6-Methoxy­carbonyl-2-methyl-1H-benzimidazol-3-ium nitrate hemihydrate

The title compound, C₁₀H₁₁N₂O₂⁺·NO₃^-·0.5H₂O, crystallizes in a monoclinic unit cell with two benzimidazolium cations, two NO₃^- anions and one water mol­ecule in the asymmetric unit. Intermolecular hydrogen bonds link the cations, anions and water mol­ecules into two-dimensional layers.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.078
• wR factor = 0.249
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         40 Perc.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C16    -   C19     ..       5.09 su
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors  for         N5
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors  for         N6
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT380_ALERT_4_C Incorrectly Oriented X(sp2)-Methyl Moiety ......        C11
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

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

   4 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
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

6-Methoxycarbonyl-2-methyl-1H-benzimidazol-3-ium nitrate hemihydrate

Crystal data

C10H11N2O2^+·NO3^−·0.5H2O	Dx = 1.438 Mg m^−3
Mr = 262.23	Melting point = 374–375 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.9107 (6) Å	Cell parameters from 937 reflections
b = 21.5276 (17) Å	θ = 2.4–25.0°
c = 14.2691 (11) Å	µ = 0.12 mm^−1
β = 94.573 (2)°	T = 293 K
V = 2422.3 (3) Å^3	Colomn, brown yellow
Z = 8	0.20 × 0.15 × 0.09 mm
F(000) = 1096

Data collection

Siemens SMART 1000 CCD area-detector diffractometer	4284 independent reflections
Radiation source: fine-focus sealed tube	1703 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 8.33 pixels mm^-1	θmax = 25.0°, θmin = 1.7°
ω scans	h = −5→9
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −25→25
Tmin = 0.977, Tmax = 0.989	l = −16→15
12579 measured reflections

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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.249	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.1161P)^2] where P = (Fo^2 + 2Fc^2)/3
4284 reflections	(Δ/σ)max = 0.002
334 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.32 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
O1W	0.301 (3)	0.4430 (8)	0.0967 (11)	0.635 (17)
H1W1	0.2140	0.4235	0.0729	0.762*
H2W1	0.3878	0.4262	0.0760	0.762*
O1	0.0866 (6)	0.10217 (18)	0.2874 (3)	0.1096 (14)
O2	0.3559 (6)	0.09091 (18)	0.3448 (3)	0.1055 (13)
O3	−0.2064 (6)	0.2921 (2)	−0.0534 (4)	0.1307 (18)
O4	−0.0157 (5)	0.35596 (18)	0.0126 (3)	0.0956 (12)
O5	0.7844 (5)	0.4881 (2)	0.4601 (4)	0.1233 (16)
O6	0.6504 (5)	0.40196 (18)	0.4493 (3)	0.1061 (13)
O7	0.5397 (5)	0.48377 (16)	0.3849 (3)	0.0901 (12)
O8	0.7327 (5)	0.29137 (18)	0.1892 (3)	0.0940 (12)
O9	0.7460 (6)	0.38918 (19)	0.2125 (3)	0.1263 (16)
O10	0.5221 (6)	0.34922 (19)	0.1424 (3)	0.1197 (15)
N1	0.3129 (6)	0.38043 (19)	0.3367 (3)	0.0780 (12)
H1A	0.3943	0.4052	0.3549	0.094*
N2	0.0684 (6)	0.3481 (2)	0.2819 (3)	0.0840 (13)
H2A	−0.0355	0.3482	0.2589	0.101*
N3	0.3823 (6)	0.11389 (18)	0.1087 (3)	0.0729 (12)
H3A	0.3795	0.0740	0.1108	0.087*
N4	0.4734 (5)	0.20724 (17)	0.1234 (3)	0.0679 (11)
H4A	0.5394	0.2383	0.1363	0.082*
N5	0.6597 (6)	0.4572 (2)	0.4318 (3)	0.0846 (14)
N6	0.6644 (7)	0.3442 (2)	0.1809 (3)	0.0836 (13)
C1	0.0982 (8)	0.4637 (3)	0.2958 (5)	0.118 (2)
H1B	−0.0173	0.4641	0.2695	0.177*
H1C	0.1676	0.4866	0.2557	0.177*
H1D	0.1048	0.4825	0.3570	0.177*
C2	0.1599 (8)	0.3981 (3)	0.3040 (4)	0.0836 (16)
C3	0.3234 (7)	0.3162 (2)	0.3373 (3)	0.0653 (13)
C4	0.4514 (7)	0.2758 (3)	0.3658 (3)	0.0741 (15)
H4B	0.5577	0.2901	0.3885	0.089*
C5	0.4166 (7)	0.2131 (2)	0.3595 (3)	0.0738 (15)
H5A	0.5000	0.1846	0.3800	0.089*
C6	0.2578 (7)	0.1914 (2)	0.3228 (3)	0.0690 (14)
C7	0.1302 (7)	0.2324 (2)	0.2935 (3)	0.0728 (14)
H7A	0.0243	0.2185	0.2692	0.087*
C8	0.1663 (7)	0.2952 (3)	0.3016 (3)	0.0688 (14)
C9	0.2187 (10)	0.1254 (3)	0.3152 (4)	0.0853 (17)
C10	0.3336 (10)	0.0230 (3)	0.3402 (5)	0.138 (3)
H10A	0.4378	0.0030	0.3624	0.207*
H10B	0.3033	0.0108	0.2764	0.207*
H10C	0.2454	0.0109	0.3789	0.207*
C11	0.6800 (7)	0.1249 (3)	0.1796 (4)	0.0945 (18)
H11A	0.6774	0.0803	0.1816	0.142*
H11B	0.7001	0.1408	0.2424	0.142*
H11C	0.7693	0.1382	0.1425	0.142*
C12	0.5155 (7)	0.1484 (2)	0.1372 (4)	0.0703 (14)
C13	0.2484 (7)	0.1512 (2)	0.0749 (3)	0.0648 (13)
C14	0.0873 (7)	0.1381 (2)	0.0379 (4)	0.0758 (15)
H14A	0.0482	0.0975	0.0304	0.091*
C15	−0.0126 (7)	0.1879 (3)	0.0126 (4)	0.0781 (15)
H15A	−0.1232	0.1810	−0.0123	0.094*
C16	0.0456 (7)	0.2493 (2)	0.0229 (3)	0.0674 (14)
C17	0.2082 (7)	0.2620 (2)	0.0598 (3)	0.0663 (13)
H17A	0.2482	0.3025	0.0671	0.080*
C18	0.3077 (6)	0.2117 (2)	0.0851 (3)	0.0586 (12)
C19	−0.0737 (8)	0.2996 (3)	−0.0104 (4)	0.0845 (16)
C20	−0.1264 (9)	0.4074 (3)	−0.0174 (5)	0.120 (2)
H20A	−0.0742	0.4459	0.0029	0.180*
H20B	−0.2329	0.4030	0.0098	0.180*
H20C	−0.1453	0.4072	−0.0847	0.180*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1W	0.67 (4)	0.47 (3)	0.73 (4)	0.09 (2)	−0.20 (3)	0.03 (2)
O1	0.107 (3)	0.086 (3)	0.135 (4)	−0.036 (3)	0.006 (3)	−0.012 (2)
O2	0.128 (4)	0.066 (3)	0.122 (3)	−0.013 (2)	0.004 (3)	−0.004 (2)
O3	0.079 (3)	0.114 (4)	0.191 (5)	0.009 (3)	−0.045 (3)	−0.007 (3)
O4	0.096 (3)	0.077 (3)	0.112 (3)	0.011 (2)	−0.004 (2)	0.001 (2)
O5	0.073 (3)	0.092 (3)	0.200 (5)	−0.015 (2)	−0.016 (3)	0.002 (3)
O6	0.103 (3)	0.061 (2)	0.150 (4)	0.004 (2)	−0.013 (3)	0.018 (2)
O7	0.076 (3)	0.073 (2)	0.118 (3)	0.013 (2)	−0.013 (2)	0.008 (2)
O8	0.089 (3)	0.064 (2)	0.127 (3)	−0.002 (2)	−0.006 (2)	0.002 (2)
O9	0.115 (3)	0.067 (3)	0.188 (4)	−0.015 (2)	−0.045 (3)	−0.017 (3)
O10	0.078 (3)	0.106 (3)	0.169 (4)	−0.007 (3)	−0.032 (3)	0.006 (3)
N1	0.076 (3)	0.064 (3)	0.092 (3)	−0.011 (2)	−0.010 (3)	0.001 (2)
N2	0.068 (3)	0.088 (3)	0.091 (3)	−0.010 (3)	−0.023 (3)	0.013 (3)
N3	0.072 (3)	0.053 (2)	0.095 (3)	−0.009 (3)	0.010 (3)	0.004 (2)
N4	0.067 (3)	0.053 (3)	0.083 (3)	−0.012 (2)	0.004 (2)	0.000 (2)
N5	0.067 (3)	0.071 (3)	0.115 (4)	0.000 (3)	−0.002 (3)	0.003 (3)
N6	0.075 (4)	0.075 (3)	0.099 (4)	−0.009 (3)	−0.004 (3)	0.007 (3)
C1	0.123 (6)	0.079 (4)	0.147 (6)	0.013 (4)	−0.020 (5)	0.018 (4)
C2	0.074 (4)	0.081 (4)	0.091 (4)	−0.008 (3)	−0.020 (3)	0.012 (3)
C3	0.061 (4)	0.073 (3)	0.062 (3)	−0.010 (3)	0.003 (3)	−0.002 (3)
C4	0.059 (3)	0.081 (4)	0.081 (4)	−0.012 (3)	−0.001 (3)	−0.015 (3)
C5	0.074 (4)	0.069 (4)	0.078 (4)	−0.004 (3)	0.001 (3)	−0.005 (3)
C6	0.074 (4)	0.067 (3)	0.066 (3)	−0.013 (3)	0.005 (3)	−0.006 (3)
C7	0.069 (4)	0.084 (4)	0.065 (3)	−0.017 (3)	−0.001 (3)	−0.003 (3)
C8	0.065 (4)	0.078 (4)	0.062 (3)	−0.007 (3)	−0.001 (3)	0.000 (3)
C9	0.098 (5)	0.076 (4)	0.083 (4)	−0.006 (4)	0.010 (4)	−0.002 (3)
C10	0.169 (7)	0.069 (4)	0.177 (7)	−0.009 (4)	0.025 (6)	−0.001 (4)
C11	0.071 (4)	0.092 (4)	0.119 (5)	0.003 (3)	−0.002 (4)	0.006 (3)
C12	0.069 (4)	0.060 (3)	0.083 (4)	−0.007 (3)	0.010 (3)	0.000 (3)
C13	0.067 (4)	0.059 (3)	0.070 (3)	−0.016 (3)	0.013 (3)	−0.003 (3)
C14	0.072 (4)	0.063 (3)	0.092 (4)	−0.015 (3)	0.006 (3)	−0.004 (3)
C15	0.062 (3)	0.079 (4)	0.093 (4)	−0.017 (3)	0.001 (3)	−0.007 (3)
C16	0.061 (3)	0.073 (3)	0.069 (3)	0.004 (3)	0.005 (3)	−0.001 (3)
C17	0.065 (4)	0.069 (3)	0.064 (3)	−0.006 (3)	0.003 (3)	−0.005 (2)
C18	0.050 (3)	0.060 (3)	0.066 (3)	−0.006 (3)	0.006 (3)	−0.002 (2)
C19	0.073 (4)	0.087 (4)	0.093 (4)	−0.005 (4)	0.006 (4)	−0.010 (3)
C20	0.130 (6)	0.097 (5)	0.134 (5)	0.047 (4)	0.012 (5)	0.005 (4)

Geometric parameters (Å, º)

O1W—H1W1	0.8539	C3—C4	1.372 (7)
O1W—H2W1	0.8485	C3—C8	1.381 (7)
O1—C9	1.197 (7)	C4—C5	1.379 (7)
O2—C9	1.354 (7)	C4—H4B	0.9300
O2—C10	1.474 (6)	C5—C6	1.401 (7)
O3—C19	1.184 (6)	C5—H5A	0.9300
O4—C19	1.329 (6)	C6—C7	1.381 (7)
O4—C20	1.455 (6)	C6—C9	1.458 (8)
O5—N5	1.230 (5)	C7—C8	1.384 (7)
O6—N5	1.219 (5)	C7—H7A	0.9300
O7—N5	1.255 (5)	C10—H10A	0.9600
O8—N6	1.260 (5)	C10—H10B	0.9600
O9—N6	1.230 (5)	C10—H10C	0.9600
O10—N6	1.218 (5)	C11—C12	1.480 (7)
N1—C2	1.318 (6)	C11—H11A	0.9600
N1—C3	1.385 (6)	C11—H11B	0.9600
N1—H1A	0.8600	C11—H11C	0.9600
N2—C2	1.321 (6)	C13—C14	1.370 (7)
N2—C8	1.393 (6)	C13—C18	1.387 (6)
N2—H2A	0.8600	C14—C15	1.364 (7)
N3—C12	1.327 (6)	C14—H14A	0.9300
N3—C13	1.384 (6)	C15—C16	1.402 (7)
N3—H3A	0.8600	C15—H15A	0.9300
N4—C12	1.321 (5)	C16—C17	1.378 (6)
N4—C18	1.383 (6)	C16—C19	1.490 (8)
N4—H4A	0.8600	C17—C18	1.370 (6)
C1—C2	1.497 (8)	C17—H17A	0.9300
C1—H1B	0.9600	C20—H20A	0.9600
C1—H1C	0.9600	C20—H20B	0.9600
C1—H1D	0.9600	C20—H20C	0.9600
H1W1—O1W—H2W1	107.5	C7—C8—N2	132.3 (5)
C9—O2—C10	116.1 (5)	O1—C9—O2	122.1 (6)
C19—O4—C20	115.7 (5)	O1—C9—C6	127.3 (7)
C2—N1—C3	110.1 (5)	O2—C9—C6	110.6 (6)
C2—N1—H1A	125.0	O2—C10—H10A	109.5
C3—N1—H1A	125.0	O2—C10—H10B	109.5
C2—N2—C8	109.4 (5)	H10A—C10—H10B	109.5
C2—N2—H2A	125.3	O2—C10—H10C	109.5
C8—N2—H2A	125.3	H10A—C10—H10C	109.5
C12—N3—C13	110.4 (4)	H10B—C10—H10C	109.5
C12—N3—H3A	124.8	C12—C11—H11A	109.5
C13—N3—H3A	124.8	C12—C11—H11B	109.5
C12—N4—C18	110.2 (4)	H11A—C11—H11B	109.5
C12—N4—H4A	124.9	C12—C11—H11C	109.5
C18—N4—H4A	124.9	H11A—C11—H11C	109.5
O6—N5—O5	121.3 (5)	H11B—C11—H11C	109.5
O6—N5—O7	119.9 (5)	N4—C12—N3	107.8 (5)
O5—N5—O7	118.9 (5)	N4—C12—C11	126.3 (5)
O10—N6—O9	122.3 (5)	N3—C12—C11	125.8 (5)
O10—N6—O8	119.8 (5)	C14—C13—N3	132.6 (5)
O9—N6—O8	117.9 (5)	C14—C13—C18	122.0 (5)
C2—C1—H1B	109.5	N3—C13—C18	105.4 (4)
C2—C1—H1C	109.5	C15—C14—C13	116.2 (5)
H1B—C1—H1C	109.5	C15—C14—H14A	121.9
C2—C1—H1D	109.5	C13—C14—H14A	121.9
H1B—C1—H1D	109.5	C14—C15—C16	122.3 (5)
H1C—C1—H1D	109.5	C14—C15—H15A	118.8
N1—C2—N2	108.7 (5)	C16—C15—H15A	118.8
N1—C2—C1	125.7 (5)	C17—C16—C15	121.0 (5)
N2—C2—C1	125.6 (6)	C17—C16—C19	121.7 (5)
C4—C3—C8	121.5 (5)	C15—C16—C19	117.2 (5)
C4—C3—N1	132.7 (5)	C18—C17—C16	116.3 (5)
C8—C3—N1	105.8 (5)	C18—C17—H17A	121.9
C3—C4—C5	117.6 (5)	C16—C17—H17A	121.9
C3—C4—H4B	121.2	C17—C18—N4	131.7 (4)
C5—C4—H4B	121.2	C17—C18—C13	122.2 (5)
C4—C5—C6	121.2 (5)	N4—C18—C13	106.2 (4)
C4—C5—H5A	119.4	O3—C19—O4	121.8 (6)
C6—C5—H5A	119.4	O3—C19—C16	125.4 (6)
C7—C6—C5	120.9 (5)	O4—C19—C16	112.8 (5)
C7—C6—C9	117.1 (5)	O4—C20—H20A	109.5
C5—C6—C9	122.0 (6)	O4—C20—H20B	109.5
C6—C7—C8	117.2 (5)	H20A—C20—H20B	109.5
C6—C7—H7A	121.4	O4—C20—H20C	109.5
C8—C7—H7A	121.4	H20A—C20—H20C	109.5
C3—C8—C7	121.6 (5)	H20B—C20—H20C	109.5
C3—C8—N2	106.1 (5)
C3—N1—C2—N2	−0.7 (6)	C18—N4—C12—N3	0.3 (5)
C3—N1—C2—C1	177.8 (5)	C18—N4—C12—C11	−178.1 (5)
C8—N2—C2—N1	0.4 (6)	C13—N3—C12—N4	0.0 (5)
C8—N2—C2—C1	−178.1 (5)	C13—N3—C12—C11	178.4 (5)
C2—N1—C3—C4	−178.6 (5)	C12—N3—C13—C14	179.7 (5)
C2—N1—C3—C8	0.8 (6)	C12—N3—C13—C18	−0.3 (5)
C8—C3—C4—C5	−1.5 (7)	N3—C13—C14—C15	179.2 (5)
N1—C3—C4—C5	177.8 (5)	C18—C13—C14—C15	−0.8 (7)
C3—C4—C5—C6	1.8 (7)	C13—C14—C15—C16	0.5 (8)
C4—C5—C6—C7	−1.2 (7)	C14—C15—C16—C17	−0.2 (8)
C4—C5—C6—C9	179.7 (5)	C14—C15—C16—C19	177.9 (5)
C5—C6—C7—C8	0.2 (7)	C15—C16—C17—C18	0.2 (7)
C9—C6—C7—C8	179.3 (4)	C19—C16—C17—C18	−177.9 (4)
C4—C3—C8—C7	0.5 (8)	C16—C17—C18—N4	179.9 (5)
N1—C3—C8—C7	−178.9 (4)	C16—C17—C18—C13	−0.5 (7)
C4—C3—C8—N2	178.9 (4)	C12—N4—C18—C17	179.1 (5)
N1—C3—C8—N2	−0.5 (5)	C12—N4—C18—C13	−0.5 (5)
C6—C7—C8—C3	0.1 (7)	C14—C13—C18—C17	0.8 (7)
C6—C7—C8—N2	−177.8 (5)	N3—C13—C18—C17	−179.2 (4)
C2—N2—C8—C3	0.1 (6)	C14—C13—C18—N4	−179.5 (4)
C2—N2—C8—C7	178.3 (5)	N3—C13—C18—N4	0.5 (5)
C10—O2—C9—O1	0.3 (8)	C20—O4—C19—O3	0.8 (8)
C10—O2—C9—C6	−179.7 (4)	C20—O4—C19—C16	−179.7 (4)
C7—C6—C9—O1	−1.1 (9)	C17—C16—C19—O3	169.9 (6)
C5—C6—C9—O1	178.0 (6)	C15—C16—C19—O3	−8.2 (9)
C7—C6—C9—O2	178.9 (4)	C17—C16—C19—O4	−9.6 (7)
C5—C6—C9—O2	−2.0 (7)	C15—C16—C19—O4	172.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O6	0.86	2.34	3.040 (6)	138
N1—H1A···O7	0.86	2.07	2.906 (6)	163
N2—H2A···O8^i	0.86	2.36	3.120 (6)	148
N2—H2A···O9^i	0.86	2.00	2.804 (7)	154
N3—H3A···O5^ii	0.86	2.43	3.135 (6)	139
N3—H3A···O7^ii	0.86	2.04	2.868 (5)	160
N4—H4A···O8	0.86	2.01	2.839 (6)	163
N4—H4A···O10	0.86	2.40	3.090 (6)	138
O1W—H1W1···O4	0.85	2.43	3.28 (2)	173
O1W—H2W1···O10	0.85	2.15	2.72 (2)	124
C1—H1B···O9^i	0.96	2.55	3.350 (8)	140
C5—H5A···O2	0.93	2.35	2.679 (6)	100
C5—H5A···O3^iii	0.93	2.49	3.140 (7)	127
C10—H10A···O1W^ii	0.96	2.47	3.42 (2)	173
C15—H15A···O6^iv	0.93	2.56	3.359 (7)	145
C17—H17A···O10	0.93	2.55	3.258 (7)	133

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