Bis­(dabconium) vanadium arsenate octahydrate, (N₂C₆H₁₄)₂[V₄As₆O₃₀H₆]·8H₂O

The title compound contains a network of [V₄As₆O₃₀H₆]^4- clusters, each of which is accompanied by two dabconium (doubly protonated 1,4-di­aza­bi­cyclo­[2.2.2]­octane) cations and eight water mol­ecules. A complex hydrogen-bonding network stabilizes the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.028
• wR factor = 0.071
• Data-to-parameter ratio = 20.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           30.21
         From the CIF: _reflns_number_total               6021
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         6669
         Completeness (_total/calc)             90.28%
          Alert C: < 95% complete

General Notes



FORMU_01  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:   C6 H25 As3 N2 O19 V2
          Atom count from _chemical_formula_moiety:C12 H50 As6 N4 O38 V4

ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.530
          Tmax scaled      0.119 Tmin scaled      0.093


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(I)

Crystal data

(C6H14N2)2[V4As6O30H6]·8H2O	F(000) = 744
Mr = 755.91	Dx = 2.239 Mg m^−3
Triclinic, P1	Melting point: decomposes before melting K
a = 9.6824 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.0733 (7) Å	Cell parameters from 3766 reflections
c = 11.8967 (7) Å	θ = 2.1–30.1°
α = 94.546 (2)°	µ = 5.32 mm^−1
β = 101.557 (2)°	T = 293 K
γ = 114.193 (2)°	Chunk, orange
V = 1121.16 (11) Å^3	0.50 × 0.40 × 0.40 mm
Z = 2

Data collection

Bruker SMART1000 CCD diffractometer	6021 independent reflections
Radiation source: fine-focus sealed tube	4987 reflections with I > 2σ()'
Graphite monochromator	Rint = 0.015
ω scans	θmax = 30.2°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −13→13
Tmin = 0.176, Tmax = 0.225	k = −10→15
7764 measured reflections	l = −16→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap and geom
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.041P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.001
6021 reflections	Δρmax = 0.60 e Å^−3
292 parameters	Δρmin = −0.82 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0025 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
V1	0.65452 (5)	0.77980 (4)	0.61404 (4)	0.02073 (10)
V2	0.58641 (5)	0.54350 (4)	0.76000 (4)	0.02084 (10)
As1	0.58581 (3)	0.78147 (2)	0.33273 (2)	0.01968 (7)
As2	0.66837 (3)	0.48861 (2)	0.47031 (2)	0.01778 (7)
As3	0.94147 (3)	0.73424 (3)	0.76272 (2)	0.02442 (8)
O1	0.6256 (2)	0.53455 (17)	0.34055 (15)	0.0209 (4)
O2	0.5701 (2)	0.31980 (17)	0.45954 (16)	0.0211 (4)
O3	0.4199 (2)	0.63745 (17)	0.28393 (17)	0.0235 (4)
O4	0.6037 (2)	0.70664 (17)	0.74747 (16)	0.0230 (4)
O5	0.6480 (2)	0.57482 (17)	0.58194 (15)	0.0196 (3)
O6	0.8654 (2)	0.83099 (18)	0.69252 (17)	0.0263 (4)
O7	0.6980 (2)	0.8180 (2)	0.24049 (18)	0.0290 (4)
O8	0.6959 (2)	0.78996 (18)	0.46561 (16)	0.0244 (4)
O9	0.8594 (2)	0.5176 (2)	0.49243 (18)	0.0294 (4)
H9	0.9168	0.5761	0.5676	0.035*
O10	1.0341 (2)	0.6813 (2)	0.68360 (19)	0.0335 (5)
O11	0.5100 (2)	0.89555 (19)	0.34370 (19)	0.0310 (5)
H11	0.5748	0.9812	0.3498	0.037*
O12	0.5439 (2)	0.5250 (2)	0.88139 (17)	0.0332 (5)
O13	0.8100 (2)	0.60699 (19)	0.81023 (17)	0.0279 (4)
O14	0.6484 (2)	0.91935 (18)	0.64181 (19)	0.0314 (4)
O15	1.0627 (3)	0.8341 (2)	0.89093 (18)	0.0403 (5)
H15	1.1588	0.8800	0.8801	0.048*
O20	0.3350 (3)	0.0102 (2)	0.8958 (2)	0.0419 (6)
H20	0.3254	0.0615	0.8419	0.050*
H21	0.3912	0.0609	0.9697	0.050*
O21	0.7046 (3)	1.1523 (2)	0.3799 (3)	0.0637 (9)
H22	0.7948	1.1896	0.3628	0.063 (13)*
H23	0.6614	1.1983	0.4117	0.24 (4)*
O22	0.6954 (3)	0.3441 (3)	0.9789 (2)	0.0537 (7)
H24	0.6056	0.3634	0.9487	0.064*
H25	0.6410	0.2866	1.0320	0.064*
O23	0.5113 (3)	0.1620 (3)	0.1110 (2)	0.0545 (7)
H26	0.4721	0.2064	0.1586	0.065*
H27	0.5648	0.1337	0.1512	0.065*
N1	1.0736 (3)	0.2422 (2)	0.7741 (2)	0.0288 (5)
H1	1.1529	0.2198	0.7688	0.035*
N2	0.8561 (3)	0.3017 (3)	0.7871 (3)	0.0387 (6)
H2	0.7766	0.3240	0.7923	0.046*
C1	0.9750 (4)	0.2232 (4)	0.6545 (3)	0.0415 (8)
H1A	0.9229	0.1285	0.6194	0.050*
H1B	1.0401	0.2720	0.6059	0.050*
C2	1.1409 (4)	0.3838 (3)	0.8336 (3)	0.0425 (8)
H2A	1.1953	0.4434	0.7852	0.051*
H2B	1.2153	0.3976	0.9069	0.051*
C3	0.9752 (4)	0.1522 (3)	0.8428 (3)	0.0386 (7)
H3A	1.0355	0.1692	0.9228	0.046*
H3B	0.9418	0.0587	0.8096	0.046*
C4	0.8543 (4)	0.2755 (5)	0.6636 (3)	0.0559 (11)
H4A	0.8790	0.3578	0.6319	0.067*
H4B	0.7511	0.2094	0.6193	0.067*
C5	1.0080 (4)	0.4143 (4)	0.8557 (5)	0.0620 (13)
H5A	1.0118	0.4225	0.9382	0.074*
H5B	1.0179	0.4986	0.8317	0.074*
C6	0.8341 (4)	0.1795 (3)	0.8397 (3)	0.0342 (7)
H6A	0.7401	0.1030	0.7936	0.041*
H6B	0.8225	0.1937	0.9181	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0214 (2)	0.01598 (19)	0.0233 (2)	0.00764 (16)	0.00426 (16)	0.00247 (16)
V2	0.0211 (2)	0.0216 (2)	0.0205 (2)	0.00935 (16)	0.00606 (16)	0.00478 (16)
As1	0.01754 (12)	0.01954 (13)	0.02521 (14)	0.00981 (9)	0.00721 (10)	0.00748 (10)
As2	0.01647 (12)	0.01708 (12)	0.02121 (13)	0.00850 (9)	0.00561 (9)	0.00252 (9)
As3	0.01895 (13)	0.02699 (14)	0.02298 (14)	0.00748 (10)	0.00215 (10)	0.00352 (10)
O1	0.0204 (8)	0.0223 (9)	0.0212 (9)	0.0095 (7)	0.0068 (7)	0.0057 (7)
O2	0.0203 (8)	0.0171 (8)	0.0267 (9)	0.0091 (7)	0.0058 (7)	0.0032 (7)
O3	0.0195 (8)	0.0195 (8)	0.0296 (10)	0.0075 (7)	0.0047 (7)	0.0046 (7)
O4	0.0256 (9)	0.0217 (9)	0.0219 (9)	0.0111 (7)	0.0063 (7)	0.0006 (7)
O5	0.0213 (8)	0.0183 (8)	0.0202 (9)	0.0096 (7)	0.0062 (7)	0.0015 (7)
O6	0.0224 (9)	0.0206 (9)	0.0307 (10)	0.0059 (7)	0.0025 (8)	0.0068 (8)
O7	0.0271 (10)	0.0367 (11)	0.0347 (11)	0.0192 (8)	0.0168 (8)	0.0168 (9)
O8	0.0212 (9)	0.0247 (9)	0.0255 (10)	0.0085 (7)	0.0044 (7)	0.0065 (7)
O9	0.0175 (9)	0.0360 (11)	0.0344 (11)	0.0132 (8)	0.0049 (8)	−0.0005 (9)
O10	0.0233 (10)	0.0400 (12)	0.0349 (12)	0.0131 (9)	0.0059 (8)	0.0020 (9)
O11	0.0246 (10)	0.0217 (9)	0.0509 (13)	0.0136 (8)	0.0099 (9)	0.0082 (9)
O12	0.0373 (12)	0.0386 (11)	0.0249 (10)	0.0151 (9)	0.0120 (9)	0.0093 (9)
O13	0.0204 (9)	0.0294 (10)	0.0315 (11)	0.0093 (8)	0.0027 (8)	0.0109 (8)
O14	0.0346 (11)	0.0191 (9)	0.0396 (12)	0.0130 (8)	0.0066 (9)	0.0015 (8)
O15	0.0286 (11)	0.0472 (13)	0.0253 (11)	0.0015 (9)	−0.0002 (9)	0.0005 (9)
O20	0.0432 (13)	0.0325 (11)	0.0351 (12)	0.0064 (10)	−0.0005 (10)	0.0095 (9)
O21	0.0466 (15)	0.0256 (12)	0.124 (3)	0.0102 (11)	0.0504 (17)	−0.0001 (14)
O22	0.0526 (16)	0.0596 (16)	0.0576 (17)	0.0308 (13)	0.0163 (13)	0.0165 (13)
O23	0.0704 (19)	0.0738 (18)	0.0350 (13)	0.0497 (16)	0.0093 (13)	0.0025 (12)
N1	0.0239 (11)	0.0364 (13)	0.0321 (13)	0.0191 (10)	0.0081 (10)	0.0039 (10)
N2	0.0261 (12)	0.0374 (14)	0.0624 (19)	0.0208 (11)	0.0165 (12)	0.0108 (13)
C1	0.0371 (17)	0.059 (2)	0.0278 (16)	0.0199 (15)	0.0092 (13)	0.0106 (14)
C2	0.0257 (15)	0.0376 (17)	0.057 (2)	0.0096 (13)	0.0097 (15)	−0.0050 (15)
C3	0.052 (2)	0.0402 (17)	0.0368 (17)	0.0277 (15)	0.0183 (15)	0.0158 (14)
C4	0.0364 (18)	0.095 (3)	0.053 (2)	0.038 (2)	0.0169 (17)	0.042 (2)
C5	0.0364 (19)	0.0291 (17)	0.114 (4)	0.0116 (14)	0.021 (2)	−0.010 (2)
C6	0.0361 (16)	0.0364 (16)	0.0297 (15)	0.0128 (13)	0.0138 (13)	0.0064 (12)

Geometric parameters (Å, º)

V1—O14	1.5819 (19)	O21—H22	0.8739
V1—O6	1.8879 (19)	O21—H23	0.8855
V1—O8	1.8892 (19)	O22—H24	0.9850
V1—O4	1.8996 (18)	O22—H25	1.0018
V1—O2^i	1.9576 (18)	O23—H26	0.9503
V1—O5	2.2443 (17)	O23—H27	0.8070
V2—O12	1.585 (2)	N1—C2	1.478 (4)
V2—O4	1.7661 (18)	N1—C1	1.491 (4)
V2—O13	1.9252 (19)	N1—C3	1.495 (4)
V2—O1^i	1.9469 (18)	N1—H1	0.9100
V2—O3^i	2.0029 (19)	N2—C4	1.470 (5)
V2—O5	2.3272 (18)	N2—C6	1.490 (4)
As1—O7	1.6539 (18)	N2—C5	1.496 (5)
As1—O3	1.6852 (18)	N2—H2	0.9100
As1—O8	1.6920 (18)	C1—C4	1.519 (5)
As1—O11	1.7098 (19)	C1—H1A	0.9700
As2—O5	1.6651 (17)	C1—H1B	0.9700
As2—O1	1.6894 (17)	C2—C5	1.522 (5)
As2—O2	1.6945 (17)	C2—H2A	0.9700
As2—O9	1.7027 (18)	C2—H2B	0.9700
As3—O10	1.648 (2)	C3—C6	1.510 (5)
As3—O13	1.6939 (18)	C3—H3A	0.9700
As3—O15	1.696 (2)	C3—H3B	0.9700
As3—O6	1.7120 (19)	C4—H4A	0.9700
O9—H9	0.9702	C4—H4B	0.9700
O11—H11	0.8835	C5—H5A	0.9700
O15—H15	0.9009	C5—H5B	0.9700
O20—H20	0.9059	C6—H6A	0.9700
O20—H21	0.9298	C6—H6B	0.9700
O14—V1—O6	99.03 (10)	As2—O9—H9	108.0
O14—V1—O8	99.98 (10)	As1—O11—H11	117.0
O6—V1—O8	93.80 (8)	As3—O13—V2	124.54 (10)
O14—V1—O4	100.12 (10)	As3—O15—H15	108.6
O6—V1—O4	86.14 (8)	H20—O20—H21	112.7
O8—V1—O4	159.65 (8)	H22—O21—H23	123.9
O14—V1—O2^i	94.53 (9)	H24—O22—H25	92.5
O6—V1—O2^i	164.97 (8)	H26—O23—H27	109.8
O8—V1—O2^i	90.22 (8)	C2—N1—C1	110.7 (3)
O4—V1—O2^i	85.09 (8)	C2—N1—C3	109.7 (2)
O14—V1—O5	175.43 (9)	C1—N1—C3	109.1 (2)
O6—V1—O5	83.30 (7)	C2—N1—H1	109.1
O8—V1—O5	83.73 (7)	C1—N1—H1	109.1
O4—V1—O5	76.04 (7)	C3—N1—H1	109.1
O2^i—V1—O5	82.74 (7)	C4—N2—C6	110.3 (3)
O12—V2—O4	102.49 (10)	C4—N2—C5	111.4 (3)
O12—V2—O13	99.81 (10)	C6—N2—C5	108.0 (3)
O4—V2—O13	92.37 (8)	C4—N2—H2	109.0
O12—V2—O1^i	98.36 (10)	C6—N2—H2	109.0
O4—V2—O1^i	90.12 (8)	C5—N2—H2	109.0
O13—V2—O1^i	160.67 (8)	N1—C1—C4	108.6 (3)
O12—V2—O3^i	98.45 (10)	N1—C1—H1A	110.0
O4—V2—O3^i	159.01 (8)	C4—C1—H1A	110.0
O13—V2—O3^i	85.55 (8)	N1—C1—H1B	110.0
O1^i—V2—O3^i	85.29 (7)	C4—C1—H1B	110.0
O12—V2—O5	178.77 (9)	H1A—C1—H1B	108.4
O4—V2—O5	76.31 (7)	N1—C2—C5	108.4 (3)
O13—V2—O5	80.52 (7)	N1—C2—H2A	110.0
O1^i—V2—O5	81.46 (7)	C5—C2—H2A	110.0
O3^i—V2—O5	82.75 (7)	N1—C2—H2B	110.0
O7—As1—O3	113.76 (10)	C5—C2—H2B	110.0
O7—As1—O8	108.98 (10)	H2A—C2—H2B	108.4
O3—As1—O8	114.53 (9)	N1—C3—C6	108.7 (2)
O7—As1—O11	109.71 (10)	N1—C3—H3A	110.0
O3—As1—O11	100.58 (9)	C6—C3—H3A	110.0
O8—As1—O11	108.86 (10)	N1—C3—H3B	110.0
O5—As2—O1	114.52 (8)	C6—C3—H3B	110.0
O5—As2—O2	112.76 (8)	H3A—C3—H3B	108.3
O1—As2—O2	110.59 (9)	N2—C4—C1	108.7 (3)
O5—As2—O9	109.41 (9)	N2—C4—H4A	110.0
O1—As2—O9	104.43 (9)	C1—C4—H4A	110.0
O2—As2—O9	104.27 (9)	N2—C4—H4B	110.0
O10—As3—O13	112.23 (10)	C1—C4—H4B	110.0
O10—As3—O15	112.17 (11)	H4A—C4—H4B	108.3
O13—As3—O15	101.20 (10)	N2—C5—C2	108.3 (3)
O10—As3—O6	111.22 (10)	N2—C5—H5A	110.0
O13—As3—O6	114.03 (9)	C2—C5—H5A	110.0
O15—As3—O6	105.38 (11)	N2—C5—H5B	110.0
As2—O1—V2^i	122.07 (9)	C2—C5—H5B	110.0
As2—O2—V1^i	122.51 (10)	H5A—C5—H5B	108.4
As1—O3—V2^i	124.36 (10)	N2—C6—C3	108.7 (2)
V2—O4—V1	119.80 (10)	N2—C6—H6A	109.9
As2—O5—V1	133.04 (9)	C3—C6—H6A	109.9
As2—O5—V2	138.98 (9)	N2—C6—H6B	109.9
V1—O5—V2	87.86 (6)	C3—C6—H6B	109.9
As3—O6—V1	127.43 (10)	H6A—C6—H6B	108.3
As1—O8—V1	132.74 (11)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O10	0.97	1.61	2.571 (3)	171
O11—H11···O21	0.88	1.75	2.629 (3)	173
O15—H15···O20^ii	0.90	1.68	2.542 (3)	158
O20—H20···O7^i	0.91	1.78	2.670 (3)	168
O20—H21···O23^iii	0.93	1.81	2.740 (4)	177
O21—H22···O10^iv	0.87	1.91	2.745 (3)	160
O21—H23···O2^v	0.89	1.99	2.868 (3)	170
O21—H23···O14^vi	0.89	2.65	3.125 (3)	115
O22—H24···O12	0.99	2.26	3.100 (3)	142
O22—H25···O23^iii	1.00	1.90	2.897 (4)	171
O23—H26···O4^i	0.95	1.86	2.808 (3)	180
O23—H27···O20^vii	0.81	2.27	2.864 (3)	131
N1—H1···O7^viii	0.91	1.68	2.591 (3)	179
N2—H2···O3^i	0.91	2.16	2.995 (3)	152
N2—H2···O22	0.91	2.52	3.114 (4)	123

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