistry has a long history and still attracts much attention owing to the varied applications of polyoxometalates in catalysis, biology, medicine, geochemistry and materials science (Pope et al., 1991; Pope et al., 1994; Rhule et al., 1998). The polyoxovanadates compose an important part of the polyoxometalate group, the decavanadate anion being ?particularly well studied? Many compounds involving decavanadate polyanions of the types [V₁₀O₂₈]⁶⁻, [HV₁₀O₂₈]⁵⁻, [H₂V₁₀O₂₈]⁴⁻, [H₃V₁₀O₂₈]³⁻ and [H₄V₁₀O₂₈]²⁻ have been reported (Arrieta et al., 1992; Durif et al., 1980; Evans et al., 1966; Zhang et al., 2004; Lee et al., 2004; Iida et al., 2004). The present work is part of a series of studies aimed at synthesizing new polyoxovanadates. The experimental powder pattern, IR spectrum and ICP–AES (inductively coupled plasma atomic emission spectrometry) of this compound are in good agreement with the results of the single-crystal X-ray diffraction analysis.

The asymmetric unit in the title compound includes one-half of a [V₁₀O₂₈]⁶⁻ anion, one-half of an [Na₂(H₂O)₁₀]²⁺ cation and a disordered H₃NCH₂CH₂NH₃²⁺ cation (Fig. 1). The structure of the decavanadate anion can be described as comprising six VO₆ octahedra (involving atoms V1, V4, V5, V1ⁱ, V4ⁱ and V5ⁱ), forming a plane with four VO₆ octahedra (those centered on atoms V2, V3, V2¹ and V3ⁱ), linked via edge-sharing, as reported by Evans (1966) [symmetry code: (i) 1 − x, 1 − y, −z]. The [Na₂(H₂O)₁₀]²⁺ dication comprises a pair of edge-sharing NaO₆ octahedra, each Na atom being surrounded by six water molecules, two of which act as bridges between the octahedra (Fig. 1 and Table 1). Such a structural unit has also been reported in Na₂CO₃.10H₂O (Taga et al., 1969) and Cs₄[Na₂(H₂O)₁₀]V₁₀O₂₈ (Piro et al., 2003).

The decavanadate anion and the [Na₂(H₂O)₁₀]²⁺ bridged cation are linked by hydrogen bonds to form an [Na₂(H₂O)₁₀V₁₀O₂₈]⁴⁻ layer (Fig. 2). Hydrogen bonds within the layers involve the H atoms of water molecules and the O atoms from the decavanadate anion (Table 2), and the H₃NCH₂CH₂NH₃²⁺ cations are located between the [Na₂(H₂O)₁₀V₁₀O₂₈]⁴⁻ layers (Fig. 3).

S2. Experimental

The title compound was obtained by hydrothermal synthesis. All reagents were of analytical grade. A 50 ml Teflon autoclave was loaded with a mixture of NaVO₃(5.00 g), H₂O (30 ml), BPO₄ (5.00 g) and NH₂CH₂CH₂NH₂ (1.0 ml) and heated at 423 K for 5 d. After hydrothermal treatment, the solution was filtered and allowed to stand in a glass beaker, where single crystals of the title compound grew in less than 2 d. These crystals were isolated in ca 30% initial yield (based on vanadium) but continued to be produced over time as the solution stood in the beaker.

S3. Refinement

H atoms were located from a difference electron density map. The positional parameters of the H atoms were fixed, with the X—H distances applied as constraints and U_iso(H) set at 1.5 (for C and N atoms) or 1.2 (for O atoms) times U_eq of the parent atom. In the region of the H₃NCH₂CH₂NH₃²⁺ cation, the difference electron density map showed two electron density features separated by a short distance (about 1 Å), and two H atoms are located nearby. As a result, we found one disorded C atom (C3) with a ca 4:1 occupancy ratio for its C3A and C3B components; similarly, we identified one disordered N atom (N4), with a similar occupancy ratio for atoms N4A and N4B. No superstructural diffraction spots were observed in any direction on the frames of data collected.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 2001) and ViewerLite (Accelrys, 2001); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A perspective view of an asymmetric unit and selected neighbors of the title compound. Displacement ellipsoids are drawn at the 20% probability level and H atoms are drawn as small spheres of arbitrary radii. [Symmetry codes: (i) 1 − x, 1 − y, −z; (ii) −x, −y, −z.]
	Fig. 2. A packing diagram of the [Na2(H2O)10V10O28]^4− layer of the title compound, viewed along the c axis. White and dark-grey octahedra represent VO6 and Na(H2O)6 groups, respectively.
	Fig. 3. A packing diagram of the title compound, viewed along the b axis. White octahedra, dark-grey octahedra, white circles and dark-grey circles represent VO6 groups, Na(H2O)6 dications, ## AUTHOR: is the dication not [Na2(H2O)10]^2+ rather than Na(H2O)6? C atoms and N atoms,respectively.

Diethylenediammonium decaaquadisodium decavanadate

Crystal data

(C2H10N2)2[Na2(H2O)10][V10O28]	F(000) = 1296
Mr = 1307.78	Dx = 2.375 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5659 reflections
a = 8.8919 (18) Å	θ = 2.1–33.5°
b = 11.080 (2) Å	µ = 2.58 mm^−1
c = 18.579 (4) Å	T = 293 K
β = 92.40 (3)°	Tablet, orange
V = 1828.8 (6) Å^3	0.2 × 0.2 × 0.2 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5660 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 33.5°, θmin = 2.1°
Detector resolution: 66.7 pixels mm^-1	h = −13→13
ω scans	k = −17→16
17284 measured reflections	l = −17→28
6815 independent reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.077P)^2] where P = (Fo^2 + 2Fc^2)/3
6815 reflections	(Δ/σ)max = 0.001
273 parameters	Δρmax = 0.97 e Å^−3
0 restraints	Δρmin = −0.76 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
V1	0.31878 (3)	0.48709 (3)	0.010859 (17)	0.01634 (8)
V2	0.55645 (4)	0.41694 (3)	0.134777 (17)	0.02083 (8)
V3	0.47091 (4)	0.74300 (3)	−0.000388 (19)	0.02088 (8)
V4	0.36091 (4)	0.64604 (3)	0.144930 (19)	0.02356 (9)
V5	0.70006 (4)	0.67408 (3)	0.122880 (19)	0.02553 (9)
O1	0.34214 (18)	0.76327 (13)	0.07124 (8)	0.0263 (3)
O2	0.51180 (15)	0.57016 (11)	0.05784 (7)	0.0174 (2)
O3	0.22059 (15)	0.54894 (13)	0.07754 (8)	0.0215 (3)
O4	0.39989 (15)	0.35245 (12)	0.06522 (7)	0.0187 (3)
O5	0.32682 (15)	0.62602 (12)	−0.04855 (7)	0.0201 (3)
O6	0.5881 (2)	0.29793 (16)	0.18186 (9)	0.0342 (4)
O7	0.41331 (17)	0.49603 (14)	0.18321 (8)	0.0248 (3)
O8	0.19431 (16)	0.40667 (13)	−0.04118 (8)	0.0237 (3)
O9	0.4386 (2)	0.86065 (14)	−0.05039 (9)	0.0329 (4)
O10	0.70817 (17)	0.51915 (15)	0.16411 (8)	0.0268 (3)
O11	0.2419 (2)	0.69210 (15)	0.20157 (9)	0.0342 (4)
O12	0.63710 (18)	0.78709 (13)	0.05315 (8)	0.0264 (3)
O13	0.53805 (19)	0.71298 (15)	0.17752 (8)	0.0292 (3)
O14	0.8410 (2)	0.73928 (18)	0.16161 (10)	0.0431 (5)
N1	0.5584 (3)	0.02031 (18)	−0.15292 (11)	0.0337 (4)
H1A	0.4880	0.0296	−0.1207	0.051*
H1B	0.6146	0.0867	−0.1542	0.051*
H1C	0.6163	−0.0425	−0.1406	0.051*
C2	0.4858 (3)	−0.0010 (2)	−0.22477 (13)	0.0361 (4)
H2A	0.5000	−0.0845	−0.2385	0.054*
H2B	0.3786	0.0153	−0.2240	0.054*
C3A	0.5596 (5)	0.0852 (3)	−0.2791 (2)	0.0361 (4)	0.813 (6)
H3A	0.6645	0.0623	−0.2817	0.054*
H3B	0.5371	0.1664	−0.2631	0.054*
C3B	0.549 (2)	0.0546 (16)	−0.2818 (11)	0.0361 (4)	0.187 (6)
N4A	0.4882 (3)	0.0721 (2)	−0.35223 (13)	0.0288 (6)	0.813 (6)
H4A	0.5877	0.0677	−0.3552	0.043*
H4B	0.4474	0.0980	−0.3940	0.043*
H4C	0.4519	−0.0007	−0.3424	0.043*
N4B	0.4584 (12)	0.1373 (10)	−0.3076 (6)	0.032 (3)	0.187 (6)
Na1	0.02070 (11)	0.07795 (8)	0.08462 (5)	0.0317 (2)
O15	−0.1840 (2)	−0.01627 (16)	0.00966 (11)	0.0394 (4)
H15A	−0.2442	−0.0708	0.0160	0.047*
H15B	−0.2456	0.0303	−0.0092	0.047*
O16	0.2255 (2)	0.19388 (16)	0.14126 (10)	0.0377 (4)
H16A	0.2222	0.1884	0.1852	0.045*
H16B	0.2794	0.2407	0.1198	0.045*
O17	0.1099 (2)	−0.06401 (16)	0.17050 (10)	0.0414 (4)
H17A	0.1050	−0.1319	0.1530	0.050*
H17B	0.1069	−0.0672	0.2146	0.050*
O18	−0.0309 (2)	0.26098 (19)	0.02314 (14)	0.0545 (6)
H18A	0.0473	0.2882	0.0078	0.065*
H18B	−0.0875	0.2633	−0.0130	0.065*
O19	−0.1451 (3)	0.1497 (3)	0.17140 (12)	0.0670 (8)
H19A	−0.2233	0.1732	0.1511	0.080*
H19B	−0.1129	0.1627	0.2128	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.01345 (14)	0.01830 (15)	0.01737 (15)	−0.00034 (10)	0.00186 (11)	0.00135 (10)
V2	0.02212 (17)	0.02402 (17)	0.01623 (15)	0.00026 (12)	−0.00070 (12)	0.00455 (11)
V3	0.02498 (17)	0.01579 (15)	0.02221 (16)	0.00094 (11)	0.00486 (13)	0.00202 (11)
V4	0.02639 (18)	0.02415 (17)	0.02071 (17)	−0.00153 (13)	0.00775 (13)	−0.00420 (12)
V5	0.02395 (18)	0.03074 (19)	0.02180 (17)	−0.00694 (13)	−0.00017 (13)	−0.00517 (13)
O1	0.0306 (8)	0.0207 (7)	0.0283 (7)	0.0032 (5)	0.0105 (6)	−0.0002 (5)
O2	0.0174 (6)	0.0180 (6)	0.0169 (6)	−0.0008 (5)	0.0021 (5)	0.0010 (5)
O3	0.0187 (6)	0.0247 (7)	0.0216 (6)	0.0008 (5)	0.0057 (5)	0.0016 (5)
O4	0.0187 (6)	0.0186 (6)	0.0189 (6)	−0.0013 (5)	0.0023 (5)	0.0030 (5)
O5	0.0174 (6)	0.0220 (6)	0.0209 (6)	0.0023 (5)	0.0010 (5)	0.0050 (5)
O6	0.0396 (10)	0.0362 (9)	0.0266 (8)	0.0054 (7)	−0.0011 (7)	0.0133 (7)
O7	0.0264 (7)	0.0306 (7)	0.0178 (6)	−0.0015 (6)	0.0046 (5)	0.0020 (5)
O8	0.0184 (6)	0.0292 (7)	0.0235 (7)	−0.0051 (5)	−0.0001 (5)	0.0007 (5)
O9	0.0399 (9)	0.0209 (7)	0.0386 (9)	0.0062 (6)	0.0091 (7)	0.0091 (6)
O10	0.0226 (7)	0.0371 (8)	0.0203 (7)	−0.0029 (6)	−0.0040 (6)	0.0024 (6)
O11	0.0403 (9)	0.0336 (8)	0.0300 (8)	0.0028 (7)	0.0163 (7)	−0.0052 (7)
O12	0.0291 (8)	0.0226 (7)	0.0277 (7)	−0.0075 (6)	0.0050 (6)	−0.0025 (6)
O13	0.0325 (8)	0.0311 (8)	0.0242 (7)	−0.0065 (6)	0.0040 (6)	−0.0083 (6)
O14	0.0394 (10)	0.0540 (12)	0.0354 (10)	−0.0201 (9)	−0.0056 (8)	−0.0091 (8)
N1	0.0436 (12)	0.0267 (9)	0.0310 (10)	0.0000 (8)	0.0046 (9)	0.0005 (7)
C2	0.0350 (9)	0.0394 (12)	0.0338 (9)	−0.0084 (9)	0.0009 (7)	−0.0021 (9)
C3A	0.0350 (9)	0.0394 (12)	0.0338 (9)	−0.0084 (9)	0.0009 (7)	−0.0021 (9)
C3B	0.0350 (9)	0.0394 (12)	0.0338 (9)	−0.0084 (9)	0.0009 (7)	−0.0021 (9)
N4A	0.0251 (11)	0.0323 (12)	0.0291 (12)	−0.0005 (9)	0.0018 (9)	0.0003 (9)
N4B	0.028 (5)	0.038 (6)	0.029 (5)	0.002 (4)	−0.001 (4)	0.000 (4)
Na1	0.0318 (5)	0.0320 (5)	0.0310 (5)	0.0006 (4)	0.0002 (4)	0.0010 (4)
O15	0.0319 (9)	0.0314 (9)	0.0557 (12)	−0.0021 (7)	0.0109 (9)	−0.0057 (8)
O16	0.0419 (10)	0.0396 (10)	0.0320 (9)	−0.0167 (8)	0.0082 (8)	0.0007 (7)
O17	0.0586 (13)	0.0321 (9)	0.0333 (9)	0.0023 (8)	0.0009 (9)	0.0029 (7)
O18	0.0289 (10)	0.0520 (12)	0.0825 (16)	−0.0002 (8)	−0.0003 (10)	0.0332 (12)
O19	0.0453 (13)	0.118 (2)	0.0382 (11)	0.0324 (14)	0.0024 (10)	−0.0074 (13)

Geometric parameters (Å, º)

V1—O2	2.1046 (15)	N1—C2	1.477 (3)
V1—O3	1.6904 (14)	N1—H1A	0.8900
V1—O4	1.9247 (14)	N1—H1B	0.8900
V1—O5	1.8972 (14)	N1—H1C	0.8900
V1—O8	1.6923 (15)	C2—C3A	1.554 (5)
V2—O2	2.2439 (13)	C2—H2A	0.97
V2—O4	1.9920 (15)	C2—H2B	0.97
V2—O5^i	2.0025 (15)	C3A—N4A	1.483 (5)
V2—O6	1.6006 (16)	C3A—H3A	0.97
V2—O7	1.8148 (15)	C3A—H3B	0.97
V2—O10	1.8270 (16)	N4A—H4A	0.89
V3—O1	1.8055 (15)	N4A—H4B	0.89
V3—O2	2.2219 (13)	N4A—H4C	0.89
V3—O4^i	2.0013 (14)	Na1—O15^ii	2.420 (2)
V3—O5	2.0065 (15)	Na1—O15	2.476 (2)
V3—O9	1.6195 (16)	Na1—O16	2.432 (2)
V3—O12	1.8135 (17)	Na1—O17	2.354 (2)
V4—O1	1.8896 (16)	Na1—O18	2.363 (2)
V4—O2	2.3038 (15)	Na1—O19	2.367 (2)
V4—O3	2.0374 (16)	O15—H15A	0.82
V4—O7	1.8594 (16)	O15—H15B	0.82
V4—O11	1.6063 (16)	O16—H16A	0.82
V4—O13	1.8215 (17)	O16—H16B	0.82
V5—O2	2.3278 (15)	O17—H17A	0.82
V5—O8^i	2.0264 (16)	O17—H17B	0.82
V5—O10	1.8799 (17)	O18—H18A	0.82
V5—O12	1.8705 (17)	O18—H18B	0.82
V5—O13	1.8477 (17)	O19—H19A	0.82
V5—O14	1.5924 (18)	O19—H19B	0.82
O3—V1—O8	106.66 (8)	V1—V4—V3	61.524 (16)
O3—V1—O5	97.51 (7)	V5—V4—V3	60.16 (3)
O8—V1—O5	97.73 (7)	V2—V4—V3	91.87 (2)
O3—V1—O4	97.08 (7)	O14—V5—O13	105.25 (9)
O8—V1—O4	96.51 (7)	O14—V5—O12	102.50 (9)
O5—V1—O4	155.74 (6)	O13—V5—O12	90.39 (8)
O3—V1—O2	87.48 (6)	O14—V5—O10	102.36 (9)
O8—V1—O2	165.85 (6)	O13—V5—O10	90.38 (7)
O5—V1—O2	80.59 (6)	O12—V5—O10	153.99 (7)
O4—V1—O2	80.80 (6)	O14—V5—O8^i	99.09 (9)
O3—V1—O2^i	165.45 (6)	O13—V5—O8^i	155.65 (7)
O8—V1—O2^i	87.86 (6)	O12—V5—O8^i	84.91 (7)
O5—V1—O2^i	81.19 (6)	O10—V5—O8^i	83.75 (7)
O4—V1—O2^i	79.82 (6)	O14—V5—O2	173.93 (8)
O2—V1—O2^i	78.00 (6)	O13—V5—O2	80.81 (6)
O3—V1—V5^i	145.05 (5)	O12—V5—O2	77.51 (6)
O8—V1—V5^i	38.40 (5)	O10—V5—O2	76.96 (6)
O5—V1—V5^i	90.18 (5)	O8^i—V5—O2	74.84 (6)
O4—V1—V5^i	88.87 (5)	O14—V5—V1^i	130.33 (8)
O2—V1—V5^i	127.46 (4)	O13—V5—V1^i	124.40 (5)
O2^i—V1—V5^i	49.46 (4)	O12—V5—V1^i	79.84 (5)
O3—V1—V4	38.71 (5)	O10—V5—V1^i	78.33 (5)
O8—V1—V4	145.35 (5)	O8^i—V5—V1^i	31.25 (4)
O5—V1—V4	90.02 (5)	O2—V5—V1^i	43.60 (4)
O4—V1—V4	89.34 (5)	O14—V5—V4	138.01 (8)
O2—V1—V4	48.77 (4)	O13—V5—V4	32.77 (5)
O2^i—V1—V4	126.76 (4)	O12—V5—V4	83.87 (5)
V5^i—V1—V4	176.098 (14)	O10—V5—V4	82.79 (5)
O6—V2—O7	103.74 (8)	O8^i—V5—V4	122.88 (5)
O6—V2—O10	103.71 (9)	O2—V5—V4	48.05 (4)
O7—V2—O10	94.43 (7)	V1^i—V5—V4	91.64 (3)
O6—V2—O4	99.26 (8)	O14—V5—V3	134.71 (8)
O7—V2—O4	90.53 (7)	O13—V5—V3	81.07 (6)
O10—V2—O4	154.57 (6)	O12—V5—V3	32.23 (5)
O6—V2—O5^i	99.00 (8)	O10—V5—V3	122.64 (5)
O7—V2—O5^i	155.40 (6)	O8^i—V5—V3	82.31 (5)
O10—V2—O5^i	89.14 (7)	O2—V5—V3	45.69 (4)
O4—V2—O5^i	76.54 (6)	V1^i—V5—V3	62.044 (18)
O6—V2—O2	173.54 (8)	V4—V5—V3	60.33 (2)
O7—V2—O2	80.88 (6)	V3—O1—V4	114.14 (8)
O10—V2—O2	80.20 (6)	V1—O2—V1^i	102.00 (6)
O4—V2—O2	75.99 (5)	V1—O2—V3	93.50 (6)
O5^i—V2—O2	75.76 (5)	V1^i—O2—V3	94.07 (5)
O6—V2—V3^i	88.57 (7)	V1—O2—V2	93.03 (5)
O7—V2—V3^i	130.55 (5)	V1^i—O2—V2	92.65 (5)
O10—V2—V3^i	129.36 (5)	V3—O2—V2	169.47 (7)
O4—V2—V3^i	40.02 (4)	V1—O2—V4	87.82 (5)
O5^i—V2—V3^i	40.22 (4)	V1^i—O2—V4	170.09 (7)
O2—V2—V3^i	84.98 (4)	V3—O2—V4	86.51 (5)
O6—V2—V4	136.92 (7)	V2—O2—V4	85.49 (5)
O7—V2—V4	33.29 (5)	V1—O2—V5	171.06 (7)
O10—V2—V4	83.27 (5)	V1^i—O2—V5	86.94 (5)
O4—V2—V4	87.39 (4)	V3—O2—V5	85.75 (5)
O5^i—V2—V4	123.81 (4)	V2—O2—V5	86.52 (5)
O2—V2—V4	48.07 (4)	V4—O2—V5	83.23 (5)
V3^i—V2—V4	119.99 (2)	V1—O3—V4	110.04 (7)
O9—V3—O1	102.70 (8)	V1—O4—V2	107.38 (7)
O9—V3—O12	102.64 (9)	V1—O4—V3^i	107.80 (6)
O1—V3—O12	95.14 (8)	V2—O4—V3^i	100.18 (6)
O9—V3—O4^i	99.94 (7)	V1—O5—V2^i	107.82 (7)
O1—V3—O4^i	155.11 (6)	V1—O5—V3	107.67 (7)
O12—V3—O4^i	89.84 (7)	V2^i—O5—V3	99.65 (6)
O9—V3—O5	99.76 (8)	V2—O7—V4	114.31 (7)
O1—V3—O5	89.79 (7)	V1—O8—V5^i	110.35 (8)
O12—V3—O5	155.37 (7)	V2—O10—V5	115.42 (8)
O4^i—V3—O5	76.24 (6)	V3—O12—V5	114.39 (8)
O9—V3—O2	174.03 (7)	V4—O13—V5	113.93 (8)
O1—V3—O2	81.04 (6)	C2—N1—H1A	109.5
O12—V3—O2	81.50 (6)	C2—N1—H1B	109.5
O4^i—V3—O2	75.59 (5)	H1A—N1—H1B	109.5
O5—V3—O2	75.45 (6)	C2—N1—H1C	109.5
O9—V3—V2^i	89.54 (7)	H1A—N1—H1C	109.5
O1—V3—V2^i	129.91 (6)	H1B—N1—H1C	109.5
O12—V3—V2^i	129.64 (5)	N1—C2—C3A	108.0 (2)
O4^i—V3—V2^i	39.80 (4)	N1—C2—H2A	109.5
O5—V3—V2^i	40.13 (4)	C3A—C2—H2A	110.6
O2—V3—V2^i	84.49 (4)	N1—C2—H2B	110.4
O9—V3—V5	135.91 (7)	C3A—C2—H2B	109.7
O1—V3—V5	84.46 (6)	H2A—C2—H2B	108.6
O12—V3—V5	33.38 (5)	N4A—C3A—C2	111.0 (3)
O4^i—V3—V5	86.46 (4)	N4B—C3A—H3A	145.6
O5—V3—V5	123.96 (4)	N4A—C3A—H3A	107.8
O2—V3—V5	48.56 (4)	C2—C3A—H3A	107.8
V2^i—V3—V5	119.18 (2)	N4A—C3A—H3B	106.5
O9—V3—V4	136.33 (6)	C2—C3A—H3B	105.8
O1—V3—V4	33.77 (5)	H3A—C3A—H3B	117.9
O12—V3—V4	83.99 (5)	C2—C3A—H4A	129.9
O4^i—V3—V4	123.42 (4)	H3A—C3A—H4A	73.4
O5—V3—V4	86.89 (4)	H3B—C3A—H4A	117.7
O2—V3—V4	47.84 (3)	C3A—N4A—H4A	70.9
V2^i—V3—V4	119.470 (18)	C3A—N4A—H4B	155.6
V5—V3—V4	59.507 (19)	H4A—N4A—H4B	109.5
O11—V4—O13	103.71 (9)	C3A—N4A—H4C	92.6
O11—V4—O7	101.23 (8)	H4A—N4A—H4C	109.5
O13—V4—O7	92.15 (8)	H4B—N4A—H4C	109.5
O11—V4—O1	102.46 (8)	O17—Na1—O18	162.56 (9)
O13—V4—O1	90.56 (8)	O17—Na1—O19	87.96 (9)
O7—V4—O1	154.78 (6)	O18—Na1—O19	85.83 (9)
O11—V4—O3	99.62 (8)	O17—Na1—O15^ii	96.12 (7)
O13—V4—O3	156.65 (6)	O18—Na1—O15^ii	90.16 (8)
O7—V4—O3	84.28 (7)	O19—Na1—O15^ii	175.91 (9)
O1—V4—O3	83.37 (7)	O17—Na1—O16	80.48 (8)
O11—V4—O2	174.28 (8)	O18—Na1—O16	83.26 (8)
O13—V4—O2	82.01 (6)	O19—Na1—O16	90.26 (9)
O7—V4—O2	78.37 (6)	O15^ii—Na1—O16	90.06 (7)
O1—V4—O2	77.19 (6)	O17—Na1—O15	108.57 (8)
O3—V4—O2	74.66 (5)	O18—Na1—O15	88.09 (8)
O11—V4—V1	130.88 (7)	O19—Na1—O15	93.46 (8)
O13—V4—V1	125.41 (5)	O15^ii—Na1—O15	85.60 (7)
O7—V4—V1	79.47 (5)	O16—Na1—O15	170.31 (7)
O1—V4—V1	78.57 (5)	O17—Na1—Na1^ii	106.93 (6)
O3—V4—V1	31.25 (4)	O18—Na1—Na1^ii	88.79 (8)
O2—V4—V1	43.40 (4)	O19—Na1—Na1^ii	135.52 (8)
O11—V4—V5	137.00 (7)	O15^ii—Na1—Na1^ii	43.40 (5)
O13—V4—V5	33.30 (5)	O16—Na1—Na1^ii	132.85 (7)
O7—V4—V5	84.83 (5)	O15—Na1—Na1^ii	42.19 (5)
O1—V4—V5	83.76 (5)	Na1^ii—O15—Na1	94.40 (7)
O3—V4—V5	123.37 (4)	Na1^ii—O15—H15A	108.1
O2—V4—V5	48.72 (4)	Na1—O15—H15A	134.4
V1—V4—V5	92.12 (3)	Na1^ii—O15—H15B	106.2
O11—V4—V2	133.58 (7)	Na1—O15—H15B	115.9
O13—V4—V2	82.74 (6)	H15A—O15—H15B	95.6
O7—V4—V2	32.40 (5)	Na1—O16—H16A	109.5
O1—V4—V2	123.63 (5)	Na1—O16—H16B	124.4
O3—V4—V2	81.97 (5)	H16A—O16—H16B	125.2
O2—V4—V2	46.44 (3)	Na1—O17—H17A	109.5
V1—V4—V2	61.78 (2)	Na1—O17—H17B	132.9
V5—V4—V2	61.123 (15)	H17A—O17—H17B	110.6
O11—V4—V3	134.47 (7)	Na1—O18—H18A	109.5
O13—V4—V3	81.28 (6)	Na1—O18—H18B	121.4
O7—V4—V3	124.01 (5)	H18A—O18—H18B	101.7
O1—V4—V3	32.08 (4)	Na1—O19—H19A	109.5
O3—V4—V3	81.68 (4)	Na1—O19—H19B	119.6
O2—V4—V3	45.64 (4)	H19A—O19—H19B	129.1

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O9^iii	0.89	2.33	2.840 (3)	116
N1—H1B···O1^i	0.89	2.29	2.953 (3)	131
N1—H1C···O16^iv	0.89	2.19	3.055 (3)	164
N4A—H4A···O3^v	0.89	2.18	2.828 (3)	129
N4A—H4B···O18^v	0.89	2.21	2.963 (4)	142
N4A—H4C···O10^vi	0.89	2.19	2.716 (3)	118
O15—H15A···O12^vii	0.82	2.03	2.835 (2)	166
O15—H15B···O9^viii	0.82	2.41	2.969 (2)	126
O16—H16A···O11^ix	0.82	2.12	2.922 (3)	168
O16—H16B···O4	0.82	1.95	2.769 (2)	177
O17—H17A···O11^iii	0.82	2.45	2.993 (3)	124
O17—H17B···O7^ix	0.82	2.04	2.814 (2)	157
O18—H18A···O8	0.82	2.09	2.871 (2)	160
O18—H18B···O1^viii	0.82	2.49	3.225 (3)	150
O19—H19A···O6^x	0.82	2.27	2.899 (3)	134
O19—H19B···O13^ix	0.82	2.19	3.009 (3)	175

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