Diethyl­enetriaminium(3+) hexa­chloro­bismuthate(III)

In the title compound, (C₄H₁₆N₃)[BiCl₆], the Bi^III atom is six-coordinate in a distorted octa­hedral geometry. The salt adopts a three-dimensional network arising from the hydrogen bonds between the cations and anions.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.031
• wR factor = 0.081
• Data-to-parameter ratio = 25.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Bi1    -   Cl5     ..      10.86 su

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.83
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Bi1    -   Cl4     ..       8.83 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Bi1
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         11
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C4 H16 N3

Alert level G
ABSTM02_ALERT_3_G  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      0.833
            Tmax scaled      0.350 Tmin scaled      0.115
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.50
           From the CIF: _reflns_number_total               3302
           Count of symmetry unique reflns         1936
           Completeness (_total/calc)            170.56%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1366
           Fraction of Friedel pairs measured     0.706
           Are heavy atom types Z>Si present        yes

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

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

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Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Diethylenetriaminium(3+) hexachlorobismuthate(III)

Crystal data

(C4H16N3)[BiCl6]	F(000) = 984
Mr = 527.88	Dx = 2.398 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6004 reflections
a = 6.8466 (3) Å	θ = 3.0–28.7°
b = 15.6680 (8) Å	µ = 13.12 mm^−1
c = 13.6328 (7) Å	T = 295 K
V = 1462.4 (1) Å^3	Block, colorless
Z = 4	0.26 × 0.15 × 0.08 mm

Data collection

Bruker APEX area-detector diffractometer	3302 independent reflections
Radiation source: fine-focus sealed tube	3119 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
φ and ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.138, Tmax = 0.420	k = −19→20
12004 measured reflections	l = −17→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.081	w = 1/[σ^2(Fo^2) + (0.048P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3302 reflections	Δρmax = 1.35 e Å^−3
129 parameters	Δρmin = −0.89 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1379 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.034 (7)

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

	x	y	z	Uiso*/Ueq
Bi1	−0.04626 (3)	0.87250 (1)	0.74634 (2)	0.0315 (1)
Cl1	−0.1992 (3)	0.9859 (1)	0.6180 (1)	0.0404 (4)
Cl2	−0.2096 (3)	0.7440 (1)	0.6523 (1)	0.0416 (4)
Cl3	0.0879 (3)	0.7609 (1)	0.8845 (1)	0.0512 (4)
Cl4	0.1199 (3)	1.00780 (9)	0.8551 (1)	0.0409 (4)
Cl5	0.2507 (3)	0.8519 (1)	0.6105 (1)	0.0486 (4)
Cl6	−0.3744 (3)	0.8900 (1)	0.8439 (2)	0.0649 (5)
N1	0.1724 (9)	1.1126 (4)	0.5229 (4)	0.049 (1)
N2	0.4934 (8)	1.0950 (3)	0.7459 (4)	0.036 (1)
N3	0.8330 (9)	1.1544 (3)	0.9500 (4)	0.040 (1)
C1	0.2676 (14)	1.0775 (5)	0.6100 (6)	0.058 (2)
C2	0.4315 (10)	1.1324 (4)	0.6501 (4)	0.037 (1)
C3	0.6488 (9)	1.1453 (4)	0.7960 (5)	0.036 (1)
C4	0.6585 (9)	1.1156 (4)	0.9023 (5)	0.039 (1)
H1a	0.1197	1.1637	0.5376	0.058*
H1b	0.0777	1.0768	0.5029	0.058*
H1c	0.2611	1.1190	0.4748	0.058*
H2a	0.3888	1.0916	0.7857	0.043*
H2b	0.5374	1.0416	0.7357	0.043*
H3a	0.9416	1.1377	0.9181	0.048*
H3b	0.8395	1.1372	1.0129	0.048*
H3c	0.8234	1.2117	0.9478	0.048*
H1d	0.3197	1.0217	0.5940	0.070*
H1e	0.1702	1.0699	0.6609	0.070*
H2c	0.5405	1.1331	0.6046	0.044*
H2d	0.3866	1.1905	0.6594	0.044*
H3d	0.6182	1.2057	0.7932	0.043*
H3e	0.7735	1.1362	0.7639	0.043*
H4a	0.5410	1.1328	0.9368	0.046*
H4b	0.6676	1.0539	0.9047	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0353 (1)	0.0288 (1)	0.0304 (1)	−0.0017 (1)	0.0034 (1)	−0.0027 (1)
Cl1	0.0447 (9)	0.0374 (8)	0.0390 (8)	0.0057 (7)	−0.0011 (7)	−0.0013 (6)
Cl2	0.0419 (8)	0.0373 (7)	0.0455 (9)	−0.0061 (7)	0.0021 (7)	−0.0061 (7)
Cl3	0.069 (1)	0.0414 (8)	0.0430 (9)	−0.0017 (9)	−0.0048 (9)	0.0066 (7)
Cl4	0.0449 (9)	0.0354 (7)	0.0425 (9)	−0.0008 (7)	−0.0006 (7)	−0.0032 (6)
Cl5	0.0474 (9)	0.0357 (8)	0.063 (1)	−0.0007 (7)	0.0154 (8)	0.0007 (7)
Cl6	0.062 (1)	0.065 (1)	0.068 (1)	−0.010 (1)	0.032 (1)	−0.015 (1)
N1	0.042 (3)	0.065 (4)	0.039 (3)	−0.001 (3)	−0.005 (2)	−0.008 (3)
N2	0.038 (2)	0.035 (2)	0.034 (3)	−0.001 (2)	−0.003 (2)	0.002 (2)
N3	0.045 (3)	0.037 (3)	0.037 (3)	0.001 (3)	−0.005 (2)	−0.001 (2)
C1	0.066 (5)	0.049 (4)	0.059 (5)	−0.011 (4)	−0.018 (4)	0.006 (3)
C2	0.041 (3)	0.035 (3)	0.034 (3)	0.000 (3)	−0.002 (3)	0.001 (2)
C3	0.033 (3)	0.038 (3)	0.036 (3)	−0.004 (3)	0.004 (3)	−0.002 (3)
C4	0.038 (3)	0.044 (3)	0.034 (3)	−0.004 (3)	−0.001 (2)	0.001 (3)

Geometric parameters (Å, º)

Bi1—Cl1	2.705 (2)	N1—H1c	0.90
Bi1—Cl2	2.636 (2)	N2—H2a	0.90
Bi1—Cl3	2.729 (2)	N2—H2b	0.90
Bi1—Cl4	2.826 (2)	N3—H3a	0.90
Bi1—Cl5	2.769 (2)	N3—H3b	0.90
Bi1—Cl6	2.625 (2)	N3—H3c	0.90
N1—C1	1.462 (9)	C1—H1d	0.97
N2—C3	1.490 (8)	C1—H1e	0.97
N2—C2	1.493 (8)	C2—H2c	0.97
N3—C4	1.490 (8)	C2—H2d	0.97
C1—C2	1.52 (1)	C3—H3d	0.97
C3—C4	1.524 (8)	C3—H3e	0.97
N1—H1a	0.90	C4—H4a	0.97
N1—H1b	0.90	C4—H4b	0.97
Cl1—Bi1—Cl2	91.33 (5)	C2—N2—H2b	108.9
Cl1—Bi1—Cl3	176.08 (6)	H2a—N2—H2b	107.7
Cl1—Bi1—Cl4	90.12 (5)	C4—N3—H3a	109.5
Cl1—Bi1—Cl5	85.87 (5)	C4—N3—H3b	109.5
Cl1—Bi1—Cl6	85.85 (6)	H3a—N3—H3b	109.5
Cl2—Bi1—Cl3	89.36 (5)	C4—N3—H3c	109.5
Cl2—Bi1—Cl4	177.37 (5)	H3a—N3—H3c	109.5
Cl2—Bi1—Cl5	84.10 (5)	H3b—N3—H3c	109.5
Cl2—Bi1—Cl6	87.90 (6)	N1—C1—H1d	108.7
Cl3—Bi1—Cl4	89.04 (5)	C2—C1—H1d	108.7
Cl3—Bi1—Cl5	98.05 (6)	N1—C1—H1e	108.7
Cl3—Bi1—Cl6	90.32 (7)	C2—C1—H1e	108.7
Cl4—Bi1—Cl6	90.03 (6)	H1d—C1—H1e	107.6
Cl4—Bi1—Cl5	98.19 (5)	N2—C2—H2c	110.2
Cl5—Bi1—Cl6	168.33 (7)	C1—C2—H2c	110.2
C3—N2—C2	113.3 (5)	N2—C2—H2d	110.2
N1—C1—C2	114.2 (6)	C1—C2—H2d	110.2
N2—C2—C1	107.6 (5)	H2c—C2—H2d	108.5
N2—C3—C4	107.8 (5)	N2—C3—H3d	110.2
N3—C4—C3	109.0 (5)	C4—C3—H3d	110.2
C1—N1—H1a	109.5	N2—C3—H3e	110.2
C1—N1—H1b	109.5	C4—C3—H3e	110.2
H1a—N1—H1b	109.5	H3d—C3—H3e	108.5
C1—N1—H1c	109.5	N3—C4—H4a	109.9
H1a—N1—H1c	109.5	C3—C4—H4a	109.9
H1b—N1—H1c	109.5	N3—C4—H4b	109.9
C3—N2—H2a	108.9	C3—C4—H4b	109.9
C2—N2—H2a	108.9	H4a—C4—H4b	108.3
C3—N2—H2b	108.9
C3—N2—C2—C1	−177.4 (6)	C2—N2—C3—C4	164.7 (5)
N1—C1—C2—N2	171.9 (6)	N2—C3—C4—N3	170.9 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1a···Cl3^i	0.90	2.34	3.188 (6)	157
N1—H1b···Cl6^ii	0.90	2.63	3.182 (6)	121
N1—H1c···Cl3^iii	0.90	2.48	3.191 (6)	137
N2—H2a···Cl4	0.90	2.45	3.259 (6)	150
N2—H2b···Cl1^iv	0.90	2.57	3.224 (6)	130
N3—H3a···Cl4^iv	0.90	2.52	3.288 (6)	143
N3—H3a···Cl2^v	0.90	2.66	3.250 (6)	124
N3—H3b···Cl1^vi	0.90	2.59	3.305 (6)	137
N3—H3c···Cl5^v	0.90	2.39	3.254 (5)	161

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x−1/2, −y+2, z−1/2; (iii) −x+1/2, −y+2, z−1/2; (iv) x+1, y, z; (v) −x+1, y+1/2, −z+3/2; (vi) −x+1/2, −y+2, z+1/2.