Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100013548/qa0423sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013548/qa0423Isup2.hkl |
CCDC reference: 153934
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1994); program(s) used to refine structure: SHELXTL; software used to prepare material for publication: SHELXTL.
(C4H12N2)2[Zn7(AsO4)6(H2O)2] | F(000) = 2880 |
Mr = 1503.46 | Dx = 3.179 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.5880 (14) Å | Cell parameters from 3669 reflections |
b = 8.3559 (7) Å | θ = 3–27.5° |
c = 23.4129 (18) Å | µ = 11.64 mm−1 |
β = 104.564 (4)° | T = 150 K |
V = 3140.9 (4) Å3 | Plate, colourless |
Z = 4 | 0.4 × 0.1 × 0.05 mm |
Siemens SMART CCD diffractometer | 3602 independent reflections |
Radiation source: fine-focus sealed tube | 2639 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
Detector resolution: 8.3 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
sets of exposures each taken over 0.6° ω rotation scans | h = −21→21 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −10→10 |
Tmin = 0.26, Tmax = 0.55 | l = −30→30 |
17378 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0275P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.065 | (Δ/σ)max = 0.001 |
S = 0.95 | Δρmax = 0.87 e Å−3 |
3602 reflections | Δρmin = −0.92 e Å−3 |
273 parameters |
Experimental. The data collection nominally covered a hemisphere of reciprocal space by a combination of five sets of exposures at a 5.0 cm crystal-to-detector distance. |
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. |
x | y | z | Uiso*/Ueq | ||
As1 | 0.26918 (3) | 0.50999 (7) | 0.54802 (2) | 0.00799 (12) | |
As2 | 0.05209 (3) | 0.28361 (7) | 0.13313 (2) | 0.00828 (12) | |
As3 | 0.17838 (3) | 0.50461 (7) | 0.30936 (2) | 0.00834 (12) | |
Zn1 | 0.30098 (4) | 0.65114 (8) | 0.42636 (3) | 0.00896 (13) | |
Zn2 | −0.14715 (4) | 0.35305 (8) | 0.07431 (3) | 0.00908 (14) | |
Zn3 | 0.24056 (4) | 0.38125 (8) | 0.19269 (3) | 0.00976 (14) | |
Zn4 | 0.0000 | 0.30442 (11) | 0.2500 | 0.00970 (19) | |
O1 | 0.3245 (2) | 0.3634 (5) | 0.58939 (16) | 0.0159 (8) | |
O2 | 0.1798 (2) | 0.4451 (5) | 0.50431 (16) | 0.0161 (9) | |
O3 | 0.2507 (2) | 0.6421 (5) | 0.59762 (16) | 0.0115 (8) | |
O4 | 0.3292 (2) | 0.6040 (5) | 0.50954 (15) | 0.0123 (8) | |
O5 | 0.0935 (2) | 0.1434 (5) | 0.09622 (16) | 0.0121 (8) | |
O6 | 0.0216 (2) | 0.1793 (4) | 0.18557 (16) | 0.0119 (8) | |
O7 | −0.0273 (2) | 0.3795 (5) | 0.08565 (16) | 0.0116 (8) | |
O8 | 0.1224 (2) | 0.4234 (4) | 0.16244 (16) | 0.0115 (8) | |
O9 | 0.2159 (2) | 0.4929 (5) | 0.38491 (15) | 0.0107 (7) | |
O10 | 0.1931 (3) | 0.6885 (5) | 0.28760 (16) | 0.0158 (8) | |
O11 | 0.0786 (2) | 0.4587 (5) | 0.29750 (17) | 0.0182 (9) | |
O12 | 0.2335 (2) | 0.3720 (5) | 0.28051 (15) | 0.0124 (8) | |
OW | 0.3168 (3) | 0.5693 (5) | 0.20120 (17) | 0.0138 (8) | |
N1 | 0.4585 (3) | 0.2146 (6) | 0.0799 (2) | 0.0162 (10) | |
N2 | 0.6076 (3) | 0.3471 (6) | 0.1519 (2) | 0.0136 (10) | |
C1 | 0.5411 (4) | 0.2887 (8) | 0.1785 (3) | 0.0139 (12) | |
C2 | 0.4585 (4) | 0.3062 (7) | 0.1344 (3) | 0.0152 (12) | |
C3 | 0.5262 (4) | 0.7284 (8) | 0.5522 (3) | 0.0170 (12) | |
C4 | 0.6086 (4) | 0.2555 (7) | 0.0968 (3) | 0.0155 (12) | |
H1 | 0.413 (4) | 0.224 (8) | 0.055 (3) | 0.020* | |
H2 | 0.470 (4) | 0.110 (9) | 0.092 (3) | 0.020* | |
H3 | 0.602 (4) | 0.438 (9) | 0.143 (3) | 0.020* | |
H4 | 0.663 (4) | 0.355 (8) | 0.173 (3) | 0.020* | |
H5 | 0.555 (4) | 0.186 (9) | 0.196 (3) | 0.020* | |
H6 | 0.543 (4) | 0.345 (9) | 0.209 (3) | 0.020* | |
H7 | 0.412 (4) | 0.267 (8) | 0.154 (3) | 0.020* | |
H8 | 0.448 (4) | 0.417 (9) | 0.126 (3) | 0.020* | |
H9 | 0.514 (4) | 0.624 (9) | 0.543 (3) | 0.020* | |
H10 | 0.526 (4) | 0.787 (8) | 0.522 (3) | 0.020* | |
H11 | 0.621 (4) | 0.158 (9) | 0.107 (3) | 0.020* | |
H12 | 0.648 (4) | 0.295 (8) | 0.084 (3) | 0.020* | |
H13 | 0.304 (4) | 0.659 (9) | 0.218 (3) | 0.020* | |
H14 | 0.322 (4) | 0.589 (9) | 0.171 (3) | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
As1 | 0.0091 (2) | 0.0074 (3) | 0.0073 (2) | −0.0003 (2) | 0.00190 (18) | −0.0005 (2) |
As2 | 0.0080 (2) | 0.0080 (3) | 0.0085 (3) | 0.0005 (2) | 0.00160 (19) | −0.0002 (2) |
As3 | 0.0090 (2) | 0.0080 (3) | 0.0082 (2) | −0.0012 (2) | 0.00239 (18) | −0.0004 (2) |
Zn1 | 0.0100 (3) | 0.0085 (3) | 0.0086 (3) | 0.0002 (2) | 0.0029 (2) | 0.0005 (2) |
Zn2 | 0.0081 (3) | 0.0085 (3) | 0.0105 (3) | 0.0003 (2) | 0.0023 (2) | 0.0009 (2) |
Zn3 | 0.0094 (3) | 0.0088 (3) | 0.0106 (3) | 0.0007 (2) | 0.0016 (2) | 0.0002 (2) |
Zn4 | 0.0101 (4) | 0.0101 (4) | 0.0087 (4) | 0.000 | 0.0020 (3) | 0.000 |
O1 | 0.027 (2) | 0.008 (2) | 0.014 (2) | 0.0042 (17) | 0.0050 (17) | 0.0036 (16) |
O2 | 0.0098 (18) | 0.028 (2) | 0.0092 (18) | −0.0066 (17) | 0.0003 (14) | −0.0074 (17) |
O3 | 0.018 (2) | 0.0077 (18) | 0.0081 (18) | 0.0043 (16) | 0.0024 (15) | 0.0036 (15) |
O4 | 0.0118 (18) | 0.017 (2) | 0.0078 (18) | −0.0038 (16) | 0.0027 (14) | 0.0020 (16) |
O5 | 0.0117 (18) | 0.0111 (19) | 0.0150 (19) | −0.0007 (16) | 0.0063 (15) | −0.0025 (16) |
O6 | 0.0170 (19) | 0.0077 (19) | 0.0117 (19) | 0.0024 (16) | 0.0047 (15) | 0.0008 (15) |
O7 | 0.0083 (17) | 0.014 (2) | 0.0119 (19) | 0.0008 (16) | 0.0017 (14) | 0.0038 (16) |
O8 | 0.0103 (18) | 0.0096 (19) | 0.0125 (19) | −0.0002 (15) | −0.0010 (14) | −0.0019 (16) |
O9 | 0.0150 (18) | 0.0092 (19) | 0.0073 (17) | −0.0031 (16) | 0.0020 (14) | −0.0032 (15) |
O10 | 0.025 (2) | 0.012 (2) | 0.0104 (19) | −0.0050 (17) | 0.0047 (16) | 0.0011 (16) |
O11 | 0.0122 (19) | 0.023 (2) | 0.022 (2) | −0.0075 (17) | 0.0084 (16) | −0.0101 (18) |
O12 | 0.0143 (19) | 0.016 (2) | 0.0082 (18) | 0.0031 (16) | 0.0046 (15) | −0.0003 (16) |
OW | 0.024 (2) | 0.010 (2) | 0.009 (2) | −0.0018 (17) | 0.0063 (17) | −0.0010 (16) |
N1 | 0.011 (2) | 0.012 (2) | 0.021 (3) | −0.001 (2) | −0.003 (2) | 0.004 (2) |
N2 | 0.015 (2) | 0.008 (2) | 0.018 (3) | −0.003 (2) | 0.0044 (19) | −0.001 (2) |
C1 | 0.014 (3) | 0.014 (3) | 0.014 (3) | 0.000 (2) | 0.005 (2) | 0.005 (2) |
C2 | 0.014 (3) | 0.014 (3) | 0.018 (3) | −0.002 (2) | 0.003 (2) | 0.000 (3) |
C3 | 0.023 (3) | 0.012 (3) | 0.017 (3) | −0.004 (3) | 0.007 (2) | 0.000 (3) |
C4 | 0.018 (3) | 0.013 (3) | 0.017 (3) | −0.001 (2) | 0.007 (2) | −0.001 (2) |
As1—O2 | 1.667 (4) | O1—Zn2vii | 1.924 (4) |
As1—O1 | 1.683 (4) | O2—Zn2iv | 1.942 (4) |
As1—O3 | 1.686 (4) | O3—Zn1i | 1.947 (4) |
As1—O4 | 1.695 (4) | O3—Zn3viii | 2.282 (4) |
As2—O8 | 1.671 (4) | O5—Zn1v | 1.953 (4) |
As2—O6 | 1.684 (4) | O9—Zn2iv | 2.031 (4) |
As2—O7 | 1.696 (4) | O10—Zn3ii | 1.940 (4) |
As2—O5 | 1.699 (4) | OW—H13 | 0.89 (7) |
As3—O11 | 1.653 (4) | OW—H14 | 0.74 (7) |
As3—O10 | 1.656 (4) | N1—C2 | 1.488 (8) |
As3—O12 | 1.682 (4) | N1—C3vi | 1.507 (8) |
As3—O9 | 1.724 (3) | N1—H1 | 0.83 (7) |
Zn1—O4 | 1.926 (4) | N1—H2 | 0.93 (7) |
Zn1—O3i | 1.947 (4) | N2—C1 | 1.480 (7) |
Zn1—O5ii | 1.953 (4) | N2—C4 | 1.503 (8) |
Zn1—O9 | 1.998 (4) | N2—H3 | 0.79 (7) |
Zn2—O1iii | 1.924 (4) | N2—H4 | 0.93 (7) |
Zn2—O2iv | 1.942 (4) | C1—C2 | 1.502 (8) |
Zn2—O7 | 1.951 (4) | C1—H5 | 0.95 (7) |
Zn2—O9iv | 2.031 (4) | C1—H6 | 0.85 (7) |
Zn3—O10v | 1.940 (4) | C2—H7 | 1.04 (6) |
Zn3—O8 | 1.942 (4) | C2—H8 | 0.96 (7) |
Zn3—OW | 1.995 (4) | C3—C4viii | 1.504 (8) |
Zn3—O12 | 2.090 (4) | C3—N1viii | 1.507 (8) |
Zn3—O3vi | 2.282 (4) | C3—H9 | 0.91 (7) |
Zn4—O6 | 1.941 (4) | C3—H10 | 0.85 (7) |
Zn4—O6iv | 1.941 (4) | C4—C3vi | 1.504 (8) |
Zn4—O11 | 1.967 (4) | C4—H11 | 0.86 (7) |
Zn4—O11iv | 1.967 (4) | C4—H12 | 0.85 (7) |
O2—As1—O1 | 112.9 (2) | As1—O4—Zn1 | 127.3 (2) |
O2—As1—O3 | 110.37 (18) | As2—O5—Zn1v | 128.3 (2) |
O1—As1—O3 | 104.32 (18) | As2—O6—Zn4 | 115.9 (2) |
O2—As1—O4 | 112.07 (18) | As2—O7—Zn2 | 129.2 (2) |
O1—As1—O4 | 109.60 (19) | As2—O8—Zn3 | 124.0 (2) |
O3—As1—O4 | 107.21 (19) | As3—O9—Zn1 | 119.3 (2) |
O8—As2—O6 | 111.64 (18) | As3—O9—Zn2iv | 114.48 (18) |
O8—As2—O7 | 106.60 (19) | Zn1—O9—Zn2iv | 124.33 (17) |
O6—As2—O7 | 113.34 (18) | As3—O10—Zn3ii | 144.7 (2) |
O8—As2—O5 | 111.18 (18) | As3—O11—Zn4 | 137.8 (2) |
O6—As2—O5 | 104.36 (18) | As3—O12—Zn3 | 122.8 (2) |
O7—As2—O5 | 109.79 (18) | Zn3—OW—H13 | 119 (4) |
O11—As3—O10 | 112.5 (2) | Zn3—OW—H14 | 108 (6) |
O11—As3—O12 | 113.7 (2) | H13—OW—H14 | 108 (7) |
O10—As3—O12 | 110.5 (2) | C2—N1—C3vi | 111.5 (5) |
O11—As3—O9 | 104.30 (18) | C2—N1—H1 | 111 (5) |
O10—As3—O9 | 108.97 (18) | C3vi—N1—H1 | 107 (5) |
O12—As3—O9 | 106.39 (18) | C2—N1—H2 | 106 (4) |
O4—Zn1—O3i | 116.76 (16) | C3vi—N1—H2 | 108 (4) |
O4—Zn1—O5ii | 105.09 (15) | H1—N1—H2 | 113 (6) |
O3i—Zn1—O5ii | 108.09 (16) | C1—N2—C4 | 111.4 (5) |
O4—Zn1—O9 | 108.56 (16) | C1—N2—H3 | 112 (5) |
O3i—Zn1—O9 | 103.96 (16) | C4—N2—H3 | 107 (5) |
O5ii—Zn1—O9 | 114.75 (16) | C1—N2—H4 | 123 (4) |
O1iii—Zn2—O2iv | 121.56 (17) | C4—N2—H4 | 105 (4) |
O1iii—Zn2—O7 | 111.70 (17) | H3—N2—H4 | 96 (6) |
O2iv—Zn2—O7 | 96.64 (15) | N2—C1—C2 | 108.9 (5) |
O1iii—Zn2—O9iv | 105.21 (16) | N2—C1—H5 | 111 (4) |
O2iv—Zn2—O9iv | 99.33 (15) | C2—C1—H5 | 118 (4) |
O7—Zn2—O9iv | 122.97 (16) | N2—C1—H6 | 107 (5) |
O10v—Zn3—O8 | 134.22 (17) | C2—C1—H6 | 111 (4) |
O10v—Zn3—OW | 108.83 (17) | H5—C1—H6 | 100 (6) |
O8—Zn3—OW | 116.77 (17) | N1—C2—C1 | 110.1 (5) |
O10v—Zn3—O12 | 84.50 (15) | N1—C2—H7 | 112 (4) |
O8—Zn3—O12 | 93.67 (15) | C1—C2—H7 | 108 (3) |
OW—Zn3—O12 | 97.00 (16) | N1—C2—H8 | 111 (4) |
O10v—Zn3—O3vi | 89.12 (15) | C1—C2—H8 | 109 (4) |
O8—Zn3—O3vi | 88.56 (14) | H7—C2—H8 | 106 (5) |
OW—Zn3—O3vi | 87.97 (15) | C4viii—C3—N1viii | 108.6 (5) |
O12—Zn3—O3vi | 172.91 (15) | C4viii—C3—H9 | 111 (4) |
O6—Zn4—O6iv | 114.8 (2) | N1viii—C3—H9 | 105 (4) |
O6—Zn4—O11 | 124.52 (16) | C4viii—C3—H10 | 109 (4) |
O6iv—Zn4—O11 | 97.99 (16) | N1viii—C3—H10 | 109 (4) |
O6—Zn4—O11iv | 97.99 (16) | H9—C3—H10 | 114 (6) |
O6iv—Zn4—O11iv | 124.52 (16) | N2—C4—C3vi | 110.2 (5) |
O11—Zn4—O11iv | 98.1 (3) | N2—C4—H11 | 107 (4) |
As1—O1—Zn2vii | 134.5 (2) | C3vi—C4—H11 | 113 (4) |
As1—O2—Zn2iv | 134.7 (2) | N2—C4—H12 | 106 (4) |
As1—O3—Zn1i | 121.7 (2) | C3vi—C4—H12 | 112 (4) |
As1—O3—Zn3viii | 133.4 (2) | H11—C4—H12 | 109 (6) |
Zn1i—O3—Zn3viii | 102.84 (16) | ||
O2—As1—O1—Zn2vii | 44.3 (4) | O10v—Zn3—O8—As2 | −13.6 (4) |
O3—As1—O1—Zn2vii | 164.1 (3) | OW—Zn3—O8—As2 | 160.8 (2) |
O4—As1—O1—Zn2vii | −81.4 (3) | O12—Zn3—O8—As2 | −99.5 (3) |
O1—As1—O2—Zn2iv | −87.0 (4) | O3vi—Zn3—O8—As2 | 73.8 (2) |
O3—As1—O2—Zn2iv | 156.7 (3) | O11—As3—O9—Zn1 | −142.4 (2) |
O4—As1—O2—Zn2iv | 37.3 (4) | O10—As3—O9—Zn1 | −22.0 (3) |
O2—As1—O3—Zn1i | −65.5 (3) | O12—As3—O9—Zn1 | 97.1 (2) |
O1—As1—O3—Zn1i | 173.0 (2) | O11—As3—O9—Zn2iv | 22.7 (3) |
O4—As1—O3—Zn1i | 56.8 (3) | O10—As3—O9—Zn2iv | 143.0 (2) |
O2—As1—O3—Zn3viii | 95.0 (3) | O12—As3—O9—Zn2iv | −97.8 (2) |
O1—As1—O3—Zn3viii | −26.5 (3) | O4—Zn1—O9—As3 | −179.9 (2) |
O4—As1—O3—Zn3viii | −142.7 (3) | O3i—Zn1—O9—As3 | 55.2 (2) |
O2—As1—O4—Zn1 | 4.4 (3) | O5ii—Zn1—O9—As3 | −62.7 (3) |
O1—As1—O4—Zn1 | 130.5 (3) | O4—Zn1—O9—Zn2iv | 16.7 (3) |
O3—As1—O4—Zn1 | −116.9 (3) | O3i—Zn1—O9—Zn2iv | −108.3 (2) |
O3i—Zn1—O4—As1 | 91.4 (3) | O5ii—Zn1—O9—Zn2iv | 133.9 (2) |
O5ii—Zn1—O4—As1 | −148.9 (3) | O11—As3—O10—Zn3ii | 139.2 (4) |
O9—Zn1—O4—As1 | −25.7 (3) | O12—As3—O10—Zn3ii | −92.5 (4) |
O8—As2—O5—Zn1v | −12.1 (3) | O9—As3—O10—Zn3ii | 24.0 (5) |
O6—As2—O5—Zn1v | −132.6 (3) | O10—As3—O11—Zn4 | 116.7 (4) |
O7—As2—O5—Zn1v | 105.6 (3) | O12—As3—O11—Zn4 | −9.9 (4) |
O8—As2—O6—Zn4 | 43.1 (3) | O9—As3—O11—Zn4 | −125.4 (4) |
O7—As2—O6—Zn4 | −77.2 (2) | O6—Zn4—O11—As3 | −14.3 (5) |
O5—As2—O6—Zn4 | 163.3 (2) | O6iv—Zn4—O11—As3 | 113.4 (4) |
O6iv—Zn4—O6—As2 | −172.7 (3) | O11iv—Zn4—O11—As3 | −119.9 (4) |
O11—Zn4—O6—As2 | −52.4 (3) | O11—As3—O12—Zn3 | 84.6 (3) |
O11iv—Zn4—O6—As2 | 53.2 (2) | O10—As3—O12—Zn3 | −43.0 (3) |
O8—As2—O7—Zn2 | −136.3 (3) | O9—As3—O12—Zn3 | −161.2 (2) |
O6—As2—O7—Zn2 | −13.0 (3) | O10v—Zn3—O12—As3 | −177.6 (3) |
O5—As2—O7—Zn2 | 103.2 (3) | O8—Zn3—O12—As3 | −43.5 (3) |
O1iii—Zn2—O7—As2 | −31.6 (3) | OW—Zn3—O12—As3 | 74.0 (3) |
O2iv—Zn2—O7—As2 | −159.5 (3) | O3vi—Zn3—O12—As3 | −151.7 (10) |
O9iv—Zn2—O7—As2 | 94.8 (3) | C4—N2—C1—C2 | −59.0 (6) |
O6—As2—O8—Zn3 | 82.2 (3) | C3vi—N1—C2—C1 | −59.2 (6) |
O7—As2—O8—Zn3 | −153.6 (2) | N2—C1—C2—N1 | 58.5 (6) |
O5—As2—O8—Zn3 | −33.9 (3) | C1—N2—C4—C3vi | 59.2 (6) |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x, y, −z+1/2; (v) −x+1/2, y−1/2, −z+1/2; (vi) x, −y+1, z−1/2; (vii) x+1/2, −y+1/2, z+1/2; (viii) x, −y+1, z+1/2. |