Four-position disorder of cationic protonated guanylurea in a stable three-dimensional network in the structure of a triple salt decavanadate complex (HGU⁺)(H₂Met²⁺)₂(H₃O⁺)(V₁₀O₂₈⁶⁻)·8H₂O

A triple salt of decavanadate, V₁₀O₂₈⁶⁻, containing mixed organic guanylurea (di­amino­methyl­ideneurea cation, HGU⁺) and metforminium(2+) (H₂Met²⁺) cations and hydro­nium (H₃O⁺) cations, has been synthesized by heating metformin hydro­chloride, picolinic acid, and sodium metavanadate in aqueous solution at pH 4 and 333 K followed by maintaining the solution at 300 K overnight to give an orange crystalline product. As commonly observed, the V₁₀O₂₈⁶⁻ anion lies on an inversion center. Charge is balanced by two H₂Met²⁺ dications and two monocations, one HGU⁺ and one H₃O⁺, substitutionally disordered about another inversion center. The HGU⁺ cation is further positionally disordered by rotation of 26.3 (4)° about an axis approximately along the direction of the three essentially collinear N atoms of the cation, thereby hydrogen bonding to two adjacent rows of cluster O atoms running diagonally across the equatorial plane of the V₁₀O₂₈⁶⁻ anion. The highly concerted nature of the HGU⁺...cluster inter­action in each orientation suggests a synthon that likely preexisted in solution and perhaps, along with heat, contributes to the degradation of the metformin to HGU⁺. The structure of the salt exhibits a complex charge-stabilized hydrogen-bonded network involving extended C₄⁴(8) chains of the water molecules and the H₂Met²⁺ cations linking the chains into two-dimensional sheets parallel to the bc plane, and V₁₀O₂₈⁶⁻ anions linking those sheets into a three-dimensional structure through Ow—H...O, N—H...O and C—H...O inter­molecular inter­actions. The disordered HGU⁺ cation and the H₃O⁺ cation occupy spaces with excess volume in the three-dimensional network structure.

Computing details

Data collection: APEX3 (Bruker, 2017); cell refinement: APEX3 (Bruker, 2017); data reduction: SAINT V8-34A (Bruker, 2013); program(s) used to solve structure: SHELXT 2014/4 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL 2016/6 (Sheldrick, 2015b); molecular graphics: ORTEP-III (Burnett & Johnson, 1996), ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010), PLATON (Spek, 2003).

hydro-diaminomethylideneurea bis(dihydro-3-(diaminomethylidene)-1,1-dimethylguanidine) bis(µ₆-oxo)-tetrakis(µ₃-oxo)-tetradecakis(µ₂-oxo)-octa-oxo- deca-vanadium(V) octahydrate

Crystal data

2(C4H13N5)^2+·(C2H7N4O)^+·(H3O)^+·(V10O28)^6^−·8(H2O)	Z = 2
Mr = 1486.06	F(000) = 1488
Monoclinic, P21/c	Dx = 2.150 Mg m^−3
a = 13.5547 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.6007 (4) Å	µ = 2.06 mm^−1
c = 14.5078 (5) Å	T = 296 K
β = 112.1471 (10)°	Plate, orange
V = 2295.09 (13) Å^3	0.35 × 0.30 × 0.15 mm

Data collection

Bruker D8 QUEST CMOS diffractometer with APEX-III CCD area-detector	4696 independent reflections
Radiation source: fine-focus sealed tube	3523 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
φ and ω scans	θmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan (Blessing, 1995), SADABS (Sheldrick, 2001)	h = −16→15
	k = −15→15
39305 measured reflections	l = −18→18

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)] = 0.036	Hydrogen site location: mixed
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0314P)^2 + 4.3679P] where P = (Fo^2 + 2Fc^2)/3
4696 reflections	(Δ/σ)max = 0.016
408 parameters	Δρmax = 0.56 e Å^−3
58 restraints	Δρmin = −0.62 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles, and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

_________________________

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

Rotationally disordered HGU+ least squares planes HGU+ plane-position Y Equation: 10.376 (0.038) x +6.707 (0.054) y +0.671 (0.041) z = 9.127 (0.034) Deviations of atoms from plane * -0.0004 (0.0008) N1GY * 0.0001 (0.0005) C1GY * 0.0004 (0.0007) N2GY * -0.0005 (0.0012) N3GY * -0.0002 (0.0013) C3GY * 0.0005 (0.0008) O3GY * 0.0000 (0.0009) N4GY Rms deviation of fitted atoms = 0.0003

HGU+ plane-position X Equation: 12.753 (0.015) x +1.440 (0.064) y -0.858 (0.040) z = 6.397 (0.046) Angle to previous plane (with approximate esd) = 26.32 ( 0.42 ) Deviations of atoms from plane * 0.0003 (0.0008) N1GX * 0.0002 (0.0005) C1GX * 0.0002 (0.0007) N2GX * -0.0013 (0.0012) N3GX * 0.0008 (0.0013) C3GX * -0.0006 (0.0008) O3GX * 0.0005 (0.0009) N4GX Rms deviation of fitted atoms = 0.0007

———- H2Met2+ Guanide least squares planes Six atom C3N3 dimethylguanide plane Equation: -1.946 (0.022) x -12.321 (0.004) y -1.264 (0.019) z = 1.703 (0.026) Deviations of atoms from plane * -0.0933 (0.0022) N3 * 0.0747 (0.0024) N4 * 0.0260 (0.0028) N5 * 0.0150 (0.0026) C2 * -0.0895 (0.0021) C3 * 0.0671 (0.0022) C4 Rms deviation of fitted atoms = 0.0679

Four atom CN3 guanide plane Equation: 12.690 (0.011) x +4.397 (0.028) y -5.681 (0.026) z = 2.275 (0.032) Angle to previous plane (with approximate esd) = 62.01 ( 0.17 ) Deviations of atoms from plane * -0.0052 (0.0010) N1 * -0.0053 (0.0010) N2 * -0.0050 (0.0010) N3 * 0.0155 (0.0030) C1 Rms deviation of fitted atoms = 0.0089

Four atom CN3 dimethylguanide plane Equation: -2.691 (0.025) x -12.091 (0.006) y -1.595 (0.025) z = 0.560 (0.030) Angle to previous plane (with approximate esd) = 59.18 ( 0.18 ) Deviations of atoms from plane * -0.0020 (0.0008) N3 * -0.0023 (0.0009) N4 * -0.0023 (0.0009) N5 * 0.0066 (0.0026) C2 Rms deviation of fitted atoms = 0.0038 _________________________

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
V1	0.52577 (4)	−0.07412 (4)	0.91875 (4)	0.01569 (12)
O1	0.60300 (16)	−0.00294 (15)	1.05765 (14)	0.0169 (4)
O123	0.50580 (17)	0.17968 (16)	0.99778 (15)	0.0191 (4)
O14	0.64401 (17)	−0.12514 (16)	0.92838 (15)	0.0206 (5)
O15	0.56552 (17)	0.11800 (16)	1.19000 (15)	0.0218 (5)
V2	0.64799 (4)	0.14233 (4)	0.99215 (4)	0.02068 (13)
O2	0.66701 (19)	0.24685 (19)	0.93839 (18)	0.0320 (6)
O231	0.54207 (16)	0.06592 (16)	0.87433 (15)	0.0183 (4)
O24	0.75260 (17)	0.05249 (17)	0.98924 (15)	0.0214 (5)
O25	0.71240 (17)	0.17490 (16)	1.12364 (16)	0.0223 (5)
V3	0.40794 (4)	0.14753 (4)	0.85635 (4)	0.01846 (13)
O3	0.42965 (19)	0.24929 (18)	0.80097 (17)	0.0298 (5)
O34	0.70618 (17)	−0.18575 (16)	1.11378 (15)	0.0206 (5)
O35	0.33343 (17)	0.06126 (17)	0.75246 (15)	0.0214 (5)
V4	0.76047 (4)	−0.07392 (4)	1.05833 (4)	0.01925 (13)
O4	0.86011 (18)	−0.13257 (18)	1.04783 (17)	0.0277 (5)
V5	0.71414 (4)	0.06542 (4)	1.21092 (4)	0.02075 (14)
O5	0.78163 (18)	0.11581 (19)	1.31742 (16)	0.0299 (6)
O45	0.81538 (16)	−0.00716 (16)	1.17887 (15)	0.0204 (5)
N1	0.7231 (3)	−0.3558 (2)	0.9403 (2)	0.0334 (7)
H11	0.703 (3)	−0.381 (3)	0.8837 (17)	0.040*
H12	0.709 (3)	−0.2943 (16)	0.950 (3)	0.040*
C1	0.7792 (3)	−0.4134 (3)	1.0176 (2)	0.0256 (7)
N2	0.8072 (3)	−0.5111 (3)	1.0080 (2)	0.0434 (9)
H21	0.793 (3)	−0.538 (3)	0.9526 (18)	0.052*
H22	0.833 (3)	−0.547 (3)	1.059 (2)	0.052*
N3	0.8044 (2)	−0.3716 (2)	1.10981 (19)	0.0246 (6)
H3	0.771 (3)	−0.319 (2)	1.114 (3)	0.030*
C2	0.8913 (3)	−0.4027 (2)	1.1937 (2)	0.0213 (7)
N4	0.9820 (2)	−0.4209 (2)	1.1840 (2)	0.0295 (7)
H41	1.036 (2)	−0.443 (3)	1.229 (2)	0.035*
H42	0.989 (3)	−0.399 (3)	1.1329 (19)	0.035*
N5	0.8783 (2)	−0.4102 (2)	1.27802 (19)	0.0242 (6)
C3	0.9714 (3)	−0.4250 (3)	1.3707 (3)	0.0367 (9)
H31C	1.026 (2)	−0.379 (3)	1.374 (3)	0.044*
H32C	0.956 (3)	−0.407 (3)	1.426 (2)	0.044*
H33C	0.992 (3)	−0.4950 (16)	1.374 (3)	0.044*
C4	0.7752 (3)	−0.3981 (4)	1.2866 (3)	0.0414 (10)
H41C	0.721 (2)	−0.411 (3)	1.2264 (18)	0.050*
H42C	0.761 (3)	−0.446 (3)	1.328 (3)	0.050*
H43C	0.767 (3)	−0.333 (2)	1.312 (3)	0.050*
O1W	0.9339 (3)	−0.1758 (3)	1.3146 (2)	0.0601 (9)
H1W1	0.9925 (19)	−0.169 (4)	1.307 (4)	0.078*
H1W2	0.885 (2)	−0.139 (4)	1.272 (3)	0.078*
O2W	1.1443 (3)	−0.1551 (2)	1.3163 (2)	0.0533 (8)
H2W1	1.134 (4)	−0.151 (4)	1.2548 (11)	0.069*
H2W2	1.189 (3)	−0.203 (3)	1.344 (3)	0.069*
O3W	1.1492 (3)	−0.1605 (2)	1.1237 (2)	0.0516 (8)
H3W1	1.172 (3)	−0.115 (2)	1.093 (3)	0.067*
H3W2	1.178 (3)	−0.2201 (17)	1.125 (4)	0.067*
O4W	0.9950 (3)	−0.3250 (3)	1.0165 (2)	0.0683 (10)
H4W1	0.967 (4)	−0.328 (4)	0.9539 (9)	0.089*
H4W2	1.015 (5)	−0.2632 (18)	1.037 (3)	0.089*
O1H	0.3919 (7)	0.6625 (7)	0.7712 (7)	0.093 (3)*	0.5
N1GX	0.5011 (6)	0.5876 (9)	0.9769 (9)	0.027 (2)*	0.25
H1G1	0.493081	0.632647	0.933839	0.032*	0.25
H1G2	0.502754	0.605328	1.031856	0.032*	0.25
C1GX	0.5111 (3)	0.4875 (9)	0.9578 (8)	0.047 (2)*	0.25
N2GX	0.5091 (5)	0.4536 (12)	0.8719 (9)	0.0378 (15)*	0.25
H2G1	0.501313	0.495795	0.826679	0.045*	0.25
H2G2	0.515702	0.390047	0.863259	0.045*	0.25
N3GX	0.5244 (5)	0.4089 (10)	1.0264 (7)	0.035 (2)*	0.25
H3GX	0.530278	0.346969	1.011729	0.042*	0.25
C3GX	0.5282 (6)	0.4341 (8)	1.1214 (8)	0.0304 (17)*	0.25
O3GX	0.5200 (7)	0.5236 (8)	1.1517 (9)	0.0454 (18)*	0.25
N4GX	0.5413 (9)	0.3515 (9)	1.1789 (9)	0.033 (2)*	0.25
H4G1	0.544263	0.358766	1.236070	0.040*	0.25
H4G2	0.546686	0.292179	1.157962	0.040*	0.25
N1GY	0.4570 (6)	0.5603 (7)	0.9335 (10)	0.027 (2)*	0.25
H1G3	0.440113	0.591751	0.880246	0.032*	0.25
H1G4	0.439000	0.583717	0.977499	0.032*	0.25
C1GY	0.5122 (4)	0.4735 (6)	0.9480 (7)	0.047 (2)*	0.25
N2GY	0.5435 (6)	0.4319 (8)	0.8810 (8)	0.0378 (15)*	0.25
H2G3	0.528291	0.460828	0.826738	0.045*	0.25
H2G4	0.578344	0.376805	0.893175	0.045*	0.25
N3GY	0.5431 (6)	0.4170 (8)	1.0340 (7)	0.035 (2)*	0.25
H3GY	0.577864	0.362864	1.037337	0.042*	0.25
C3GY	0.5203 (6)	0.4441 (7)	1.1171 (7)	0.0304 (17)*	0.25
O3GY	0.4697 (7)	0.5213 (8)	1.1277 (9)	0.0454 (18)*	0.25
N4GY	0.5623 (9)	0.3722 (9)	1.1864 (9)	0.033 (2)*	0.25
H4G3	0.555447	0.377482	1.240073	0.040*	0.25
H4G4	0.595300	0.322080	1.176141	0.040*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0160 (3)	0.0152 (2)	0.0159 (3)	0.0007 (2)	0.0060 (2)	−0.0011 (2)
O1	0.0173 (11)	0.0167 (10)	0.0165 (10)	0.0010 (8)	0.0060 (9)	0.0025 (8)
O123	0.0190 (11)	0.0165 (10)	0.0205 (11)	0.0003 (8)	0.0061 (9)	0.0008 (8)
O14	0.0206 (12)	0.0214 (11)	0.0212 (11)	0.0029 (9)	0.0095 (9)	−0.0017 (9)
O15	0.0234 (12)	0.0227 (11)	0.0187 (11)	0.0007 (9)	0.0075 (9)	−0.0037 (9)
V2	0.0181 (3)	0.0182 (3)	0.0249 (3)	−0.0020 (2)	0.0071 (2)	0.0050 (2)
O2	0.0292 (14)	0.0256 (12)	0.0424 (15)	−0.0022 (10)	0.0149 (11)	0.0100 (11)
O231	0.0195 (12)	0.0190 (11)	0.0172 (10)	−0.0001 (9)	0.0076 (9)	0.0033 (9)
O24	0.0189 (12)	0.0223 (11)	0.0244 (11)	−0.0012 (9)	0.0099 (9)	0.0023 (9)
O25	0.0206 (12)	0.0171 (11)	0.0283 (12)	−0.0021 (9)	0.0083 (10)	−0.0027 (9)
V3	0.0179 (3)	0.0168 (3)	0.0202 (3)	0.0015 (2)	0.0067 (2)	0.0054 (2)
O3	0.0286 (13)	0.0261 (12)	0.0350 (13)	0.0032 (10)	0.0122 (11)	0.0137 (11)
O34	0.0202 (12)	0.0169 (10)	0.0240 (11)	0.0032 (9)	0.0073 (9)	0.0026 (9)
O35	0.0219 (12)	0.0246 (12)	0.0169 (11)	0.0022 (9)	0.0064 (9)	0.0020 (9)
V4	0.0168 (3)	0.0196 (3)	0.0215 (3)	0.0014 (2)	0.0074 (2)	−0.0013 (2)
O4	0.0231 (13)	0.0297 (13)	0.0323 (13)	0.0051 (10)	0.0127 (10)	−0.0011 (10)
V5	0.0182 (3)	0.0234 (3)	0.0187 (3)	−0.0005 (2)	0.0047 (2)	−0.0042 (2)
O5	0.0264 (14)	0.0346 (13)	0.0242 (12)	−0.0031 (10)	0.0046 (10)	−0.0082 (10)
O45	0.0168 (11)	0.0212 (11)	0.0217 (11)	0.0006 (9)	0.0054 (9)	−0.0002 (9)
N1	0.047 (2)	0.0266 (16)	0.0199 (15)	0.0057 (14)	0.0051 (14)	−0.0046 (13)
C1	0.0273 (19)	0.0247 (17)	0.0227 (17)	0.0011 (14)	0.0071 (14)	−0.0020 (14)
N2	0.064 (2)	0.0290 (18)	0.0272 (17)	0.0148 (16)	0.0056 (17)	−0.0092 (14)
N3	0.0287 (16)	0.0236 (15)	0.0194 (14)	0.0095 (12)	0.0066 (12)	−0.0021 (11)
C2	0.0259 (18)	0.0141 (15)	0.0225 (16)	0.0041 (12)	0.0074 (14)	−0.0011 (12)
N4	0.0247 (17)	0.0383 (18)	0.0257 (16)	0.0077 (13)	0.0096 (13)	0.0055 (14)
N5	0.0255 (16)	0.0271 (15)	0.0202 (14)	0.0082 (12)	0.0088 (12)	0.0016 (11)
C3	0.035 (2)	0.047 (2)	0.0239 (19)	0.0163 (18)	0.0056 (17)	0.0045 (18)
C4	0.034 (2)	0.057 (3)	0.035 (2)	0.014 (2)	0.0160 (18)	0.010 (2)
O1W	0.067 (2)	0.0490 (19)	0.054 (2)	0.0073 (17)	0.0115 (18)	0.0203 (15)
O2W	0.071 (2)	0.0434 (18)	0.0459 (17)	0.0288 (15)	0.0230 (17)	0.0079 (14)
O3W	0.059 (2)	0.0453 (18)	0.063 (2)	0.0065 (15)	0.0376 (17)	0.0148 (16)
O4W	0.073 (3)	0.085 (3)	0.0413 (18)	−0.021 (2)	0.0147 (18)	0.0152 (18)

Geometric parameters (Å, º)

V1—O14	1.683 (2)	N4—H42	0.827 (17)
V1—O15^i	1.689 (2)	N5—C4	1.457 (5)
V1—O231	1.920 (2)	N5—C3	1.469 (4)
V1—O123^i	1.952 (2)	C3—H31C	0.923 (17)
V1—O1	2.091 (2)	C3—H32C	0.922 (17)
V1—O1^i	2.135 (2)	C3—H33C	0.920 (17)
O1—V3^i	2.244 (2)	C4—H41C	0.920 (17)
O1—V2	2.250 (2)	C4—H42C	0.919 (17)
O1—V4	2.311 (2)	C4—H43C	0.922 (17)
O1—V5	2.330 (2)	O1W—H1W1	0.848 (10)
O123—V2	2.015 (2)	O1W—H1W2	0.848 (10)
O123—V3	2.020 (2)	O2W—H2W1	0.852 (10)
O14—V4	2.054 (2)	O2W—H2W2	0.847 (10)
O15—V5	2.032 (2)	O3W—H3W1	0.845 (10)
V2—O2	1.600 (2)	O3W—H3W2	0.844 (10)
V2—O25	1.820 (2)	O4W—H4W1	0.844 (10)
V2—O24	1.827 (2)	O4W—H4W2	0.840 (10)
V2—O231	2.015 (2)	N1GX—C1GX	1.310 (8)
O231—V3	2.018 (2)	N1GX—H1G1	0.8200
O24—V4	1.864 (2)	N1GX—H1G2	0.8200
O25—V5	1.867 (2)	C1GX—N2GX	1.309 (8)
V3—O3	1.598 (2)	C1GX—N3GX	1.366 (5)
V3—O34^i	1.822 (2)	N2GX—H2G1	0.8200
V3—O35	1.824 (2)	N2GX—H2G2	0.8200
V3—V5^i	3.1102 (7)	N3GX—C3GX	1.398 (3)
O34—V4	1.903 (2)	N3GX—H3GX	0.8200
O35—V5^i	1.872 (2)	C3GX—O3GX	1.231 (4)
V4—O4	1.596 (2)	C3GX—N4GX	1.304 (7)
V4—O45	1.827 (2)	N4GX—H4G1	0.8200
V5—O5	1.600 (2)	N4GX—H4G2	0.8200
V5—O45	1.849 (2)	N1GY—C1GY	1.297 (7)
N1—C1	1.311 (4)	N1GY—H1G3	0.8200
N1—H11	0.826 (17)	N1GY—H1G4	0.8200
N1—H12	0.822 (17)	C1GY—N2GY	1.308 (8)
C1—N2	1.311 (4)	C1GY—N3GY	1.358 (5)
C1—N3	1.357 (4)	N2GY—H2G3	0.8200
N2—H21	0.824 (17)	N2GY—H2G4	0.8200
N2—H22	0.826 (17)	N3GY—C3GY	1.395 (3)
N3—C2	1.393 (4)	N3GY—H3GY	0.8200
N3—H3	0.818 (17)	C3GY—O3GY	1.233 (4)
C2—N5	1.303 (4)	C3GY—N4GY	1.313 (7)
C2—N4	1.310 (4)	N4GY—H4G3	0.8200
N4—H41	0.827 (17)	N4GY—H4G4	0.8200
O14—V1—O15^i	106.96 (10)	O5—V5—O25	102.60 (11)
O14—V1—O231	98.76 (10)	O45—V5—O25	90.90 (9)
O15^i—V1—O231	97.11 (10)	O5—V5—O35^i	101.36 (11)
O14—V1—O123^i	96.48 (10)	O45—V5—O35^i	90.99 (9)
O15^i—V1—O123^i	95.84 (10)	O25—V5—O35^i	154.83 (10)
O231—V1—O123^i	156.15 (9)	O5—V5—O15	100.87 (11)
O14—V1—O1	88.21 (9)	O45—V5—O15	155.78 (9)
O15^i—V1—O1	164.78 (10)	O25—V5—O15	84.23 (9)
O231—V1—O1	81.38 (8)	O35^i—V5—O15	83.81 (9)
O123^i—V1—O1	80.88 (8)	O5—V5—O1	175.17 (10)
O14—V1—O1^i	166.17 (9)	O45—V5—O1	81.44 (8)
O15^i—V1—O1^i	86.76 (9)	O25—V5—O1	77.74 (8)
O231—V1—O1^i	80.81 (8)	O35^i—V5—O1	77.74 (8)
O123^i—V1—O1^i	80.02 (8)	O15—V5—O1	74.34 (8)
O1—V1—O1^i	78.04 (8)	O5—V5—V3^i	133.48 (9)
V1—O1—V1^i	101.96 (8)	O45—V5—V3^i	81.48 (7)
V1—O1—V3^i	94.22 (8)	O25—V5—V3^i	123.75 (7)
V1^i—O1—V3^i	92.91 (8)	O35^i—V5—V3^i	32.21 (6)
V1—O1—V2	93.38 (8)	O15—V5—V3^i	81.62 (6)
V1^i—O1—V2	93.77 (8)	O1—V5—V3^i	46.02 (5)
V3^i—O1—V2	168.63 (10)	V4—O45—V5	113.29 (11)
V1—O1—V4	87.95 (7)	C1—N1—H11	120 (3)
V1^i—O1—V4	170.10 (10)	C1—N1—H12	118 (3)
V3^i—O1—V4	86.44 (7)	H11—N1—H12	122 (4)
V2—O1—V4	85.40 (7)	N2—C1—N1	121.8 (3)
V1—O1—V5	170.77 (10)	N2—C1—N3	119.6 (3)
V1^i—O1—V5	87.27 (7)	N1—C1—N3	118.5 (3)
V3^i—O1—V5	85.64 (7)	C1—N2—H21	121 (3)
V2—O1—V5	85.50 (7)	C1—N2—H22	117 (3)
V4—O1—V5	82.83 (7)	H21—N2—H22	122 (4)
V1^i—O123—V2	107.62 (10)	C1—N3—C2	124.6 (3)
V1^i—O123—V3	106.26 (10)	C1—N3—H3	117 (3)
V2—O123—V3	100.59 (9)	C2—N3—H3	118 (3)
V1—O14—V4	109.54 (10)	N5—C2—N4	123.5 (3)
V1^i—O15—V5	111.63 (11)	N5—C2—N3	118.2 (3)
O2—V2—O25	102.91 (11)	N4—C2—N3	118.3 (3)
O2—V2—O24	103.27 (11)	C2—N4—H41	124 (3)
O25—V2—O24	95.40 (10)	C2—N4—H42	118 (3)
O2—V2—O231	100.02 (11)	H41—N4—H42	117 (4)
O25—V2—O231	154.63 (9)	C2—N5—C4	123.1 (3)
O24—V2—O231	89.73 (9)	C2—N5—C3	119.7 (3)
O2—V2—O123	99.20 (11)	C4—N5—C3	117.1 (3)
O25—V2—O123	89.61 (9)	N5—C3—H31C	111 (3)
O24—V2—O123	155.22 (9)	N5—C3—H32C	111 (3)
O231—V2—O123	76.08 (8)	H31C—C3—H32C	104 (4)
O2—V2—O1	173.99 (10)	N5—C3—H33C	108 (3)
O25—V2—O1	80.80 (8)	H31C—C3—H33C	112 (4)
O24—V2—O1	80.91 (8)	H32C—C3—H33C	110 (3)
O231—V2—O1	75.50 (8)	N5—C4—H41C	110 (3)
O123—V2—O1	75.95 (8)	N5—C4—H42C	115 (3)
V1—O231—V2	106.85 (9)	H41C—C4—H42C	102 (4)
V1—O231—V3	107.43 (10)	N5—C4—H43C	113 (3)
V2—O231—V3	100.67 (9)	H41C—C4—H43C	112 (4)
V2—O24—V4	113.87 (11)	H42C—C4—H43C	103 (4)
V2—O25—V5	115.00 (11)	H1W1—O1W—H1W2	111 (3)
O3—V3—O34^i	103.96 (11)	H2W1—O2W—H2W2	110 (3)
O3—V3—O35	102.26 (11)	H3W1—O3W—H3W2	111 (3)
O34^i—V3—O35	95.68 (10)	H4W1—O4W—H4W2	112 (3)
O3—V3—O231	98.40 (10)	C1GX—N1GX—H1G1	120.0
O34^i—V3—O231	155.28 (9)	C1GX—N1GX—H1G2	120.0
O35—V3—O231	89.67 (9)	H1G1—N1GX—H1G2	120.0
O3—V3—O123	100.07 (11)	N2GX—C1GX—N1GX	123.3 (9)
O34^i—V3—O123	89.81 (9)	N2GX—C1GX—N3GX	113.9 (9)
O35—V3—O123	154.95 (9)	N1GX—C1GX—N3GX	122.7 (9)
O231—V3—O123	75.90 (8)	C1GX—N2GX—H2G1	120.0
O3—V3—O1^i	173.68 (10)	C1GX—N2GX—H2G2	120.0
O34^i—V3—O1^i	80.93 (8)	H2G1—N2GX—H2G2	120.0
O35—V3—O1^i	81.00 (8)	C1GX—N3GX—C3GX	119.9 (9)
O231—V3—O1^i	76.09 (8)	C1GX—N3GX—H3GX	120.0
O123—V3—O1^i	75.75 (8)	C3GX—N3GX—H3GX	120.0
O3—V3—V5^i	135.35 (9)	O3GX—C3GX—N4GX	120.8 (9)
O34^i—V3—V5^i	84.48 (7)	O3GX—C3GX—N3GX	125.9 (9)
O35—V3—V5^i	33.18 (7)	N4GX—C3GX—N3GX	113.3 (8)
O231—V3—V5^i	87.00 (6)	C3GX—N4GX—H4G1	120.0
O123—V3—V5^i	124.03 (6)	C3GX—N4GX—H4G2	120.0
O1^i—V3—V5^i	48.34 (5)	H4G1—N4GX—H4G2	120.0
V3^i—O34—V4	113.78 (10)	C1GY—N1GY—H1G3	120.0
V3—O35—V5^i	114.61 (11)	C1GY—N1GY—H1G4	120.0
O4—V4—O45	104.50 (11)	H1G3—N1GY—H1G4	120.0
O4—V4—O24	102.90 (11)	N1GY—C1GY—N2GY	123.1 (9)
O45—V4—O24	92.37 (10)	N1GY—C1GY—N3GY	123.4 (8)
O4—V4—O34	99.99 (11)	N2GY—C1GY—N3GY	113.5 (7)
O45—V4—O34	91.10 (9)	C1GY—N2GY—H2G3	120.0
O24—V4—O34	155.17 (9)	C1GY—N2GY—H2G4	120.0
O4—V4—O14	98.75 (10)	H2G3—N2GY—H2G4	120.0
O45—V4—O14	156.63 (9)	C1GY—N3GY—C3GY	125.0 (9)
O24—V4—O14	84.64 (9)	C1GY—N3GY—H3GY	117.5
O34—V4—O14	82.50 (9)	C3GY—N3GY—H3GY	117.5
O4—V4—O1	172.77 (10)	O3GY—C3GY—N4GY	123.3 (10)
O45—V4—O1	82.43 (8)	O3GY—C3GY—N3GY	128.0 (10)
O24—V4—O1	78.55 (8)	N4GY—C3GY—N3GY	108.7 (8)
O34—V4—O1	77.56 (8)	C3GY—N4GY—H4G3	120.0
O14—V4—O1	74.26 (8)	C3GY—N4GY—H4G4	120.0
O5—V5—O45	103.34 (11)	H4G3—N4GY—H4G4	120.0
O15^i—V1—O14—V4	179.26 (10)	V2—O25—V5—O1	−8.61 (11)
O231—V1—O14—V4	79.01 (11)	V2—O25—V5—V3^i	−7.91 (15)
O123^i—V1—O14—V4	−82.59 (11)	O4—V4—O45—V5	−178.69 (12)
O1—V1—O14—V4	−1.98 (10)	O24—V4—O45—V5	77.33 (12)
O1^i—V1—O14—V4	−8.1 (5)	O34—V4—O45—V5	−78.08 (12)
O2—V2—O24—V4	174.30 (12)	O14—V4—O45—V5	−4.6 (3)
O25—V2—O24—V4	69.65 (12)	O1—V4—O45—V5	−0.78 (10)
O231—V2—O24—V4	−85.47 (12)	O5—V5—O45—V4	−179.85 (12)
O123—V2—O24—V4	−31.2 (3)	O25—V5—O45—V4	−76.67 (12)
O1—V2—O24—V4	−10.11 (11)	O35^i—V5—O45—V4	78.23 (12)
O2—V2—O25—V5	−175.99 (13)	O15—V5—O45—V4	1.2 (3)
O24—V2—O25—V5	−71.03 (13)	O1—V5—O45—V4	0.78 (10)
O231—V2—O25—V5	29.8 (3)	V3^i—V5—O45—V4	47.34 (10)
O123—V2—O25—V5	84.66 (12)	N2—C1—N3—C2	27.4 (5)
O1—V2—O25—V5	8.83 (11)	N1—C1—N3—C2	−155.6 (3)
O3—V3—O35—V5^i	−176.45 (12)	C1—N3—C2—N5	−140.1 (3)
O34^i—V3—O35—V5^i	−70.80 (12)	C1—N3—C2—N4	41.1 (5)
O231—V3—O35—V5^i	85.02 (12)	N4—C2—N5—C4	−174.9 (4)
O123—V3—O35—V5^i	31.0 (3)	N3—C2—N5—C4	6.4 (5)
O1^i—V3—O35—V5^i	9.06 (11)	N4—C2—N5—C3	8.9 (5)
V2—O24—V4—O4	−177.33 (12)	N3—C2—N5—C3	−169.7 (3)
V2—O24—V4—O45	−71.86 (12)	N2GX—C1GX—N3GX—C3GX	179.89 (10)
V2—O24—V4—O34	25.9 (3)	N1GX—C1GX—N3GX—C3GX	−0.17 (16)
V2—O24—V4—O14	84.90 (12)	C1GX—N3GX—C3GX—O3GX	0.3 (2)
V2—O24—V4—O1	9.92 (10)	C1GX—N3GX—C3GX—N4GX	−179.93 (12)
V2—O25—V5—O5	176.32 (13)	N1GY—C1GY—N3GY—C3GY	−0.07 (18)
V2—O25—V5—O45	72.43 (13)	N2GY—C1GY—N3GY—C3GY	179.96 (12)
V2—O25—V5—O35^i	−21.8 (3)	C1GY—N3GY—C3GY—O3GY	0.0 (3)
V2—O25—V5—O15	−83.80 (12)	C1GY—N3GY—C3GY—N4GY	−179.96 (13)

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O35^ii	0.83 (2)	1.98 (2)	2.808 (3)	175 (4)
N1—H12···O4	0.82 (2)	2.86 (3)	3.407 (4)	126 (3)
N1—H12···O34	0.82 (2)	2.75 (3)	3.378 (4)	134 (3)
N1—H12···O14	0.82 (2)	2.28 (2)	3.080 (4)	163 (4)
N2—H21···O5^iii	0.82 (2)	2.15 (2)	2.964 (4)	171 (4)
N3—H3···O34	0.82 (2)	1.90 (2)	2.705 (3)	171 (4)
N4—H41···O45^iv	0.83 (2)	2.11 (2)	2.926 (4)	168 (4)
C3—H32C···O4^v	0.92 (2)	2.61 (2)	3.511 (5)	164 (3)
C3—H33C···O4^iv	0.92 (2)	2.57 (3)	3.379 (4)	147 (3)
N2—H22···O2W^iv	0.83 (2)	2.19 (2)	2.993 (4)	164 (4)
N4—H42···O4W	0.83 (2)	1.96 (2)	2.777 (4)	170 (4)
C3—H32C···O4W^v	0.92 (2)	3.17 (3)	3.741 (5)	122 (3)
C4—H42C···O3W^iv	0.92 (2)	2.94 (3)	3.560 (6)	126 (3)
O1W—H1W1···O2W	0.85 (1)	2.02 (1)	2.855 (5)	169 (5)
O2W—H2W1···O3W	0.85 (1)	1.99 (2)	2.822 (4)	164 (4)
O4W—H4W2···O3W	0.84 (1)	2.20 (3)	2.938 (5)	146 (5)
O4W—H4W1···O1W^iii	0.84 (1)	1.90 (2)	2.727 (5)	167 (5)
O1W—H1W2···O34	0.85 (1)	2.70 (4)	3.354 (4)	135 (4)
O1W—H1W2···O45	0.85 (1)	2.13 (2)	2.931 (4)	157 (4)
O2W—H2W2···O25^iv	0.85 (1)	1.97 (2)	2.801 (3)	167 (4)
O3W—H3W1···O24^vi	0.85 (1)	2.01 (2)	2.820 (3)	160 (4)
O3W—H3W2···O2^vi	0.84 (1)	2.61 (4)	3.145 (4)	122 (3)
O3W—H3W2···O5^iv	0.84 (1)	2.22 (2)	2.991 (4)	152 (4)
N1—H11···O3GY^i	0.83 (2)	2.89 (4)	3.195 (10)	105 (3)
C4—H41C···O3GX^vii	0.92 (2)	2.66 (3)	3.416 (10)	141 (3)
N1GX—H1G2···O3GX	0.82	1.96	2.581 (17)	132
N1GY—H1G4···O3GY	0.82	2.20	2.800 (19)	130
N1GX—H1G1···O123^viii	0.82	2.56	2.961 (12)	111
N2GX—H2G2···O2	0.82	2.64	3.277 (13)	136
N2GX—H2G2···O3	0.82	2.13	2.830 (13)	144
N3GX—H3GX···O123	0.82	2.13	2.915 (13)	160
N4GX—H4G1···O231^ix	0.82	2.23	3.016 (14)	161
N4GX—H4G1···O3^ix	0.82	2.50	3.010 (11)	121
N4GX—H4G2···O123	0.82	2.60	3.297 (14)	144
N4GX—H4G2···O15	0.82	2.24	2.958 (12)	147
N2GY—H2G4···O2	0.82	1.99	2.807 (11)	174
N2GY—H2G3···O15^x	0.82	2.44	2.963 (11)	123
N3GY—H3GY···O123	0.82	2.49	3.046 (10)	126
N3GY—H3GY···O2	0.82	2.64	3.331 (12)	143
N4GY—H4G4···O15	0.82	2.62	3.204 (11)	129
N4GY—H4G3···O231^ix	0.82	2.15	2.945 (14)	165
N1GX—H1G1···O1h	0.82	2.27	2.942 (15)	140
N2GX—H2G1···O1h	0.82	2.52	3.137 (17)	133
N1GY—H1G3···O1h	0.82	1.72	2.532 (15)	173
distanes—O1h···O
O1h···O231^xi			2.857 (9)
O1h···O2^xi			3.030 (9)
O1h···O3^xi			3.171 (9)
O1h···O15^viii			2.838 (9)
O1h···O25^viii			3.186 (9)
O1h···O3W^xii			3.177 (10)

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, y−1/2, −z+3/2; (iii) x, −y−1/2, z−1/2; (iv) −x+2, y−1/2, −z+5/2; (v) x, −y−1/2, z+1/2; (vi) −x+2, −y, −z+2; (vii) x, y−1, z; (viii) −x+1, −y+1, −z+2; (ix) x, −y+1/2, z+1/2; (x) x, −y+1/2, z−1/2; (xi) −x+1, y+1/2, −z+3/2; (xii) x−1, −y−1/2, z−3/2.