Crystal structure of posnjakite formed in the first crystal water-cooling line of the ANSTO Melbourne Australian Synchrotron MX1 Double Crystal Monochromator

Exceptionally large crystals of posnjakite, Cu₄SO₄(OH)₆(H₂O), formed during corrosion of a Swagelock(tm) Snubber copper gasket within the MX1 beamline at the ANSTO-Melbourne, Australian Synchrotron. The crystal structure was solved using synchrotron radiation and revealed a structure based upon [Cu₄(OH)₆(H₂O)O] sheets, which contain Jahn–Teller-distorted Cu octa­hedra.

Key indicators

• Single-crystal synchrotron study
• T = 100 K
• Mean [sigma](Cu-O) = 0.007 Å
• Disorder in main residue
• R factor = 0.029
• wR factor = 0.074
• Data-to-parameter ratio = 11.2

checkCIF/PLATON results

No syntax errors found



Alert level A
CELL004_ALERT_1_A  _cell_measurement_theta_min is missing
            Minimum theta of reflections used to measure unit cell.
            The following tests will not be performed.
            CELLT_01

Author Response: Value not reported by XDS

CELL005_ALERT_1_A  _cell_measurement_theta_max is missing
            Maximum theta of reflections used to measure unit cell.
            The following tests will not be performed.
            CELLT_01

Author Response: Value not reported by XDS

DIFF019_ALERT_1_A  _diffrn_standards_number is missing
            Number of standards used in measurement.

Author Response: Value not reported by XDS

DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.

Author Response: Value not reported by XDS

DIFF022_ALERT_1_A  _diffrn_standards_decay_% is missing
            Percentage decrease in standards intensity.

Author Response: Value not reported by XDS

PLAT184_ALERT_1_A Missing _cell_measurement_theta_min Value ......     Please Do !

Author Response: Value not reported by XDS

PLAT185_ALERT_1_A Missing _cell_measurement_theta_max Value ......     Please Do !

Author Response: Value not reported by XDS

Alert level B
PLAT090_ALERT_3_B Poor Data / Parameter Ratio (Zmax > 18) ........       5.78 Note
PLAT987_ALERT_1_B The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check

Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7A      ..O13B     .       2.64 Ang.
PLAT975_ALERT_2_C Check Calcd Resid. Dens.  0.51A   From O11             0.58 eA-3
PLAT975_ALERT_2_C Check Calcd Resid. Dens.  0.51A   From O1              0.52 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  0.84A   From O6             -0.53 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  0.82A   From O3             -0.50 eA-3
PLAT976_ALERT_2_C Check Calcd Resid. Dens.  1.01A   From O2             -0.45 eA-3

Alert level G
ABSMU01_ALERT_1_G  Calculation of _exptl_absorpt_correction_mu
                not performed for this radiation type.
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         23 Note
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          3 Info
PLAT112_ALERT_2_G ADDSYM Detects New (Pseudo) Symm. Elem         I         84 %Fit
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          5 Report
PLAT173_ALERT_4_G The CIF-Embedded .res File Contains DANG Records          1 Report
PLAT300_ALERT_4_G Atom Site Occupancy of S1A        Constrained at        0.7 Check
PLAT300_ALERT_4_G Atom Site Occupancy of S1B        Constrained at        0.3 Check
PLAT300_ALERT_4_G Atom Site Occupancy of O13A       Constrained at        0.7 Check
PLAT300_ALERT_4_G Atom Site Occupancy of O14A       Constrained at        0.7 Check
PLAT300_ALERT_4_G Atom Site Occupancy of O13B       Constrained at        0.3 Check
PLAT300_ALERT_4_G Atom Site Occupancy of O14B       Constrained at        0.3 Check
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        19% Note
PLAT794_ALERT_5_G Tentative Bond Valency for Cu4       (II)      .       2.06 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         19 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          6 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          3 Note
PLAT955_ALERT_1_G Reported (CIF) and Actual (FCF) Lmax Differ by .          1 Units

   7 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  18 ALERT level G = General information/check it is not something unexpected

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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: All were present while crystals were growing with the exception of Stuart Maills who assisted with minerallogy

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: AS QEGUI; cell refinement: XDS (Kabsch, 2010); data reduction: XDS (Kabsch, 2010)); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: shelXle (Hübschle et al., 2011), ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[[hexa-µ-hydroxido-tetracopper(II)] sulfate monohydrate]

Crystal data

Cu4(SO)4(OH)6(H2O)	F(000) = 456
Mr = 470.28	Dx = 3.370 Mg m^−3
Monoclinic, Pn	Synchrotron radiation, λ = 0.71074 Å
a = 7.8400 (16) Å	Cell parameters from 96 reflections
b = 6.3400 (13) Å	µ = 9.33 mm^−1
c = 9.768 (2) Å	T = 100 K
β = 107.32 (3)°	Plate, blue
V = 463.51 (18) Å^3	0.15 × 0.10 × 0.05 mm
Z = 2

Data collection

MX1 Beamline Australian Synchrotron diffractometer	1652 reflections with I > 2σ(I)
Radiation source: Double Crystal Monochromator	Rint = 0.019
Silicon 111 scans	θmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
Tmin = 0.517, Tmax = 0.746	k = −7→7
5709 measured reflections	l = −12→11
1763 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	Only H-atom coordinates refined
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.0447P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.074	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.67 e Å^−3
1763 reflections	Δρmin = −0.92 e Å^−3
157 parameters	Absolute structure: Flack x determined using 745 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
19 restraints	Absolute structure parameter: 0.128 (16)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.64047 (12)	0.74631 (16)	0.76709 (10)	0.0112 (2)
Cu2	0.40646 (10)	0.48699 (12)	0.51341 (8)	0.0113 (4)
Cu3	0.37581 (9)	0.98271 (12)	0.52445 (7)	0.0117 (4)
Cu4	0.14420 (12)	0.75064 (16)	0.26663 (9)	0.0108 (2)
O1	0.4814 (10)	0.4981 (7)	0.7249 (8)	0.0150 (14)
H1	0.398 (10)	0.481 (12)	0.765 (10)	0.022*
O2	0.5487 (8)	0.2232 (8)	0.5561 (7)	0.0129 (11)
H2	0.625 (9)	0.211 (12)	0.502 (8)	0.019*
O3	0.4523 (10)	0.9538 (8)	0.7302 (7)	0.0157 (12)
H3	0.382 (10)	0.941 (14)	0.779 (8)	0.024*
O4	0.3320 (10)	0.4581 (8)	0.3087 (7)	0.0132 (12)
H4	0.408 (10)	0.436 (12)	0.263 (8)	0.020*
O5	0.2300 (9)	0.7197 (7)	0.4785 (7)	0.0145 (11)
H5	0.134 (9)	0.715 (12)	0.505 (9)	0.022*
O6	0.3032 (10)	1.0043 (7)	0.3128 (7)	0.0124 (13)
H6	0.376 (10)	1.021 (11)	0.262 (9)	0.019*
O11	0.6098 (9)	0.7456 (7)	0.5254 (8)	0.0170 (12)*
O12	0.7217 (8)	0.6493 (7)	0.3281 (6)	0.0221 (10)*
S1A	0.7607 (9)	0.7811 (8)	0.4618 (7)	0.0195 (19)*	0.7
O13A	0.7641 (12)	1.0103 (9)	0.4267 (9)	0.0178 (16)*	0.7
O14A	0.9297 (11)	0.7171 (13)	0.5649 (9)	0.0204 (17)*	0.7
S1B	0.7426 (14)	0.7916 (17)	0.4462 (11)	0.009 (3)*	0.3
O13B	0.699 (2)	1.008 (2)	0.3789 (19)	0.019 (4)*	0.3
O14B	0.922 (2)	0.799 (3)	0.5522 (17)	0.018 (4)*	0.3
O7	0.6288 (8)	0.7998 (8)	0.0410 (7)	0.0207 (10)
H7B	0.645 (10)	0.722 (10)	0.117 (6)	0.031*
H7A	0.526 (6)	0.869 (11)	0.020 (8)	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0116 (4)	0.0092 (4)	0.0113 (4)	0.0003 (2)	0.0010 (3)	0.0002 (2)
Cu2	0.0131 (9)	0.0097 (4)	0.0097 (6)	0.0000 (4)	0.0012 (5)	0.0004 (4)
Cu3	0.0124 (9)	0.0108 (4)	0.0098 (6)	0.0000 (5)	0.0002 (5)	−0.0005 (5)
Cu4	0.0124 (4)	0.0094 (4)	0.0094 (4)	−0.0011 (2)	0.0011 (3)	0.0001 (2)
O1	0.016 (4)	0.016 (2)	0.013 (3)	−0.0010 (19)	0.005 (2)	0.0006 (16)
O2	0.013 (3)	0.014 (3)	0.011 (2)	0.001 (2)	0.002 (2)	−0.0001 (18)
O3	0.017 (3)	0.018 (3)	0.013 (3)	0.000 (2)	0.006 (2)	0.000 (2)
O4	0.015 (3)	0.014 (3)	0.010 (3)	0.001 (2)	0.003 (2)	−0.001 (2)
O5	0.016 (3)	0.015 (2)	0.014 (2)	−0.001 (2)	0.006 (2)	0.000 (2)
O6	0.010 (3)	0.014 (3)	0.013 (3)	−0.0005 (18)	0.003 (2)	0.0006 (17)
O7	0.018 (2)	0.021 (3)	0.022 (3)	0.002 (2)	0.005 (2)	0.004 (2)

Geometric parameters (Å, º)

Cu1—O3	1.929 (7)	Cu4—O5	1.986 (7)
Cu1—O4^i	1.933 (7)	Cu4—O1^v	1.993 (6)
Cu1—O1	1.974 (6)	Cu4—O6	2.002 (6)
Cu1—O6^ii	1.997 (6)	Cu4—O4	2.327 (6)
Cu1—O11	2.300 (7)	Cu4—O3^vi	2.363 (6)
Cu1—Cu3	3.0399 (14)	O1—H1	0.87 (6)
Cu1—Cu2^i	3.0558 (14)	O2—H2	0.91 (6)
Cu2—O4	1.918 (7)	O3—H3	0.83 (6)
Cu2—O1	1.974 (7)	O4—H4	0.86 (6)
Cu2—O5	1.981 (6)	O5—H5	0.87 (6)
Cu2—O2	1.984 (5)	O6—H6	0.86 (6)
Cu2—O11	2.265 (6)	O11—S1B	1.499 (11)
Cu2—Cu4^i	3.0194 (14)	O11—S1A	1.508 (8)
Cu3—O3	1.927 (7)	O12—S1B	1.435 (11)
Cu3—O6	1.979 (7)	O12—S1A	1.503 (6)
Cu3—O5	1.996 (6)	S1A—O14A	1.463 (9)
Cu3—O2^iii	2.002 (6)	S1A—O13A	1.495 (8)
Cu3—O11	2.370 (6)	S1B—O14B	1.479 (17)
Cu3—O7^iv	2.422 (6)	S1B—O13B	1.516 (19)
Cu3—Cu4	3.0135 (14)	O7—H7B	0.87 (3)
Cu4—O2^v	1.975 (7)	O7—H7A	0.89 (3)
O3—Cu1—O4^i	178.6 (4)	O6—Cu4—O4	106.4 (3)
O3—Cu1—O1	96.0 (3)	O2^v—Cu4—O3^vi	75.5 (2)
O4^i—Cu1—O1	85.0 (3)	O5—Cu4—O3^vi	103.8 (2)
O3—Cu1—O6^ii	84.5 (3)	O1^v—Cu4—O3^vi	104.9 (3)
O4^i—Cu1—O6^ii	94.5 (3)	O6—Cu4—O3^vi	73.9 (2)
O1—Cu1—O6^ii	179.1 (4)	O4—Cu4—O3^vi	178.4 (3)
O3—Cu1—O11	88.2 (3)	O2^v—Cu4—Cu3	140.94 (16)
O4^i—Cu1—O11	93.0 (2)	O5—Cu4—Cu3	40.93 (15)
O1—Cu1—O11	85.3 (3)	O1^v—Cu4—Cu3	138.3 (2)
O6^ii—Cu1—O11	95.5 (2)	O6—Cu4—Cu3	40.5 (2)
O3—Cu1—Cu3	37.9 (2)	O4—Cu4—Cu3	92.84 (17)
O4^i—Cu1—Cu3	143.3 (2)	O3^vi—Cu4—Cu3	86.39 (18)
O1—Cu1—Cu3	89.3 (2)	O2^v—Cu4—Cu2^v	40.42 (15)
O6^ii—Cu1—Cu3	91.51 (19)	O5—Cu4—Cu2^v	137.68 (16)
O11—Cu1—Cu3	50.39 (16)	O1^v—Cu4—Cu2^v	40.2 (2)
O3—Cu1—Cu2^i	141.5 (2)	O6—Cu4—Cu2^v	140.9 (2)
O4^i—Cu1—Cu2^i	37.3 (2)	O4—Cu4—Cu2^v	87.18 (17)
O1—Cu1—Cu2^i	91.1 (2)	O3^vi—Cu4—Cu2^v	93.56 (17)
O6^ii—Cu1—Cu2^i	88.07 (19)	Cu3—Cu4—Cu2^v	178.43 (5)
O11—Cu1—Cu2^i	130.19 (16)	Cu1—O1—Cu2	102.7 (3)
Cu3—Cu1—Cu2^i	179.32 (4)	Cu1—O1—Cu4^i	105.2 (4)
O4—Cu2—O1	176.5 (2)	Cu2—O1—Cu4^i	99.1 (3)
O4—Cu2—O5	84.9 (3)	Cu1—O1—H1	122 (5)
O1—Cu2—O5	97.4 (3)	Cu2—O1—H1	116 (6)
O4—Cu2—O2	96.7 (2)	Cu4^i—O1—H1	110 (5)
O1—Cu2—O2	80.6 (3)	Cu4^i—O2—Cu2	99.4 (2)
O5—Cu2—O2	169.6 (3)	Cu4^i—O2—Cu3^vii	104.7 (3)
O4—Cu2—O11	96.6 (2)	Cu2—O2—Cu3^vii	107.3 (3)
O1—Cu2—O11	86.2 (3)	Cu4^i—O2—H2	120 (5)
O5—Cu2—O11	85.1 (2)	Cu2—O2—H2	112 (5)
O2—Cu2—O11	104.8 (3)	Cu3^vii—O2—H2	112 (5)
O4—Cu2—Cu4^i	136.77 (17)	Cu3—O3—Cu1	104.1 (3)
O1—Cu2—Cu4^i	40.67 (17)	Cu3—O3—Cu4^ii	93.9 (2)
O5—Cu2—Cu4^i	137.9 (2)	Cu1—O3—Cu4^ii	95.5 (3)
O2—Cu2—Cu4^i	40.18 (19)	Cu3—O3—H3	124 (6)
O11—Cu2—Cu4^i	93.75 (18)	Cu1—O3—H3	115 (6)
O4—Cu2—Cu1^v	37.7 (2)	Cu4^ii—O3—H3	119 (6)
O1—Cu2—Cu1^v	139.7 (2)	Cu2—O4—Cu1^v	105.0 (3)
O5—Cu2—Cu1^v	86.97 (19)	Cu2—O4—Cu4	95.1 (2)
O2—Cu2—Cu1^v	88.10 (19)	Cu1^v—O4—Cu4	94.9 (3)
O11—Cu2—Cu1^v	134.10 (19)	Cu2—O4—H4	121 (5)
Cu4^i—Cu2—Cu1^v	120.91 (4)	Cu1^v—O4—H4	113 (5)
O3—Cu3—O6	178.0 (3)	Cu4—O4—H4	123 (5)
O3—Cu3—O5	97.7 (2)	Cu2—O5—Cu4	104.8 (3)
O6—Cu3—O5	81.7 (3)	Cu2—O5—Cu3	105.1 (3)
O3—Cu3—O2^iii	85.7 (3)	Cu4—O5—Cu3	98.4 (2)
O6—Cu3—O2^iii	94.6 (2)	Cu2—O5—H5	123 (5)
O5—Cu3—O2^iii	170.8 (3)	Cu4—O5—H5	105 (6)
O3—Cu3—O11	86.3 (3)	Cu3—O5—H5	117 (5)
O6—Cu3—O11	91.7 (2)	Cu3—O6—Cu1^vi	104.7 (3)
O5—Cu3—O11	82.0 (2)	Cu3—O6—Cu4	98.4 (3)
O2^iii—Cu3—O11	89.7 (2)	Cu1^vi—O6—Cu4	105.8 (4)
O3—Cu3—O7^iv	89.5 (2)	Cu3—O6—H6	125 (6)
O6—Cu3—O7^iv	92.5 (3)	Cu1^vi—O6—H6	105 (5)
O5—Cu3—O7^iv	94.3 (2)	Cu4—O6—H6	116 (5)
O2^iii—Cu3—O7^iv	94.3 (2)	S1B—O11—Cu2	134.4 (5)
O11—Cu3—O7^iv	174.0 (2)	S1A—O11—Cu2	135.5 (4)
O3—Cu3—Cu4	138.42 (17)	S1B—O11—Cu1	130.7 (5)
O6—Cu3—Cu4	41.10 (16)	S1A—O11—Cu1	124.6 (4)
O5—Cu3—Cu4	40.70 (19)	Cu2—O11—Cu1	84.9 (2)
O2^iii—Cu3—Cu4	135.46 (18)	S1B—O11—Cu3	122.0 (5)
O11—Cu3—Cu4	88.09 (17)	S1A—O11—Cu3	127.2 (3)
O7^iv—Cu3—Cu4	92.24 (15)	Cu2—O11—Cu3	85.8 (2)
O3—Cu3—Cu1	37.98 (19)	Cu1—O11—Cu3	81.2 (2)
O6—Cu3—Cu1	139.99 (19)	O14A—S1A—O13A	110.7 (6)
O5—Cu3—Cu1	88.6 (2)	O14A—S1A—O12	110.6 (5)
O2^iii—Cu3—Cu1	88.94 (17)	O13A—S1A—O12	110.8 (5)
O11—Cu3—Cu1	48.41 (18)	O14A—S1A—O11	109.6 (5)
O7^iv—Cu3—Cu1	127.04 (15)	O13A—S1A—O11	108.0 (5)
Cu4—Cu3—Cu1	120.83 (4)	O12—S1A—O11	107.1 (4)
O2^v—Cu4—O5	177.5 (3)	O12—S1B—O14B	116.1 (10)
O2^v—Cu4—O1^v	80.3 (3)	O12—S1B—O11	111.2 (7)
O5—Cu4—O1^v	97.6 (3)	O14B—S1B—O11	107.9 (9)
O2^v—Cu4—O6	100.6 (3)	O12—S1B—O13B	105.3 (9)
O5—Cu4—O6	81.3 (3)	O14B—S1B—O13B	108.6 (12)
O1^v—Cu4—O6	178.1 (4)	O11—S1B—O13B	107.3 (10)
O2^v—Cu4—O4	105.9 (2)	Cu3^viii—O7—H7B	118 (5)
O5—Cu4—O4	74.8 (2)	Cu3^viii—O7—H7A	113 (5)
O1^v—Cu4—O4	74.8 (2)	H7B—O7—H7A	112 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O12^ix	0.87 (6)	1.86 (6)	2.693 (9)	160 (7)
O7—H7B···O12	0.87 (3)	2.02 (4)	2.844 (7)	158 (7)
O2—H2···O13A^vii	0.91 (6)	1.95 (6)	2.746 (9)	144 (7)
O2—H2···O13B^vii	0.91 (6)	1.96 (7)	2.731 (18)	141 (7)
O3—H3···O13A^iv	0.83 (6)	1.96 (6)	2.757 (10)	161 (9)
O3—H3···O13B^iv	0.83 (6)	1.99 (7)	2.799 (19)	164 (9)
O7—H7A···O13A^vi	0.89 (3)	2.13 (3)	2.995 (10)	167 (7)
O4—H4···O14A^v	0.86 (6)	2.22 (7)	2.929 (9)	141 (7)
O4—H4···O14B^v	0.86 (6)	2.57 (7)	3.239 (18)	136 (7)
O5—H5···O14A^x	0.87 (6)	1.86 (6)	2.727 (9)	177 (8)
O5—H5···O14B^x	0.87 (6)	1.93 (6)	2.763 (17)	162 (7)
O6—H6···O13B	0.86 (6)	2.45 (8)	2.98 (2)	120 (7)
O6—H6···O14B^vi	0.86 (6)	2.47 (7)	3.211 (17)	145 (7)
O7—H7A···O13B^vi	0.89 (3)	2.64 (4)	3.489 (18)	161 (7)
O7—H7A···O14B^vi	0.89 (3)	2.31 (6)	3.034 (19)	139 (7)

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