New X-ray diffraction studies on the crystal structure of ferroelectric [4-NH
2C
5H
4NH][SbCl
4] indicate that in the broad temperature range from 240 to 304 K covering the three intermediate phases, the crystal structure is modulated. Phase II is incommensurately modulated with modulation vector
q = β
b*, β varying from 0.60 to 0.66 and monoclinic
C2/
c(0β0)
s0 superspace group. Ferroelectric phase III is commensurate with
q =
b* and
Cc(0β0)0 symmetry. Polar phase IV is incommensurately modulated with β varying from 0.66 to 0.70 and
Cc(0β0)0 superspace group. In all phases only first-order satellites are observed along the
b* direction. Two types of periodic deformation are present in the structure of modulated phases. The 4-aminopyridinium cations are subjected to occupation modulation whereas [SbCl
4]
−n chains are displacively modulated. The paraelectric–ferroelectric phase transition is an example of the incommensurate–commensurate transition of the lock-in type. A new mechanism for this transformation is proposed.
Supporting information
B-IncStrDB reference: 13372Ei2XS4
CCDC references: 1827094; 1827095; 1827096; 1827097; 1827098
For all structures, data collection: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); cell refinement: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); data reduction: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015).
Crystal data top
C5H7Cl4N2Sb | F(000) = 680 |
Mr = 358.7 | Dx = 2.117 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5267 reflections |
a = 13.4747 (4) Å | θ = 3.3–29.2° |
b = 12.9393 (4) Å | µ = 3.35 mm−1 |
c = 7.7611 (2) Å | T = 320 K |
β = 123.733 (2)° | Prism |
V = 1125.34 (6) Å3 | 0.23 × 0.16 × 0.10 mm |
Z = 4 | |
Data collection top
Xcalibur, Atlas diffractometer | 1419 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 1295 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 10.6249 pixels mm-1 | θmax = 29.4°, θmin = 2.4° |
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | h = −18→17 |
Tmin = 0.852, Tmax = 1.000 | k = −17→17 |
7260 measured reflections | l = −10→10 |
Refinement top
Refinement on F2 | 0 constraints |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.094 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
S = 1.95 | (Δ/σ)max = 0.029 |
1295 reflections | Δρmax = 0.84 e Å−3 |
39 parameters | Δρmin = −0.56 e Å−3 |
13 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Sb | 0.5 | 0.57454 (2) | 0.75 | 0.04426 (19) | |
Cl1 | 0.37927 (11) | 0.70152 (10) | 0.4950 (2) | 0.0784 (6) | |
Cl2 | 0.64928 (10) | 0.58102 (8) | 0.6295 (2) | 0.0647 (5) | |
Na | 0.1597 (8) | 0.6524 (10) | 0.0512 (15) | 0.099 (4) | 0.5 |
N1a | −0.1256 (8) | 0.5220 (7) | −0.4734 (14) | 0.099 (4) | 0.5 |
C2a | −0.0378 (9) | 0.4598 (7) | −0.3230 (17) | 0.099 (4) | 0.5 |
C3a | 0.0607 (9) | 0.5040 (8) | −0.1533 (17) | 0.099 (4) | 0.5 |
C4a | 0.0638 (7) | 0.6117 (8) | −0.1316 (15) | 0.099 (4) | 0.5 |
C5a | −0.0249 (9) | 0.6775 (7) | −0.2815 (18) | 0.099 (4) | 0.5 |
C6a | −0.1179 (9) | 0.6290 (7) | −0.4571 (16) | 0.099 (4) | 0.5 |
H1n1a | −0.187525 | 0.493855 | −0.581753 | 0.1183* | 0.5 |
H1c3a | 0.126061 | 0.462108 | −0.051507 | 0.1183* | 0.5 |
H1c5a | −0.02161 | 0.751086 | −0.2639 | 0.1183* | 0.5 |
H1c2a | −0.0452 | 0.3859 | −0.3362 | 0.1183* | 0.5 |
H1c6a | −0.1782 | 0.6703 | −0.5697 | 0.1183* | 0.5 |
H1na | 0.2149 | 0.6116 | 0.1444 | 0.1183* | 0.5 |
H2na | 0.1647 | 0.7188 | 0.0727 | 0.1183* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sb | 0.0434 (2) | 0.0487 (2) | 0.0417 (2) | 0 | 0.02426 (16) | 0 |
Cl1 | 0.0731 (6) | 0.0751 (7) | 0.0876 (7) | 0.0245 (5) | 0.0450 (6) | 0.0343 (6) |
Cl2 | 0.0505 (5) | 0.0800 (7) | 0.0650 (6) | −0.0007 (4) | 0.0330 (5) | −0.0027 (4) |
Na | 0.104 (4) | 0.122 (4) | 0.109 (4) | −0.030 (3) | 0.084 (4) | −0.037 (3) |
N1a | 0.104 (4) | 0.122 (4) | 0.109 (4) | −0.030 (3) | 0.084 (4) | −0.037 (3) |
C2a | 0.104 (4) | 0.122 (4) | 0.109 (4) | −0.030 (3) | 0.084 (4) | −0.037 (3) |
C3a | 0.104 (4) | 0.122 (4) | 0.109 (4) | −0.030 (3) | 0.084 (4) | −0.037 (3) |
C4a | 0.104 (4) | 0.122 (4) | 0.109 (4) | −0.030 (3) | 0.084 (4) | −0.037 (3) |
C5a | 0.104 (4) | 0.122 (4) | 0.109 (4) | −0.030 (3) | 0.084 (4) | −0.037 (3) |
C6a | 0.104 (4) | 0.122 (4) | 0.109 (4) | −0.030 (3) | 0.084 (4) | −0.037 (3) |
Geometric parameters (Å, º) top
Sb—Cl1 | 2.3848 (12) | Sb—Cl2i | 2.6488 (18) |
Sb—Cl1i | 2.3848 (12) | Sb—Cl2ii | 3.1927 (11) |
Sb—Cl2 | 2.6488 (18) | Sb—Cl2iii | 3.1927 (11) |
| | | |
Cl1—Sb—Cl1i | 92.90 (4) | Cl1i—Sb—Cl2iii | 83.04 (4) |
Cl1—Sb—Cl2 | 89.26 (5) | Cl2—Sb—Cl2i | 176.37 (3) |
Cl1—Sb—Cl2i | 88.24 (5) | Cl2—Sb—Cl2ii | 84.67 (4) |
Cl1—Sb—Cl2ii | 83.04 (4) | Cl2—Sb—Cl2iii | 97.63 (4) |
Cl1—Sb—Cl2iii | 171.87 (5) | Cl2i—Sb—Cl2ii | 97.63 (4) |
Cl1i—Sb—Cl2 | 88.24 (5) | Cl2i—Sb—Cl2iii | 84.67 (4) |
Cl1i—Sb—Cl2i | 89.26 (5) | Cl2ii—Sb—Cl2iii | 101.83 (3) |
Cl1i—Sb—Cl2ii | 171.87 (5) | | |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1, z+1/2. |
Crystal data top
C5H7Cl4N2Sb | F(000) = 680 |
Mr = 358.69 | Dx = 2.091 Mg m−3 |
Monoclinic, C2/c(0β0)s0† | Mo Kα radiation, λ = 0.71073 Å |
q = 0.586000b* | Cell parameters from 9808 reflections |
a = 13.3923 Å | θ = 3.3–29.1° |
b = 12.815 Å | µ = 3.38 mm−1 |
c = 7.8256 Å | T = 290 K |
β = 123.735° | Prism |
V = 1116.90 Å3 | 0.23 × 0.16 × 0.10 mm |
Z = 4 | |
† Symmetry operations: (1) x1, x2, x3, x4; (2) −x1, x2, −x3+1/2, x4+1/2; (3) −x1, −x2, −x3, −x4; (4) x1, −x2, x3+1/2, −x4+1/2; (5) x1+1/2, x2+1/2, x3, x4; (6) −x1+1/2, x2+1/2, −x3+1/2, x4+1/2; (7) −x1+1/2, −x2+1/2, −x3, −x4; (8) x1+1/2, −x2+1/2, x3+1/2, −x4+1/2.
|
Data collection top
Xcalibur, Atlas diffractometer | 4209 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 2539 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 10.6249 pixels mm-1 | θmax = 29.4°, θmin = 2.4° |
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | h = −17→18 |
Tmin = 0.840, Tmax = 1.000 | k = −18→18 |
21939 measured reflections | l = −10→10 |
Refinement top
Refinement on F2 | 28 constraints |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.095 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
S = 1.82 | (Δ/σ)max = 0.049 |
2539 reflections | Δρmax = 0.52 e Å−3 |
133 parameters | Δρmin = −0.71 e Å−3 |
0 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Sb1 | 0.5 | 0.573560 (18) | 0.75 | 0.03484 (16) | |
Cl2 | 0.37993 (7) | 0.70182 (7) | 0.49724 (13) | 0.0598 (4) | |
Cl3 | 0.65132 (7) | 0.58010 (6) | 0.63310 (14) | 0.0515 (4) | |
Naa | 0.1529 (8) | 0.6567 (7) | 0.0376 (13) | 0.075 (3) | 0.5 |
C3aa | −0.0255 (10) | 0.6792 (10) | −0.2875 (17) | 0.053 (4) | 0.5 |
C2aa | −0.1162 (12) | 0.6301 (14) | −0.455 (2) | 0.083 (5) | 0.4964 |
N1aa | −0.1272 (13) | 0.5277 (13) | −0.477 (2) | 0.101 (4) | 0.5 |
C6aa | −0.0440 (15) | 0.4658 (11) | −0.327 (3) | 0.083 (5) | 0.5 |
C5aa | 0.0521 (13) | 0.5063 (9) | −0.151 (2) | 0.067 (4) | 0.5 |
C4aa | 0.0613 (10) | 0.6123 (7) | −0.1310 (17) | 0.052 (3) | 0.5 |
H1naa | 0.201224 | 0.618743 | 0.144936 | 0.0896* | 0.5 |
H2naa | 0.164406 | 0.723652 | 0.040527 | 0.0896* | 0.5 |
H1c3aa | −0.020035 | 0.753805 | −0.275539 | 0.0641* | 0.5 |
H1c2aa | −0.177153 | 0.672471 | −0.564569 | 0.0996* | 0.5 |
H1c6aa | −0.052276 | 0.391434 | −0.344508 | 0.1* | 0.5 |
H1c5aa | 0.111394 | 0.461602 | −0.043598 | 0.0806* | 0.5 |
H1n1aa | −0.187995 | 0.500705 | −0.589147 | 0.1208* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sb1 | 0.03412 (19) | 0.0376 (2) | 0.03173 (19) | 0 | 0.01759 (14) | 0 |
Cl2 | 0.0560 (5) | 0.0570 (5) | 0.0613 (5) | 0.0162 (3) | 0.0294 (4) | 0.0223 (4) |
Cl3 | 0.0419 (4) | 0.0597 (5) | 0.0528 (5) | −0.0001 (3) | 0.0262 (4) | −0.0026 (3) |
Naa | 0.061 (3) | 0.092 (4) | 0.065 (3) | −0.005 (3) | 0.031 (3) | −0.016 (3) |
C3aa | 0.056 (4) | 0.063 (4) | 0.049 (4) | 0.000 (2) | 0.034 (3) | 0.002 (2) |
C2aa | 0.077 (5) | 0.120 (6) | 0.072 (5) | 0.000 (5) | 0.053 (5) | −0.014 (5) |
N1aa | 0.057 (4) | 0.194 (8) | 0.065 (4) | −0.051 (4) | 0.043 (3) | −0.063 (4) |
C6aa | 0.108 (6) | 0.085 (5) | 0.102 (5) | −0.029 (5) | 0.086 (5) | −0.025 (5) |
C5aa | 0.089 (4) | 0.046 (3) | 0.084 (4) | 0.000 (3) | 0.059 (4) | −0.008 (3) |
C4aa | 0.054 (3) | 0.059 (3) | 0.058 (3) | −0.002 (3) | 0.041 (3) | −0.006 (3) |
Geometric parameters (Å, º) top | Average | Minimum | Maximum |
Sb1—Cl2 | 2.3833 (11) | 2.3796 (12) | 2.3886 (12) |
Sb1—Cl2i | 2.3833 (11) | 2.3796 (12) | 2.3886 (12) |
Sb1—Cl3 | 2.6493 (17) | 2.6179 (18) | 2.6810 (18) |
Sb1—Cl3i | 2.6487 (17) | 2.6179 (18) | 2.6810 (18) |
| | | |
Cl2—Sb1—Cl2i | 92.64 (4) | 92.63 (4) | 92.66 (4) |
Cl2—Sb1—Cl3 | 89.12 (5) | 88.09 (5) | 90.12 (5) |
Cl2—Sb1—Cl3i | 88.42 (5) | 87.98 (5) | 88.92 (5) |
Cl2i—Sb1—Cl3 | 88.42 (5) | 87.98 (5) | 88.92 (5) |
Cl2i—Sb1—Cl3i | 89.14 (5) | 88.09 (5) | 90.12 (5) |
Cl3—Sb1—Cl3i | 176.18 (3) | 175.98 (3) | 176.39 (3) |
Symmetry code: (i) −x1+1, x2, −x3+3/2, x4+1/2. |
Crystal data top
C5H7Cl4N2Sb | F(000) = 675 |
Mr = 358.69 | Dx = 2.157 Mg m−3 |
Monoclinic, Cc(0β0)0† | Mo Kα radiation, λ = 0.71073 Å |
q = 0.666667b* | Cell parameters from 11628 reflections |
a = 13.33 (2) Å | θ = 3.2–29.1° |
b = 12.690 (9) Å | µ = 3.42 mm−1 |
c = 7.87 (2) Å | T = 260 K |
β = 123.8 (2)° | Prism |
V = 1106 (3) Å3 | 0.23 × 0.16 × 0.10 mm |
Z = 4 | |
† Symmetry operations: (1) x1, x2, x3, x4; (2) x1, −x2, x3+1/2, −x4; (3) x1+1/2, x2+1/2, x3, x4; (4) x1+1/2, −x2+1/2, x3+1/2, −x4.
|
Data collection top
Xcalibur, Atlas diffractometer | 7836 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 5379 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 10.6249 pixels mm-1 | θmax = 29.6°, θmin = 2.4° |
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | h = −17→18 |
Tmin = 0.858, Tmax = 1.000 | k = −17→17 |
21857 measured reflections | l = −10→10 |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.036 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
wR(F2) = 0.121 | (Δ/σ)max = 0.029 |
S = 2.26 | Δρmax = 1.06 e Å−3 |
5379 reflections | Δρmin = −0.84 e Å−3 |
151 parameters | Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974) |
20 restraints | Extinction coefficient: −320 (140) |
3 constraints | Absolute structure: 2585 of Friedel pairs used in the refinement |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Sb | 0.52316 (3) | 0.572651 (17) | 0.71584 (4) | 0.02826 (14) | |
Cl1a | 0.40429 (13) | 0.70193 (12) | 0.4637 (2) | 0.0465 (7) | |
Cl1b | 0.64468 (13) | 0.70128 (12) | 0.96745 (19) | 0.0461 (7) | |
Cl2a | 0.67566 (14) | 0.58027 (12) | 0.5982 (2) | 0.0379 (11) | |
Cl2b | 0.37023 (16) | 0.57969 (13) | 0.8267 (2) | 0.0459 (13) | |
Naa | 0.1844 (3) | 0.6582 (4) | 0.0154 (4) | 0.0640 (16) | 0.6 |
C5aa | 0.0097 (8) | 0.6799 (7) | −0.3078 (11) | 0.0640 (16) | 0.6 |
C6aa | −0.0853 (8) | 0.6322 (7) | −0.4842 (11) | 0.0640 (16) | 0.6 |
N1aa | −0.0941 (7) | 0.5242 (7) | −0.5028 (10) | 0.0640 (16) | 0.6 |
C2aa | −0.0109 (7) | 0.4600 (8) | −0.3501 (10) | 0.0640 (16) | 0.6 |
C3aa | 0.0875 (7) | 0.4988 (6) | −0.1713 (11) | 0.0640 (16) | 0.6 |
C4aa | 0.0919 (4) | 0.6073 (4) | −0.1607 (5) | 0.0640 (16) | 0.6 |
H1a | 0.188291 | 0.726659 | 0.01968 | 0.0768* | 0.6 |
H2a | 0.238129 | 0.621355 | 0.120581 | 0.0768* | 0.6 |
H1c5aa | 0.018135 | 0.754821 | −0.288552 | 0.0768* | 0.6 |
H1c6aa | −0.14542 | 0.675304 | −0.594509 | 0.0768* | 0.6 |
H1c2aa | −0.021417 | 0.385092 | −0.367974 | 0.0768* | 0.6 |
H1c3aa | 0.147671 | 0.454415 | −0.063794 | 0.0768* | 0.6 |
H1n1aa | −0.154208 | 0.496296 | −0.614633 | 0.0768* | 0.6 |
Nba | −0.1268 (4) | 0.6204 (4) | −0.5880 (4) | 0.062 (2) | 0.4 |
C5ba | 0.0321 (10) | 0.6931 (6) | −0.2608 (11) | 0.062 (2) | 0.4 |
C6ba | 0.1268 (9) | 0.6775 (7) | −0.0632 (11) | 0.062 (2) | 0.4 |
N1ba | 0.1653 (7) | 0.5763 (7) | 0.0011 (10) | 0.062 (2) | 0.4 |
C2ba | 0.1023 (8) | 0.4898 (7) | −0.1188 (11) | 0.062 (2) | 0.4 |
C3ba | 0.0027 (8) | 0.5065 (6) | −0.3155 (11) | 0.062 (2) | 0.4 |
C4ba | −0.0251 (4) | 0.6083 (5) | −0.3877 (6) | 0.062 (2) | 0.4 |
H1ba | −0.140533 | 0.680443 | −0.650729 | 0.0745* | 0.4 |
H2ba | −0.176189 | 0.567897 | −0.649548 | 0.0745* | 0.4 |
H1n1ba | 0.231314 | 0.566144 | 0.120866 | 0.0745* | 0.4 |
H1c5ba | 0.005402 | 0.763388 | −0.311052 | 0.0745* | 0.4 |
H1c4ba | 0.16552 | 0.735979 | 0.028287 | 0.0745* | 0.4 |
H1c2ba | 0.127171 | 0.41963 | −0.066396 | 0.0745* | 0.4 |
H1c3ba | −0.045686 | 0.448493 | −0.399565 | 0.0745* | 0.4 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sb | 0.02837 (16) | 0.02888 (18) | 0.02555 (16) | −0.0003 (2) | 0.01376 (12) | 0.0001 (2) |
Cl1a | 0.0442 (7) | 0.0430 (9) | 0.0463 (8) | 0.0121 (7) | 0.0214 (6) | 0.0183 (7) |
Cl1b | 0.0446 (7) | 0.0436 (9) | 0.0434 (8) | −0.0125 (7) | 0.0203 (6) | −0.0108 (7) |
Cl2a | 0.0287 (10) | 0.0424 (12) | 0.0391 (14) | 0.0020 (6) | 0.0166 (10) | −0.0004 (7) |
Cl2b | 0.0414 (13) | 0.0505 (14) | 0.0484 (16) | 0.0013 (7) | 0.0265 (12) | 0.0028 (8) |
Naa | 0.0558 (18) | 0.090 (2) | 0.0585 (17) | −0.0149 (16) | 0.0395 (14) | −0.0240 (15) |
C5aa | 0.0558 (18) | 0.090 (2) | 0.0585 (17) | −0.0149 (16) | 0.0395 (14) | −0.0240 (15) |
C6aa | 0.0558 (18) | 0.090 (2) | 0.0585 (17) | −0.0149 (16) | 0.0395 (14) | −0.0240 (15) |
N1aa | 0.0558 (18) | 0.090 (2) | 0.0585 (17) | −0.0149 (16) | 0.0395 (14) | −0.0240 (15) |
C2aa | 0.0558 (18) | 0.090 (2) | 0.0585 (17) | −0.0149 (16) | 0.0395 (14) | −0.0240 (15) |
C3aa | 0.0558 (18) | 0.090 (2) | 0.0585 (17) | −0.0149 (16) | 0.0395 (14) | −0.0240 (15) |
C4aa | 0.0558 (18) | 0.090 (2) | 0.0585 (17) | −0.0149 (16) | 0.0395 (14) | −0.0240 (15) |
Nba | 0.070 (2) | 0.0538 (19) | 0.072 (2) | −0.0040 (18) | 0.045 (2) | −0.0024 (19) |
C5ba | 0.070 (2) | 0.0538 (19) | 0.072 (2) | −0.0040 (18) | 0.045 (2) | −0.0024 (19) |
C6ba | 0.070 (2) | 0.0538 (19) | 0.072 (2) | −0.0040 (18) | 0.045 (2) | −0.0024 (19) |
N1ba | 0.070 (2) | 0.0538 (19) | 0.072 (2) | −0.0040 (18) | 0.045 (2) | −0.0024 (19) |
C2ba | 0.070 (2) | 0.0538 (19) | 0.072 (2) | −0.0040 (18) | 0.045 (2) | −0.0024 (19) |
C3ba | 0.070 (2) | 0.0538 (19) | 0.072 (2) | −0.0040 (18) | 0.045 (2) | −0.0024 (19) |
C4ba | 0.070 (2) | 0.0538 (19) | 0.072 (2) | −0.0040 (18) | 0.045 (2) | −0.0024 (19) |
Geometric parameters (Å, º) top | Average | Minimum | Maximum |
Sb—Cl1a | 2.382 (5) | 2.380 (6) | 2.382 (6) |
Sb—Cl1b | 2.380 (6) | 2.374 (6) | 2.384 (6) |
Sb—Cl2a | 2.665 (8) | 2.643 (8) | 2.697 (8) |
Sb—Cl2ai | 3.191 (6) | 3.163 (8) | 3.206 (8) |
Sb—Cl2b | 2.630 (8) | 2.595 (9) | 2.662 (9) |
Sb—Cl2bii | 3.219 (6) | 3.180 (8) | 3.266 (8) |
Naa—C4aa | 1.401 (7) | 1.401 (7) | 1.402 (7) |
C5aa—C6aa | 1.395 (11) | 1.394 (11) | 1.396 (11) |
C5aa—C4aa | 1.409 (9) | 1.408 (10) | 1.410 (10) |
C6aa—N1aa | 1.379 (13) | 1.378 (13) | 1.380 (13) |
N1aa—C2aa | 1.364 (11) | 1.363 (11) | 1.365 (11) |
C2aa—C3aa | 1.377 (11) | 1.376 (11) | 1.378 (11) |
C3aa—C4aa | 1.381 (9) | 1.380 (9) | 1.382 (9) |
Nba—C4ba | 1.429 (8) | 1.429 (8) | 1.429 (8) |
C5ba—C6ba | 1.391 (12) | 1.391 (12) | 1.391 (12) |
C5ba—C4ba | 1.399 (10) | 1.399 (10) | 1.399 (10) |
C6ba—N1ba | 1.393 (13) | 1.393 (13) | 1.393 (13) |
N1ba—C2ba | 1.408 (12) | 1.408 (12) | 1.408 (12) |
C2ba—C3ba | 1.410 (11) | 1.410 (11) | 1.410 (11) |
C3ba—C4ba | 1.395 (10) | 1.395 (10) | 1.395 (10) |
| | | |
Cl1a—Sb—Cl1b | 92.8 (3) | 91.9 (3) | 93.3 (3) |
Cl1a—Sb—Cl2a | 88.2 (2) | 87.34 (19) | 89.2 (2) |
Cl1a—Sb—Cl2ai | 171.30 (13) | 169.17 (12) | 173.61 (13) |
Cl1a—Sb—Cl2b | 88.5 (2) | 88.24 (19) | 89.0 (2) |
Cl1a—Sb—Cl2bii | 81.1 (3) | 79.7 (3) | 83.4 (3) |
Cl1b—Sb—Cl2a | 88.1 (2) | 87.44 (19) | 88.8 (2) |
Cl1b—Sb—Cl2ai | 81.5 (3) | 80.4 (3) | 82.2 (3) |
Cl1b—Sb—Cl2b | 89.7 (2) | 88.45 (19) | 91.3 (2) |
Cl1b—Sb—Cl2bii | 170.02 (13) | 168.27 (13) | 170.97 (14) |
Cl2a—Sb—Cl2ai | 98.1 (2) | 95.2 (2) | 100.0 (2) |
Cl2a—Sb—Cl2b | 175.56 (10) | 175.38 (9) | 175.74 (8) |
Cl2a—Sb—Cl2bii | 83.8 (2) | 83.1 (2) | 85.2 (2) |
Cl2ai—Sb—Cl2b | 84.9 (2) | 84.2 (2) | 86.3 (2) |
Cl2ai—Sb—Cl2bii | 105.3 (3) | 105.2 (3) | 105.4 (2) |
Cl2b—Sb—Cl2bii | 98.0 (2) | 96.3 (2) | 100.8 (2) |
Symmetry codes: (i) x1, −x2+1, x3+1/2, −x4; (ii) x1, −x2+1, x3−1/2, −x4. |
Crystal data top
C5H7Cl4N2Sb | F(000) = 680 |
Mr = 358.69 | Dx = 2.192 Mg m−3 |
Monoclinic, Cc(0β0)0† | Mo Kα radiation, λ = 0.71073 Å |
q = 0.668000b* | Cell parameters from 6364 reflections |
a = 13.30 (2) Å | θ = 3.3–29.1° |
b = 12.660 (18) Å | µ = 3.42 mm−1 |
c = 7.89 (2) Å | T = 245 K |
β = 123.8 (2)° | Prism |
V = 1103 (4) Å3 | 0.23 × 0.16 × 0.10 mm |
Z = 4 | |
† Symmetry operations: (1) x1, x2, x3, x4; (2) x1, −x2, x3+1/2, −x4; (3) x1+1/2, x2+1/2, x3, x4; (4) x1+1/2, −x2+1/2, x3+1/2, −x4.
|
Data collection top
Xcalibur, Atlas diffractometer | 7751 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 4489 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 10.6249 pixels mm-1 | θmax = 29.4°, θmin = 2.4° |
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | h = −17→18 |
Tmin = 0.843, Tmax = 1.000 | k = −17→17 |
20894 measured reflections | l = −10→10 |
Refinement top
Refinement on Fsqr | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.052 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
wR(F2) = 0.067 | (Δ/σ)max = 0.073 |
S = 1.90 | Δρmax = 1.32 e Å−3 |
4489 reflections | Δρmin = −1.24 e Å−3 |
135 parameters | Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974) |
26 restraints | Extinction coefficient: −420 (120) |
3 constraints | Absolute structure: 2000 of Friedel pairs used in the refinement |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Sb1 | 0.50070 (4) | 0.57246 (2) | 0.74945 (8) | 0.0283 (2) | |
Cl1a | 0.3818 (3) | 0.70087 (16) | 0.5013 (5) | 0.0471 (16) | |
Cl1b | 0.6215 (2) | 0.70322 (14) | 1.0037 (4) | 0.0358 (13) | |
Cl2a | 0.6515 (2) | 0.57925 (15) | 0.6339 (4) | 0.0346 (14) | |
Cl2b | 0.3442 (3) | 0.58118 (17) | 0.8601 (6) | 0.0452 (19) | |
Naa | 0.1702 (7) | 0.6597 (5) | 0.0634 (10) | 0.034* | 0.6 |
C5aa | −0.0132 (9) | 0.6767 (4) | −0.2755 (13) | 0.0478* | 0.6 |
C6aa | −0.1072 (8) | 0.6315 (6) | −0.4532 (11) | 0.0421* | 0.6 |
N1aa | −0.1166 (7) | 0.5225 (5) | −0.4665 (11) | 0.043* | 0.6 |
C2aa | −0.0291 (9) | 0.4586 (5) | −0.3095 (14) | 0.0417* | 0.6 |
C3aa | 0.0695 (8) | 0.5033 (5) | −0.1344 (13) | 0.0411* | 0.6 |
C4aa | 0.0743 (8) | 0.6128 (4) | −0.1196 (11) | 0.0382* | 0.6 |
H1naa | 0.23143 | 0.621482 | 0.153043 | 0.0408* | 0.6 |
H2naa | 0.167648 | 0.726583 | 0.085938 | 0.0408* | 0.6 |
H1c5aa | −0.00842 | 0.752055 | −0.259655 | 0.0574* | 0.6 |
H1c6aa | −0.165065 | 0.674902 | −0.565634 | 0.0505* | 0.6 |
H1c2aa | −0.03691 | 0.383151 | −0.322237 | 0.0501* | 0.6 |
H1c3aa | 0.132006 | 0.460113 | −0.027539 | 0.0494* | 0.6 |
H1n1aa | −0.178167 | 0.493454 | −0.574669 | 0.0516* | 0.6 |
Nba | −0.1635 (12) | 0.6286 (7) | −0.5629 (16) | 0.0585* | 0.4 |
C5ba | 0.0022 (11) | 0.6929 (5) | −0.2460 (16) | 0.0448* | 0.4 |
C6ba | 0.1048 (10) | 0.6803 (7) | −0.0504 (15) | 0.044* | 0.4 |
N1ba | 0.1446 (9) | 0.5788 (9) | 0.0240 (14) | 0.0386* | 0.4 |
C2ba | 0.0848 (13) | 0.4896 (7) | −0.096 (2) | 0.0694* | 0.4 |
C3ba | −0.0215 (11) | 0.5029 (6) | −0.2873 (19) | 0.0321* | 0.4 |
C4ba | −0.0601 (10) | 0.6046 (7) | −0.3635 (14) | 0.0418* | 0.4 |
H1nba | −0.186117 | 0.693899 | −0.597613 | 0.0702* | 0.4 |
H2nba | −0.203645 | 0.577924 | −0.649319 | 0.0702* | 0.4 |
H1c5ba | −0.025952 | 0.762489 | −0.30024 | 0.0537* | 0.4 |
H1c6ba | 0.147703 | 0.740763 | 0.0321 | 0.0528* | 0.4 |
H1c2ba | 0.116893 | 0.420202 | −0.0464 | 0.0833* | 0.4 |
H1c3ba | −0.067797 | 0.442653 | −0.366019 | 0.0385* | 0.4 |
H1n1ba | 0.207823 | 0.570439 | 0.147542 | 0.0463* | 0.4 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sb1 | 0.0287 (2) | 0.0246 (2) | 0.0340 (3) | 0.0056 (3) | 0.0190 (2) | 0.0043 (3) |
Cl1a | 0.0452 (17) | 0.0444 (12) | 0.061 (2) | 0.0134 (12) | 0.0351 (17) | 0.0179 (12) |
Cl1b | 0.0268 (13) | 0.0292 (9) | 0.0302 (15) | −0.0047 (9) | 0.0027 (13) | −0.0056 (9) |
Cl2a | 0.0229 (14) | 0.0408 (12) | 0.0363 (19) | −0.0005 (9) | 0.0141 (14) | −0.0104 (10) |
Cl2b | 0.0382 (18) | 0.0376 (13) | 0.065 (3) | −0.0024 (10) | 0.0317 (19) | −0.0077 (11) |
Geometric parameters (Å, º) top | Average | Minimum | Maximum |
Sb1—Cl1a | 2.359 (6) | 2.352 (7) | 2.372 (7) |
Sb1—Cl1b | 2.406 (6) | 2.381 (7) | 2.426 (7) |
Sb1—Cl2a | 2.628 (9) | 2.564 (9) | 2.697 (9) |
Sb1—Cl2ai | 3.191 (7) | 3.128 (8) | 3.246 (8) |
Sb1—Cl2b | 2.673 (10) | 2.639 (11) | 2.708 (11) |
Sb1—Cl2bii | 3.239 (7) | 3.189 (9) | 3.304 (9) |
Naa—C4aa | 1.428 (16) | 1.419 (18) | 1.469 (18) |
C5aa—C6aa | 1.389 (16) | 1.381 (18) | 1.429 (18) |
C5aa—C4aa | 1.396 (14) | 1.388 (16) | 1.436 (16) |
C6aa—N1aa | 1.392 (19) | 1.38 (2) | 1.43 (2) |
N1aa—C2aa | 1.401 (17) | 1.393 (19) | 1.441 (19) |
C2aa—C3aa | 1.398 (17) | 1.39 (2) | 1.44 (2) |
Nba—C4ba | 1.48 (2) | 1.43 (3) | 1.71 (3) |
C5ba—C6ba | 1.43 (3) | 1.39 (3) | 1.66 (3) |
C5ba—C4ba | 1.44 (2) | 1.39 (2) | 1.66 (2) |
C6ba—N1ba | 1.43 (3) | 1.39 (3) | 1.65 (3) |
N1ba—C2ba | 1.44 (3) | 1.40 (3) | 1.67 (3) |
C2ba—C3ba | 1.43 (3) | 1.39 (3) | 1.66 (3) |
C3ba—C4ba | 1.43 (2) | 1.39 (2) | 1.66 (2) |
| | | |
Cl1a—Sb1—Cl1b | 92.6 (3) | 91.6 (3) | 93.7 (3) |
Cl1a—Sb1—Cl2a | 88.9 (2) | 87.0 (2) | 90.9 (2) |
Cl1a—Sb1—Cl2ai | 170.06 (19) | 169.20 (18) | 170.8 (2) |
Cl1a—Sb1—Cl2b | 87.6 (2) | 85.9 (2) | 89.2 (2) |
Cl1a—Sb1—Cl2bii | 81.3 (3) | 79.9 (3) | 82.5 (3) |
Cl1b—Sb1—Cl2a | 89.0 (2) | 86.5 (2) | 91.3 (2) |
Cl1b—Sb1—Cl2ai | 81.2 (3) | 78.9 (3) | 83.4 (2) |
Cl1b—Sb1—Cl2b | 88.9 (2) | 87.1 (2) | 90.5 (2) |
Cl1b—Sb1—Cl2bii | 170.83 (17) | 167.47 (18) | 174.42 (15) |
Cl2a—Sb1—Cl2ai | 98.67 (19) | 96.7 (2) | 100.45 (18) |
Cl2a—Sb1—Cl2b | 175.48 (11) | 174.03 (11) | 176.95 (10) |
Cl2a—Sb1—Cl2bii | 84.3 (2) | 82.41 (19) | 86.3 (2) |
Cl2ai—Sb1—Cl2b | 84.6 (2) | 82.8 (2) | 86.4 (2) |
Cl2ai—Sb1—Cl2bii | 105.7 (2) | 105.4 (2) | 106.0 (2) |
Cl2b—Sb1—Cl2bii | 97.4 (2) | 93.9 (2) | 100.69 (19) |
Symmetry codes: (i) x1, −x2+1, x3+1/2, −x4; (ii) x1, −x2+1, x3−1/2, −x4. |
Crystal data top
C5H7Cl4N2Sb | F(000) = 680 |
Mr = 358.69 | Dx = 2.190 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yabc | Cell parameters from 8893 reflections |
a = 13.2080 (4) Å | θ = 3.3–29.1° |
b = 12.526 (4) Å | µ = 3.47 mm−1 |
c = 7.9251 (3) Å | T = 200 K |
β = 123.914 (2)° | Prism |
V = 1088.1 (4) Å3 | 0.23 × 0.16 × 0.10 mm |
Z = 4 | |
Data collection top
Xcalibur, Atlas diffractometer | 2744 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 2519 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 10.6249 pixels mm-1 | θmax = 29.5°, θmin = 2.5° |
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | h = −18→17 |
Tmin = 0.841, Tmax = 1.000 | k = −17→17 |
14021 measured reflections | l = −10→10 |
Refinement top
Refinement on Fsqr | 0 constraints |
R[F2 > 2σ(F2)] = 0.014 | H-atom parameters constrained |
wR(F2) = 0.030 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
S = 1.20 | (Δ/σ)max = 0.020 |
2744 reflections | Δρmax = 0.70 e Å−3 |
109 parameters | Δρmin = −0.73 e Å−3 |
0 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Sb | 0.511351 (12) | 0.571387 (9) | 0.759189 (15) | 0.01917 (8) | |
Cl1a | 0.40620 (4) | 0.71383 (4) | 0.52663 (6) | 0.0283 (2) | |
Cl1b | 0.64651 (4) | 0.69029 (4) | 1.02697 (6) | 0.0290 (2) | |
Cl2a | 0.66408 (5) | 0.57125 (3) | 0.63829 (9) | 0.0294 (2) | |
Cl2b | 0.35467 (5) | 0.58915 (4) | 0.86125 (7) | 0.0264 (2) | |
N | 0.16653 (15) | 0.65019 (12) | 0.0625 (2) | 0.0348 (8) | |
C5 | −0.00912 (17) | 0.68284 (18) | −0.2746 (2) | 0.0283 (9) | |
C6 | −0.1047 (2) | 0.64168 (19) | −0.4507 (3) | 0.0364 (9) | |
N1 | −0.12220 (17) | 0.53468 (16) | −0.4766 (3) | 0.0386 (8) | |
C2 | −0.0455 (2) | 0.46623 (18) | −0.3300 (4) | 0.0385 (12) | |
C3 | 0.0533 (2) | 0.50224 (16) | −0.1492 (3) | 0.0319 (10) | |
C4 | 0.07266 (16) | 0.61308 (13) | −0.1166 (2) | 0.0247 (8) | |
H1n | 0.176746 | 0.718631 | 0.084184 | 0.0417* | |
H2n | 0.217141 | 0.605788 | 0.156704 | 0.0417* | |
H5 | 0.002704 | 0.758687 | −0.257763 | 0.0339* | |
H6 | −0.16061 | 0.688935 | −0.558501 | 0.0437* | |
H2 | −0.060125 | 0.390862 | −0.352103 | 0.0462* | |
H3 | 0.108761 | 0.452678 | −0.046122 | 0.0382* | |
H1 | −0.184369 | 0.509994 | −0.590372 | 0.0463* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sb | 0.01957 (9) | 0.01811 (10) | 0.01690 (9) | −0.00087 (4) | 0.00838 (7) | 0.00009 (3) |
Cl1a | 0.0276 (2) | 0.0253 (2) | 0.0255 (2) | 0.00385 (18) | 0.0108 (2) | 0.00684 (16) |
Cl1b | 0.0267 (2) | 0.0262 (2) | 0.0238 (2) | −0.00599 (18) | 0.00778 (19) | −0.00451 (16) |
Cl2a | 0.0254 (3) | 0.0293 (3) | 0.0326 (3) | 0.00092 (16) | 0.0157 (2) | −0.00077 (16) |
Cl2b | 0.0239 (2) | 0.0260 (2) | 0.0268 (2) | −0.00205 (17) | 0.0126 (2) | −0.00051 (17) |
N | 0.0298 (9) | 0.0358 (9) | 0.0259 (8) | −0.0016 (8) | 0.0076 (7) | −0.0069 (7) |
C5 | 0.0332 (10) | 0.0259 (11) | 0.0252 (9) | 0.0024 (7) | 0.0159 (8) | 0.0033 (7) |
C6 | 0.0295 (11) | 0.0507 (13) | 0.0246 (10) | 0.0048 (10) | 0.0125 (9) | 0.0031 (9) |
N1 | 0.0274 (9) | 0.0595 (12) | 0.0287 (9) | −0.0159 (9) | 0.0156 (8) | −0.0190 (8) |
C2 | 0.0502 (14) | 0.0338 (12) | 0.0453 (13) | −0.0157 (11) | 0.0351 (12) | −0.0171 (10) |
C3 | 0.0393 (12) | 0.0267 (10) | 0.0329 (11) | 0.0003 (8) | 0.0222 (10) | −0.0018 (8) |
C4 | 0.0255 (9) | 0.0268 (9) | 0.0244 (9) | 0.0012 (8) | 0.0155 (8) | −0.0009 (7) |
Geometric parameters (Å, º) top
Sb—Cl1a | 2.3775 (10) | C5—C6 | 1.357 (2) |
Sb—Cl1b | 2.3835 (7) | C5—C4 | 1.410 (2) |
Sb—Cl2a | 2.6728 (9) | C6—N1 | 1.356 (3) |
Sb—Cl2ai | 3.2155 (8) | N1—C2 | 1.341 (3) |
Sb—Cl2b | 2.6181 (7) | C2—C3 | 1.368 (3) |
Sb—Cl2bii | 3.2068 (10) | C3—C4 | 1.409 (3) |
| | | |
Cl1a—Sb—Cl1b | 92.56 (3) | Cl2a—Sb—Cl2b | 174.602 (16) |
Cl1a—Sb—Cl2a | 87.35 (2) | Cl2a—Sb—Cl2bii | 101.77 (2) |
Cl1a—Sb—Cl2ai | 82.39 (2) | Cl2ai—Sb—Cl2b | 95.06 (2) |
Cl1a—Sb—Cl2b | 87.43 (2) | Cl2ai—Sb—Cl2bii | 106.82 (2) |
Cl1a—Sb—Cl2bii | 167.34 (2) | Cl2b—Sb—Cl2bii | 83.17 (2) |
Cl1b—Sb—Cl2a | 88.82 (2) | C6—N1—C2 | 121.22 (16) |
Cl1b—Sb—Cl2ai | 172.66 (2) | N1—C2—C3 | 121.0 (2) |
Cl1b—Sb—Cl2b | 90.02 (2) | N—C4—C5 | 121.47 (16) |
Cl1b—Sb—Cl2bii | 79.02 (3) | N—C4—C3 | 120.06 (14) |
Cl2a—Sb—Cl2ai | 85.64 (2) | C5—C4—C3 | 118.47 (14) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1n···Cl2aiii | 0.87 | 2.69 | 3.544 (3) | 168.60 |
N—H2n···Cl2ai | 0.87 | 2.68 | 3.522 (2) | 163.63 |
N1—H1···Cl2biv | 0.87 | 2.41 | 3.2684 (17) | 167.80 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (iii) x−1/2, −y+3/2, z−1/2; (iv) −x, −y+1, −z. |