catena-Poly­[[[aqua­zinc(II)]-μ-2,2′-di­thio­dibenzoato] bis(N,N-di­methyl­form­amide)]

In the title compound, {[Zn(C₁₄H₈O₄S₂)(H₂O)]·2C₃H₇NO}_n, the 2,2′-di­thio­di­benzene­carboxyl­ate anion, which acts as a bridge, is tetradentate to water-coordinated zinc(II) ions, forming a polymeric double-chain ribbon. The geometry around the zinc(II) ion is that of a square pyramid. The coordinated water mol­ecules and uncoordinated N,N-di­methyl­form­amide mol­ecules are linked by hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.054
• wR factor = 0.125
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        Zn1
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....         N1
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....         N2
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C5     ..  O1      ..      98.00 Deg.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C12    ..  O4      ..      98.00 Deg.
PLAT731_ALERT_1_C Bond    Calc     0.84(4), Rep   0.841(19) ......       2.11 su-Rat
              O7   -H7B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(4), Rep   0.841(19) ......       2.11 su-Rat
              O7   -H7B     1.555   1.555
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.12 Ratio

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

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

---

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

catena-Poly[[[aquazinc(II)]-µ-2,2'-dithiodibenzoato] bis(N,N-dimethylformamide)]

Crystal data

[Zn(C14H8O4S2)(H2O)]·2C3H7NO	F(000) = 1104
Mr = 533.90	Dx = 1.519 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2880 reflections
a = 11.0956 (4) Å	θ = 2.4–26.6°
b = 17.2715 (7) Å	µ = 1.27 mm^−1
c = 12.2400 (5) Å	T = 298 K
β = 95.695 (2)°	Block, colorless
V = 2334.07 (16) Å^3	0.46 × 0.18 × 0.10 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer	4193 independent reflections
Radiation source: fine-focus sealed tube	3417 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
φ and ω scans	θmax = 25.2°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→12
Tmin = 0.592, Tmax = 0.883	k = −20→20
12296 measured reflections	l = −13→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0625P)^2 + 1.0746P] where P = (Fo^2 + 2Fc^2)/3
4193 reflections	(Δ/σ)max = 0.001
299 parameters	Δρmax = 0.70 e Å^−3
3 restraints	Δρmin = −0.37 e Å^−3

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
Zn1	0.07980 (4)	1.00722 (2)	0.10573 (3)	0.02753 (16)
S1	0.58129 (8)	0.89190 (6)	0.00181 (8)	0.0378 (3)
S2	0.40381 (9)	0.88921 (6)	0.03420 (9)	0.0389 (3)
O1	0.9447 (2)	0.93215 (17)	0.1400 (2)	0.0471 (7)
O2	0.8241 (2)	0.91937 (16)	−0.0164 (2)	0.0433 (7)
O3	0.1616 (2)	0.91547 (16)	0.0383 (2)	0.0429 (7)
O4	0.0408 (3)	0.90437 (17)	−0.1170 (2)	0.0509 (8)
O5	0.6026 (4)	0.5253 (4)	0.1808 (5)	0.136 (2)
O6	1.0911 (4)	0.9377 (2)	0.4198 (3)	0.0761 (11)
O7	0.1672 (3)	1.01165 (19)	0.2529 (2)	0.0466 (8)
N1	0.4067 (4)	0.5473 (2)	0.1749 (4)	0.0638 (11)
N2	0.9378 (4)	0.8761 (3)	0.4929 (3)	0.0703 (12)
C1	0.6589 (3)	0.8310 (2)	0.1041 (3)	0.0292 (8)
C2	0.6002 (4)	0.7732 (2)	0.1569 (3)	0.0398 (10)
H2	0.5177	0.7655	0.1387	0.048*
C3	0.6615 (4)	0.7266 (2)	0.2362 (3)	0.0480 (11)
H3	0.6209	0.6872	0.2691	0.058*
C4	0.7828 (4)	0.7390 (3)	0.2658 (3)	0.0484 (11)
H4	0.8246	0.7078	0.3188	0.058*
C5	0.8418 (4)	0.7974 (2)	0.2171 (3)	0.0390 (9)
H5	0.9233	0.8062	0.2393	0.047*
C6	0.7833 (3)	0.8438 (2)	0.1351 (3)	0.0293 (8)
C7	0.8560 (3)	0.9037 (2)	0.0825 (3)	0.0328 (9)
C8	0.3346 (3)	0.8170 (2)	−0.0567 (3)	0.0294 (8)
C9	0.4017 (4)	0.7580 (2)	−0.0985 (3)	0.0410 (10)
H9	0.4841	0.7541	−0.0766	0.049*
C10	0.3476 (4)	0.7050 (2)	−0.1717 (4)	0.0488 (11)
H10	0.3938	0.6658	−0.1988	0.059*
C11	0.2265 (4)	0.7096 (3)	−0.2050 (4)	0.0543 (12)
H11	0.1901	0.6733	−0.2539	0.065*
C12	0.1590 (4)	0.7681 (2)	−0.1657 (4)	0.0463 (11)
H12	0.0771	0.7717	−0.1900	0.056*
C13	0.2101 (3)	0.8221 (2)	−0.0905 (3)	0.0335 (9)
C14	0.1316 (3)	0.8857 (2)	−0.0537 (3)	0.0350 (9)
C15	0.3857 (9)	0.5905 (5)	0.0815 (7)	0.183 (5)
H15A	0.4612	0.6011	0.0524	0.274*
H15B	0.3477	0.6384	0.0983	0.274*
H15C	0.3336	0.5624	0.0282	0.274*
C16	0.3016 (8)	0.5319 (6)	0.2356 (7)	0.146 (3)
H16A	0.3285	0.5222	0.3113	0.218*
H16B	0.2588	0.4875	0.2048	0.218*
H16C	0.2487	0.5761	0.2303	0.218*
C17	0.5092 (7)	0.5223 (4)	0.2174 (6)	0.091 (2)
H17	0.5095	0.4987	0.2858	0.109*
C18	0.8085 (5)	0.8662 (4)	0.4948 (5)	0.093 (2)
H18A	0.7666	0.8937	0.4343	0.139*
H18B	0.7844	0.8862	0.5625	0.139*
H18C	0.7887	0.8122	0.4889	0.139*
C19	1.0156 (7)	0.8415 (5)	0.5798 (5)	0.130 (3)
H19A	1.0986	0.8505	0.5676	0.196*
H19B	1.0005	0.7868	0.5815	0.196*
H19C	0.9997	0.8641	0.6486	0.196*
C20	0.9852 (6)	0.9220 (3)	0.4201 (4)	0.0640 (14)
H20	0.9319	0.9436	0.3651	0.077*
H7A	0.2430 (18)	1.014 (3)	0.264 (4)	0.077*
H7B	0.141 (4)	0.984 (3)	0.302 (3)	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0188 (2)	0.0391 (3)	0.0246 (2)	−0.00161 (18)	0.00164 (16)	−0.00028 (18)
S1	0.0261 (5)	0.0414 (6)	0.0451 (6)	−0.0033 (4)	−0.0011 (4)	0.0097 (5)
S2	0.0257 (5)	0.0414 (6)	0.0486 (6)	0.0014 (4)	−0.0013 (4)	−0.0122 (5)
O1	0.0303 (16)	0.063 (2)	0.0479 (17)	−0.0201 (14)	0.0048 (13)	−0.0039 (14)
O2	0.0356 (16)	0.0516 (18)	0.0435 (17)	−0.0134 (13)	0.0078 (13)	0.0122 (14)
O3	0.0390 (16)	0.0475 (17)	0.0425 (16)	0.0099 (13)	0.0053 (13)	−0.0093 (13)
O4	0.0324 (16)	0.0615 (19)	0.0573 (18)	0.0177 (14)	−0.0035 (14)	−0.0048 (15)
O5	0.047 (3)	0.226 (6)	0.130 (5)	0.028 (3)	−0.016 (3)	−0.031 (4)
O6	0.080 (3)	0.099 (3)	0.052 (2)	−0.018 (2)	0.017 (2)	0.0158 (19)
O7	0.0389 (17)	0.071 (2)	0.0292 (15)	−0.0099 (15)	−0.0015 (13)	0.0062 (13)
N1	0.041 (2)	0.069 (3)	0.079 (3)	0.008 (2)	−0.010 (2)	−0.003 (2)
N2	0.085 (3)	0.080 (3)	0.049 (2)	−0.023 (3)	0.020 (2)	−0.001 (2)
C1	0.0253 (19)	0.032 (2)	0.0311 (19)	0.0007 (15)	0.0056 (15)	0.0004 (16)
C2	0.031 (2)	0.040 (2)	0.050 (2)	−0.0054 (18)	0.0092 (19)	0.0035 (19)
C3	0.056 (3)	0.044 (3)	0.046 (3)	−0.006 (2)	0.016 (2)	0.013 (2)
C4	0.055 (3)	0.048 (3)	0.042 (2)	0.011 (2)	0.004 (2)	0.013 (2)
C5	0.032 (2)	0.042 (2)	0.042 (2)	0.0052 (18)	−0.0007 (18)	0.0016 (19)
C6	0.0266 (19)	0.032 (2)	0.0298 (19)	0.0025 (16)	0.0055 (15)	−0.0025 (16)
C7	0.027 (2)	0.037 (2)	0.036 (2)	0.0003 (17)	0.0087 (17)	−0.0007 (17)
C8	0.0248 (19)	0.032 (2)	0.0316 (19)	−0.0018 (15)	0.0033 (15)	−0.0018 (16)
C9	0.034 (2)	0.040 (2)	0.049 (3)	0.0067 (18)	0.0063 (19)	−0.0019 (19)
C10	0.051 (3)	0.040 (2)	0.057 (3)	0.007 (2)	0.011 (2)	−0.014 (2)
C11	0.058 (3)	0.045 (3)	0.059 (3)	−0.009 (2)	0.001 (2)	−0.018 (2)
C12	0.030 (2)	0.047 (3)	0.060 (3)	−0.0065 (19)	−0.003 (2)	−0.008 (2)
C13	0.027 (2)	0.036 (2)	0.038 (2)	−0.0013 (16)	0.0037 (16)	−0.0003 (17)
C14	0.024 (2)	0.037 (2)	0.046 (2)	−0.0005 (17)	0.0122 (18)	0.0025 (19)
C15	0.192 (10)	0.176 (9)	0.161 (8)	−0.056 (8)	−0.079 (7)	0.097 (7)
C16	0.107 (6)	0.206 (9)	0.132 (7)	−0.033 (6)	0.050 (6)	−0.052 (7)
C17	0.086 (5)	0.093 (5)	0.089 (5)	0.009 (4)	−0.010 (4)	−0.022 (4)
C18	0.093 (5)	0.116 (5)	0.076 (4)	−0.028 (4)	0.036 (4)	−0.011 (4)
C19	0.123 (6)	0.183 (8)	0.084 (5)	−0.043 (6)	0.007 (4)	0.070 (5)
C20	0.094 (4)	0.062 (3)	0.038 (3)	−0.008 (3)	0.013 (3)	0.000 (2)

Geometric parameters (Å, º)

Zn1—O7	1.960 (3)	C3—H3	0.9300
Zn1—O3	2.041 (3)	C4—C5	1.371 (6)
Zn1—O2^i	2.042 (2)	C4—H4	0.9300
Zn1—O4^ii	2.044 (3)	C5—C6	1.394 (5)
Zn1—O1^iii	2.056 (3)	C5—H5	0.9300
Zn1—Zn1^ii	2.9979 (8)	C6—C7	1.496 (5)
S1—C1	1.790 (4)	C8—C9	1.389 (5)
S1—S2	2.0475 (14)	C8—C13	1.405 (5)
S2—C8	1.793 (4)	C9—C10	1.376 (6)
O1—C7	1.253 (4)	C9—H9	0.9300
O1—Zn1^iv	2.056 (3)	C10—C11	1.366 (6)
O2—C7	1.256 (4)	C10—H10	0.9300
O2—Zn1^i	2.042 (2)	C11—C12	1.373 (6)
O3—C14	1.254 (5)	C11—H11	0.9300
O4—C14	1.251 (5)	C12—C13	1.391 (5)
O4—Zn1^ii	2.044 (3)	C12—H12	0.9300
O5—C17	1.171 (8)	C13—C14	1.499 (5)
O6—C20	1.207 (6)	C15—H15A	0.9600
O7—H7A	0.840 (19)	C15—H15B	0.9600
O7—H7B	0.841 (19)	C15—H15C	0.9600
N1—C17	1.278 (8)	C16—H16A	0.9600
N1—C15	1.365 (8)	C16—H16B	0.9600
N1—C16	1.468 (8)	C16—H16C	0.9600
N2—C20	1.338 (6)	C17—H17	0.9300
N2—C19	1.432 (8)	C18—H18A	0.9600
N2—C18	1.448 (7)	C18—H18B	0.9600
C1—C2	1.386 (5)	C18—H18C	0.9600
C1—C6	1.411 (5)	C19—H19A	0.9600
C2—C3	1.386 (6)	C19—H19B	0.9600
C2—H2	0.9300	C19—H19C	0.9600
C3—C4	1.375 (6)	C20—H20	0.9300
O7—Zn1—O3	101.68 (12)	C9—C8—C13	119.0 (3)
O7—Zn1—O2^i	103.34 (12)	C9—C8—S2	121.8 (3)
O3—Zn1—O2^i	89.36 (12)	C13—C8—S2	119.2 (3)
O7—Zn1—O4^ii	100.13 (13)	C10—C9—C8	120.8 (4)
O3—Zn1—O4^ii	158.12 (11)	C10—C9—H9	119.6
O2^i—Zn1—O4^ii	87.27 (12)	C8—C9—H9	119.6
O7—Zn1—O1^iii	98.11 (12)	C11—C10—C9	120.6 (4)
O3—Zn1—O1^iii	87.44 (12)	C11—C10—H10	119.7
O2^i—Zn1—O1^iii	158.51 (11)	C9—C10—H10	119.7
O4^ii—Zn1—O1^iii	87.83 (12)	C10—C11—C12	119.5 (4)
O7—Zn1—Zn1^ii	172.90 (9)	C10—C11—H11	120.3
O3—Zn1—Zn1^ii	80.50 (8)	C12—C11—H11	120.3
O2^i—Zn1—Zn1^ii	83.37 (8)	C11—C12—C13	121.6 (4)
O4^ii—Zn1—Zn1^ii	77.65 (8)	C11—C12—H12	119.2
O1^iii—Zn1—Zn1^ii	75.15 (8)	C13—C12—H12	119.2
C1—S1—S2	104.87 (12)	C12—C13—C8	118.5 (4)
C8—S2—S1	104.85 (13)	C12—C13—C14	118.6 (3)
C7—O1—Zn1^iv	132.9 (3)	C8—C13—C14	122.8 (3)
C7—O2—Zn1^i	122.5 (2)	O4—C14—O3	125.2 (4)
C14—O3—Zn1	126.4 (3)	O4—C14—C13	117.4 (4)
C14—O4—Zn1^ii	130.0 (3)	O3—C14—C13	117.4 (3)
Zn1—O7—H7A	123 (3)	N1—C15—H15A	109.5
Zn1—O7—H7B	118 (3)	N1—C15—H15B	109.5
H7A—O7—H7B	109 (3)	H15A—C15—H15B	109.5
C17—N1—C15	126.6 (7)	N1—C15—H15C	109.5
C17—N1—C16	116.9 (6)	H15A—C15—H15C	109.5
C15—N1—C16	116.4 (7)	H15B—C15—H15C	109.5
C20—N2—C19	119.6 (5)	N1—C16—H16A	109.5
C20—N2—C18	122.4 (5)	N1—C16—H16B	109.5
C19—N2—C18	117.6 (5)	H16A—C16—H16B	109.5
C2—C1—C6	118.7 (3)	N1—C16—H16C	109.5
C2—C1—S1	122.2 (3)	H16A—C16—H16C	109.5
C6—C1—S1	119.1 (3)	H16B—C16—H16C	109.5
C3—C2—C1	121.6 (4)	O5—C17—N1	127.9 (8)
C3—C2—H2	119.2	O5—C17—H17	116.0
C1—C2—H2	119.2	N1—C17—H17	116.0
C4—C3—C2	119.6 (4)	N2—C18—H18A	109.5
C4—C3—H3	120.2	N2—C18—H18B	109.5
C2—C3—H3	120.2	H18A—C18—H18B	109.5
C5—C4—C3	119.8 (4)	N2—C18—H18C	109.5
C5—C4—H4	120.1	H18A—C18—H18C	109.5
C3—C4—H4	120.1	H18B—C18—H18C	109.5
C4—C5—C6	121.8 (4)	N2—C19—H19A	109.5
C4—C5—H5	119.1	N2—C19—H19B	109.5
C6—C5—H5	119.1	H19A—C19—H19B	109.5
C5—C6—C1	118.5 (3)	N2—C19—H19C	109.5
C5—C6—C7	118.3 (3)	H19A—C19—H19C	109.5
C1—C6—C7	123.2 (3)	H19B—C19—H19C	109.5
O1—C7—O2	126.0 (4)	O6—C20—N2	125.7 (5)
O1—C7—C6	117.2 (3)	O6—C20—H20	117.2
O2—C7—C6	116.8 (3)	N2—C20—H20	117.2
C1—S1—S2—C8	−96.55 (18)	C1—C6—C7—O2	−30.1 (5)
O7—Zn1—O3—C14	174.6 (3)	S1—S2—C8—C9	24.1 (3)
O2^i—Zn1—O3—C14	−81.9 (3)	S1—S2—C8—C13	−153.2 (3)
O4^ii—Zn1—O3—C14	−0.9 (5)	C13—C8—C9—C10	0.0 (6)
O1^iii—Zn1—O3—C14	76.8 (3)	S2—C8—C9—C10	−177.3 (3)
Zn1^ii—Zn1—O3—C14	1.5 (3)	C8—C9—C10—C11	0.0 (7)
S2—S1—C1—C2	23.6 (3)	C9—C10—C11—C12	0.8 (7)
S2—S1—C1—C6	−154.2 (3)	C10—C11—C12—C13	−1.6 (7)
C6—C1—C2—C3	−2.1 (6)	C11—C12—C13—C8	1.6 (6)
S1—C1—C2—C3	−179.8 (3)	C11—C12—C13—C14	178.3 (4)
C1—C2—C3—C4	1.8 (7)	C9—C8—C13—C12	−0.8 (6)
C2—C3—C4—C5	0.2 (7)	S2—C8—C13—C12	176.5 (3)
C3—C4—C5—C6	−2.0 (6)	C9—C8—C13—C14	−177.3 (3)
C4—C5—C6—C1	1.7 (6)	S2—C8—C13—C14	0.0 (5)
C4—C5—C6—C7	−177.1 (4)	Zn1^ii—O4—C14—O3	6.6 (6)
C2—C1—C6—C5	0.3 (5)	Zn1^ii—O4—C14—C13	−173.9 (2)
S1—C1—C6—C5	178.2 (3)	Zn1—O3—C14—O4	−4.9 (6)
C2—C1—C6—C7	179.0 (3)	Zn1—O3—C14—C13	175.7 (2)
S1—C1—C6—C7	−3.1 (5)	C12—C13—C14—O4	−24.8 (5)
Zn1^iv—O1—C7—O2	−4.2 (6)	C8—C13—C14—O4	151.7 (4)
Zn1^iv—O1—C7—C6	173.9 (2)	C12—C13—C14—O3	154.7 (4)
Zn1^i—O2—C7—O1	3.3 (5)	C8—C13—C14—O3	−28.8 (5)
Zn1^i—O2—C7—C6	−174.8 (2)	C15—N1—C17—O5	−7.2 (12)
C5—C6—C7—O1	−29.7 (5)	C16—N1—C17—O5	176.5 (8)
C1—C6—C7—O1	151.6 (4)	C19—N2—C20—O6	0.3 (9)
C5—C6—C7—O2	148.6 (4)	C18—N2—C20—O6	173.5 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O5^v	0.84 (2)	1.79 (2)	2.613 (5)	166 (5)
O7—H7B···O6^iii	0.84 (2)	1.78 (2)	2.619 (4)	172 (5)
C2—H2···S2	0.93	2.74	3.220 (4)	113
C5—H5···O1	0.93	2.51	2.796 (5)	98
C9—H9···S1	0.93	2.75	3.216 (4)	112
C12—H12···O4	0.93	2.50	2.788 (5)	98
C15—H15A···O5	0.96	2.48	2.820 (11)	101
C19—H19A···O6	0.96	2.35	2.761 (8)	105

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