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The title compound, {[Zn
2(C
2HN
9)
2(H
2O)
6][Zn
2(C
2HN
9)
2(H
2O)
6]·2H
2O}
n, consists of one dinuclear [Zn(C
2HN
9)(H
2O)
3]
2 molecule, in which the two C
2HN
9− monoanions each
N,
N′-chelate a [Zn(H
2O)
3] unit while using a third N atom to bind to the other triaquazinc unit. In the second [Zn(C
2HN
9)(H
2O)
3] unit, the monoanion similarly
N,
N′-chelates a triaquazinc unit, but the bridging interaction furnishes a zigzag chain structure. For both Zn centres, a
mer-ZnN
3O
3 octahedral coordination arises. A network of N—H
N, O—H
N and O—H
O hydrogen bonds helps to establish the structure.
Supporting information
CCDC reference: 672614
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (N-N) = 0.003 Å
- R factor = 0.020
- wR factor = 0.054
- Data-to-parameter ratio = 11.7
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT222_ALERT_3_A Large Non-Solvent H Ueq(max)/Ueq(min) ... 5.50 Ratio
| Author Response: The diffraction measurements were sufficiently good for all H atoms
to be refined; their temperature factors were also refined.
|
Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio
PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) ..... 10 Ang.
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.38
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.07
PLAT731_ALERT_1_C Bond Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Ra
O1 -H12 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Ra
O3 -H31 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.87(3), Rep 0.860(10) ...... 3.00 su-Ra
O4 -H41 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.86(3), Rep 0.860(10) ...... 3.00 su-Ra
O4 -H42 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.85(3), Rep 0.840(10) ...... 3.00 su-Ra
O8 -H8 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Ra
O1 -H12 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Ra
O3 -H31 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.87(3), Rep 0.860(10) ...... 3.00 su-Ra
O4 -H41 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.86(3), Rep 0.860(10) ...... 3.00 su-Ra
O4 -H42 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.85(3), Rep 0.840(10) ...... 3.00 su-Ra
O8 -H8 1.555 1.555
PLAT736_ALERT_1_C H...A Calc 1.99(3), Rep 2.000(10) ...... 3.00 su-Ra
H41 -N3 1.555 1.555
PLAT736_ALERT_1_C H...A Calc 2.21(3), Rep 2.200(10) ...... 3.00 su-Ra
H61 -N6 1.555 3.565
PLAT736_ALERT_1_C H...A Calc 2.14(3), Rep 2.150(10) ...... 3.00 su-Ra
H8 -N12 1.555 2.775
Alert level G
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 4048
Count of symmetry unique reflns 2339
Completeness (_total/calc) 173.07%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1709
Fraction of Friedel pairs measured 0.731
Are heavy atom types Z>Si present yes
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.93
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn2 (2) 1.95
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 22
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
19 ALERT level C = Check and explain
4 ALERT level G = General alerts; check
16 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 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
2 ALERT type 4 Improvement, methodology, query or suggestion
2 ALERT type 5 Informative message, check
Zinc chloride (40.9 mg, 0.3 mmol), sodium azide (39.0 mg, 0.6 mmol), sodium
dicyanamide (26.7 mg, 0.3 mmol) and water (10 ml) were heated in a 25-ml
Teflon-lined, stainless-steel Parr bom at 433 K for 72 h. The bomb was then
was cooled to room temperature at 10 K h-1; the colourless blocks of (I)
that formed were separated manually.
All hydrogen atoms were located in a difference Fourier map, and were refined
with distance restraints of O—H = N—H = 0.85 (1) Å; for the water
H-atoms, the H···H distances were restrained to 1.39 (1) Å. Their
Uiso values were refined.
Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
catena-poly[µ-5,5'-iminoditetrazolato-
κ3N,
N':
N''-bis[triaquazinc(II)]
bis[[triaquazinc(II)]-µ-5,5'-iminoditetrazolato-
κ3N,
N':
N''] dihydrate]
top
Crystal data top
[Zn2(C2HN9)2(H2O)6][Zn2(C2HN9)2(H2O)6]·2H2O | F(000) = 1128 |
Mr = 1118.18 | Dx = 2.107 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 9121 reflections |
a = 10.1201 (1) Å | θ = 1.7–27.5° |
b = 23.7418 (3) Å | µ = 2.81 mm−1 |
c = 7.3346 (1) Å | T = 295 K |
V = 1762.28 (4) Å3 | Block, colourless |
Z = 2 | 0.32 × 0.17 × 0.06 mm |
Data collection top
Bruker APEXII CCD diffractometer | 4048 independent reflections |
Radiation source: fine-focus sealed tube | 3844 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.581, Tmax = 0.850 | k = −30→30 |
25915 measured reflections | l = −9→8 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.020 | All H-atom parameters refined |
wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.0363P)2P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
4048 reflections | Δρmax = 0.29 e Å−3 |
345 parameters | Δρmin = −0.43 e Å−3 |
22 restraints | Absolute structure: Flack (1983), with 1710 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.026 (8) |
Crystal data top
[Zn2(C2HN9)2(H2O)6][Zn2(C2HN9)2(H2O)6]·2H2O | V = 1762.28 (4) Å3 |
Mr = 1118.18 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 10.1201 (1) Å | µ = 2.81 mm−1 |
b = 23.7418 (3) Å | T = 295 K |
c = 7.3346 (1) Å | 0.32 × 0.17 × 0.06 mm |
Data collection top
Bruker APEXII CCD diffractometer | 4048 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3844 reflections with I > 2σ(I) |
Tmin = 0.581, Tmax = 0.850 | Rint = 0.034 |
25915 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.020 | All H-atom parameters refined |
wR(F2) = 0.054 | Δρmax = 0.29 e Å−3 |
S = 1.01 | Δρmin = −0.43 e Å−3 |
4048 reflections | Absolute structure: Flack (1983), with 1710 Friedel pairs |
345 parameters | Absolute structure parameter: 0.026 (8) |
22 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.49499 (2) | 0.66550 (1) | 0.47415 (3) | 0.01664 (6) | |
Zn2 | 0.36506 (2) | 0.93580 (1) | 0.01708 (3) | 0.01744 (7) | |
O1 | 0.4922 (2) | 0.6553 (1) | 0.7651 (2) | 0.0220 (3) | |
O2 | 0.6009 (2) | 0.5884 (1) | 0.4700 (3) | 0.0289 (4) | |
O3 | 0.5257 (2) | 0.6696 (1) | 0.1956 (2) | 0.0274 (4) | |
O4 | 0.3686 (2) | 0.9250 (1) | 0.3053 (2) | 0.0290 (4) | |
O5 | 0.1591 (1) | 0.9271 (1) | 0.0271 (3) | 0.0296 (4) | |
O6 | 0.3553 (2) | 0.9439 (1) | −0.2721 (2) | 0.0250 (3) | |
O7 | 1.0000 | 1.0000 | −0.1726 (3) | 0.0292 (5) | |
O8 | 1.0000 | 1.0000 | 0.3201 (3) | 0.0287 (5) | |
N1 | 0.3582 (1) | 0.7342 (1) | 0.4689 (3) | 0.0199 (4) | |
N2 | 0.3877 (2) | 0.7884 (1) | 0.4371 (3) | 0.0286 (5) | |
N3 | 0.2826 (2) | 0.8193 (1) | 0.4451 (3) | 0.0285 (5) | |
N4 | 0.1772 (2) | 0.7861 (1) | 0.4804 (3) | 0.0194 (4) | |
N5 | 0.1544 (2) | 0.6870 (1) | 0.5283 (3) | 0.0263 (4) | |
N6 | 0.1094 (2) | 0.5914 (1) | 0.4621 (3) | 0.0265 (4) | |
N7 | 0.1864 (2) | 0.5479 (1) | 0.4106 (3) | 0.0272 (4) | |
N8 | 0.3081 (2) | 0.5631 (1) | 0.3983 (3) | 0.0240 (4) | |
N9 | 0.3177 (2) | 0.6185 (1) | 0.4429 (3) | 0.0192 (4) | |
N10 | 0.5769 (2) | 0.9319 (1) | 0.0183 (3) | 0.0175 (3) | |
N11 | 0.6602 (2) | 0.9751 (1) | 0.0585 (2) | 0.0186 (4) | |
N12 | 0.7751 (2) | 0.9552 (1) | 0.1032 (3) | 0.0225 (4) | |
N13 | 0.7735 (2) | 0.8986 (1) | 0.0949 (3) | 0.0223 (4) | |
N14 | 0.6126 (2) | 0.8310 (1) | 0.0127 (3) | 0.0262 (4) | |
N15 | 0.4512 (2) | 0.7600 (1) | −0.0351 (3) | 0.0270 (4) | |
N16 | 0.3182 (2) | 0.7617 (1) | −0.0593 (3) | 0.0277 (5) | |
N17 | 0.2775 (2) | 0.8133 (1) | −0.0559 (3) | 0.0269 (4) | |
N18 | 0.3817 (2) | 0.8482 (1) | −0.0277 (3) | 0.0215 (4) | |
C1 | 0.22764 (2) | 0.7341 (1) | 0.4936 (3) | 0.0168 (4) | |
C2 | 0.19376 (2) | 0.6338 (1) | 0.4795 (3) | 0.0191 (4) | |
C3 | 0.65014 (2) | 0.8860 (1) | 0.0409 (3) | 0.0178 (4) | |
C4 | 0.48487 (2) | 0.8141 (1) | −0.0158 (3) | 0.0188 (4) | |
H5 | 0.073 (1) | 0.691 (1) | 0.543 (4) | 0.03 (1)* | |
H14 | 0.671 (2) | 0.807 (1) | 0.025 (3) | 0.02 (1)* | |
H11 | 0.423 (2) | 0.641 (1) | 0.810 (4) | 0.04 (1)* | |
H12 | 0.505 (3) | 0.688 (1) | 0.807 (4) | 0.05 (1)* | |
H21 | 0.667 (2) | 0.580 (1) | 0.406 (4) | 0.08 (1)* | |
H22 | 0.571 (2) | 0.560 (1) | 0.526 (3) | 0.04 (1)* | |
H31 | 0.496 (3) | 0.702 (1) | 0.167 (5) | 0.08 (1)* | |
H32 | 0.608 (1) | 0.669 (1) | 0.173 (4) | 0.05 (1)* | |
H41 | 0.333 (3) | 0.894 (1) | 0.343 (5) | 0.09 (2)* | |
H42 | 0.448 (2) | 0.927 (2) | 0.345 (6) | 0.11 (2)* | |
H51 | 0.119 (2) | 0.905 (1) | 0.095 (3) | 0.04 (1)* | |
H52 | 0.112 (2) | 0.946 (1) | −0.043 (3) | 0.03 (1)* | |
H61 | 0.429 (2) | 0.931 (1) | −0.310 (5) | 0.10 (2)* | |
H62 | 0.345 (3) | 0.977 (1) | −0.320 (4) | 0.04 (1)* | |
H7 | 1.055 (2) | 1.018 (1) | −0.236 (4) | 0.05 (1)* | |
H8 | 1.066 (2) | 1.007 (2) | 0.253 (4) | 0.06 (1)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0119 (1) | 0.0156 (1) | 0.0225 (1) | 0.0007 (1) | 0.0007 (1) | 0.0002 (1) |
Zn2 | 0.0152 (1) | 0.0136 (1) | 0.0236 (1) | 0.0002 (1) | −0.0010 (1) | 0.0002 (1) |
O1 | 0.021 (1) | 0.021 (1) | 0.025 (1) | −0.005 (1) | 0.004 (1) | −0.001 (1) |
O2 | 0.022 (1) | 0.019 (1) | 0.046 (1) | 0.004 (1) | 0.006 (1) | 0.002 (1) |
O3 | 0.023 (1) | 0.033 (1) | 0.026 (1) | 0.005 (1) | 0.005 (1) | 0.003 (1) |
O4 | 0.034 (1) | 0.029 (1) | 0.024 (1) | −0.005 (1) | 0.000 (1) | 0.005 (1) |
O5 | 0.016 (1) | 0.024 (1) | 0.049 (1) | −0.002 (1) | 0.001 (1) | 0.007 (1) |
O6 | 0.029 (1) | 0.022 (1) | 0.023 (1) | 0.005 (7) | −0.001 (1) | 0.003 (1) |
O7 | 0.024 (1) | 0.032 (1) | 0.031 (1) | −0.004 (1) | 0.000 | 0.000 |
O8 | 0.025 (1) | 0.031 (1) | 0.030 (1) | −0.003 (1) | 0.000 | 0.000 |
N1 | 0.011 (1) | 0.015 (1) | 0.033 (1) | 0.000 (1) | 0.001 (1) | 0.000 (1) |
N2 | 0.014 (1) | 0.016 (1) | 0.056 (1) | 0.001 (1) | 0.003 (1) | 0.004 (1) |
N3 | 0.014 (1) | 0.018 (1) | 0.053 (1) | 0.000 (1) | 0.004 (1) | 0.006 (1) |
N4 | 0.013 (1) | 0.015 (1) | 0.031 (1) | −0.001 (1) | 0.000 (1) | 0.001 (1) |
N5 | 0.011 (1) | 0.015 (1) | 0.053 (1) | 0.002 (1) | 0.008 (1) | −0.001 (1) |
N6 | 0.016 (1) | 0.019 (1) | 0.045 (1) | −0.002 (1) | −0.001 (1) | −0.002 (1) |
N7 | 0.019 (1) | 0.019 (1) | 0.044 (1) | −0.002 (1) | −0.001 (1) | −0.009 (1) |
N8 | 0.020 (1) | 0.019 (1) | 0.033 (1) | 0.000 (1) | 0.001 (1) | −0.006 (1) |
N9 | 0.014 (1) | 0.015 (1) | 0.029 (1) | 0.001 (1) | 0.000 (1) | −0.004 (1) |
N10 | 0.015 (1) | 0.012 (1) | 0.026 (1) | −0.001 (1) | −0.002 (1) | 0.000 (1) |
N11 | 0.015 (1) | 0.015 (1) | 0.025 (1) | 0.000 (1) | −0.002 (1) | 0.001 (1) |
N12 | 0.018 (1) | 0.016 (1) | 0.034 (1) | 0.001 (1) | −0.006 (1) | 0.002 (1) |
N13 | 0.016 (1) | 0.016 (1) | 0.035 (1) | −0.001 (1) | −0.005 (1) | 0.001 (1) |
N14 | 0.015 (1) | 0.012 (1) | 0.052 (1) | 0.002 (1) | −0.008 (1) | −0.002 (1) |
N15 | 0.021 (1) | 0.014 (1) | 0.046 (1) | 0.000 (1) | −0.006 (1) | −0.001 (1) |
N16 | 0.019 (1) | 0.014 (1) | 0.050 (1) | −0.002 (1) | −0.007 (1) | −0.002 (1) |
N17 | 0.019 (1) | 0.018 (1) | 0.044 (1) | −0.003 (1) | −0.007 (1) | −0.002 (1) |
N18 | 0.018 (1) | 0.017 (1) | 0.030 (1) | −0.001 (1) | −0.004 (1) | −0.002 (1) |
C1 | 0.011 (1) | 0.017 (1) | 0.022 (1) | 0.002 (1) | 0.000 (1) | 0.000 (1) |
C2 | 0.014 (1) | 0.017 (1) | 0.026 (1) | 0.001 (1) | 0.001 (1) | 0.000 (1) |
C3 | 0.016 (1) | 0.016 (1) | 0.022 (1) | 0.000 (1) | −0.002 (1) | 0.000 (1) |
C4 | 0.018 (1) | 0.014 (1) | 0.024 (1) | −0.001 (1) | −0.003 (1) | −0.001 (1) |
Geometric parameters (Å, º) top
Zn1—O2 | 2.122 (2) | N10—N11 | 1.360 (2) |
Zn1—O1 | 2.148 (2) | N11—N12 | 1.297 (2) |
Zn1—O3 | 2.069 (2) | N12—N13 | 1.345 (2) |
Zn1—N1 | 2.140 (2) | N13—C3 | 1.343 (3) |
Zn1—N4i | 2.199 (2) | N14—C4 | 1.369 (2) |
Zn1—N9 | 2.125 (2) | N14—C3 | 1.375 (3) |
Zn2—O4 | 2.130 (2) | N15—C4 | 1.336 (2) |
Zn2—O5 | 2.096 (1) | N15—N16 | 1.359 (2) |
Zn2—O6 | 2.132 (2) | N16—N17 | 1.291 (2) |
Zn2—N10 | 2.146 (2) | N17—N18 | 1.357 (2) |
Zn2—N11ii | 2.152 (2) | N18—C4 | 1.324 (2) |
Zn2—N18 | 2.113 (2) | O1—H11 | 0.85 (1) |
N1—C1 | 1.334 (2) | O1—H12 | 0.85 (1) |
N1—N2 | 1.341 (2) | O2—H21 | 0.84 (1) |
N2—N3 | 1.293 (2) | O2—H22 | 0.84 (1) |
N3—N4 | 1.351 (2) | O3—H31 | 0.85 (1) |
N4—C1 | 1.338 (2) | O3—H32 | 0.85 (1) |
N5—C1 | 1.366 (2) | O4—H41 | 0.86 (1) |
N5—C2 | 1.371 (2) | O4—H42 | 0.86 (1) |
N6—C2 | 1.326 (3) | O5—H51 | 0.82 (1) |
N6—N7 | 1.350 (2) | O5—H52 | 0.83 (1) |
N7—N8 | 1.287 (3) | O6—H61 | 0.86 (1) |
N8—N9 | 1.360 (2) | O6—H62 | 0.86 (1) |
N9—C2 | 1.333 (2) | O7—H7 | 0.84 (1) |
N10—C3 | 1.329 (2) | O8—H8 | 0.84 (1) |
| | | |
O3—Zn1—O2 | 87.17 (7) | N11—N10—Zn2 | 126.0 (2) |
O3—Zn1—N9 | 92.61 (7) | N12—N11—N10 | 109.6 (2) |
O2—Zn1—N9 | 88.41 (6) | N12—N11—Zn2ii | 120.1 (1) |
O3—Zn1—N1 | 92.48 (7) | N10—N11—Zn2ii | 129.6 (1) |
O2—Zn1—N1 | 169.88 (6) | N11—N12—N13 | 110.0 (2) |
N9—Zn1—N1 | 81.50 (6) | C3—N13—N12 | 104.3 (2) |
O3—Zn1—O1 | 171.28 (6) | C4—N14—C3 | 124.2 (2) |
O2—Zn1—O1 | 85.62 (7) | C4—N15—N16 | 103.7 (2) |
N9—Zn1—O1 | 92.09 (6) | N17—N16—N15 | 110.1 (2) |
N1—Zn1—O1 | 95.47 (7) | N16—N17—N18 | 109.5 (2) |
O3—Zn1—N4i | 89.94 (7) | C4—N18—N17 | 104.5 (2) |
O2—Zn1—N4i | 91.70 (6) | C4—N18—Zn2 | 130.8 (1) |
N9—Zn1—N4i | 177.45 (7) | N17—N18—Zn2 | 124.3 (1) |
N1—Zn1—N4i | 98.42 (6) | N1—C1—N4 | 111.5 (2) |
O1—Zn1—N4i | 85.38 (7) | N1—C1—N5 | 124.3 (2) |
O5—Zn2—N18 | 89.26 (6) | N4—C1—N5 | 124.2 (2) |
O5—Zn2—O4 | 88.29 (7) | N6—C2—N9 | 112.3 (2) |
N18—Zn2—O4 | 91.94 (7) | N6—C2—N5 | 122.5 (2) |
O5—Zn2—O6 | 89.87 (7) | N9—C2—N5 | 125.2 (2) |
N18—Zn2—O6 | 86.46 (7) | N10—C3—N13 | 111.9 (2) |
O4—Zn2—O6 | 177.58 (6) | N10—C3—N14 | 127.3 (2) |
O5—Zn2—N10 | 171.56 (6) | N13—C3—N14 | 120.8 (2) |
N18—Zn2—N10 | 83.05 (6) | N18—C4—N15 | 112.3 (2) |
O4—Zn2—N10 | 88.49 (7) | N18—C4—N14 | 125.1 (2) |
O6—Zn2—N10 | 93.12 (7) | N15—C4—N14 | 122.6 (2) |
O5—Zn2—N11ii | 88.51 (6) | Zn1—O1—H11 | 116 (2) |
N18—Zn2—N11ii | 177.60 (6) | Zn1—O1—H12 | 105 (2) |
O4—Zn2—N11ii | 88.90 (7) | H11—O1—H12 | 112 (2) |
O6—Zn2—N11ii | 92.63 (6) | Zn1—O2—H21 | 128 (2) |
N10—Zn2—N11ii | 99.22 (6) | Zn1—O2—H22 | 120 (2) |
C1—N1—N2 | 104.2 (2) | H21—O2—H22 | 111 (2) |
C1—N1—Zn1 | 129.6 (1) | Zn1—O3—H31 | 103 (3) |
N2—N1—Zn1 | 126.2 (1) | Zn1—O3—H32 | 110 (2) |
N3—N2—N1 | 110.6 (2) | H31—O3—H32 | 108 (2) |
N2—N3—N4 | 109.2 (2) | Zn2—O4—H41 | 114 (3) |
C1—N4—N3 | 104.5 (2) | Zn2—O4—H42 | 111 (3) |
C1—N4—Zn1iii | 142.3 (1) | H41—O4—H42 | 109 (2) |
N3—N4—Zn1iii | 112.7 (1) | Zn2—O5—H51 | 125 (2) |
C1—N5—C2 | 123.2 (2) | Zn2—O5—H52 | 120 (2) |
C2—N6—N7 | 103.7 (2) | H51—O5—H52 | 116 (2) |
N8—N7—N6 | 110.9 (2) | Zn2—O6—H61 | 104 (3) |
N7—N8—N9 | 108.9 (2) | Zn2—O6—H62 | 120 (2) |
C2—N9—N8 | 104.2 (2) | H61—O6—H62 | 108 (2) |
C2—N9—Zn1 | 129.0 (1) | C1—N5—H5 | 118 (2) |
N8—N9—Zn1 | 126.4 (1) | C2—N5—H5 | 115 (2) |
C3—N10—N11 | 104.3 (2) | C4—N14—H14 | 119 (2) |
C3—N10—Zn2 | 126.4 (1) | C3—N14—H14 | 116 (2) |
| | | |
O3—Zn1—N1—C1 | 109.4 (2) | N16—N17—N18—C4 | 0.3 (3) |
O2—Zn1—N1—C1 | 21.6 (6) | N16—N17—N18—Zn2 | −173.2 (2) |
N9—Zn1—N1—C1 | 17.11 (19) | O5—Zn2—N18—C4 | −164.9 (2) |
O1—Zn1—N1—C1 | −74.2 (2) | O4—Zn2—N18—C4 | −76.6 (2) |
N4i—Zn1—N1—C1 | −160.3 (2) | O6—Zn2—N18—C4 | 105.2 (2) |
O3—Zn1—N1—N2 | −69.9 (2) | N10—Zn2—N18—C4 | 11.6 (2) |
O2—Zn1—N1—N2 | −157.8 (4) | O5—Zn2—N18—N17 | 6.7 (2) |
N9—Zn1—N1—N2 | −162.2 (2) | O4—Zn2—N18—N17 | 95.0 (2) |
O1—Zn1—N1—N2 | 106.5 (2) | O6—Zn2—N18—N17 | −83.2 (2) |
N4i—Zn1—N1—N2 | 20.4 (2) | N10—Zn2—N18—N17 | −176.8 (2) |
C1—N1—N2—N3 | 1.1 (3) | N2—N1—C1—N4 | −0.8 (3) |
Zn1—N1—N2—N3 | −179.5 (2) | Zn1—N1—C1—N4 | 179.8 (2) |
N1—N2—N3—N4 | −1.0 (3) | N2—N1—C1—N5 | 179.3 (2) |
N2—N3—N4—C1 | 0.4 (3) | Zn1—N1—C1—N5 | −0.2 (3) |
N2—N3—N4—Zn1iii | 174.0 (2) | N3—N4—C1—N1 | 0.3 (3) |
C2—N6—N7—N8 | 0.1 (3) | Zn1iii—N4—C1—N1 | −170.0 (2) |
N6—N7—N8—N9 | 0.3 (3) | N3—N4—C1—N5 | −179.8 (2) |
N7—N8—N9—C2 | −0.6 (2) | Zn1iii—N4—C1—N5 | 9.9 (4) |
N7—N8—N9—Zn1 | 173.3 (2) | C2—N5—C1—N1 | −24.1 (4) |
O3—Zn1—N9—C2 | −112.6 (2) | C2—N5—C1—N4 | 156.0 (2) |
O2—Zn1—N9—C2 | 160.3 (2) | N7—N6—C2—N9 | −0.5 (3) |
N1—Zn1—N9—C2 | −20.5 (2) | N7—N6—C2—N5 | 179.0 (2) |
O1—Zn1—N9—C2 | 74.7 (2) | N8—N9—C2—N6 | 0.7 (3) |
O3—Zn1—N9—N8 | 75.0 (2) | Zn1—N9—C2—N6 | −173.0 (2) |
O2—Zn1—N9—N8 | −12.1 (2) | N8—N9—C2—N5 | −178.8 (2) |
N1—Zn1—N9—N8 | 167.1 (2) | Zn1—N9—C2—N5 | 7.5 (3) |
O1—Zn1—N9—N8 | −97.7 (2) | C1—N5—C2—N6 | −159.0 (2) |
N18—Zn2—N10—C3 | −17.7 (2) | C1—N5—C2—N9 | 20.4 (4) |
O4—Zn2—N10—C3 | 74.4 (2) | N11—N10—C3—N13 | 0.8 (2) |
O6—Zn2—N10—C3 | −103.8 (2) | Zn2—N10—C3—N13 | −159.4 (2) |
N11ii—Zn2—N10—C3 | 163.0 (2) | N11—N10—C3—N14 | −178.3 (2) |
N18—Zn2—N10—N11 | −173.7 (2) | Zn2—N10—C3—N14 | 21.6 (3) |
O4—Zn2—N10—N11 | −81.6 (2) | N12—N13—C3—N10 | −0.7 (3) |
O6—Zn2—N10—N11 | 100.3 (2) | N12—N13—C3—N14 | 178.4 (2) |
N11ii—Zn2—N10—N11 | 7.1 (2) | C4—N14—C3—N10 | −11.1 (4) |
C3—N10—N11—N12 | −0.5 (2) | C4—N14—C3—N13 | 169.9 (2) |
Zn2—N10—N11—N12 | 159.7 (2) | N17—N18—C4—N15 | 0.1 (3) |
C3—N10—N11—Zn2ii | 169.1 (2) | Zn2—N18—C4—N15 | 172.9 (2) |
Zn2—N10—N11—Zn2ii | −30.7 (2) | N17—N18—C4—N14 | 180.0 (2) |
N10—N11—N12—N13 | 0.1 (2) | Zn2—N18—C4—N14 | −7.1 (4) |
Zn2ii—N11—N12—N13 | −170.7 (1) | N16—N15—C4—N18 | −0.4 (3) |
N11—N12—N13—C3 | 0.4 (2) | N16—N15—C4—N14 | 179.7 (2) |
C4—N15—N16—N17 | 0.6 (3) | C3—N14—C4—N18 | 3.0 (4) |
N15—N16—N17—N18 | −0.5 (3) | C3—N14—C4—N15 | −177.1 (2) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x+1, −y+2, z; (iii) x−1/2, −y+3/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N2iii | 0.84 (1) | 1.94 (1) | 2.773 (2) | 171 (3) |
N14—H14···N16iv | 0.82 (1) | 2.23 (1) | 3.049 (2) | 176 (2) |
O1—H11···N13iii | 0.85 (1) | 1.91 (1) | 2.754 (2) | 175 (2) |
O1—H12···N15v | 0.85 (1) | 2.14 (2) | 2.915 (2) | 153 (2) |
O2—H21···O6iv | 0.84 (1) | 2.22 (1) | 3.053 (2) | 172 (4) |
O2—H22···O8iii | 0.84 (1) | 1.96 (1) | 2.796 (2) | 173 (3) |
O3—H31···N15 | 0.85 (1) | 2.07 (2) | 2.835 (3) | 148 (3) |
O3—H32···N17iv | 0.85 (1) | 1.96 (1) | 2.776 (2) | 160 (3) |
O4—H41···N3 | 0.86 (1) | 2.00 (1) | 2.847 (2) | 169 (3) |
O4—H42···N6i | 0.86 (1) | 2.20 (2) | 3.000 (3) | 155 (3) |
O5—H51···O1iii | 0.82 (1) | 2.19 (1) | 3.000 (2) | 170 (2) |
O5—H52···O7vi | 0.83 (1) | 1.96 (1) | 2.781 (2) | 169 (3) |
O6—H61···N6iv | 0.86 (1) | 2.20 (1) | 3.042 (3) | 167 (3) |
O6—H62···N7vii | 0.86 (1) | 1.84 (1) | 2.701 (2) | 176 (3) |
O7—H7···N8viii | 0.84 (1) | 2.12 (1) | 2.959 (2) | 179 (3) |
O8—H8···N12ix | 0.84 (1) | 2.15 (1) | 2.974 (2) | 166 (4) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) x+1/2, −y+3/2, −z; (v) x, y, z+1; (vi) x−1, y, z; (vii) −x+1/2, y+1/2, −z; (viii) −x+3/2, y+1/2, −z; (ix) −x+2, −y+2, z. |
Experimental details
Crystal data |
Chemical formula | [Zn2(C2HN9)2(H2O)6][Zn2(C2HN9)2(H2O)6]·2H2O |
Mr | 1118.18 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 295 |
a, b, c (Å) | 10.1201 (1), 23.7418 (3), 7.3346 (1) |
V (Å3) | 1762.28 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.81 |
Crystal size (mm) | 0.32 × 0.17 × 0.06 |
|
Data collection |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.581, 0.850 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25915, 4048, 3844 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.054, 1.01 |
No. of reflections | 4048 |
No. of parameters | 345 |
No. of restraints | 22 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.29, −0.43 |
Absolute structure | Flack (1983), with 1710 Friedel pairs |
Absolute structure parameter | 0.026 (8) |
Selected bond lengths (Å) topZn1—O2 | 2.122 (2) | Zn2—O4 | 2.130 (2) |
Zn1—O1 | 2.148 (2) | Zn2—O5 | 2.096 (1) |
Zn1—O3 | 2.069 (2) | Zn2—O6 | 2.132 (2) |
Zn1—N1 | 2.140 (2) | Zn2—N10 | 2.146 (2) |
Zn1—N4i | 2.199 (2) | Zn2—N11ii | 2.152 (2) |
Zn1—N9 | 2.125 (2) | Zn2—N18 | 2.113 (2) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x+1, −y+2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N2iii | 0.84 (1) | 1.94 (1) | 2.773 (2) | 171 (3) |
N14—H14···N16iv | 0.82 (1) | 2.23 (1) | 3.049 (2) | 176 (2) |
O1—H11···N13iii | 0.85 (1) | 1.91 (1) | 2.754 (2) | 175 (2) |
O1—H12···N15v | 0.85 (1) | 2.14 (2) | 2.915 (2) | 153 (2) |
O2—H21···O6iv | 0.84 (1) | 2.22 (1) | 3.053 (2) | 172 (4) |
O2—H22···O8iii | 0.84 (1) | 1.96 (1) | 2.796 (2) | 173 (3) |
O3—H31···N15 | 0.85 (1) | 2.07 (2) | 2.835 (3) | 148 (3) |
O3—H32···N17iv | 0.85 (1) | 1.96 (1) | 2.776 (2) | 160 (3) |
O4—H41···N3 | 0.86 (1) | 2.00 (1) | 2.847 (2) | 169 (3) |
O4—H42···N6i | 0.86 (1) | 2.20 (2) | 3.000 (3) | 155 (3) |
O5—H51···O1iii | 0.82 (1) | 2.19 (1) | 3.000 (2) | 170 (2) |
O5—H52···O7vi | 0.83 (1) | 1.96 (1) | 2.781 (2) | 169 (3) |
O6—H61···N6iv | 0.86 (1) | 2.20 (1) | 3.042 (3) | 167 (3) |
O6—H62···N7vii | 0.86 (1) | 1.84 (1) | 2.701 (2) | 176 (3) |
O7—H7···N8viii | 0.84 (1) | 2.12 (1) | 2.959 (2) | 179 (3) |
O8—H8···N12ix | 0.84 (1) | 2.15 (1) | 2.974 (2) | 166 (4) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) x+1/2, −y+3/2, −z; (v) x, y, z+1; (vi) x−1, y, z; (vii) −x+1/2, y+1/2, −z; (viii) −x+3/2, y+1/2, −z; (ix) −x+2, −y+2, z. |
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Bis(5-tetrazolyl)amine is a high-nitrogen fuel; see Jones et al. (2006). Its synthesis in four steps, starting from cyanic chloride, is reported by Nedel'ko et al. (2005). The synthesis from sodium azide and sodium dicyanamide in water is reported by Marecek et al. (2004). For the crystal structures of the copper complexes, see Klapötke et al. (2006); Manfred et al. (2005). The structures of several metal derivatives have been deposited with the Cambridge Structural Database (Version 5.28, November 2006; Allen, 2002) as private communications. The title zinc derivative, (I), (Fig. 1) is readily synthesized from sodium azide, sodium dicyanamide and zinc chloride in a hydothermal reaction.
The complex structure of (I) consists of one dinuclear [Zn(C2HN9)2(H2O)3]2 moiety in which the two C2HN9- monoanions each N,N'-chelate to a Zn(H2O)3 triaquazinc unit while using its third nitrogen atom to bind to the other triaquazinc unit. In the second Zn(C2HN9)2(H2O)3 unit, the monoanion similarly N,N'-chelates to a triaquazinc unit, but the bridging interaction furnishes a zigzag chain structure (Fig. 1) For both zinc centres, a mer-ZnN3O3 octahedral coordination arises (Table 1). Two uncoordinated water molecules complete the structure. A complex network of N—H···N, O—H···N and O—H···O hydrogen bonds helps to establish the structure (Table 2).