1,4,8,11-Tetra­aza­cyclo­decane-1,4,8,11-tetraium bis­(aqua­penta­fluoro­aluminate) dihydrate

The title compound, (C₁₀H₂₈N₄)[AlF₅(H₂O)]₂·2H₂O, obtained solvothermally at 473 K and isostructural with the iron analogue, consists of isolated [AlF₅(H₂O)] octahedral anions and centrosymmetric tetraprotonated 1,4,8,11-tetra­aza­cyclo­decane (cyclamH₄⁴⁺) moieties connected by a network of N—H...X (X = O,F) hydrogen bonds. One water mol­ecule participates in the aluminium coordination, whereas the second water mol­ecule connects two neighbouring [AlF₅(H₂O)] octahedra via F1...H2WB—O2—H2WA...F3 bridges.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.063
• wR factor = 0.151
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5
PLAT414_ALERT_2_C Short Intra D-H..H-X       H1A    ..  H5A      =       1.96 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: STADI4 (Stoe & Cie, 1998); cell refinement: STADI4 (Stoe & Cie, 1998); data reduction: X-RED (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 Farrugia, 1997); software used to prepare material for publication: enCIFer (CCDC, 2003).

1,4,8,11-Tetraazacyclodecane-1,4,8,11-tetraium bis(aquapentafluoroaluminate) dihydrate

Crystal data

(C10H28N4)[AlF5(H2O)]2·2H2O	F(000) = 544
Mr = 520.37	Dx = 1.709 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 32 reflections
a = 8.4930 (8) Å	θ = 2.5–10°
b = 8.932 (1) Å	µ = 0.26 mm^−1
c = 13.434 (2) Å	T = 293 K
β = 97.141 (8)°	Parallelepiped, colorless
V = 1011.2 (2) Å^3	0.08 × 0.06 × 0.04 mm
Z = 2

Data collection

Siemens AED2 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 2.7°
Graphite monochromator	h = −11→11
2θ/ω scans	k = 0→12
2955 measured reflections	l = 0→18
2955 independent reflections	3 standard reflections every 120 min
1591 reflections with I > 2σ(I)	intensity decay: 15%

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0473P)^2 + 0.517P] where P = (Fo^2 + 2Fc^2)/3
2955 reflections	(Δ/σ)max < 0.001
148 parameters	Δρmax = 0.45 e Å^−3
6 restraints	Δρmin = −0.47 e Å^−3

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
Al	0.34962 (11)	0.21382 (12)	0.06661 (8)	0.0178 (2)
F1	0.3863 (2)	0.3257 (3)	0.17890 (16)	0.0324 (5)
F2	0.4504 (2)	0.3417 (3)	−0.00278 (17)	0.0329 (5)
F3	0.2390 (2)	0.0843 (3)	0.13107 (16)	0.0335 (5)
F4	0.5146 (2)	0.1058 (2)	0.09959 (16)	0.0319 (5)
F5	0.1823 (2)	0.3229 (2)	0.03060 (15)	0.0232 (5)
O1	0.3038 (3)	0.0969 (3)	−0.0546 (2)	0.0302 (6)
H1WA	0.357 (4)	0.027 (3)	−0.073 (3)	0.036*
H1WB	0.212 (2)	0.088 (4)	−0.081 (3)	0.036*
O2	0.0375 (3)	0.0195 (4)	0.8369 (3)	0.0479 (9)
H2WA	−0.031 (4)	0.000 (6)	0.873 (3)	0.058*
H2WB	0.007 (5)	0.068 (5)	0.787 (2)	0.058*
N1	0.2341 (3)	0.0972 (3)	0.5466 (2)	0.0219 (6)
H1A	0.2650	0.0067	0.5270	0.026*
H1B	0.1275	0.1003	0.5344	0.026*
N2	0.3241 (3)	0.0578 (3)	0.3272 (2)	0.0219 (6)
H2A	0.2853	−0.0263	0.3520	0.026*
H2B	0.2937	0.0588	0.2606	0.026*
C1	0.2989 (4)	0.2118 (4)	0.4837 (3)	0.0246 (7)
H1C	0.4138	0.2108	0.4974	0.029*
H1D	0.2626	0.3096	0.5023	0.029*
C2	0.5509 (4)	−0.0952 (4)	0.3105 (3)	0.0253 (8)
H2C	0.4945	−0.1761	0.3387	0.030*
H2D	0.5308	−0.1022	0.2380	0.030*
C3	0.2799 (4)	0.1101 (5)	0.6576 (3)	0.0290 (8)
H3A	0.2450	0.2067	0.6796	0.035*
H3B	0.2243	0.0335	0.6907	0.035*
C4	0.2521 (4)	0.1894 (4)	0.3728 (3)	0.0273 (8)
H4A	0.1376	0.1796	0.3607	0.033*
H4B	0.2806	0.2789	0.3382	0.033*
C5	0.4908 (4)	0.0525 (4)	0.3441 (3)	0.0266 (8)
H5A	0.5259	0.0665	0.4150	0.032*
H5B	0.5345	0.1330	0.3076	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al	0.0138 (4)	0.0195 (5)	0.0198 (5)	0.0021 (4)	0.0013 (3)	0.0001 (4)
F1	0.0273 (11)	0.0366 (14)	0.0310 (12)	0.0051 (9)	−0.0049 (9)	−0.0142 (10)
F2	0.0170 (10)	0.0407 (13)	0.0409 (13)	−0.0052 (9)	0.0037 (9)	0.0106 (11)
F3	0.0255 (10)	0.0455 (14)	0.0289 (11)	−0.0104 (10)	0.0015 (9)	0.0126 (10)
F4	0.0223 (10)	0.0353 (13)	0.0357 (12)	0.0139 (9)	−0.0058 (9)	−0.0045 (10)
F5	0.0142 (9)	0.0267 (11)	0.0283 (11)	0.0042 (8)	0.0011 (7)	0.0015 (9)
O1	0.0199 (12)	0.0372 (17)	0.0317 (14)	0.0080 (11)	−0.0040 (11)	−0.0127 (12)
O2	0.0246 (15)	0.070 (2)	0.0464 (19)	−0.0048 (15)	−0.0067 (13)	0.0148 (18)
N1	0.0132 (12)	0.0292 (17)	0.0235 (14)	0.0025 (11)	0.0028 (11)	−0.0016 (13)
N2	0.0187 (13)	0.0255 (16)	0.0209 (14)	−0.0051 (12)	0.0001 (11)	−0.0006 (12)
C1	0.0233 (16)	0.0219 (18)	0.0287 (18)	−0.0017 (15)	0.0040 (14)	−0.0006 (16)
C2	0.0234 (16)	0.029 (2)	0.0237 (17)	0.0001 (15)	0.0022 (13)	−0.0027 (15)
C3	0.0238 (17)	0.037 (2)	0.0271 (18)	0.0045 (16)	0.0072 (14)	−0.0025 (17)
C4	0.0204 (16)	0.031 (2)	0.0304 (19)	0.0053 (15)	0.0028 (14)	0.0061 (16)
C5	0.0179 (16)	0.029 (2)	0.0316 (19)	−0.0007 (14)	−0.0042 (14)	−0.0005 (16)

Geometric parameters (Å, º)

Al—F4	1.713 (2)	N2—H2A	0.9000
Al—F5	1.741 (2)	N2—H2B	0.9000
Al—F2	1.762 (2)	C1—C4	1.506 (5)
Al—F3	1.781 (2)	C1—H1C	0.9700
Al—F1	1.804 (2)	C1—H1D	0.9700
Al—O1	1.933 (3)	C2—C3^i	1.454 (5)
O1—H1WA	0.83 (2)	C2—C5	1.503 (5)
O1—H1WB	0.82 (2)	C2—H2C	0.9700
O2—H2WA	0.82 (4)	C2—H2D	0.9700
O2—H2WB	0.81 (2)	C3—H3A	0.9700
N1—C1	1.478 (4)	C3—H3B	0.9700
N1—C3	1.497 (4)	C4—H4A	0.9700
N1—H1A	0.9000	C4—H4B	0.9700
N1—H1B	0.9000	C5—H5A	0.9700
N2—C5	1.407 (4)	C5—H5B	0.9700
N2—C4	1.491 (5)
F4—Al—F5	178.87 (12)	N1—C1—C4	113.8 (3)
F4—Al—F2	93.80 (11)	N1—C1—H1C	108.8
F5—Al—F2	85.63 (11)	C4—C1—H1C	108.8
F4—Al—F3	88.40 (12)	N1—C1—H1D	108.8
F5—Al—F3	92.12 (11)	C4—C1—H1D	108.8
F2—Al—F3	176.81 (12)	H1C—C1—H1D	107.7
F4—Al—F1	92.57 (11)	C3^i—C2—C5	110.6 (3)
F5—Al—F1	88.43 (11)	C3^i—C2—H2C	109.5
F2—Al—F1	92.20 (12)	C5—C2—H2C	109.5
F3—Al—F1	90.00 (12)	C3^i—C2—H2D	109.5
F4—Al—O1	89.21 (11)	C5—C2—H2D	109.5
F5—Al—O1	89.79 (11)	H2C—C2—H2D	108.1
F2—Al—O1	87.99 (13)	C2^i—C3—N1	114.3 (3)
F3—Al—O1	89.74 (12)	C2^i—C3—H3A	108.7
F1—Al—O1	178.19 (12)	N1—C3—H3A	108.7
Al—O1—H1WA	127 (3)	C2^i—C3—H3B	108.7
Al—O1—H1WB	120 (3)	N1—C3—H3B	108.7
H1WA—O1—H1WB	109 (3)	H3A—C3—H3B	107.6
H2WA—O2—H2WB	115 (3)	N2—C4—C1	116.1 (3)
C1—N1—C3	116.6 (3)	N2—C4—H4A	108.3
C1—N1—H1A	108.1	C1—C4—H4A	108.3
C3—N1—H1A	108.1	N2—C4—H4B	108.3
C1—N1—H1B	108.1	C1—C4—H4B	108.3
C3—N1—H1B	108.1	H4A—C4—H4B	107.4
H1A—N1—H1B	107.3	N2—C5—C2	110.7 (3)
C5—N2—C4	114.6 (3)	N2—C5—H5A	109.5
C5—N2—H2A	108.6	C2—C5—H5A	109.5
C4—N2—H2A	108.6	N2—C5—H5B	109.5
C5—N2—H2B	108.6	C2—C5—H5B	109.5
C4—N2—H2B	108.6	H5A—C5—H5B	108.1
H2A—N2—H2B	107.6

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1WA···F4^ii	0.83 (2)	1.68 (2)	2.501 (3)	172 (4)
O1—H1WB···O2^iii	0.82 (2)	1.84 (2)	2.626 (4)	161 (4)
O2—H2WA···F3^iv	0.82 (4)	1.92 (4)	2.610 (4)	141 (5)
O2—H2WB···F1^v	0.81 (2)	1.92 (2)	2.718 (4)	166 (4)
N1—H1A···F5^vi	0.90	1.89	2.787 (4)	173
N1—H1A···F2^vi	0.90	2.34	2.789 (4)	111
N1—H1B···F2^v	0.90	1.61	2.478 (3)	161
N2—H2A···F1^vi	0.90	1.97	2.732 (4)	141
N2—H2A···F5^vi	0.90	2.07	2.842 (4)	144
N2—H2B···F3	0.90	1.76	2.655 (4)	173

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