Diethyl­enetriaminium hexa­fluoro­aluminate dihydrate

The title compound, (C₄H₁₆N₃)[AlF₆]·2H₂O, was obtained under solvothermal conditions at 463 K for 48 h, involving in situ generation of diethyl­enetriamine from tris­(2-amino­ethyl)amine. The structure has been determined by single-crystal X-ray diffraction. The [AlF₆]^3- anions and triproton­ated amine cations build infinite layers, which are hydrogen-bonded to water mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.063
• wR factor = 0.207
• Data-to-parameter ratio = 21.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         Al

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          6
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       2.00 Ratio
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C4 H16 N3
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O

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

   4 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
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: enCIFer (CCDC, 2003).

diethylenetriamine hexafluoroaluminate dihydrate

Crystal data

(C4H16N3)[AlF6]·2H2O	F(000) = 592
Mr = 283.20	Dx = 1.615 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6018 reflections
a = 6.4667 (2) Å	θ = 2.3–33.4°
b = 10.5817 (5) Å	µ = 0.25 mm^−1
c = 17.1328 (8) Å	T = 293 K
β = 96.411 (2)°	Parallelepiped, colourless
V = 1165.04 (9) Å^3	0.34 × 0.10 × 0.04 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3375 independent reflections
Radiation source: fine-focus sealed tube	2698 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 512x512 pixels mm^-1	θmax = 30.0°, θmin = 2.3°
φ and ω scans	h = −7→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995)	k = −14→14
Tmin = 0.921, Tmax = 0.990	l = −24→24
16145 measured 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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.207	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.1271P)^2 + 0.4385P] where P = (Fo^2 + 2Fc^2)/3
3375 reflections	(Δ/σ)max = 0.044
160 parameters	Δρmax = 0.95 e Å^−3
6 restraints	Δρmin = −0.53 e Å^−3

Special details

Experimental. (Blessing, 1995)

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	0.26872 (8)	0.24870 (5)	0.05856 (3)	0.0293 (2)
F1	0.4627 (2)	0.14752 (14)	0.01975 (8)	0.0474 (4)
F2	0.0750 (3)	0.35680 (18)	0.08598 (12)	0.0689 (5)
F3	0.3336 (3)	0.36568 (14)	−0.01207 (12)	0.0620 (5)
F4	0.1958 (3)	0.12817 (16)	0.12306 (9)	0.0529 (4)
F5	0.0754 (3)	0.18665 (17)	−0.01632 (9)	0.0556 (4)
F6	0.4572 (3)	0.3060 (3)	0.13147 (14)	0.0968 (9)
N1	0.4679 (3)	0.19239 (16)	−0.13713 (9)	0.0318 (4)
H1A	0.4467	0.1845	−0.0863	0.062 (2)*
H1B	0.3782	0.2506	−0.1592	0.062 (2)*
C1	0.4277 (4)	0.0689 (2)	−0.17782 (13)	0.0390 (5)
H1C	0.5318	0.0085	−0.1565	0.062 (2)*
H1D	0.4427	0.0795	−0.2331	0.062 (2)*
C2	0.2152 (4)	0.0161 (2)	−0.16985 (13)	0.0417 (5)
H2A	0.1119	0.0807	−0.1848	0.062 (2)*
H2B	0.1888	−0.0542	−0.2060	0.062 (2)*
N2	0.1908 (3)	−0.02768 (18)	−0.08952 (11)	0.0365 (4)
H2C	0.2983	−0.0765	−0.0721	0.062 (2)*
H2D	0.0734	−0.0717	−0.0901	0.062 (2)*
H2E	0.1861	0.0388	−0.0579	0.062 (2)*
C3	0.6871 (4)	0.2360 (2)	−0.14237 (15)	0.0444 (5)
H3A	0.7816	0.1819	−0.1095	0.062 (2)*
H3B	0.7183	0.2261	−0.1961	0.062 (2)*
C4	0.7267 (4)	0.3706 (2)	−0.11784 (14)	0.0460 (5)
H4A	0.8558	0.3984	−0.1361	0.062 (2)*
H4B	0.6156	0.4230	−0.1430	0.062 (2)*
N3	0.7401 (3)	0.38956 (18)	−0.03216 (12)	0.0394 (4)
H3C	0.6210	0.3659	−0.0150	0.062 (2)*
H3D	0.7633	0.4709	−0.0211	0.062 (2)*
H3E	0.8440	0.3434	−0.0086	0.062 (2)*
OW1	0.8119 (3)	0.1028 (2)	−0.31059 (12)	0.0566 (5)
H1W1	0.918 (3)	0.126 (3)	−0.3369 (17)	0.062 (2)*
H2W1	0.693 (2)	0.137 (3)	−0.3338 (18)	0.062 (2)*
OW2	0.2017 (4)	0.3516 (2)	−0.22012 (11)	0.0598 (5)
H1W2	0.195 (6)	0.4326 (13)	−0.2050 (16)	0.062 (2)*
H2W2	0.223 (5)	0.350 (3)	−0.2712 (8)	0.062 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Al	0.0235 (3)	0.0335 (3)	0.0324 (3)	−0.0049 (2)	0.0095 (2)	−0.0060 (2)
F1	0.0521 (8)	0.0542 (8)	0.0380 (7)	0.0257 (7)	0.0145 (6)	0.0053 (6)
F2	0.0639 (11)	0.0741 (11)	0.0754 (12)	0.0199 (9)	0.0374 (9)	−0.0092 (9)
F3	0.0693 (11)	0.0384 (7)	0.0862 (13)	0.0013 (7)	0.0429 (10)	0.0120 (7)
F4	0.0451 (8)	0.0671 (10)	0.0470 (8)	−0.0102 (7)	0.0068 (6)	0.0192 (7)
F5	0.0509 (9)	0.0624 (10)	0.0482 (8)	−0.0029 (7)	−0.0172 (7)	−0.0033 (7)
F6	0.0601 (12)	0.147 (2)	0.0808 (15)	−0.0397 (14)	−0.0018 (10)	−0.0569 (16)
N1	0.0334 (8)	0.0348 (8)	0.0285 (7)	0.0001 (6)	0.0084 (6)	−0.0014 (6)
C1	0.0432 (11)	0.0395 (11)	0.0362 (10)	−0.0036 (8)	0.0134 (8)	−0.0063 (8)
C2	0.0399 (11)	0.0503 (12)	0.0336 (10)	−0.0067 (9)	−0.0016 (8)	−0.0042 (9)
N2	0.0303 (8)	0.0395 (9)	0.0394 (9)	−0.0080 (7)	0.0022 (6)	0.0012 (7)
C3	0.0365 (11)	0.0544 (13)	0.0449 (12)	−0.0073 (9)	0.0157 (9)	−0.0111 (10)
C4	0.0482 (13)	0.0470 (12)	0.0433 (12)	−0.0133 (10)	0.0083 (9)	0.0061 (9)
N3	0.0360 (9)	0.0342 (8)	0.0482 (10)	−0.0029 (7)	0.0056 (7)	−0.0038 (7)
OW1	0.0425 (10)	0.0816 (14)	0.0479 (10)	0.0070 (9)	0.0148 (7)	0.0205 (9)
OW2	0.0784 (14)	0.0619 (12)	0.0374 (9)	0.0191 (10)	−0.0011 (9)	0.0027 (8)

Geometric parameters (Å, º)

Al—F6	1.7532 (18)	C1—C2	1.504 (3)
Al—F4	1.7852 (15)	C1—H1C	0.9700
Al—F2	1.7973 (16)	C1—H1D	0.9700
Al—F5	1.8113 (15)	C2—N2	1.477 (3)
Al—F3	1.8127 (16)	C2—H2A	0.9700
Al—F1	1.8300 (14)	C2—H2B	0.9700
F1—F3	2.494 (2)	N2—H2C	0.8900
F1—F5	2.546 (2)	N2—H2D	0.8900
F1—F6	2.548 (3)	N2—H2E	0.8900
F1—F4	2.615 (2)	C3—C4	1.499 (3)
F2—F3	2.501 (2)	C3—H3A	0.9700
F2—F5	2.513 (2)	C3—H3B	0.9700
F2—F6	2.564 (3)	C4—N3	1.475 (3)
F2—F4	2.599 (3)	C4—H4A	0.9700
F3—F5	2.521 (2)	C4—H4B	0.9700
F3—F6	2.578 (3)	N3—H3C	0.8900
F4—F5	2.505 (2)	N3—H3D	0.8900
F4—F6	2.523 (3)	N3—H3E	0.8900
N1—C1	1.491 (3)	OW1—H1W1	0.892 (10)
N1—C3	1.503 (3)	OW1—H2W1	0.900 (10)
N1—H1A	0.9000	OW2—H1W2	0.898 (10)
N1—H1B	0.9000	OW2—H2W2	0.901 (10)
F6—Al—F4	90.95 (12)	N1—C1—H1D	108.9
F6—Al—F2	92.48 (12)	C2—C1—H1D	108.9
F4—Al—F2	93.02 (9)	H1C—C1—H1D	107.7
F6—Al—F5	178.97 (12)	N2—C2—C1	113.25 (18)
F4—Al—F5	88.30 (8)	N2—C2—H2A	108.9
F2—Al—F5	88.27 (10)	C1—C2—H2A	108.9
F6—Al—F3	92.59 (12)	N2—C2—H2B	108.9
F4—Al—F3	176.35 (9)	C1—C2—H2B	108.9
F2—Al—F3	87.70 (8)	H2A—C2—H2B	107.7
F5—Al—F3	88.15 (9)	C2—N2—H2C	109.5
F6—Al—F1	90.61 (10)	C2—N2—H2D	109.5
F4—Al—F1	92.65 (8)	H2C—N2—H2D	109.5
F2—Al—F1	173.49 (8)	C2—N2—H2E	109.5
F5—Al—F1	88.71 (8)	H2C—N2—H2E	109.5
F3—Al—F1	86.43 (7)	H2D—N2—H2E	109.5
F5—F1—F6	88.82 (7)	C4—C3—N1	114.0 (2)
F3—F1—F4	89.43 (6)	C4—C3—H3A	108.7
F5—F2—F6	89.17 (8)	N1—C3—H3A	108.7
F3—F2—F4	89.65 (7)	C4—C3—H3B	108.7
F1—F3—F2	92.93 (7)	N1—C3—H3B	108.7
F5—F3—F6	88.69 (8)	H3A—C3—H3B	107.6
F5—F4—F6	90.29 (8)	N3—C4—C3	113.45 (19)
F2—F4—F1	87.98 (6)	N3—C4—H4A	108.9
F4—F5—F3	91.37 (7)	C3—C4—H4A	108.9
F2—F5—F1	91.43 (7)	N3—C4—H4B	108.9
F1—F6—F2	90.21 (7)	C3—C4—H4B	108.9
F4—F6—F3	89.65 (7)	H4A—C4—H4B	107.7
C1—N1—C3	110.95 (16)	C4—N3—H3C	109.5
C1—N1—H1A	109.4	C4—N3—H3D	109.5
C3—N1—H1A	109.4	H3C—N3—H3D	109.5
C1—N1—H1B	109.4	C4—N3—H3E	109.5
C3—N1—H1B	109.4	H3C—N3—H3E	109.5
H1A—N1—H1B	108.0	H3D—N3—H3E	109.5
N1—C1—C2	113.38 (18)	H1W1—OW1—H2W1	109.4 (15)
N1—C1—H1C	108.9	H1W2—OW2—H2W2	108.5 (15)
C2—C1—H1C	108.9