mer-Bis(diethyl­enetriamine)zinc(II) dichloride

At 93 K, in the title compound, [Zn(C₄H₁₃N₃)₂]Cl₂, the Zn^II atom is coordinated by six N atoms from two diethyl­enetriamine ligands in a distorted octa­hedral geometry. In contrast to the previously determined chloride and bromide monohydrates, this compound is anhydrous. There is extensive hydrogen bonding between the amine H atoms in the cation and the chloride anions.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.022
• wR factor = 0.057
• Data-to-parameter ratio = 23.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT411_ALERT_2_B Short Inter H...H Contact  H2AB   ..  H2AB    ..       2.06 Ang.

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.746     1.000
            Tmin and Tmax expected:      0.288     0.505
            RR =      1.308
            Please check that your absorption correction is appropriate.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.31
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.50
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.68 mm
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn     -   N1A     ..       5.44 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn     -   N2B     ..       5.41 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn     -   N3B     ..       5.88 su
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            N2B -ZN  -N2A -C2A   149.80  0.20   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         11
            N2B -ZN  -N2A -C3A   -83.80  0.30   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         26
            N2A -ZN  -N2B -C2B   168.60  0.20   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         31
            N2A -ZN  -N2B -C3B   -65.70  0.30   1.555   1.555   1.555   1.555
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         26

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      0.505
            Tmax scaled      0.505 Tmin scaled      0.377

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

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

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

mer-Bis(diethylenetriamine)zinc(II) dichloride

Crystal data

[Zn(C4H13N3)2]Cl2	F(000) = 720
Mr = 342.62	Dx = 1.492 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.2492 (9) Å	Cell parameters from 9578 reflections
b = 10.8810 (9) Å	θ = 2.4–28.3°
c = 12.4813 (10) Å	µ = 1.95 mm^−1
β = 93.218 (1)°	T = 93 K
V = 1525.3 (2) Å^3	Irregular, colorless
Z = 4	0.68 × 0.55 × 0.35 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer	3697 independent reflections
Radiation source: fine-focus sealed tube	3416 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
Tmin = 0.746, Tmax = 1.000	k = −14→14
11570 measured reflections	l = −16→16

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)] = 0.022	H-atom parameters constrained
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0265P)^2 + 0.733P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3697 reflections	Δρmax = 0.45 e Å^−3
155 parameters	Δρmin = −0.34 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: 0.0022 (5)

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
Zn	0.778844 (13)	0.037886 (14)	0.203807 (12)	0.01141 (6)
Cl1	0.42930 (3)	0.18088 (4)	0.30621 (3)	0.02493 (10)
Cl2	0.93845 (3)	0.21497 (3)	−0.06434 (3)	0.01518 (8)
N1A	0.78129 (10)	−0.13748 (11)	0.10922 (10)	0.0165 (2)
H1AC	0.8563	−0.1715	0.1138	0.020*
H1AD	0.7286	−0.1932	0.1353	0.020*
N2A	0.70711 (10)	0.10296 (11)	0.05244 (9)	0.0135 (2)
H2AC	0.7697	0.1326	0.0143	0.016*
N3A	0.72170 (11)	0.22729 (11)	0.24755 (10)	0.0153 (2)
H3AC	0.6579	0.2232	0.2905	0.018*
H3AD	0.7830	0.2673	0.2849	0.018*
N1B	0.63017 (11)	−0.03666 (11)	0.29001 (10)	0.0159 (2)
H1BC	0.5658	0.0155	0.2834	0.019*
H1BD	0.6077	−0.1120	0.2622	0.019*
N2B	0.87277 (10)	−0.00320 (11)	0.35494 (10)	0.0141 (2)
H2BC	0.8781	0.0686	0.3954	0.017*
N3B	0.96943 (10)	0.06246 (12)	0.16330 (10)	0.0146 (2)
H3BC	0.9886	0.0049	0.1131	0.018*
H3BD	0.9794	0.1392	0.1342	0.018*
C1A	0.74635 (13)	−0.10590 (15)	−0.00322 (12)	0.0199 (3)
H1AA	0.7120	−0.1790	−0.0407	0.024*
H1AB	0.8173	−0.0796	−0.0407	0.024*
C2A	0.65545 (13)	−0.00307 (15)	−0.00582 (12)	0.0183 (3)
H2AA	0.6335	0.0201	−0.0810	0.022*
H2AB	0.5826	−0.0307	0.0281	0.022*
C3A	0.62504 (12)	0.20590 (14)	0.06961 (11)	0.0159 (3)
H3AA	0.5510	0.1751	0.0994	0.019*
H3AB	0.6040	0.2478	0.0007	0.019*
C4A	0.68786 (13)	0.29470 (13)	0.14778 (12)	0.0170 (3)
H4AA	0.7597	0.3286	0.1163	0.020*
H4AB	0.6342	0.3638	0.1634	0.020*
C1B	0.67136 (14)	−0.04912 (14)	0.40408 (12)	0.0194 (3)
H1BA	0.6210	−0.1094	0.4399	0.023*
H1BB	0.6647	0.0309	0.4409	0.023*
C2B	0.80023 (13)	−0.09189 (15)	0.41111 (12)	0.0193 (3)
H2BA	0.8294	−0.0981	0.4872	0.023*
H2BB	0.8063	−0.1741	0.3778	0.023*
C3B	0.99408 (13)	−0.04377 (14)	0.33476 (12)	0.0171 (3)
H3BA	0.9917	−0.1262	0.3010	0.021*
H3BB	1.0426	−0.0491	0.4033	0.021*
C4B	1.04902 (12)	0.04858 (14)	0.26054 (12)	0.0158 (3)
H4BA	1.0594	0.1288	0.2973	0.019*
H4BB	1.1282	0.0193	0.2408	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.00992 (9)	0.01047 (10)	0.01377 (9)	0.00038 (5)	0.00000 (6)	0.00091 (6)
Cl1	0.02301 (19)	0.02110 (19)	0.0316 (2)	0.01042 (15)	0.00986 (15)	0.00538 (15)
Cl2	0.01264 (16)	0.01602 (17)	0.01697 (16)	0.00206 (12)	0.00182 (11)	0.00329 (12)
N1A	0.0110 (5)	0.0134 (6)	0.0255 (6)	0.0001 (4)	0.0036 (5)	−0.0013 (5)
N2A	0.0099 (5)	0.0144 (6)	0.0162 (6)	0.0006 (4)	0.0006 (4)	0.0002 (5)
N3A	0.0149 (6)	0.0137 (6)	0.0169 (6)	0.0008 (4)	−0.0021 (4)	−0.0009 (5)
N1B	0.0131 (6)	0.0132 (6)	0.0216 (6)	0.0010 (4)	0.0028 (5)	0.0002 (5)
N2B	0.0135 (6)	0.0127 (6)	0.0162 (6)	0.0001 (4)	0.0011 (4)	0.0014 (5)
N3B	0.0130 (6)	0.0146 (6)	0.0161 (6)	0.0009 (4)	−0.0007 (4)	0.0024 (5)
C1A	0.0160 (7)	0.0205 (7)	0.0232 (7)	0.0019 (6)	0.0011 (6)	−0.0085 (6)
C2A	0.0131 (7)	0.0218 (8)	0.0196 (7)	0.0006 (6)	−0.0035 (5)	−0.0053 (6)
C3A	0.0137 (6)	0.0158 (7)	0.0181 (7)	0.0031 (5)	−0.0017 (5)	0.0017 (5)
C4A	0.0172 (7)	0.0116 (6)	0.0219 (7)	0.0014 (5)	−0.0006 (5)	0.0026 (5)
C1B	0.0203 (7)	0.0177 (7)	0.0206 (7)	−0.0006 (6)	0.0065 (6)	0.0029 (6)
C2B	0.0210 (7)	0.0182 (7)	0.0186 (7)	−0.0014 (6)	0.0014 (6)	0.0065 (6)
C3B	0.0146 (7)	0.0187 (7)	0.0179 (7)	0.0043 (5)	−0.0017 (5)	0.0028 (5)
C4B	0.0111 (6)	0.0189 (7)	0.0171 (7)	0.0004 (5)	−0.0020 (5)	−0.0006 (5)

Geometric parameters (Å, º)

Zn—N2A	2.1332 (12)	N3B—H3BC	0.9200
Zn—N2B	2.1566 (12)	N3B—H3BD	0.9200
Zn—N1B	2.1943 (12)	C1A—C2A	1.515 (2)
Zn—N3A	2.2356 (12)	C1A—H1AA	0.9900
Zn—N1A	2.2448 (12)	C1A—H1AB	0.9900
Zn—N3B	2.2462 (12)	C2A—H2AA	0.9900
N1A—C1A	1.477 (2)	C2A—H2AB	0.9900
N1A—H1AC	0.9200	C3A—C4A	1.519 (2)
N1A—H1AD	0.9200	C3A—H3AA	0.9900
N2A—C2A	1.4663 (19)	C3A—H3AB	0.9900
N2A—C3A	1.4749 (18)	C4A—H4AA	0.9900
N2A—H2AC	0.9300	C4A—H4AB	0.9900
N3A—C4A	1.4766 (18)	C1B—C2B	1.520 (2)
N3A—H3AC	0.9200	C1B—H1BA	0.9900
N3A—H3AD	0.9200	C1B—H1BB	0.9900
N1B—C1B	1.478 (2)	C2B—H2BA	0.9900
N1B—H1BC	0.9200	C2B—H2BB	0.9900
N1B—H1BD	0.9200	C3B—C4B	1.521 (2)
N2B—C2B	1.4673 (18)	C3B—H3BA	0.9900
N2B—C3B	1.4694 (18)	C3B—H3BB	0.9900
N2B—H2BC	0.9300	C4B—H4BA	0.9900
N3B—C4B	1.4749 (18)	C4B—H4BB	0.9900
N2A—Zn—N2B	170.36 (5)	H3BC—N3B—H3BD	108.1
N2A—Zn—N1B	107.23 (5)	N1A—C1A—C2A	109.61 (12)
N2B—Zn—N1B	81.02 (5)	N1A—C1A—H1AA	109.7
N2A—Zn—N3A	79.09 (4)	C2A—C1A—H1AA	109.7
N2B—Zn—N3A	96.37 (5)	N1A—C1A—H1AB	109.7
N1B—Zn—N3A	89.05 (4)	C2A—C1A—H1AB	109.7
N2A—Zn—N1A	80.30 (5)	H1AA—C1A—H1AB	108.2
N2B—Zn—N1A	105.30 (5)	N2A—C2A—C1A	108.80 (12)
N1B—Zn—N1A	88.62 (4)	N2A—C2A—H2AA	109.9
N3A—Zn—N1A	157.55 (5)	C1A—C2A—H2AA	109.9
N2A—Zn—N3B	94.56 (4)	N2A—C2A—H2AB	109.9
N2B—Zn—N3B	78.15 (4)	C1A—C2A—H2AB	109.9
N1B—Zn—N3B	156.61 (5)	H2AA—C2A—H2AB	108.3
N3A—Zn—N3B	103.67 (5)	N2A—C3A—C4A	107.70 (11)
N1A—Zn—N3B	86.72 (4)	N2A—C3A—H3AA	110.2
C1A—N1A—Zn	106.95 (9)	C4A—C3A—H3AA	110.2
C1A—N1A—H1AC	110.3	N2A—C3A—H3AB	110.2
Zn—N1A—H1AC	110.3	C4A—C3A—H3AB	110.2
C1A—N1A—H1AD	110.3	H3AA—C3A—H3AB	108.5
Zn—N1A—H1AD	110.3	N3A—C4A—C3A	108.32 (11)
H1AC—N1A—H1AD	108.6	N3A—C4A—H4AA	110.0
C2A—N2A—C3A	115.83 (11)	C3A—C4A—H4AA	110.0
C2A—N2A—Zn	107.32 (9)	N3A—C4A—H4AB	110.0
C3A—N2A—Zn	109.40 (8)	C3A—C4A—H4AB	110.0
C2A—N2A—H2AC	108.0	H4AA—C4A—H4AB	108.4
C3A—N2A—H2AC	108.0	N1B—C1B—C2B	109.27 (12)
Zn—N2A—H2AC	108.0	N1B—C1B—H1BA	109.8
C4A—N3A—Zn	108.42 (9)	C2B—C1B—H1BA	109.8
C4A—N3A—H3AC	110.0	N1B—C1B—H1BB	109.8
Zn—N3A—H3AC	110.0	C2B—C1B—H1BB	109.8
C4A—N3A—H3AD	110.0	H1BA—C1B—H1BB	108.3
Zn—N3A—H3AD	110.0	N2B—C2B—C1B	108.97 (12)
H3AC—N3A—H3AD	108.4	N2B—C2B—H2BA	109.9
C1B—N1B—Zn	107.45 (9)	C1B—C2B—H2BA	109.9
C1B—N1B—H1BC	110.2	N2B—C2B—H2BB	109.9
Zn—N1B—H1BC	110.2	C1B—C2B—H2BB	109.9
C1B—N1B—H1BD	110.2	H2BA—C2B—H2BB	108.3
Zn—N1B—H1BD	110.2	N2B—C3B—C4B	108.59 (11)
H1BC—N1B—H1BD	108.5	N2B—C3B—H3BA	110.0
C2B—N2B—C3B	115.53 (12)	C4B—C3B—H3BA	110.0
C2B—N2B—Zn	107.21 (9)	N2B—C3B—H3BB	110.0
C3B—N2B—Zn	109.05 (9)	C4B—C3B—H3BB	110.0
C2B—N2B—H2BC	108.3	H3BA—C3B—H3BB	108.4
C3B—N2B—H2BC	108.3	N3B—C4B—C3B	108.67 (12)
Zn—N2B—H2BC	108.3	N3B—C4B—H4BA	110.0
C4B—N3B—Zn	110.21 (8)	C3B—C4B—H4BA	110.0
C4B—N3B—H3BC	109.6	N3B—C4B—H4BB	110.0
Zn—N3B—H3BC	109.6	C3B—C4B—H4BB	110.0
C4B—N3B—H3BD	109.6	H4BA—C4B—H4BB	108.3
Zn—N3B—H3BD	109.6
N2A—Zn—N1A—C1A	6.31 (9)	N1A—Zn—N2B—C2B	−66.84 (10)
N2B—Zn—N1A—C1A	−165.65 (8)	N3B—Zn—N2B—C2B	−150.06 (10)
N1B—Zn—N1A—C1A	114.04 (9)	N2A—Zn—N2B—C3B	−65.7 (3)
N3A—Zn—N1A—C1A	29.88 (16)	N1B—Zn—N2B—C3B	144.99 (10)
N3B—Zn—N1A—C1A	−88.89 (9)	N3A—Zn—N2B—C3B	−126.99 (9)
N2B—Zn—N2A—C2A	149.8 (2)	N1A—Zn—N2B—C3B	58.92 (10)
N1B—Zn—N2A—C2A	−62.03 (9)	N3B—Zn—N2B—C3B	−24.30 (9)
N3A—Zn—N2A—C2A	−147.59 (9)	N2A—Zn—N3B—C4B	168.69 (9)
N1A—Zn—N2A—C2A	23.46 (8)	N2B—Zn—N3B—C4B	−4.93 (9)
N3B—Zn—N2A—C2A	109.34 (9)	N1B—Zn—N3B—C4B	−32.47 (17)
N2B—Zn—N2A—C3A	−83.8 (3)	N3A—Zn—N3B—C4B	88.83 (10)
N1B—Zn—N2A—C3A	64.39 (10)	N1A—Zn—N3B—C4B	−111.32 (10)
N3A—Zn—N2A—C3A	−21.17 (9)	Zn—N1A—C1A—C2A	−34.50 (13)
N1A—Zn—N2A—C3A	149.88 (9)	C3A—N2A—C2A—C1A	−172.48 (12)
N3B—Zn—N2A—C3A	−124.24 (9)	Zn—N2A—C2A—C1A	−49.96 (13)
N2A—Zn—N3A—C4A	−9.54 (9)	N1A—C1A—C2A—N2A	57.94 (16)
N2B—Zn—N3A—C4A	161.86 (9)	C2A—N2A—C3A—C4A	169.70 (12)
N1B—Zn—N3A—C4A	−117.28 (9)	Zn—N2A—C3A—C4A	48.28 (12)
N1A—Zn—N3A—C4A	−33.21 (16)	Zn—N3A—C4A—C3A	37.69 (12)
N3B—Zn—N3A—C4A	82.55 (9)	N2A—C3A—C4A—N3A	−57.63 (14)
N2A—Zn—N1B—C1B	−164.25 (9)	Zn—N1B—C1B—C2B	−38.17 (13)
N2B—Zn—N1B—C1B	10.61 (9)	C3B—N2B—C2B—C1B	−167.66 (12)
N3A—Zn—N1B—C1B	−85.99 (9)	Zn—N2B—C2B—C1B	−45.87 (13)
N1A—Zn—N1B—C1B	116.34 (9)	N1B—C1B—C2B—N2B	57.85 (16)
N3B—Zn—N1B—C1B	37.88 (16)	C2B—N2B—C3B—C4B	170.63 (12)
N2A—Zn—N2B—C2B	168.6 (2)	Zn—N2B—C3B—C4B	49.84 (13)
N1B—Zn—N2B—C2B	19.23 (9)	Zn—N3B—C4B—C3B	32.25 (13)
N3A—Zn—N2B—C2B	107.25 (9)	N2B—C3B—C4B—N3B	−54.73 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AC···Cl2^i	0.92	2.47	3.3410 (12)	158
N1A—H1AD···Cl1^ii	0.92	2.39	3.3035 (12)	172
N2A—H2AC···Cl2	0.93	2.36	3.2876 (12)	174
N3A—H3AC···Cl1	0.92	2.63	3.4468 (13)	148
N3A—H3AD···Cl2^iii	0.92	2.50	3.3480 (13)	153
N1B—H1BC···Cl1	0.92	2.39	3.2865 (13)	164
N1B—H1BD···Cl1^ii	0.92	2.44	3.3535 (13)	174
N2B—H2BC···Cl2^iii	0.93	2.49	3.3635 (13)	156
N3B—H3BC···Cl2^i	0.92	2.61	3.4432 (13)	151
N3B—H3BD···Cl2	0.92	2.63	3.2919 (13)	130

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