catena-Poly[[dodeca­aqua­(μ₃-benzene-1,3,5-tricarboxyl­ato)dinickel(II)zinc(II)]-μ-benzene-1,3,5-tricarboxyl­ato]

The asymmetric unit of the title polymer, [ZnNi₂(C₉H₃O₆)₂(H₂O)₁₂]_n, contains one Zn^II atom on a twofold rotation axis and one Ni^II atom in a general position. Benzene-1,3,5-tricarboxyl­ate anions bridge the Zn^II and Co^II atoms in two different coordination modes, forming a one-dimensional polymeric linear chain structure; the chains are further linked by O—H...O hydrogen bonds, forming a three-dimensional network. One anion is in a general position and bridges two Ni^II atoms, with the third carboxylate group uncoordinated; the other lies on the same twofold rotation axis as the Zn^II atom, which it chelates while simultaneously coordinating two Ni^II atoms in monodentate fashion.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.025
• wR factor = 0.054
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.89 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.00 Ratio
PLAT417_ALERT_2_C Short Inter D-H..H-D       H10B   ..  H12A    ..       2.14 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7B    ..  O3      ..       2.64 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12A   ..  O7      ..       2.64 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.21 Ratio
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       0.01

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           28.68
           From the CIF: _reflns_number_total               3463
           Count of symmetry unique reflns         1819
           Completeness (_total/calc)            190.38%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1644
           Fraction of Friedel pairs measured     0.904
           Are heavy atom types Z>Si present        yes

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

   0 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
   1 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure.

catena-Poly[[dodecaaqua(µ₃-benzene-1,3,5- tricarboxylato)dinickel(II)zinc(II)]-µ-benzene-1,3,5-tricarboxylato]

Crystal data

[ZnNi2(C9H3O6)2(H2O)12]	F(000) = 832
Mr = 813.21	Dx = 2.002 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71070 Å
a = 17.354 (2) Å	Cell parameters from 2231 reflections
b = 12.9180 (14) Å	θ = 2.0–28.7°
c = 6.4764 (10) Å	µ = 2.37 mm^−1
β = 111.685 (4)°	T = 113 K
V = 1349.1 (3) Å^3	Block, colorless
Z = 2	0.22 × 0.16 × 0.12 mm

Data collection

Rigaku Saturn diffractometer	3463 independent reflections
Radiation source: rotating anode	3025 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.039
Detector resolution: 7.31 pixels mm^-1	θmax = 28.7°, θmin = 2.0°
ω scans	h = −23→23
Absorption correction: multi-scan (Jacobson, 1998)	k = −17→17
Tmin = 0.608, Tmax = 0.764	l = −8→8
8938 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.025	w = 1/[σ^2(Fo^2) + (0.0159P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.054	(Δ/σ)max = 0.001
S = 0.98	Δρmax = 0.45 e Å^−3
3463 reflections	Δρmin = −0.40 e Å^−3
209 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0125 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1648 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.000 (14)

Special details

Experimental. IR (KBr, ν cm^-1): 3449, 1617, 1520, 1474, 1437, 1372, 719

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
Ni1	0.258412 (19)	0.73689 (2)	0.22861 (5)	0.00527 (8)
Zn1	0.0000	0.02421 (3)	0.0000	0.01056 (11)
O1	0.35297 (11)	0.83991 (13)	0.2986 (3)	0.0088 (4)
O2	0.28469 (11)	0.98453 (13)	0.1456 (3)	0.0097 (4)
O3	0.56898 (13)	1.32368 (15)	0.5742 (3)	0.0209 (5)
O4	0.15815 (11)	0.64398 (14)	0.1669 (3)	0.0082 (4)
O5	0.21708 (11)	0.49879 (14)	0.3484 (3)	0.0106 (4)
O6	0.06569 (11)	0.16737 (14)	0.1102 (3)	0.0106 (4)
O7	0.23541 (11)	0.80243 (15)	0.4971 (3)	0.0124 (4)
H7A	0.2519	0.8635	0.5399	0.019*
H7B	0.2157	0.7678	0.5778	0.019*
O8	0.34087 (11)	0.62779 (14)	0.4276 (3)	0.0100 (4)
H8A	0.3059	0.5795	0.4110	0.015*
H8B	0.3635	0.6465	0.5626	0.015*
O9	0.27741 (11)	0.67585 (14)	−0.0499 (3)	0.0135 (4)
H9A	0.3258	0.6824	−0.0522	0.020*
H9B	0.2577	0.6168	−0.1005	0.020*
O10	0.17681 (11)	0.84111 (14)	0.0150 (3)	0.0091 (4)
H10A	0.1553	0.8235	−0.1209	0.014*
H10B	0.2118	0.8898	0.0361	0.014*
O11	−0.05812 (11)	0.01901 (15)	0.2353 (3)	0.0143 (4)
H11A	−0.0794	0.0648	0.2922	0.021*
H11B	−0.0549	−0.0358	0.3106	0.021*
O12	0.08357 (13)	−0.07178 (17)	0.2079 (3)	0.0237 (5)
H12A	0.1149	−0.1096	0.1652	0.036*
H12B	0.0737	−0.1038	0.3102	0.036*
C1	0.42702 (16)	0.99745 (19)	0.3907 (4)	0.0057 (5)
C2	0.42687 (17)	1.1051 (2)	0.3914 (4)	0.0075 (6)
H2	0.3767	1.1416	0.3175	0.011*
C3	0.5000	1.1597 (3)	0.5000	0.0081 (8)
C4	0.5000	0.9450 (3)	0.5000	0.0068 (7)
H4	0.5000	0.8715	0.5000	0.010*
C5	0.34880 (15)	0.9364 (2)	0.2699 (4)	0.0076 (5)
C6	0.5000	1.2756 (3)	0.5000	0.0117 (9)
C7	0.07372 (16)	0.49353 (19)	0.1069 (4)	0.0064 (5)
C8	0.07329 (16)	0.3861 (2)	0.1084 (4)	0.0063 (5)
H8	0.1232	0.3493	0.1838	0.009*
C9	0.0000	0.3323 (3)	0.0000	0.0067 (7)
C10	0.0000	0.5469 (3)	0.0000	0.0074 (7)
H10	0.0000	0.6205	0.0000	0.011*
C11	0.15575 (16)	0.5495 (2)	0.2156 (4)	0.0075 (5)
C12	0.0000	0.2182 (3)	0.0000	0.0072 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.00359 (14)	0.00308 (15)	0.00875 (16)	−0.00037 (14)	0.00181 (11)	−0.00049 (14)
Zn1	0.0098 (2)	0.0072 (2)	0.0146 (2)	0.000	0.00444 (18)	0.000
O1	0.0079 (9)	0.0051 (9)	0.0132 (10)	−0.0009 (7)	0.0037 (8)	0.0007 (8)
O2	0.0060 (9)	0.0101 (10)	0.0112 (10)	−0.0006 (7)	0.0010 (8)	0.0021 (7)
O3	0.0280 (13)	0.0103 (11)	0.0125 (11)	−0.0058 (10)	−0.0063 (9)	0.0010 (9)
O4	0.0069 (9)	0.0042 (9)	0.0130 (10)	−0.0006 (7)	0.0030 (8)	0.0009 (8)
O5	0.0070 (9)	0.0096 (10)	0.0135 (10)	0.0004 (7)	0.0018 (8)	0.0022 (8)
O6	0.0079 (10)	0.0059 (9)	0.0155 (10)	0.0013 (8)	0.0014 (8)	0.0018 (8)
O7	0.0156 (10)	0.0098 (10)	0.0140 (10)	−0.0030 (8)	0.0078 (8)	−0.0030 (8)
O8	0.0072 (10)	0.0081 (10)	0.0125 (10)	−0.0024 (8)	0.0010 (8)	−0.0018 (9)
O9	0.0072 (9)	0.0096 (10)	0.0266 (12)	−0.0035 (8)	0.0095 (9)	−0.0067 (9)
O10	0.0073 (9)	0.0077 (10)	0.0112 (10)	−0.0007 (8)	0.0021 (8)	0.0002 (8)
O11	0.0203 (10)	0.0074 (9)	0.0200 (10)	0.0043 (9)	0.0132 (8)	0.0005 (9)
O12	0.0287 (13)	0.0262 (13)	0.0242 (12)	0.0191 (11)	0.0190 (10)	0.0135 (11)
C1	0.0061 (12)	0.0081 (13)	0.0029 (12)	−0.0016 (9)	0.0016 (10)	0.0000 (9)
C2	0.0101 (14)	0.0082 (14)	0.0045 (14)	0.0009 (11)	0.0032 (11)	0.0010 (11)
C3	0.0118 (19)	0.010 (2)	0.0024 (17)	0.000	0.0024 (15)	0.000
C4	0.0121 (18)	0.0029 (16)	0.0084 (18)	0.000	0.0076 (14)	0.000
C5	0.0085 (12)	0.0090 (13)	0.0082 (13)	0.0005 (10)	0.0064 (10)	−0.0018 (11)
C6	0.017 (2)	0.0082 (19)	0.0044 (19)	0.000	−0.0018 (16)	0.000
C7	0.0076 (12)	0.0077 (12)	0.0049 (13)	−0.0021 (10)	0.0036 (10)	−0.0005 (10)
C8	0.0066 (12)	0.0090 (13)	0.0041 (13)	−0.0006 (10)	0.0031 (10)	0.0007 (10)
C9	0.0085 (18)	0.0068 (18)	0.0078 (18)	0.000	0.0065 (15)	0.000
C10	0.0140 (19)	0.0034 (18)	0.0084 (18)	0.000	0.0082 (15)	0.000
C11	0.0080 (12)	0.0083 (13)	0.0067 (13)	0.0006 (10)	0.0034 (10)	−0.0004 (10)
C12	0.0060 (16)	0.008 (2)	0.0085 (18)	0.000	0.0038 (14)	0.000

Geometric parameters (Å, º)

Ni1—O4	2.0282 (19)	O10—H10B	0.8499
Ni1—O1	2.0296 (18)	O11—H11A	0.8499
Ni1—O10	2.0697 (18)	O11—H11B	0.8500
Ni1—O8	2.0815 (18)	O12—H12A	0.8500
Ni1—O7	2.1007 (18)	O12—H12B	0.8500
Ni1—O9	2.1030 (18)	C1—C4	1.379 (3)
Zn1—O12	2.003 (2)	C1—C2	1.391 (4)
Zn1—O12^i	2.003 (2)	C1—C5	1.514 (3)
Zn1—O11^i	2.1166 (19)	C2—C3	1.394 (3)
Zn1—O11	2.1166 (19)	C2—H2	0.9500
Zn1—O6	2.1512 (18)	C3—C2^ii	1.394 (3)
Zn1—O6^i	2.1512 (18)	C3—C6	1.496 (6)
O1—C5	1.259 (3)	C4—C1^ii	1.379 (3)
O2—C5	1.269 (3)	C4—H4	0.9500
O3—C6	1.275 (3)	C6—O3^ii	1.275 (3)
O4—C11	1.265 (3)	C7—C8	1.387 (3)
O5—C11	1.275 (3)	C7—C10	1.392 (3)
O6—C12	1.280 (2)	C7—C11	1.518 (3)
O7—H7A	0.8500	C8—C9	1.391 (3)
O7—H7B	0.8500	C8—H8	0.9500
O8—H8A	0.8499	C9—C8^i	1.391 (3)
O8—H8B	0.8500	C9—C12	1.474 (5)
O9—H9A	0.8498	C10—C7^i	1.392 (3)
O9—H9B	0.8499	C10—H10	0.9500
O10—H10A	0.8499	C12—O6^i	1.280 (2)
O4—Ni1—O1	174.81 (8)	H10A—O10—H10B	112.2
O4—Ni1—O10	85.87 (7)	Zn1—O11—H11A	133.5
O1—Ni1—O10	91.13 (7)	Zn1—O11—H11B	119.4
O4—Ni1—O8	93.71 (8)	H11A—O11—H11B	106.2
O1—Ni1—O8	89.52 (7)	Zn1—O12—H12A	121.9
O10—Ni1—O8	176.73 (8)	Zn1—O12—H12B	121.4
O4—Ni1—O7	89.42 (8)	H12A—O12—H12B	108.1
O1—Ni1—O7	86.34 (7)	C4—C1—C2	119.5 (3)
O10—Ni1—O7	89.93 (7)	C4—C1—C5	119.2 (2)
O8—Ni1—O7	93.30 (7)	C2—C1—C5	121.3 (2)
O4—Ni1—O9	90.24 (7)	C1—C2—C3	120.4 (3)
O1—Ni1—O9	93.87 (7)	C1—C2—H2	119.8
O10—Ni1—O9	87.48 (7)	C3—C2—H2	119.8
O8—Ni1—O9	89.28 (7)	C2—C3—C2^ii	119.2 (4)
O7—Ni1—O9	177.41 (8)	C2—C3—C6	120.41 (18)
O12—Zn1—O12^i	103.49 (13)	C2^ii—C3—C6	120.41 (18)
O12—Zn1—O11^i	92.59 (8)	C1^ii—C4—C1	121.2 (3)
O12^i—Zn1—O11^i	85.16 (8)	C1^ii—C4—H4	119.4
O12—Zn1—O11	85.16 (8)	C1—C4—H4	119.4
O12^i—Zn1—O11	92.59 (8)	O1—C5—O2	124.6 (2)
O11^i—Zn1—O11	176.36 (11)	O1—C5—C1	116.6 (2)
O12—Zn1—O6	98.39 (8)	O2—C5—C1	118.8 (2)
O12^i—Zn1—O6	156.73 (8)	O3—C6—O3^ii	121.7 (4)
O11^i—Zn1—O6	86.04 (7)	O3—C6—C3	119.17 (18)
O11—Zn1—O6	97.10 (7)	O3^ii—C6—C3	119.17 (18)
O12—Zn1—O6^i	156.73 (8)	C8—C7—C10	119.5 (3)
O12^i—Zn1—O6^i	98.39 (8)	C8—C7—C11	118.7 (2)
O11^i—Zn1—O6^i	97.10 (7)	C10—C7—C11	121.8 (2)
O11—Zn1—O6^i	86.04 (7)	C7—C8—C9	120.2 (3)
O6—Zn1—O6^i	61.44 (9)	C7—C8—H8	119.9
C5—O1—Ni1	128.23 (17)	C9—C8—H8	119.9
C11—O4—Ni1	128.80 (17)	C8—C9—C8^i	120.0 (4)
C12—O6—Zn1	90.15 (17)	C8—C9—C12	120.00 (18)
Ni1—O7—H7A	120.0	C8^i—C9—C12	120.00 (18)
Ni1—O7—H7B	122.7	C7—C10—C7^i	120.6 (3)
H7A—O7—H7B	116.8	C7—C10—H10	119.7
Ni1—O8—H8A	97.1	C7^i—C10—H10	119.7
Ni1—O8—H8B	113.2	O4—C11—O5	124.6 (2)
H8A—O8—H8B	112.1	O4—C11—C7	117.1 (2)
Ni1—O9—H9A	116.6	O5—C11—C7	118.3 (2)
Ni1—O9—H9B	119.9	O6—C12—O6^i	118.3 (3)
H9A—O9—H9B	109.9	O6—C12—C9	120.87 (16)
Ni1—O10—H10A	116.6	O6^i—C12—C9	120.86 (16)
Ni1—O10—H10B	95.9
O10—Ni1—O1—C5	18.9 (2)	C2—C1—C5—O2	8.6 (4)
O8—Ni1—O1—C5	−164.3 (2)	C2—C3—C6—O3	−170.71 (17)
O7—Ni1—O1—C5	−71.0 (2)	C2^ii—C3—C6—O3	9.29 (17)
O9—Ni1—O1—C5	106.4 (2)	C2—C3—C6—O3^ii	9.29 (17)
O10—Ni1—O4—C11	168.5 (2)	C2^ii—C3—C6—O3^ii	−170.71 (17)
O8—Ni1—O4—C11	−8.2 (2)	C10—C7—C8—C9	1.3 (4)
O7—Ni1—O4—C11	−101.5 (2)	C11—C7—C8—C9	−176.52 (18)
O9—Ni1—O4—C11	81.1 (2)	C7—C8—C9—C8^i	−0.67 (18)
O12—Zn1—O6—C12	−167.67 (10)	C7—C8—C9—C12	179.33 (18)
O12^i—Zn1—O6—C12	32.3 (2)	C8—C7—C10—C7^i	−0.66 (18)
O11^i—Zn1—O6—C12	100.29 (10)	C11—C7—C10—C7^i	177.1 (3)
O11—Zn1—O6—C12	−81.55 (10)	Ni1—O4—C11—O5	12.6 (4)
O6^i—Zn1—O6—C12	0.0	Ni1—O4—C11—C7	−167.36 (16)
C4—C1—C2—C3	0.6 (4)	C8—C7—C11—O4	163.5 (2)
C5—C1—C2—C3	−178.71 (19)	C10—C7—C11—O4	−14.3 (4)
C1—C2—C3—C2^ii	−0.29 (18)	C8—C7—C11—O5	−16.5 (4)
C1—C2—C3—C6	179.71 (18)	C10—C7—C11—O5	165.7 (2)
C2—C1—C4—C1^ii	−0.28 (17)	Zn1—O6—C12—O6^i	0.0
C5—C1—C4—C1^ii	179.0 (3)	Zn1—O6—C12—C9	180.0
Ni1—O1—C5—O2	−16.8 (4)	C8—C9—C12—O6	4.31 (15)
Ni1—O1—C5—C1	164.38 (16)	C8^i—C9—C12—O6	−175.69 (15)
C4—C1—C5—O1	8.2 (3)	C8—C9—C12—O6^i	−175.69 (15)
C2—C1—C5—O1	−172.5 (2)	C8^i—C9—C12—O6^i	4.31 (15)
C4—C1—C5—O2	−170.72 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O5^iii	0.85	1.89	2.740 (3)	175
O7—H7B···O9^iv	0.85	2.54	3.199 (3)	135
O7—H7B···O3^v	0.85	2.64	3.119 (3)	117
O8—H8A···O5	0.85	1.78	2.615 (3)	168
O8—H8B···O6^iii	0.85	2.04	2.875 (3)	168
O9—H9A···O6^vi	0.85	2.06	2.892 (2)	166
O9—H9B···O2^vii	0.85	1.84	2.676 (3)	167
O10—H10A···O3^viii	0.85	1.99	2.785 (3)	155
O10—H10B···O2	0.85	1.71	2.546 (3)	166
O10—H10B···O1	0.85	2.50	2.927 (3)	112
O11—H11A···O8^v	0.85	2.06	2.866 (3)	158
O11—H11B···O3^ix	0.85	2.01	2.846 (3)	167
O12—H12A···O10^x	0.85	1.81	2.634 (2)	163
O12—H12A···O7^x	0.85	2.64	3.073 (3)	113
O12—H12B···O3^xi	0.85	1.98	2.821 (3)	171

Symmetry codes: (iii) −x+1/2, y+1/2, −z+1; (iv) x, y, z+1; (v) x−1/2, y−1/2, z; (vi) −x+1/2, y+1/2, −z; (vii) −x+1/2, y−1/2, −z; (viii) x−1/2, y−1/2, z−1; (ix) −x+1/2, y−3/2, −z+1; (x) x, y−1, z; (xi) x−1/2, y−3/2, z.