Crystal structure of layered bis(ethylenediamine)nickel hexavanadate as a new representative of the V₆O₁₄ series

A new [Ni(NH₂CH₂CH₂NH₂)₂](V₆O₁₄) compound has been synthesized hydrothermally and was found to crystallize in the monoclinic system. The single-crystal X-ray data leads to a disordered structure, which can be decomposed into two ordered models with different stacking of the V₆O₁₄ layers. The structure of the layer is the same in both models and represents a new member of the V₆O₁₄ series. All known structures from this series are constructed from the same chain of square pyramids (SP), which share alternatively adjacent or opposite edges of their bases. The differences lie in the orientation of the SP chains which are joined together by sharing corners with tetrahedra to form the layers. Combinatorial analysis of the V₆O₁₄ structures was conducted, yielding ten possible symmetry groups for the series of V₆O₁₄ layers. The known structures belong only to the three simplest cases with the highest symmetry.

Computing details

Data collection: SMART (Siemens, 1995) for OD-en2NiV6O14. Cell refinement: SAINT (Siemens, 1995) for OD-en2NiV6O14. Data reduction: SAINT for OD-en2NiV6O14. Program(s) used to solve structure: CSD (Akeslrud et al., 1993) for OD-en2NiV6O14. Program(s) used to refine structure: CSD for OD-en2NiV6O14. Molecular graphics: ORTEPIII (Farrugia, 1997), CrystalDesigner (1997) for OD-en2NiV6O14. Software used to prepare material for publication: CSD for OD-en2NiV6O14.

(OD-en2NiV6O14) bis-ethylenediamine nickel hexavanadium tetradecaoxide

Crystal data

(NH2CH2CH2NH2)2NiV6O14	F(000) = 692
Mr = 708.59	Dx = 2.497 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.9311 (11) Å	Cell parameters from 1430 reflections
b = 17.127 (2) Å	θ = 4.7–28°
c = 6.6270 (8) Å	µ = 3.90 mm^−1
β = 111.610 (2)°	T = 295 K
V = 942.4 (3) Å^3	Plate, black
Z = 2	0.41 × 0.16 × 0.06 mm

Data collection

Siemens Smart CCD diffractometer	1684 independent reflections
Radiation source: sealed tube	1267 reflections with Fo > 4σ(Fo)
Graphite monochromator	Rint = 0.051
ω scans	θmax = 28°, θmin = 3.1°
Absorption correction: multi-scan SADABS (sheldrick, 1996)	h = −8→2
Tmin = 0.641, Tmax = 0.777	k = −11→4
3679 measured reflections	l = −21→20

Refinement

Refinement on F	H-atom parameters not refined
Least-squares matrix: full with fixed elements per cycle	w = 1/[σ(Fo)^2 + 0.002Fo^2)]
R[F^2 > 2σ(F^2)] = 0.060	(Δ/σ)max = 0.01
wR(F^2) = 0.0637	Δρmax = 0.93 e Å^−3
1267 reflections	Δρmin = 1.22 e Å^−3
165 parameters

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
V1	0.50362 (1)	0.20999 (7)	0.1424 (2)	0.0079 (5)
V2	0.2310 (3)	0.2133 (2)	0.2810 (5)	0.0099 (4)	0.5
V3	0.7774 (3)	0.2894 (2)	0.0584 (5)	0.0107 (4)	0.5
V4	0.1761 (3)	0.2878 (2)	0.7532 (5)	0.0099 (4)	0.5
V5	0.8294 (3)	0.2133 (2)	0.5882 (5)	0.0107 (4)	0.5
O1	0.5012 (6)	0.1194 (3)	0.0690 (8)	0.017 (2)
O2	0.1915 (7)	0.1213 (3)	0.2816 (9)	0.023 (2)
O3	0.8104 (7)	0.3796 (3)	0.1123 (9)	0.025 (2)
O4	0.277 (2)	0.2578 (8)	0.574 (2)	0.013 (2)	0.5
O5	0.735 (2)	0.2399 (8)	0.303 (2)	0.017 (2)	0.5
O6	0.4683 (14)	0.2191 (7)	0.404 (2)	0.016 (2)	0.5
O7	−0.0196 (14)	0.2669 (7)	0.644 (2)	0.019 (2)	0.5
O8	0.269 (2)	0.2373 (8)	0.018 (2)	0.013 (2)	0.5
O9	0.736 (2)	0.2686 (8)	0.752 (2)	0.017 (2)	0.5
O10	0.5417 (14)	0.2807 (7)	−0.055 (2)	0.016 (2)	0.5
O11	1.0262 (14)	0.2304 (7)	0.671 (2)	0.019 (2)	0.5
Ni	0.5	0.5	0.5	0.0125 (6)
C1	0.1524 (10)	0.5164 (6)	0.3504 (14)	0.028 (4)
C2	0.1855 (11)	0.4566 (6)	0.201 (2)	0.033 (4)
N1	0.2871 (9)	0.5160 (4)	0.5629 (11)	0.025 (3)
N2	0.3419 (8)	0.4757 (4)	0.1903 (10)	0.021 (3)
H1	0.05398	0.50396	0.36866	0.05066*
H2	0.14310	0.56683	0.28603	0.05066*
H3	0.10262	0.45748	0.05737	0.05066*
H4	0.18760	0.40419	0.25675	0.05066*
H5	0.27280	0.47393	0.64993	0.05066*
H6	0.28996	0.56364	0.63726	0.05066*
H7	0.33109	0.52004	0.09848	0.05066*
H8	0.38157	0.43301	0.13069	0.05066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0041 (7)	0.0121 (7)	0.0077 (7)	0.0000 (5)	0.0023 (7)	−0.0002 (5)
O1	0.016 (3)	0.018 (3)	0.015 (3)	−0.004 (2)	0.004 (3)	−0.007 (2)
O2	0.027 (4)	0.016 (3)	0.027 (4)	−0.005 (3)	0.012 (3)	−0.001 (3)
O3	0.033 (4)	0.017 (3)	0.028 (3)	−0.005 (3)	0.014 (3)	−0.005 (3)
Ni	0.0115 (8)	0.0142 (8)	0.0116 (8)	−0.0012 (6)	0.0041 (7)	0.0011 (6)
C1	0.006 (5)	0.045 (7)	0.026 (6)	0.004 (4)	−0.001 (5)	0.007 (5)
C2	0.008 (5)	0.050 (7)	0.025 (6)	−0.003 (5)	−0.012 (5)	0.000 (5)
N1	0.030 (4)	0.024 (4)	0.031 (4)	−0.004 (3)	0.022 (4)	0.001 (3)
N2	0.018 (4)	0.028 (4)	0.016 (4)	0.002 (3)	0.003 (4)	−0.001 (3)

Geometric parameters (Å, º)

V1—O1	1.624 (6)	V5—O7^vii	1.559 (13)
V1—O6	1.876 (12)	V5—O3^i	1.614 (7)
V1—O10	1.900 (12)	V5—O11	1.663 (14)
V1—O10^i	1.916 (12)	V5—O5	1.823 (13)
V1—O6^ii	1.927 (12)	V5—O9	1.853 (15)
V1—O9^ii	1.97 (2)	V5—O10^i	2.392 (13)
V1—O4^ii	1.98 (2)	O1—Ni^viii	2.095 (5)
V1—O8	2.01 (2)	O6—O10^i	0.61 (2)
V2—O2	1.617 (6)	O7—O11^v	0.73 (2)
V2—O4^ii	1.646 (14)	Ni—N2	2.060 (6)
V2—O8^i	1.707 (13)	Ni—N2^ix	2.060 (6)
V2—O11^iii	1.955 (13)	Ni—N1	2.109 (8)
V2—O6	1.973 (13)	Ni—N1^ix	2.109 (8)
V3—O3	1.590 (7)	C1—H2	0.953
V3—O5^ii	1.673 (13)	C1—H1	0.954
V3—O9^ii	1.765 (15)	C1—N1	1.477 (12)
V3—O7^iv	1.944 (13)	C1—C2	1.527 (14)
V3—O10	1.963 (13)	C2—H3	0.967
V4—O2^i	1.569 (6)	C2—H4	0.969
V4—O11^v	1.586 (13)	C2—N2	1.461 (13)
V4—O7	1.666 (13)	N1—H6	0.949
V4—O4	1.809 (15)	N1—H5	0.960
V4—O8^vi	1.857 (13)	N2—H7	0.956
V4—O6^i	2.430 (13)	N2—H8	0.958
O1—V1—O6	111.6 (4)	O5—V5—O9	110.2 (7)
O1—V1—O10	112.9 (4)	O5—V5—O10^i	64.0 (6)
O1—V1—O10^i	111.8 (4)	O9—V5—O10^i	63.9 (6)
O1—V1—O6^ii	112.1 (4)	V1—O1—Ni^viii	175.3 (3)
O1—V1—O9^ii	100.6 (5)	V4^ii—O2—V2	16.4 (2)
O1—V1—O4^ii	107.3 (5)	V3—O3—V5^ii	15.6 (2)
O1—V1—O8	101.7 (5)	V2^i—O4—V2	155.1 (9)
O6—V1—O10	135.5 (5)	V2^i—O4—V1^i	105.8 (7)
O6—V1—O10^i	18.5 (5)	V2—O4—V1^i	99.0 (6)
O6—V1—O6^ii	132.3 (5)	V3^i—O5—V3	156.4 (9)
O6—V1—O9^ii	99.1 (6)	V3^i—O5—V1	105.2 (7)
O6—V1—O4^ii	71.6 (6)	V3—O5—V1	98.4 (6)
O6—V1—O8	81.5 (6)	O10^i—O6—V1	84.5 (16)
O10—V1—O10^i	131.2 (5)	O10^i—O6—V1^i	78.4 (16)
O10—V1—O6^ii	18.3 (5)	O10^i—O6—V2	176.4 (19)
O10—V1—O9^ii	72.7 (6)	V1—O6—V1^i	141.1 (7)
O10—V1—O4^ii	95.2 (6)	V1—O6—V2	97.8 (6)
O10—V1—O8	89.7 (6)	V1^i—O6—V2	101.3 (6)
O10^i—V1—O6^ii	136.1 (5)	O11^v—O7—V5^v	85.0 (14)
O10^i—V1—O9^ii	80.9 (6)	O11^v—O7—V4	71.0 (14)
O10^i—V1—O4^ii	89.3 (6)	V5^v—O7—V4	155.1 (9)
O10^i—V1—O8	99.5 (6)	V2^ii—O8—V2	153.4 (9)
O6^ii—V1—O9^ii	91.0 (6)	V2^ii—O8—V1	108.3 (7)
O6^ii—V1—O4^ii	78.0 (6)	V2—O8—V1	94.8 (6)
O6^ii—V1—O8	71.7 (6)	V3^i—O9—V3^vi	147.8 (9)
O9^ii—V1—O4^ii	152.0 (6)	V3^i—O9—V1^i	108.2 (7)
O9^ii—V1—O8	155.6 (6)	V3^vi—O9—V1^i	96.8 (7)
O4^ii—V1—O8	10.3 (6)	O6^ii—O10—V1	83.3 (16)
O2—V2—O4^ii	114.6 (6)	O6^ii—O10—V1^ii	77.0 (16)
O2—V2—O8^i	116.7 (6)	O6^ii—O10—V3	173.7 (19)
O2—V2—O11^iii	107.8 (5)	V1—O10—V1^ii	140.0 (7)
O2—V2—O6	104.5 (4)	V1—O10—V3	103.0 (6)
O4^ii—V2—O8^i	126.5 (7)	V1^ii—O10—V3	98.3 (6)
O4^ii—V2—O11^iii	91.6 (6)	O7^vii—O11—V4^vii	83.2 (14)
O4^ii—V2—O6	76.7 (6)	O7^vii—O11—V5	69.0 (13)
O8^i—V2—O11^iii	86.4 (6)	V4^vii—O11—V5	151.5 (9)
O8^i—V2—O6	77.2 (6)	N2—Ni—N2^ix	180.0 (3)
O11^iii—V2—O6	147.6 (5)	N2—Ni—O1^x	91.9 (2)
O3—V3—O5^ii	118.2 (6)	N2—Ni—O1^i	88.1 (2)
O3—V3—O9^ii	117.0 (6)	N2—Ni—N1	83.5 (3)
O3—V3—O7^iv	109.9 (5)	N2—Ni—N1^ix	96.5 (3)
O3—V3—O10	104.1 (5)	N2^ix—Ni—O1^x	88.1 (2)
O5^ii—V3—O9^ii	122.6 (7)	N2^ix—Ni—O1^i	91.9 (2)
O5^ii—V3—O7^iv	89.1 (6)	N2^ix—Ni—N1	96.5 (3)
O5^ii—V3—O10	77.4 (6)	N2^ix—Ni—N1^ix	83.5 (3)
O9^ii—V3—O7^iv	86.1 (6)	O1^x—Ni—O1^i	180.0 (2)
O9^ii—V3—O10	75.7 (6)	O1^x—Ni—N1	89.1 (3)
O7^iv—V3—O10	145.8 (5)	O1^x—Ni—N1^ix	90.9 (3)
O2^i—V4—O11^v	133.0 (5)	O1^i—Ni—N1	90.9 (3)
O2^i—V4—O7	107.3 (5)	O1^i—Ni—N1^ix	89.1 (3)
O2^i—V4—O4	108.5 (5)	N1—Ni—N1^ix	180.0 (3)
O2^i—V4—O8^vi	111.1 (5)	H2—C1—H1	109.07
O2^i—V4—O6^i	88.0 (4)	H2—C1—N1	109.72
O11^v—V4—O7	25.8 (6)	H2—C1—C2	108.83
O11^v—V4—O4	99.2 (7)	H1—C1—N1	110.05
O11^v—V4—O8^vi	93.5 (7)	H1—C1—C2	109.86
O11^v—V4—O6^i	138.9 (6)	N1—C1—C2	109.3 (8)
O7—V4—O4	110.4 (7)	H3—C2—H4	106.79
O7—V4—O8^vi	109.9 (6)	H3—C2—N2	110.36
O7—V4—O6^i	164.7 (6)	H3—C2—C1	111.55
O4—V4—O8^vi	109.5 (7)	H4—C2—N2	109.93
O4—V4—O6^i	62.4 (6)	H4—C2—C1	110.83
O8^vi—V4—O6^i	63.5 (5)	N2—C2—C1	107.4 (8)
O7^vii—V5—O3^i	132.1 (6)	H6—N1—H5	108.50
O7^vii—V5—O11	26.0 (6)	H6—N1—C1	110.34
O7^vii—V5—O5	97.2 (7)	H6—N1—Ni	111.11
O7^vii—V5—O9	95.5 (7)	H5—N1—C1	109.57
O7^vii—V5—O10^i	141.0 (6)	H5—N1—Ni	110.50
O3^i—V5—O11	106.2 (5)	C1—N1—Ni	106.8 (6)
O3^i—V5—O5	108.9 (5)	H7—N2—H8	108.04
O3^i—V5—O9	111.1 (5)	H7—N2—C2	109.49
O3^i—V5—O10^i	86.9 (4)	H7—N2—Ni	110.18
O11—V5—O5	109.0 (7)	H8—N2—C2	110.79
O11—V5—O9	111.3 (7)	H8—N2—Ni	110.08
O11—V5—O10^i	166.9 (6)	C2—N2—Ni	108.3 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H5···O2^i	0.960	2.101	3.044	166.99
N1—H6···O3^ix	0.949	2.366	3.157	140.59
N2—H7···O3^xi	0.956	2.280	3.163	153.16
N2—H8···O2^ii	0.958	2.491	3.036	116.01

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2; (ix) −x+1, −y+1, −z+1; (xi) −x+1, −y+1, −z.

(Ordered-en2NiV6O14) bis-ethylenediamine nickel hexavanadium tetradecaoxide

Crystal data

(NH2CH2CH2NH2)2NiV6O14	β = 111.610 (2)°
Mr = 708.59	V = 1884.9 (7) Å^3
Monoclinic, P21/n	Z = 4
a = 17.862 (2) Å	F(000) = 1384
b = 17.127 (2) Å	Dx = 2.497 Mg m^−3
c = 6.6270 (8) Å

Data collection

h = →	l = →
k = →

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

	x	y	z	Uiso*/Ueq
Ni1	0.5	0.5	0.5	0.0098 (4)
Ni1a	0.5	0	1	0.0098 (4)
V1	0.50181 (7)	0.20999 (7)	0.1424 (2)	0.0071 (4)
V2	0.3655 (2)	0.2133 (2)	0.2810 (5)	0.0099 (4)
V3	0.6387 (2)	0.2894 (2)	0.0584 (5)	0.0107 (4)
V4	0.3380 (2)	0.2878 (2)	0.7532 (5)	0.0099 (4)
V5	0.6647 (2)	0.2133 (2)	0.5882 (5)	0.0107 (4)
V1a	0.50181 (7)	0.29001 (7)	0.6424 (2)	0.0071 (4)
O1	0.5006 (3)	0.1194 (3)	0.0690 (8)	0.013 (2)
O2	0.3457 (3)	0.1213 (3)	0.2816 (9)	0.017 (2)
O3	0.6552 (4)	0.3796 (3)	0.1123 (9)	0.018 (2)
O4	0.3884 (9)	0.2578 (8)	0.574 (2)	0.013 (2)
O5	0.6177 (9)	0.2399 (8)	0.303 (2)	0.017 (2)
O6	0.4842 (7)	0.2191 (7)	0.404 (2)	0.016 (2)
O7	0.2402 (7)	0.2669 (7)	0.644 (2)	0.019 (2)
O8	0.3843 (9)	0.2373 (8)	0.018 (2)	0.013 (2)
O9	0.6181 (9)	0.2686 (8)	0.752 (2)	0.017 (2)
O10	0.5208 (7)	0.2807 (7)	−0.055 (2)	0.016 (2)
O11	0.7631 (7)	0.2305 (7)	0.671 (2)	0.019 (2)
O1a	0.5006 (3)	0.3806 (3)	0.5690 (8)	0.013 (2)
O2a	0.3457 (3)	0.3787 (3)	0.7816 (9)	0.017 (2)
O3a	0.6552 (4)	0.1204 (3)	0.6123 (9)	0.018 (2)
N1	0.3935 (4)	0.5160 (4)	0.5629 (11)	0.020 (2)
N2	0.4210 (4)	0.4757 (4)	0.1903 (10)	0.017 (2)
N1a	0.3935 (4)	−0.0160 (4)	1.0629 (11)	0.020 (2)
N2a	0.4210 (4)	0.0243 (4)	0.6903 (10)	0.017 (2)
C1	0.3262 (5)	0.5164 (6)	0.3504 (14)	0.026 (3)
C2	0.3428 (6)	0.4566 (6)	0.201 (2)	0.029 (3)
C1a	0.3262 (5)	−0.0164 (6)	0.8504 (14)	0.026 (3)
C2a	0.3428 (6)	0.0434 (6)	0.701 (2)	0.029 (3)
H1	0.27699	0.50396	0.36866	0.05066*
H2	0.32155	0.56683	0.28603	0.05066*
H3	0.30131	0.45748	0.05737	0.05066*
H4	0.34380	0.40419	0.25675	0.05066*
H5	0.38640	0.47393	0.64993	0.05066*
H6	0.39498	0.56364	0.63726	0.05066*
H7	0.41555	0.52004	0.09848	0.05066*
H8	0.44079	0.43301	0.13069	0.05066*
H1a	0.27699	−0.00396	0.86866	0.05066*
H2a	0.32155	−0.06683	0.78603	0.05066*
H3a	0.30131	0.04252	0.55737	0.05066*
H4a	0.34380	0.09581	0.75675	0.05066*
H5a	0.38640	0.02607	1.14993	0.05066*
H6a	0.39498	−0.06364	1.13726	0.05066*
H7a	0.41555	−0.02004	0.59848	0.05066*
H8a	0.44079	0.06699	0.63069	0.05066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0029 (2)	0.0143 (8)	0.0116 (8)	−0.0006 (3)	0.0021 (4)	0.0011 (6)
Ni1a	0.0029 (2)	0.0143 (8)	0.0116 (8)	0.0006 (3)	0.0021 (4)	−0.0011 (6)
V1	0.0010 (2)	0.0122 (7)	0.0077 (7)	0.0000 (3)	0.0012 (3)	−0.0002 (5)
V1a	0.0010 (2)	0.0122 (7)	0.0077 (7)	0.0000 (3)	0.0012 (3)	0.0002 (5)
O1	0.0041 (8)	0.018 (3)	0.015 (3)	−0.0018 (13)	0.0019 (14)	−0.007 (2)
O2	0.0067 (9)	0.016 (3)	0.027 (4)	−0.0023 (13)	0.006 (2)	−0.001 (3)
O3	0.0083 (9)	0.017 (3)	0.028 (3)	−0.0024 (14)	0.007 (2)	−0.005 (3)
O1a	0.0041 (8)	0.018 (3)	0.015 (3)	0.0018 (13)	0.0019 (14)	0.007 (2)
O2a	0.0067 (9)	0.016 (3)	0.027 (4)	0.0023 (13)	0.006 (2)	0.001 (3)
O3a	0.0083 (9)	0.017 (3)	0.028 (3)	0.0024 (14)	0.007 (2)	0.005 (3)
N1	0.0074 (11)	0.024 (4)	0.031 (4)	−0.002 (2)	0.011 (2)	0.001 (3)
N2	0.0044 (10)	0.028 (4)	0.016 (4)	0.0009 (15)	0.002 (2)	−0.001 (3)
N1a	0.0074 (11)	0.024 (4)	0.031 (4)	0.002 (2)	0.011 (2)	−0.001 (3)
N2a	0.0044 (10)	0.028 (4)	0.016 (4)	−0.0009 (15)	0.002 (2)	0.001 (3)
C1	0.0016 (13)	0.045 (7)	0.026 (6)	0.002 (2)	−0.001 (3)	0.007 (5)
C2	0.0021 (13)	0.050 (7)	0.025 (6)	−0.002 (2)	−0.006 (3)	0.000 (5)
C1a	0.0016 (13)	0.045 (7)	0.026 (6)	−0.002 (2)	−0.001 (3)	−0.007 (5)
C2a	0.0021 (13)	0.050 (7)	0.025 (6)	0.002 (2)	−0.006 (3)	0.000 (5)

Geometric parameters (Å, º)

Ni1—N2	2.060 (6)	V5—O3a	1.614 (6)
Ni1—N2^i	2.060 (6)	V5—O11	1.663 (14)
Ni1—O1a	2.095 (5)	V5—O5	1.823 (13)
Ni1—O1a^i	2.095 (5)	V5—O9	1.853 (15)
Ni1—N1	2.109 (8)	V1a—O1a	1.624 (5)
Ni1—N1^i	2.109 (8)	V1a—O10^iii	1.916 (12)
Ni1a—N2a	2.060 (6)	V1a—O6	1.927 (12)
Ni1a—N2a^ii	2.060 (6)	V1a—O9	1.97 (2)
Ni1a—O1^iii	2.095 (5)	V1a—O4	1.98 (2)
Ni1a—O1^iv	2.095 (5)	N1—H6	0.949
Ni1a—N1a	2.109 (8)	N1—H5	0.960
Ni1a—N1a^ii	2.109 (8)	N1—C1	1.477 (11)
V1—O1	1.624 (5)	N2—H7	0.956
V1—O6	1.876 (13)	N2—H8	0.958
V1—O10	1.900 (13)	N2—C2	1.461 (14)
V1—O8	2.01 (2)	N1a—H6a	0.949
V1—O5	2.01 (2)	N1a—H5a	0.960
V2—O2	1.617 (6)	N1a—C1a	1.477 (11)
V2—O8	1.934 (14)	N2a—H7a	0.956
V2—O11^v	1.955 (14)	N2a—H8a	0.958
V2—O6	1.973 (14)	N2a—C2a	1.461 (14)
V2—O4	1.983 (13)	C1—H2	0.953
V3—O3	1.590 (6)	C1—H1	0.954
V3—O7^vi	1.944 (14)	C1—C2	1.527 (15)
V3—O9^vii	1.958 (13)	C2—H3	0.967
V3—O10	1.963 (14)	C2—H4	0.969
V3—O5	1.981 (14)	C1a—H2a	0.953
V4—O2a	1.569 (6)	C1a—H1a	0.954
V4—O7	1.666 (14)	C1a—C2a	1.527 (15)
V4—O4	1.809 (15)	C2a—H3a	0.967
V4—O8^iii	1.857 (13)	C2a—H4a	0.969
N2—Ni1—N2^i	180.0 (3)	O10^iii—V1a—O6	136.1 (5)
N2—Ni1—O1a	88.1 (2)	O10^iii—V1a—O9	80.9 (6)
N2—Ni1—O1a^i	91.9 (2)	O10^iii—V1a—O4	89.3 (6)
N2—Ni1—N1	83.5 (3)	O6—V1a—O9	91.0 (6)
N2—Ni1—N1^i	96.5 (3)	O6—V1a—O4	78.0 (6)
N2^i—Ni1—O1a	91.9 (2)	O9—V1a—O4	152.0 (6)
N2^i—Ni1—O1a^i	88.1 (2)	V1—O1—Ni1a^vii	175.3 (3)
N2^i—Ni1—N1	96.5 (3)	V4—O4—V2	141.2 (8)
N2^i—Ni1—N1^i	83.5 (3)	V4—O4—V1a	118.9 (8)
O1a—Ni1—O1a^i	180.0 (2)	V2—O4—V1a	99.0 (6)
O1a—Ni1—N1	90.9 (2)	V5—O5—V3	143.3 (8)
O1a—Ni1—N1^i	89.1 (2)	V5—O5—V1	118.3 (8)
O1a^i—Ni1—N1	89.1 (2)	V3—O5—V1	98.4 (6)
O1a^i—Ni1—N1^i	90.9 (2)	V1—O6—V1a	141.1 (7)
N1—Ni1—N1^i	180.0 (3)	V1—O6—V2	97.8 (6)
N2a—Ni1a—N2a^ii	180.0 (3)	V1a—O6—V2	101.3 (6)
N2a—Ni1a—O1^iii	88.1 (2)	V4—O7—V3^viii	161.7 (8)
N2a—Ni1a—O1^iv	91.9 (2)	V4^vii—O8—V2	141.8 (8)
N2a—Ni1a—N1a	83.5 (3)	V4^vii—O8—V1	122.0 (8)
N2a—Ni1a—N1a^ii	96.5 (3)	V2—O8—V1	94.8 (6)
N2a^ii—Ni1a—O1^iii	91.9 (2)	V5—O9—V3^iii	138.3 (8)
N2a^ii—Ni1a—O1^iv	88.1 (2)	V5—O9—V1a	121.4 (8)
N2a^ii—Ni1a—N1a	96.5 (3)	V3^iii—O9—V1a	96.8 (6)
N2a^ii—Ni1a—N1a^ii	83.5 (3)	V1—O10—V1a^vii	140.0 (7)
O1^iii—Ni1a—O1^iv	180.0 (2)	V1—O10—V3	103.0 (6)
O1^iii—Ni1a—N1a	90.9 (2)	V1a^vii—O10—V3	98.3 (6)
O1^iii—Ni1a—N1a^ii	89.1 (2)	V5—O11—V2^ix	160.1 (8)
O1^iv—Ni1a—N1a	89.1 (2)	V1a—O1a—Ni1	175.3 (3)
O1^iv—Ni1a—N1a^ii	90.9 (2)	H6—N1—H5	108.51
N1a—Ni1a—N1a^ii	180.0 (3)	H6—N1—C1	110.34
O1—V1—O6	111.6 (4)	H6—N1—Ni1	111.11
O1—V1—O10	112.9 (4)	H5—N1—C1	109.56
O1—V1—O8	101.7 (5)	H5—N1—Ni1	110.50
O1—V1—O5	107.4 (5)	C1—N1—Ni1	106.8 (5)
O6—V1—O10	135.5 (6)	H7—N2—H8	108.04
O6—V1—O8	81.5 (6)	H7—N2—C2	109.49
O6—V1—O5	89.0 (6)	H7—N2—Ni1	110.18
O10—V1—O8	89.7 (6)	H8—N2—C2	110.79
O10—V1—O5	77.9 (6)	H8—N2—Ni1	110.08
O8—V1—O5	150.9 (6)	C2—N2—Ni1	108.3 (6)
O2—V2—O8	108.6 (5)	H6a—N1a—H5a	108.51
O2—V2—O11^v	107.8 (5)	H6a—N1a—C1a	110.34
O2—V2—O6	104.5 (5)	H6a—N1a—Ni1a	111.11
O2—V2—O4	109.8 (5)	H5a—N1a—C1a	109.56
O8—V2—O11^v	90.5 (6)	H5a—N1a—Ni1a	110.50
O8—V2—O6	81.0 (6)	C1a—N1a—Ni1a	106.8 (5)
O8—V2—O4	139.3 (6)	H7a—N2a—H8a	108.04
O11^v—V2—O6	147.6 (6)	H7a—N2a—C2a	109.49
O11^v—V2—O4	90.1 (6)	H7a—N2a—Ni1a	110.18
O6—V2—O4	77.0 (6)	H8a—N2a—C2a	110.79
O3—V3—O7^vi	109.9 (5)	H8a—N2a—Ni1a	110.08
O3—V3—O9^vii	111.0 (5)	C2a—N2a—Ni1a	108.3 (6)
O3—V3—O10	104.1 (5)	H2—C1—H1	109.07
O3—V3—O5	107.9 (5)	H2—C1—N1	109.72
O7^vi—V3—O9^vii	90.6 (6)	H2—C1—C2	108.82
O7^vi—V3—O10	145.8 (6)	H1—C1—N1	110.05
O7^vi—V3—O5	89.2 (6)	H1—C1—C2	109.86
O9^vii—V3—O10	79.9 (6)	N1—C1—C2	109.3 (8)
O9^vii—V3—O5	138.5 (6)	H3—C2—H4	106.79
O10—V3—O5	77.3 (6)	H3—C2—N2	110.36
O2a—V4—O7	107.3 (5)	H3—C2—C1	111.55
O2a—V4—O4	108.5 (5)	H4—C2—N2	109.93
O2a—V4—O8^iii	111.1 (5)	H4—C2—C1	110.83
O7—V4—O4	110.4 (7)	N2—C2—C1	107.4 (8)
O7—V4—O8^iii	109.9 (7)	H2a—C1a—H1a	109.07
O4—V4—O8^iii	109.5 (7)	H2a—C1a—N1a	109.72
O3a—V5—O11	106.2 (5)	H2a—C1a—C2a	108.82
O3a—V5—O5	108.9 (5)	H1a—C1a—N1a	110.05
O3a—V5—O9	111.1 (5)	H1a—C1a—C2a	109.86
O11—V5—O5	109.0 (7)	N1a—C1a—C2a	109.3 (8)
O11—V5—O9	111.3 (7)	H3a—C2a—H4a	106.79
O5—V5—O9	110.2 (7)	H3a—C2a—N2a	110.36
O1a—V1a—O10^iii	111.8 (4)	H3a—C2a—C1a	111.55
O1a—V1a—O6	112.1 (4)	H4a—C2a—N2a	109.93
O1a—V1a—O9	100.7 (5)	H4a—C2a—C1a	110.83
O1a—V1a—O4	107.3 (5)	N2a—C2a—C1a	107.4 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H5···O2a	0.960	2.101	3.044	166.99
N1—H6···O3^i	0.949	2.366	3.157	140.59
N2—H7···O3^x	0.956	2.280	3.163	153.16
N2—H8···O2a^vii	0.958	2.491	3.036	116.01
N1a—H5a···O2^iii	0.960	2.101	3.044	166.99
N1a—H6a···O3a^ii	0.949	2.366	3.157	140.59
N2a—H7a···O3a^iv	0.956	2.280	3.163	153.16
N2a—H8a···O2	0.958	2.491	3.036	116.01

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